CN107486161A - A kind of adsorbent for heavy metal and its application - Google Patents

A kind of adsorbent for heavy metal and its application Download PDF

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Publication number
CN107486161A
CN107486161A CN201710692888.3A CN201710692888A CN107486161A CN 107486161 A CN107486161 A CN 107486161A CN 201710692888 A CN201710692888 A CN 201710692888A CN 107486161 A CN107486161 A CN 107486161A
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China
Prior art keywords
adsorbent
heavy metal
tobacco
cigarette stalk
surface area
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710692888.3A
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Chinese (zh)
Inventor
王爱国
张艳玲
尹启生
梁太波
牟文君
田阳阳
张仕祥
王建伟
过伟民
戴华鑫
郭建华
王广山
胡利伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou Tobacco Research Institute of CNTC
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Zhengzhou Tobacco Research Institute of CNTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou Tobacco Research Institute of CNTC filed Critical Zhengzhou Tobacco Research Institute of CNTC
Priority to CN201710692888.3A priority Critical patent/CN107486161A/en
Publication of CN107486161A publication Critical patent/CN107486161A/en
Pending legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/24Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/28Treatment of tobacco products or tobacco substitutes by chemical substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid 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 physical properties
    • B01J20/28004Sorbent size or size distribution, e.g. particle size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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 form
    • B01J20/28016Particle form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28059Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

The present invention relates to a kind of adsorbent for heavy metal and its application.The preparation of the adsorbent for heavy metal includes:Using tobacco stem cigarette stalk as raw material, carry out increasing the mixed solvent immersion treatment of specific surface area processing, low mass molecule alcohol and aqueous slkali composition successively, separation of solid and liquid, produce the adsorbent for heavy metal.Adsorbent for heavy metal provided by the invention, using tobacco stem cigarette stalk as raw material, obtain adsorbent after the mixed solvent modification of increased specific surface area processing, low mass molecule alcohol and aqueous slkali composition successively;Cigarette stalk is homologous with tobacco leaf, and constituent is essentially identical with tobacco leaf, will not bring non-tobacco composition into tobacco extraction liquid;Cigarette stalk has the potential adsorption site of substantial amounts of metal ion in itself simultaneously, and modified processing can be that the absorption of heavy metal ion creates conditions, and adsorption test proves that the adsorbent shows good suction-operated to the heavy metal ion in tobacco extraction liquid.

