CN106179239A - The preparation method and applications of pomelo peel modified amido functionalization adsorbent - Google Patents

The preparation method and applications of pomelo peel modified amido functionalization adsorbent Download PDF

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CN106179239A
CN106179239A CN201610550185.2A CN201610550185A CN106179239A CN 106179239 A CN106179239 A CN 106179239A CN 201610550185 A CN201610550185 A CN 201610550185A CN 106179239 A CN106179239 A CN 106179239A
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pomelo peel
adsorbent
functionalization
modified amido
water
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梁珑
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    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The present invention discloses the preparation method and applications of a kind of pomelo peel modified amido functionalization adsorbent.Preparation process is: with pomelo peel as raw material, cleaned, carry out after drying pulverizing, sieving, obtaining the pomelo peel powder of pretreatment, one kettle way is substituted, ring-opening reaction carries out surface-functionalized modification to material in employing, finally gives the pomelo peel adsorbing material that amino functional is modified;The product that the present invention obtains is powder, and sundown has compact structure of fibrous tissue, and inside exists substantial amounts of hole;Rich in functional groups such as amino, hydroxyl and carbonyls, parabens emerging pollutant, the heavy metal copper that exceeds standard, chromium and methylene blue dye etc. in water there is excellent adsorption effect.It is simple that the present invention has preparation method, with low cost, resulting materials is cheap and easy to get, good biocompatibility, environmental friendliness, containing the chelating group of a large amount of functionalization, it is possible to achieve anion, cation adsorb simultaneously with remove and there is advantages such as can being recycled for multiple times.

Description

The preparation method and applications of pomelo peel modified amido functionalization adsorbent
Technical field
The present invention relates to a kind of methods and applications technology utilizing useless pomelo peel to prepare amino functional adsorbent, be specially The preparation method of pomelo peel modified amido functionalization adsorbent, and utilize pomelo peel amino functional absorption prepared by the present invention Exceed standard in water novel environmental pollutant, the heavy metal copper that exceeds standard, chromium and methylene blue dye pigment etc. are removed in agent, reach innoxious place Manage and realize the purposes such as fwaater resources protection.
Background technology
Emerging pollutant (emerging contaminants, ECs) refer to " new identification or the most unconfirmed ", " not by method Rule specification " and the chemical pollutant of " health and ecological environment are had potential or essence threat ".The kind of emerging pollutant Class mainly includes Pharmaceuticals and personal care products, incretion interferent, persistent pollutant, perfluorochemical, drinking water disinfection By-product and other industrial chemical matter etc..Though the existence concentration that emerging pollutant are in the environment is low (generally at μ g/L to ng/L Between), but can persistently be present in environment, accumulated by Food chain and human health is caused adverse effect, there is height Poison, persistently, biological accumulation, the characteristic such as Long-distance Migrating.By biological accumulation effect, pass to be positioned at the people on biological chain top During class, the toxicity of these materials can be amplified to 70,000 times, enter people know from experience cause that neurobehavioral is not normal, endocrine regulation, reproduction The increase etc. of system and immune system destruction, abnormal development and tumor.But, in the design of tradition water treatment technology usually not In view of the removal of emerging pollutant, research energy is efficient, high selectivity material, and is applied to remove emerging pollutant in water (ECs) have great importance.
The pigment such as heavy metal and dyestuff that exceeds standard is widely present in water environment, and has latent to water environment and human health In impact, also result in the extensive concern of people in recent years.Currently for emerging pollutant and exceed standard heavy metal and dyestuff isochrome The removal technique of element mainly has: coagulant sedimentation, active carbon adsorption, membrane process, advanced oxidation processes (ozone oxidation, chlorine oxygen Change, photocatalysis) etc..But removal efficiency is the highest, and advanced oxidation, nanofiltration/reverse osmosis even depth process process energy consumption and cost The most of a relatively high.There is challenge in the research about their minimizing technology the most always.
