CN1803275A - Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal - Google Patents
Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal Download PDFInfo
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- CN1803275A CN1803275A CN200510045500.8A CN200510045500A CN1803275A CN 1803275 A CN1803275 A CN 1803275A CN 200510045500 A CN200510045500 A CN 200510045500A CN 1803275 A CN1803275 A CN 1803275A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 71
- 239000003463 adsorbent Substances 0.000 title claims abstract description 63
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000741 silica gel Substances 0.000 title claims description 21
- 229910002027 silica gel Inorganic materials 0.000 title claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims 1
- 238000003381 deacetylation reaction Methods 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000077 silane Inorganic materials 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- WNWMJFBAIXMNOF-UHFFFAOYSA-N trimethyl(propyl)silane Chemical compound CCC[Si](C)(C)C WNWMJFBAIXMNOF-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002118 epoxides Chemical group 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- ZQTSZJGZGSXNAY-UHFFFAOYSA-N C1(C2C(O2)O1)OCC(O)CO Chemical compound C1(C2C(O2)O1)OCC(O)CO ZQTSZJGZGSXNAY-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a new-typed heavy metal ion adsorbent of silica loading crosslinking chitosan in the environment-protection domain, which is characterized by the following: the metal ion adsorbent adapts gamma-epoxy propyl-trimethyl silane with epoxy group and soluble inorganic silane agent as chitosan crosslinking agent; the chitosan crosslinking action is accomplished by the reaction of chitosan and epoxy group and the silane agent hydrolysis and condensation course. The invention displays simple course without organic solvent and environmental pollution, which can dispose the waste water with heavy metal ion.
Description
[technical field]
The present invention relates to a kind of adsorbent for heavy metal, particularly a kind of novel silica gel loaded cross-linked chitosan adsorbent for heavy metal.The invention belongs to field of environment protection, belong to especially and contain harmful heavy metal ion discarded object or waste water treatment field.
[background technology]
Heavy metal generally extensively is present in occurring in nature with natural concentration.Yet, human increasing along with development of modern industry in recent decades to exploitation, smelting, processing and the commercial manufacturing activities of heavy metal, cause many heavy metals to enter atmosphere, water, soil environment, cause the serious environmental pollution.At present, as one of global important pollution sources, heavy metals such as mercury, lead, copper, nickel are serious day by day to the harm that human health causes, and the improvement of heavy metal pollution caused people's extensive concern.The improvement method mainly concentrates on the microorganism reparation and chemistry is repaired.Owing to utilize microbiological treatment heavy metal cost higher, therefore at present to the improvement of heavy metal still based on chemical repairing methods such as chemical reduction method, electrolysis, ion-exchange, sedimentation flocculence, hyperfiltrationes.Wherein, be most widely used with the chemical settling flocculence again.Yet the flocculant of use belongs to chemicals (as calcium hydroxide etc.) more, and its production process itself will pollute environment, and the precipitum instability that contains heavy metal ion that produces when administering, and causes secondary pollution easily.Therefore, exploitation preparation technology is simple, with low cost, effect obvious, the significant and broad prospect of application of adsorbent for heavy metal of non-secondary pollution, is one of emphasis of one section environmental technology field research in period from now on.
Shitosan (Chitosan) is the important derivatives of natural class polysaccharide chitin, extensively being present in the cell membrane of the shells of shellfish such as shrimp crab and insect etc. and many rudimentary plants such as Homonemeae, is that the occurring in nature reserves are only second to the abundantest cellulosic natural macromolecular material.In the last few years, attach great importance to the development and utilization of this resource in the world.Owing to contain a large amount of free amine groups and hydroxyl in the chitosan molecule, can form stable chelate with heavy metal ion, thus shitosan and derivative thereof be used to contain the research of aspects such as processing, precious metal ion enrichment and recovery of industrial wastewater of heavy metal ion as metal ion adsorbent very active.In addition, shitosan is to people and biological nontoxic, and is biodegradable at occurring in nature, is typical environment-friendly material.Yet shitosan is used for when the sour environment adsorbing metal ions, can be run off by the protonated and water-soluble adsorbent that causes because of the amino in the molecule, is unfavorable for regeneration.Therefore, usually shitosan is carried out crosslinking Treatment to overcome its solubility in acid before use.Usually the crosslinking agent that adopts has glutaraldehyde, formaldehyde, epoxychloropropane, glycerine diepoxypropyl ether etc.It should be noted that and use the cross-linking process of these crosslinking agents need use a large amount of organic solvents usually, make the process of preparation adsorbent produce a large amount of sewage.In addition, cross-linked chitosan also has the granulation difficulty, and proportion is little, and the speed of sedimentation waits shortcoming slowly from solution, has greatly limited being extensive use of of this type of adsorbent.