Description

A kind of adsorbent for heavy metal and its application
Technical field
The invention belongs to the removal field of heavy metal ions from tobacco extract, and in particular to a kind of heavy metal ion adsorbed Agent and its application.
Background technology
Tobacco extraction liquid is that the water-soluble substances in the tobacco materials such as tobacco leaf, offal, offal is extracted into water to obtain A kind of liquid.It can be used for producing reconstituted tobacco after tobacco extraction liquid is concentrated.In recent years, with the hair of Harm reduction techniques tar reduction technology Exhibition, reconstituted tobacco mix rate continuous improvement in high-grade cigarette, turn into important raw material of cigarette.
In the aspiration procedure of traditional cigarette, the heavy metal in pipe tobacco is migrated and is absorbed by the body such as flue gas, therefore Content of beary metal is too high in tobacco product can seriously endanger health.Research shows, lead in the cigarette product of China part, cadmium, The content of beary metal such as arsenic are higher than Canadian like product.In tobacco leaf content of beary metal depend on planting soil, tobacco bred, The Multiple factors such as agronomic measures, from the point of view of current research conditions, reduce the cost of content of beary metal needs in tobacco-growing soil very The high or time is very long, and reduces arranging for content of beary metal in tobacco leaf by the seed selection and agronomic measures of low Cd uptake kind Apply the achievement for not yet obtaining be adapted to actual production at present.From tobacco extraction liquid, heavy metal ions from tobacco extract is reduced Content, turning into reduces one of effective way of heavy metal ion content in tobacco product.
Authorization Notice No. is that CN102406230B patent discloses a kind of removal of heavy metal ions from tobacco extract Method, it is that tobacco extraction liquid is first passed through to electrolysis unit after pulse filter filters to carry out electrolysis processing, then by sun Ion exchange resin column processing, so as to remove the heavy metal ion in tobacco extraction liquid.Authorization Notice No. is CN102960850B Patent disclose a kind of manufacture method of modified extract and for reducing tobacco sheets by paper making method heavy metal ion content Method, this method is to be fabricated to extract solution using modified red stilbite, then extract solution is applied in the production of reconstituted tobacoo.On Though the method for stating can reduce heavy metal ions from tobacco extract content, higher cost, complex process or may be to tobacco be present The problems such as non-plant derived components are mixed in extract.
Authorization Notice No. discloses one kind for CN103386293B patent and uses dyers' grapes root system to be made as raw material The adsorbent of tobacco extraction liquid, obtain preferable adsorption effect;Because dyers' grapes are botanical materials, non-plant can be greatly avoided Source material enters tobacco extraction liquid, but dyers' grapes are still non-tobacco source material, may be brought into tobacco extraction liquid Some non-tobacco compositions, and then influence the quality of tobacco extraction liquid and subsequent product.
The content of the invention
, may be to cigarette so as to solve existing adsorbent it is an object of the invention to provide a kind of adsorbent for heavy metal The problem of non-tobacco composition being brought into careless extract.
Second object of the present invention is that providing above-mentioned adsorbent is reducing heavy metal ions from tobacco extract content The application of aspect.
To achieve the above object, the technical solution adopted in the present invention is:
A kind of adsorbent for heavy metal, it is prepared by the method comprised the following steps:Using tobacco stem cigarette stalk as original Material, the processing of increase specific surface area is carried out successively, the mixed solvent immersion treatment that low mass molecule alcohol and aqueous slkali form, separation of solid and liquid, Produce the adsorbent for heavy metal.
Adsorbent for heavy metal provided by the invention, using tobacco stem cigarette stalk as raw material, increased specific surface area successively Adsorbent is obtained after the mixed solvent modification of processing, low mass molecule alcohol and aqueous slkali composition;Cigarette stalk is homologous with tobacco leaf, forms into It is point essentially identical with tobacco leaf, non-tobacco composition will not be brought into;Cigarette stalk has the potential adsorption potential of substantial amounts of metal ion in itself simultaneously Point, modified processing can be that the absorption of heavy metal ion creates conditions, and adsorption test proves the adsorbent to tobacco extraction liquid In heavy metal ion show good suction-operated.
The increase specific surface area processing is that dry cigarette stalk crushing is obtained increasing to the cigarette stalk material of specific surface area.Institute The moisture content for stating dry cigarette stalk is not more than 5%.Preferably, temperature cigarette stalk being dried is 50~60 DEG C.By by cigarette Stalk crushes, and increases the specific surface area of adsorbent, contributes to metal adsorption site fully to appear.Its other party can also be used at this Formula improves the specific surface area of cigarette stalk, such as thinly slices cigarette stalk or other profiled shapes.Cigarette stalk can be Flue-cured Tobacco stalk, white rib One or more in cigarette cigarette stalk, Maryland cigarette stalk, Oriental Tobacco stalk.
Preferably, the specific surface area of cigarette stalk material is not less than 0.009m2/g。0.009m2/ g corresponds to the mesh of maximum particle diameter 20, Diameter 0.84mm, density 0.8g/cm3, it is assumed that material is calculated when being solid light face ball.
Preferably, the particle diameter of cigarette stalk material is not more than 0.84mm.It is further preferred that the particle diameter of cigarette stalk material is not more than 0.25mm。
Preferably, the low mass molecule alcohol is methanol and/or ethanol.The aqueous slkali is NaOH solution or KOH solution, alkali soluble OH in liquid-Concentration be 0.1~1.0mol/L.It is further preferred that the volume ratio of low mass molecule alcohol and aqueous slkali for (0.5~ 2.0):1.
Preferably, it is immersed in the lower progress of vibration auxiliary.It is further preferred that the vibration is circumferential oscillation, rotating speed 100 ~200r/min.
Preferably, the time of immersion is 12~48h.Whether soak time can be according to using vibration auxiliary or different vibration bar Part is adjusted.