Biological adsorption agent, compared with traditional adsorbent, has a following principal character: (1) wide adaptability, can be at multiple pH Operate under value, temperature and the course of processing;(2) metal selective is high, can from solution Adsorption of Heavy Metal Ions and not by alkali metal The interference of ion;(3) concentration of metal ions impact is little, at low dense (< 10mg L-1) and high concentration (> 100mg L-1All have under) There is good metal adsorption ability;(4) good to Organic substance tolerance, Organic Pollution (≤5000mg L-1) do not affect metal from The absorption of son;(5) regeneration capacity is strong, step is simple, and after regeneration, absorbability is without substantially reducing.But utilize former slag to carry out absorption to deposit Relatively low at absorbability, the problems such as chemical oxygen consumption (COC) increase are caused in water owing to soluble organic matter dissolves.Therefore, have Necessity carries out chemical modification to improve adsorption capacity and chemical stability to it.
Fructus Citri grandis is one of China's main fruit, a large amount of plantation in many areas in south.Pomelo peel account for full weight 55%~ 54%.Generally pomelo peel is not utilized just abandons, and causes significant wastage.Owing to the white flock layer inside pomelo peel containing Substantial amounts of cellulose, family is commonly used to deodorant for refregerator.Pomelo peel contains a large amount of cellulose, hemicellulose, lignin and pectin, institute Can be used in theory prepare adsorbent, in order to remove the pollutant of environment.But by its direct applied adsorption efficiency also The highest.Such as pomelo peel is 169.5mg/g to dye adsorption amounts such as methylene blues.If useless pomelo peel can be carried out functional group to repair Decorations, it is possible to become the adsorbent with good adsorption properties, undoubtedly in resource regeneration and recycling, turn waste into wealth Etc. aspect there is important and positive meaning.
At present, although people have done certain research to from the modified technique of pomelo peel, but dietary fiber is focused primarily upon Thick extraction, how it is chemically modified and less for the research of environmental contaminants adsorbent." changing of the report such as Xu Zheng Property fruit peel to Cr VI Study on adsorption properties in water " (scientific and technological information, 2013,5,66-68) with 1% TGA soak also Pomelo peel, and Cr VI absorption in the water are modified in stirring, and adsorption efficiency there are no is obviously improved.Huang Donglan, " the Fructus Citri grandis of report Sub-skin saponification is cross-linking modified and to Cu in aqueous solution2+Study on adsorption properties " (food industry technology, 2015,36 (10), 225-228) use ethanol, NaOH and MgCl2During pomelo peel is processed, the most not unmodified and its activity modified Group, therefore absorption property and the selectivity of target contaminant are not improved significantly by resulting materials;And reaction time is relatively Long, complex operation, functional group's ratio is wayward, and therefore, its application is by bigger restriction.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, it is provided that a kind of simple to operate, efficiency is high, toxicity is low and more environmentally-friendly The preparation method of pomelo peel modified amido functionalization adsorbent.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of pomelo peel modified amido functionalization The preparation method of adsorbent, with useless pomelo peel as raw material, through over cleaning, is dried, pulverizes, sieves, and then uses one kettle way through taking Generation, ring-opening reaction carry out surface-functionalized modification to material, finally give pomelo peel modified amido functionalization adsorbent (amino merit The pomelo peel adsorbing material that energyization is modified).
A kind of preparation method of the pomelo peel modified amido functionalization adsorbent of the present invention, concrete preparation process includes:
(1) pomelo peel is carried out roguing, pulverizes after drying, sieve, obtain the pomelo peel powder of pretreatment;
(2) weigh the pomelo peel powder of step (1) gained, distribute it to the epoxychloropropane that volume ratio is 0.5~4:1 With (V in the mixed solution of organic solventEpoxychloropropane: VOrganic solvent=0.5~4:1);The pomelo peel powder of step (1) gained and epoxy The solid-to-liquid ratio of chloropropane is the 20~500g:100mL (shaddock peel powder of the epoxychloropropane corresponding 20~500g of i.e. every 100ml End);Then 0.5-10h is reacted at 50-100 DEG C under stirring, it is achieved hydroxyl (hydroxyl on its surface herein, the tool to its surface Body is the surface hydroxyl of the chemical composition in pomelo peel powder) carry out epoxidation modification;
(3) in the reaction system of step (2) epoxidation modification, organic polyamine is added so that organic multicomponent amine is whole The volume fraction of reaction system solution is 10-50%;Then proceeding at 50-100 DEG C of stirring reaction 0.5-10h, sucking filtration, under room temperature Distillation washing is washed to pH=7;By gained solid 40-100 DEG C of drying, obtain amino functional adsorbent.