The purpose of this invention is to provide and a kind ofly prepare simple, function admirable, be applicable to the adsorbent for heavy metal that heavy metal ion-containing waste water is handled.The cross-linking reagent that the present invention adopts is for containing epoxide group, water miscible γ-Huan Yangbingyangbingjisanjiayangjiguiwan, the preparation of adsorbent for heavy metal need not any organic solvent, preparation process is simple, non-environmental-pollution, gained adsorbent for heavy metal have stable in properties, adsorption rate is fast, good to the adsorption of metal ions performance.On silica gel, gained adsorbent for heavy metal mechanical strength height, sedimentation are rapid with chitosan loaded in the present invention.Compare advantage such as it is low that goods of the present invention also have price, simple and easy to use with the external chemical synthesis adsorbent that adopts usually.
[summary of the invention]
At the problem that existing glycan substrate adsorbent for heavy metal exists, the invention provides that a kind of preparation process is simple, good adsorption performance, cheap, environmental friendliness, adsorbent for heavy metal simple and easy to use.
Adsorbent for heavy metal of the present invention is finished by following steps:
---a adds shitosan 2-4g in 1mol/L 100mL acetum, magnetic agitation 30min filters;
---b adds inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan 2-8mL, magnetic agitation 30min in filtrate;
---c adds 100-200 order silica gel 50g in solution, stir ultrasonic 40min;
---d is poured into solution in the culture dish, stirs, and room temperature leaves standstill 48h;
---e soaks 30min with the gained solid in 0.01mol/L 100mL sodium hydroxide solution, distilled water is washed till neutrality, and 40 ℃ of oven dry get silica gel loaded cross-linked chitosan adsorbent for heavy metal.
The crosslinked of shitosan of the present invention realized by cross-linking reagent.Water miscible γ-Huan Yangbingyangbingjisanjiayangjiguiwan crosslinking agent contains difunctional: silicon methoxyl group and epoxide group.On the one hand, as shown in Figure 1: the silicon methoxyl group can form inorganic oxide network by the hydrolysis in solution, condensation.Silica gel be coated with stain in the liquid acetic acid component and preparation process in the volatilization gradually of solution all can quicken the formation of this inorganic oxide network.On the other hand, as shown in Figure 2: the amino in the chitosan molecule and the reaction of epoxide group, can realize crosslinked between the shitosan chain and shitosan successfully is incorporated in the inorganic network.The silanol groups that abundant hydroxyl, amino and inorganic silane component produces in the chitosan molecule can provide a large amount of hydrogen bonds to form the site, is very beneficial for obtaining in the silica gel surface preparation material of even structure, function admirable.
The adsorbent for heavy metal of the present invention's preparation, when processing contains the waste water of heavy metal ion, simple to operate.Adsorbent can be used as the column chromatography filled media, dynamically adsorbs the removal heavy metal ion by column chromatography; Also this adsorbent directly can be joined in the waste water, make solution fully contact the purpose that reaches Adsorption of Heavy Metal Ions with adsorbent by stirring or shaking.And adsorbent can be easily by depositing or centrifugal removing naturally.
Silica gel has high specific area and good mechanical strength.The present invention is with the chitosan loaded adsorbent for heavy metal for preparing on silica gel, during this adsorbent for heavy metal Adsorption of Heavy Metal Ions, the shitosan layer contact-making surface on heavy metal ion in the solution and silica gel surface is big, makes that this adsorbent for heavy metal adsorption rate is fast, mechanical strength is high, sedimentation is rapid.
With heavy metal ion Cu
2+Be example, detect the adsorption effect of adsorbent.The instrument that detects concentration of heavy metal ion be Sol AAR S2 type atomic absorption spectrophotometer (Thermo Electron Corporation, UK).
(1) this adsorbent for heavy metal dynamically adsorbs heavy metal ion as the column chromatography filled media
This adsorbent for heavy metal is soaked into the back wet method internal diameter of packing in water be the glass chromatography column of 2.6cm, post height of bed 10cm.With the flow velocity of 2mL/min Cu by 100mg/L
2+Standard liquid (pH=5.0) flows out liquid and measures the content that flows out the metal ion in the liquid with atomic absorption spectrophotometer after collecting post, goes up sample standard liquid volume when the record metal ion begins to reveal.The result shows that this adsorbent for heavy metal dynamically adsorbs heavy metal ion as the column chromatography filled media, and when pH=5.0, every gram adsorbent is to Cu
2+Adsorbance be 4.39mg.
(2) this adsorbent for heavy metal is to the vibration absorption of heavy metal
Take by weighing the 1g adsorbent, the vinyon centrifuge tube of packing into is measured the Cu of certain volume 100mg/L
2+Standard liquid (pH=5.0) places this centrifuge tube, screws the centrifuge tube lid, the certain hour that vibrates in oscillator, the Cu before and after the absorption
2+Concentration records with atomic absorption spectrophotometer.To Cu
2+Concentration compared before and after standard liquid was crossed post, calculated heavy metal ion adsorbed amount according to formula (1).