After solid-liquid processing, solid phase is washed with water, in 50 DEG C~80 DEG C drying, produces adsorbent for heavy metal.
The adsorbent for heavy metal of the present invention, cigarette stalk storage is big, cost is cheap, is readily available, modifying processing step letter It is single, easily operated, make gained low adsorbent cost, be easy to industrialized production;Adsorbent after use, can after diluted acid elutes To reuse, the cost of heavy metal ions from tobacco extract adsorption treatment is reduced.
Application of the above-mentioned adsorbent for heavy metal in terms of heavy metal ions from tobacco extract content is reduced, including: Adsorbent for heavy metal and tobacco extraction liquid are mixed, adsorbent for heavy metal is isolated after adsorption equilibrium.
Preferably, adsorb and carried out in the case where vibration aids in.It is further preferred that the vibration is circumferential oscillation, rotating speed 100 ~200r/min.
The adsorbent can be eluted by diluted acid reuse after use.The diluted acid is nitric acid, hydrochloric acid, sulfuric acid, acetic acid In one kind or any combination, the concentration of diluted acid is 0.01~1.0mol/L.
When being removed applied to heavy metal ions from tobacco extract, this method clearance is higher, and has prevented to tobacco The possibility of non-tobacco derived components is added in extract.This method directly can make in the production technology link of tobacco extraction liquid With process cycle is short, high treating effect.
Brief description of the drawings
Fig. 1 is preparation and the process for using figure of the adsorbent for heavy metal of the present invention.
Embodiment
Embodiments of the present invention are described further with reference to specific embodiment.In following examples, tobacco extraction The preparation process for taking liquid is:The offal sample of tobacco leaf in the middle part of flue-cured tobacco is chosen, 20.0g offals is weighed, is put into 2000ml triangular flasks, 1000ml water is added, is placed on shaking table and 2h is vibrated with 200r/min, is filtered with the nylon leaching film that aperture is 40 μm, filtrate is cigarette Careless extract.Using before Agilent ICPMS7500 measure absorption in tobacco extraction liquid cadmium and lead content be respectively 73.3 μ g/L, 8.3μg/L。
Embodiment 1
The adsorbent for heavy metal of the present embodiment, preparation flow figure using following methods as shown in figure 1, prepared:
1) dry cigarette stalk is ground, obtains the cigarette stalk powder (being designated as A powder) that particle diameter is 0.15mm~0.25mm;
2) weigh 5.0g A powder, and be separately added into 100mL ethanol and NaOH solution composition alcohol alkali modification liquid (NaOH is molten The concentration of liquid is 0.4mol/L, and ethanol, the volume ratio of NaOH solution are 1:1), (circumferential oscillation, turn after shaking table oscillation treatment 22h Speed is 150r/min), filtered, then cleaned 3 times with deionized water, 55 DEG C of drying obtain alcohol alkali modification with 150 mesh nylon screens Adsorbent A.
When being adsorbed using the adsorbent for heavy metal of the present embodiment to the heavy metal ion in tobacco extraction liquid, claim Alcohol alkali modification adsorbent A 0.2g is taken, adds tobacco extraction liquid 15mL, vibration absorption 2.0h, filtering under 150r/min rotating speed Adsorbent for heavy metal is separated with tobacco extraction liquid.Adsorbent for heavy metal is after 0.5mol/L salpeter solution elution It is reusable.
Using tobacco extraction liquid of the Agilent ICPMS7500 measure after the processing of alcohol alkali modification adsorbent A, its cadmium and lead contain Amount respectively 25.2 μ g/L and 2.1 μ g/L clearances are respectively 65.6% and 74.7%, are greatly reduced in tobacco extraction liquid The content of cadmium and lead.
Embodiment 2
The adsorbent for heavy metal of the present embodiment, is prepared using following methods:
1) dry cigarette stalk is ground, obtains the cigarette stalk powder (being designated as B powder) that particle diameter is 0.25mm~0.42mm;
2) 5.0g B powder is weighed, adds the alcohol alkali modification liquid (concentration of KOH solution of 100mL methanol and KOH solution composition For 0.2mol/L, methanol, the volume ratio of KOH solution are 1:2), (circumferential oscillation, rotating speed 120r/ after shaking table oscillation treatment 36h Min), filtered, then cleaned 3 times with deionized water, 55 DEG C of drying obtain alcohol alkali modification adsorbent with 150 mesh nylon screens.
When being adsorbed using the adsorbent for heavy metal of the present embodiment to the heavy metal ion in tobacco extraction liquid, claim Alcohol alkali modification adsorbent 0.2g is taken, adds tobacco extraction liquid 15mL, the vibration absorption 2.5h under 120r/min rotating speed, filtering will Adsorbent for heavy metal separates with tobacco extraction liquid.
The tobacco extraction liquid after alcohol alkali modification sorbent treatment is determined using Agilent ICPMS7500, its cadmium and lead contain Amount respectively 24.9 μ g/L and 2.2 μ g/L, clearance are respectively 66.0% and 73.5%.
Embodiment 3
The adsorbent for heavy metal of the present embodiment, is prepared using following methods:
1) dry cigarette stalk is ground, obtains the cigarette stalk powder (being designated as C powder) that particle diameter is 0.42mm~0.84mm;
2) 5.0g C powder is weighed, adds the mixed solvent (concentration of NaOH solution of 100mL ethanol and NaOH solution composition For 0.6mol/L, ethanol, the volume ratio of NaOH solution are 2:1), (circumferential oscillation, rotating speed 180r/ after shaking table oscillation treatment 40h Min), filtered, then cleaned 3 times with deionized water, 55 DEG C of drying obtain alcohol alkali modification adsorbent with 150 mesh nylon screens.
When being adsorbed using the adsorbent of the present embodiment to the heavy metal ion in tobacco extraction liquid, alcohol alkali modification is weighed Adsorbent 0.2g, tobacco extraction liquid 15mL is added, vibration absorption 3.0h, is filtered heavy metal ion under 200r/min rotating speed Adsorbent separates with tobacco extraction liquid.
The tobacco extraction liquid after alcohol alkali modification sorbent treatment is determined using Agilent ICPMS7500, its cadmium and lead contain Amount is respectively that 31.4 μ g/L and 2.5 μ g/L, clearance respectively reach 57.2% and 69.9%.
In the other embodiment of adsorbent, can using cigarette stalk thinly sliced or other profiled shapes by the way of increase The specific surface area of cigarette stalk, the adsorption effect suitable with the performance of embodiment 1~3 can be played.