In step of the present invention (1), being dried of pomelo peel can use natural air drying or 50-100 DEG C of drying in an oven 2~24 hours;The sieve used that sieves is 40-150 mesh sieve.
Organic solvent used in step of the present invention (2) is in ethanol, propylene glycol, glycerol, N,N-dimethylformamide One.
Epoxychloropropane and organic solvent volume ratio preferably 1~2:1 in step of the present invention (2);Pomelo peel powder and ring The solid-to-liquid ratio of oxygen chloropropane is preferably 50~200g:100mL.
Organic multicomponent amine used in step of the present invention (3) is in ethylenediamine, Diethylenetriamine, three second tetramines, tetren A kind of;Organic multicomponent amine is preferably 15-25% in the volume fraction of whole solution;Reaction temperature is preferably 60~90 DEG C, reaction Time is preferably 1~4h, and stir speed (S.S.) is 150~300 revs/min, and (above-mentioned reaction temperature, time and stir speed (S.S.) are equally applicable to Step (2));Preferred 40-80 DEG C of drying baker baking temperature.
The application in absorption pollutant of the pomelo peel modified amido functionalization adsorbent of the present invention, concrete may be used for Parabens emerging pollutant, the heavy metal copper that exceeds standard, chromium and the absorption of coloring matter and removal in water.
Preferred according to the present invention, the application of described sub-skin modified amido functionalization adsorbent, for p-Hydroxybenzoate The absorption of the pigments such as class emerging pollutant, the heavy metal copper that exceeds standard, chromium and methylene blue dye and removal.Method is as follows: in room temperature Under oscillating condition, putting into the amino functional modification pomelo peel adsorbing material of the present invention, dosage is adsorbent in every liter of waste water Content is 0.5~5g, and oscillation rate is 100~300 revs/min, and the time is 30~180 minutes;Parabens in water Emerging pollutant can be more than 99% with the clearance of coloring matter.
Pomelo peel modified amido functionalization adsorbent of the present invention remove the pH condition of p-Hydroxybenzoate in water be 1.0~ 12.0, preferably pH are 6.0~8.0;The pH condition of heavy metal copper (II) of exceeding standard in water is 1.0~6.0, preferably pH be 3.0~ 4.0;The pH condition of chromium (VI) is 1.0~12.0, and preferably pH is 2.0~4.0;The pH condition of methylene blue dye pigment is 1.0 ~12.0, preferably pH is 8.0~10.0.After the most above-mentioned pH is input pomelo peel modified amido functionalization adsorbent of the present invention The pH of waste water.
Pomelo peel modified amido functionalization adsorbent of the present invention can remove the dirt of water cationic and anionic simultaneously Dye thing.When pH is 3.0~4.0, to the going of chromium (VI) solution containing copper (II) that concentration is 100mg/L and 200mg/L simultaneously Except rate is up to 99%.
Pomelo peel modified amido functionalization adsorbent of the present invention can regenerate, and adsorbent acid or alkali after using take off Attached, after 5 times recycle adsorption efficiency remain to keep about 90% or more than.
Advantages of the present invention and beneficial effect:
1. the present invention is with pomelo peel as raw material, by cleaning, be dried, pulverize, sieving, is substituted further, ring-opening reaction Material is carried out surface-functionalized modification, finally gives the pomelo peel adsorbing material that amino functional is modified.;The inventive method obtains The product obtained is powder, and sundown has compact structure of fibrous tissue, and inside exists substantial amounts of hole (see accompanying drawing 2 institute Show);Rich in functional group'ss (shown in accompanying drawing 3) such as amino, hydroxyl and carbonyls;This raw material is easy to get, good biocompatibility, environment friend Well, can realize turning waste into wealth, and containing the chelating group of a large amount of amino functionals, it is possible to achieve novel environmental pollutant, color Element and anion, cation heavy metal contaminants adsorb simultaneously and remove, and have advantages such as can being recycled for multiple times.