In the formula: Q is the adsorbance (mg/g) of every gram ABSORBENTS ABSORPTION metal ion; C
0, C is respectively the initial concentration of heavy metal ion in the solution and the equilibrium concentration (mg/L) after the absorption; V is the volume (mL) that is adsorbed heavy metal ion solution; W is the dry weight (g) of adsorbent.
Experimental result shows that this adsorbent for heavy metal is to the vibration absorption of heavy metal ion, and this adsorbent of every gram is to Cu during pH=5.0
2+Adsorbance be 4.17mg.
The adsorbent for heavy metal regeneration that the present invention makes is convenient.The adsorbent of Adsorption of Heavy Metal Ions is soaked in the hydrochloric acid solution of 0.1mol/L behind the 1h, the adsorbent taking-up is washed till neutrality with distilled water, soak 10min at the sodium hydroxide solution of 0.05mol/L then, distillation wash neutrality dry after this adsorbent promptly reusable.
The adsorbent for heavy metal that the present invention makes has good stable in acid, after the acetum of 1mol/L shakes extracting 2h to this adsorbent for heavy metal, do not detect shitosan in the solution, illustrates that this adsorbent has good stable in acid.
Advantage of the present invention and effect:
1, the present invention on silica gel, makes it equably wrap in silica gel surface by crosslinking agent is crosslinked with chitosan loaded, and the gained adsorbent is solid solid particle.This method has been improved evenly spherical shortcoming of soft, the difficult one-tenth of solubility in acid, the matter of glycan substrate.Simultaneously, the adsorbent for heavy metal mechanical strength height of the present invention's preparation, but rapid subsidence.
2, the crosslinking agent of the present invention's employing is water miscible inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan, and the preparation process reaction condition gentleness of adsorbent for heavy metal need not any organic solvent, environmental friendliness.
3, the adsorbent for heavy metal high adsorption capacity that makes of the present invention, the maximum adsorbable Cu of 1g adsorbent
2+4.39mg.
4, the adsorbent for heavy metal regenerability that makes of the present invention is good, and regeneration back absorption property does not have significant change.
5, the adsorbent for heavy metal that makes of the present invention has good stable in acid.
It is easy to operate when 6, the adsorbent for heavy metal that makes of the present invention uses.The adsorbent for heavy metal of preparation can be used as the column chromatography filler, dynamically adsorb the removal heavy metal ion by column chromatography, also directly join in the solution that contains heavy metal ion, reach the purpose of adsorbing heavy metal by stirring or shaking, and adsorbent can be removed easily.
[description of drawings]
Fig. 1, cross-linking reagent hydrolysis, condensation course schematic diagram.
Fig. 2, chitosan crosslinked process schematic diagram.
[specific embodiment]
The present invention adds refining shitosan 2g in 1mol/L 100mL acetum, magnetic agitation 30min, and filter cloth filters the back and removes insoluble residue; In filtrate, add inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan 2mL, behind the magnetic agitation 30min, in solution, add 100-200 order silica gel 50g while stirring, stir ultrasonic 40min; Suspension is poured in the culture dish, stirs, room temperature leaves standstill 48h to solid drying; Take out adsorbent the gained solid soaked 30min in 0.01mol/L 100mL sodium hydroxide solution after, distilled water is washed till neutrality, and 40 ℃ of oven dry can obtain silica gel loaded cross-linked chitosan adsorbent for heavy metal.
Claims (4)
1, a kind of novel silica gel loaded cross-linked chitosan adsorbent for heavy metal is characterized in that this adsorbent for heavy metal prepares by following steps:
---a adds shitosan 2-4g in 1mol/L 100mL acetum, magnetic agitation 30min filters;
---b adds crosslinking agent 2mL, magnetic agitation 30min in filtrate;
---c adds 100-200 order silica gel 20-50g in solution, stir ultrasonic 40min;
---d is poured into solution in the culture dish, stirs, and room temperature leaves standstill 48h;
---e soaks 30min with the gained solid in 0.01mol/L 100mL sodium hydroxide solution, distilled water is washed till neutrality, and 40 ℃ of oven dry get silica gel loaded cross-linked chitosan adsorbent for heavy metal.
2, novel silica gel loaded cross-linked chitosan adsorbent for heavy metal according to claim 1, the deacetylation that it is characterized in that shitosan is 98%.
3, a kind of novel silica gel loaded cross-linked chitosan adsorbent for heavy metal according to claim 1, the molecular weight that it is characterized in that shitosan is 3.2 * 10
4G/mol.
4, a kind of novel silica gel loaded cross-linked chitosan adsorbent for heavy metal according to claim 1, crosslinking agent is a γ-Huan Yangbingyangbingjisanjiayangjiguiwan among the step b.
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Family Cites Families (2)
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Cited By (29)
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