Claims (10)

1. a kind of adsorbent for heavy metal, it is characterised in that be prepared by the method comprised the following steps:With tobacco stem Cigarette stalk is raw material, carries out increasing the mixed solvent immersion treatment of specific surface area processing, low mass molecule alcohol and aqueous slkali composition successively, Gu Liquid separates, and produces the adsorbent for heavy metal.
2. adsorbent for heavy metal as claimed in claim 1, it is characterised in that the increase specific surface area processing is will be dry Dry cigarette stalk crushes, and obtains increasing the cigarette stalk material of specific surface area.
3. adsorbent for heavy metal as claimed in claim 2, it is characterised in that the specific surface area of the cigarette stalk material is not small In 0.009m2/g。
4. adsorbent for heavy metal as claimed in claim 2, it is characterised in that the particle diameter of the cigarette stalk material is not more than 0.84mm。
5. adsorbent for heavy metal as claimed in claim 1, it is characterised in that the low mass molecule alcohol is methanol and/or second Alcohol.
6. adsorbent for heavy metal as claimed in claim 1, it is characterised in that the aqueous slkali is NaOH solution or KOH Solution, OH in aqueous slkali-Concentration be 0.1~1.0mol/L.
7. the adsorbent for heavy metal as described in claim 1 or 5 or 6, it is characterised in that the body of low mass molecule alcohol and aqueous slkali Product ratio is (0.5~2.0):1.
8. adsorbent for heavy metal as claimed in claim 1, it is characterised in that be immersed in the lower progress of vibration auxiliary.
9. the adsorbent for heavy metal as described in claim 1 or 8, it is characterised in that the time of immersion is 12~48h.
10. a kind of adsorbent for heavy metal as claimed in claim 1 is reducing heavy metal ions from tobacco extract content The application of aspect, it is characterised in that including:Adsorbent for heavy metal and tobacco extraction liquid are mixed, separated after adsorption equilibrium Go out adsorbent for heavy metal.
CN201710692888.3A 2017-08-14 2017-08-14 A kind of adsorbent for heavy metal and its application Pending CN107486161A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110788131A (en) * 2019-12-01 2020-02-14 杜廷芹 Soil remediation method and device
CN113856639A (en) * 2021-10-19 2021-12-31 湖北中烟工业有限责任公司 Preparation method and application of adsorbent for low-grade tobacco leaf solid phase extraction

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CN104383890A (en) * 2014-11-26 2015-03-04 云南省农业科学院质量标准与检测技术研究所 Soil heavy metal ion absorbent and preparation method thereof
CN105056900A (en) * 2015-07-27 2015-11-18 刘雷 Heavy metal ion absorbent preparation method on basis of wastes
CN106693919A (en) * 2017-01-18 2017-05-24 浙江工业大学 Adsorbent for adsorbing heavy metal ions and application of adsorbent

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110788131A (en) * 2019-12-01 2020-02-14 杜廷芹 Soil remediation method and device
CN110788131B (en) * 2019-12-01 2021-11-05 山东省环境保护科学研究设计院有限公司 Soil remediation method and device
CN113856639A (en) * 2021-10-19 2021-12-31 湖北中烟工业有限责任公司 Preparation method and application of adsorbent for low-grade tobacco leaf solid phase extraction

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