2. the pomelo peel modified amido functionalization adsorbent of the present invention, is experimentally confirmed: this invention operating procedure is simple, Pomelo peel modified amido functionalization adsorbent even particle size distribution with low cost, that obtain, stable in properties;To para hydroxybenzene in water Formate ester novel environmental pollutant, heavy metal and methylene blue pigment etc. have high adsorption capacity, are effectively to remove waste water The potential adsorbent of middle harmful substance.Amino functional modification pomelo peel adsorbing material of the present invention can regenerate, after using Adsorbent acid or alkali desorption, after 5 times recycle, adsorption efficiency remains to keep about 90%.
Accompanying drawing explanation
Fig. 1 is that the pomelo peel that utilizes of the present invention prepares the schematic flow sheet of amino functional adsorbent.
Fig. 2 is according to embodiments of the present invention, the scanning electron microscope (SEM) of the pomelo peel modified amido functionalization adsorbent obtained Photo.
Fig. 3 is according to embodiments of the present invention, the infrared spectrogram of the pomelo peel modified amido functionalization adsorbent obtained.
Fig. 4 is that the pomelo peel modified amido functionalization adsorbent prepared of the embodiment of the present invention is in water 4 kinds of para hydroxybenzene first The adsorption isothermal curve of acid esters.
Fig. 5 be pomelo peel modified amido functionalization adsorbent prepared by the embodiment of the present invention be Cu to heavy metal ion in water (II) adsorption isothermal curve.
Fig. 6 be pomelo peel modified amido functionalization adsorbent prepared by the embodiment of the present invention be Cr to heavy metal ion in water (VI) adsorption isothermal curve;
Fig. 7 is that the pomelo peel modified amido functionalization adsorbent prepared of the embodiment of the present invention is to water Methylene Blue dyestuff Adsorption isothermal curve.
Fig. 8 is that different pH value amino functional shaddock peel adsorbent is adsorbed containing the copper (II) that concentration is 100mg/L simultaneously Adsorption rate curve with the waste water of the chromium (VI) of 200mg/L;
Fig. 9 is that the pomelo peel modified amido functionalization adsorbent prepared of the embodiment of the present invention is in water 4 kinds of para hydroxybenzene first The sorption cycle of acid esters uses figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings and present disclosure is described further by specific embodiment, the purpose of the present invention and effect are made Fruit becomes apparent from, but the present invention is not limited solely to following example.Preparation technology flow chart of the present invention is as it is shown in figure 1, concrete Step is with reference to each embodiment.
Embodiment 1
(1) pulverize after useless pomelo peel being carried out roguing, natural air drying, cross 100 mesh sieves, obtain the Fructus Citri grandis of pretreatment Sub-corium farinosum end;
(2) weighing 10g step (1) gained pretreated pomelo peel powder, distributing it to 20mL volume ratio is 1.2:1 Epoxychloropropane and ethanol mixed solution in, stir under 250 revs/min, react 1h at 75 DEG C, the hydroxyl on its surface is carried out Epoxidation modification;Adding 4mL ethylenediamine further, continue to react 2h, sucking filtration at 75 DEG C, under room temperature, distillation washing is repeatedly to pH= 7;Gained solid is placed in drying baker 60 DEG C of drying, obtains amino functional adsorbent.
The operating procedure of embodiment 2~6 is shown in Table 1 institute with embodiment 1, raw material, composition of raw materials and preparation condition parameter Show.
Table 1 embodiment of the present invention 1~6 raw material components and preparation parameter
Pomelo peel modified amido functionalization sample of sorbent prepared by the embodiment of the present invention by scanning electron microscope (SEM), It is characterized by the means such as infrared spectrum (FTIR), and is applied to p-Hydroxybenzoate in water, heavy metal and methylene blue Deng absorption and removal.
Fig. 2 and Fig. 3 is the scanning of the pomelo peel modified amido functionalization adsorbent that 1 obtains according to embodiments of the present invention respectively Electromicroscopic photograph and infrared spectrum;
As shown in Figure 2, the amino functional adsorbent utilizing pomelo peel waste material to prepare gained has compact fibrous tissue Structure, there is substantial amounts of hole in inside;From the infrared spectrum of Fig. 3 sample it can be seen that amino functional adsorbent~ 3418cm-1Wide and strong adsorption peak occurs ,-the OH ,-COOH and-NH of material surface can be attributed to2Absworption peak;~2929cm-1 For saturated C-H stretching vibration adsorption peak ,~1734cm-1Place is C=O stretching vibration, illustrates that pomelo peel contains carbonyl, because Fructus Citri grandis Sub-skin contains a large amount of cellulose, hemicellulose, lignin and pectin, so these carbonyls are very likely from acid or ester.~ 1634cm-1For C=O contracting vibration, it it is xylan hemicellulose character peak;1438~1253cm-1For the saturated CH of cellulose2Scissors are shaken Dynamic characteristic peak and the skeletal vibration of sugar ring;~1058cm-1For cellulose C-O-C stretching vibration characteristic peak;~612cm-1For sugar ring Deformation vibration characteristic peak.Above-mentioned sign illustrates that this invention operating procedure is simple, with low cost, the amino functional absorption obtained Agent is evenly distributed, stable in properties.
Embodiment 1 is presented herein below carries out adsorption applications to p-Hydroxybenzoate, copper, chromium and methylene blue dye etc. in water Example.
Application examples 1:
Embodiment 1 gained amino functional shaddock peel adsorbent is applied to absorption to the methyl parahydroxybenzoate in water (MPB), ethylparaben (EPB), propyl p-hydroxybenzoate (PPB), butyl p-hydroxybenzoate (BPB) 4 kinds are newly Type pollutant.PH value 6.5, adsorption time 30min, to the methyl parahydroxybenzoate (MPB) in water, P-hydroxybenzoic acid Ethyl ester (EPB), propyl p-hydroxybenzoate (PPB), the saturated extent of adsorption of butyl p-hydroxybenzoate (BPB) are respectively 680mg/ G, 685mg/g, 685mg/g, 690mg/g.
Application examples 2:
Embodiment 1 gained amino functional shaddock peel adsorbent is applied to absorption to copper (II) ion in water.PH takes Value 4.0, adsorption time 30min, the saturated extent of adsorption to copper (II) ion is 128mg/g.
Application examples 3:
Embodiment 1 gained amino functional shaddock peel adsorbent is applied to absorption to chromium (VI) ion in water.PH takes Value 2.5, adsorption time 30min, the saturated extent of adsorption to chromium (VI) ion is 370mg/g.
Application examples 4:
Embodiment 1 gained amino functional shaddock peel adsorbent is applied to absorption to the methylene blue dye in water.pH Value 8.0, adsorption time 60min, the saturated extent of adsorption to methylene blue dye is 156mg/g.
Fig. 3-7 is that (Fig. 4 is 4 kinds of p-Hydroxybenzoates to amino functional ABSORBENTS ABSORPTION metal ion, and Fig. 5 is Cu (II), Fig. 6 be Cr (VI), Fig. 7 be the adsorption isothermal curve of methylene blue dye.)
Application examples 5:
Embodiment 1 gained amino functional shaddock peel adsorbent is applied to process to contain concentration be 100mg/L's simultaneously The waste water of the chromium (VI) of copper (II) and 200mg/L.PH value 3.0, adsorption time 60min, to copper (II) and chromium (VI) clearance It is respectively 99.8% and 99.5%.
Fig. 8 is that different pH value amino functional shaddock peel adsorbent is adsorbed containing the copper (II) that concentration is 100mg/L simultaneously Adsorption rate curve with the waste water of the chromium (VI) of 200mg/L.
Application examples 6: by the P-hydroxybenzoic acid of embodiment 1 gained amino functional shaddock peel adsorbent absorption 100mg/L After ester, the HCl of the material 0.1mol/L after absorption is that desorbing agent carries out eluting, and investigates its recycling effect.Fig. 9 is ammonia The recycling figure of base functionalization shaddock peel adsorbent absorption p-Hydroxybenzoate.Result shows pomelo peel amino functional warp After recycling for 5 times, the adsorption efficiency of p-Hydroxybenzoate remains to keep about 90%, and material can be recycled for multiple times.
Pomelo peel modified amido functionalization adsorbent of the present invention, is experimentally confirmed: this invention operating procedure is simple, With low cost, the pomelo peel modified amido functionalization adsorbent obtained has compact structure of fibrous tissue, and internal existence is a large amount of Hole;Rich in the functional groups such as amino, hydroxyl and carbonyl, stable in properties;To p-Hydroxybenzoate, heavy metal and methylene in water Base cyanine etc. has high adsorption capacity, is effectively to remove the potential adsorbent of harmful substance in waste water.Amino merit of the present invention The modified pomelo peel adsorbing material of energyization can regenerate, and after 5 times recycle, adsorption efficiency remains to keep about 90%.

Claims (10)

1. the preparation method of a pomelo peel modified amido functionalization adsorbent, it is characterised in that: with useless pomelo peel as raw material, warp Over cleaning, it is dried, pulverizes, sieves, then use replacement, ring-opening reaction that material is carried out surface-functionalized modification, finally give Pomelo peel modified amido functionalization adsorbent.
The preparation method of pomelo peel modified amido functionalization adsorbent the most according to claim 1, it is characterised in that: concrete Preparation process includes:
(1) pomelo peel is carried out, is dried, pulverizes, sieves, obtain the pomelo peel powder of pretreatment;
(2) weigh the pomelo peel powder of step (1) gained, distribute it to epoxychloropropane that volume ratio is 0.5~4:1 and have In the mixed solution of machine solvent;The pomelo peel powder of step (1) gained and the solid-to-liquid ratio of epoxychloropropane are 20~500g: 100mL;Then 0.5-10h is reacted at 50-100 DEG C under stirring;
(3) in the reaction system of step (2) epoxidation modification, organic polyamine is added so that organic multicomponent amine is in whole reaction The volume fraction of system solution is 10-50%;Then at 50-100 DEG C of stirring reaction 0.5-10h, sucking filtration, it is washed to pH=7;Will Gained solid, 40-100 DEG C of drying, obtains amino functional adsorbent.
The preparation method of pomelo peel modified amido functionalization adsorbent the most according to claim 2, it is characterised in that: described In step (1) pomelo peel dry employing natural air drying or in an oven 50-100 DEG C dry 2~24 hours;Sieve the sieve used Son is 40-150 mesh sieve.
The preparation method of pomelo peel modified amido functionalization adsorbent the most according to claim 2, it is characterised in that: step (2) organic solvent described in is the one in ethanol, propylene glycol, glycerol, N,N-dimethylformamide;Epoxy in step (2) Chloropropane is 1~2:1 with organic solvent volume ratio;Pomelo peel powder is 50~200g with the solid-to-liquid ratio of epoxychloropropane: 100mL。
The preparation method of pomelo peel modified amido functionalization adsorbent the most according to claim 2, it is characterised in that: step (3) organic multicomponent amine used in is a kind of in ethylenediamine, Diethylenetriamine, three second tetramines, tetren;Organic multicomponent amine is whole The volume fraction of individual reaction system solution is 15-25%.Reaction temperature is 60~90 DEG C, and the response time is 1~4h, stir speed (S.S.) Being 150~300 revs/min, drying baker baking temperature is 40-80 DEG C.
6. the pomelo peel modified amido functionalization adsorbent application in absorption pollutant.
The pomelo peel modified amido functionalization adsorbent the most according to claim 6 application in absorption pollutant, it is special Levy and be: concrete parabens emerging pollutant, the heavy metal copper that exceeds standard, chromium, coloring matter and water in water The absorption of the pollutant of cationic and anionic and removal.
The pomelo peel modified amido functionalization adsorbent the most according to claim 7 application in absorption pollutant, it is special Levy and be: adsorb as follows with the method removed: under the conditions of shaken at room temperature, put into pomelo peel modified amido functionalization adsorbent, Dosage is that in every liter of waste water, adsorbent content is 0.5~5g, and oscillation rate is 100~300 revs/min, and the time is 30~180 points Clock.
The pomelo peel modified amido functionalization adsorbent the most according to claim 8 application in absorption pollutant, it is special Levy and be: pomelo peel modified amido functionalization adsorbent is removed the pH condition of parabens emerging pollutant in water and is 1.0~12.0, the pH removing in water the heavy metal copper that exceeds standard is 1.0~6.0, remove the pH of chromium in water is 1.0~12.0, removes water The pH of the pollutant that the pH condition of middle coloring matter is 1.0~12.0, remove water cationic and anionic is 3.0~4.0.
The pomelo peel modified amido functionalization adsorbent the most according to claim 8 application in absorption pollutant, it is special Levy and be: described pomelo peel modified amido functionalization adsorbent can regenerate, the adsorbent acid after using or alkali desorption, Through 5 times recycle after adsorption efficiency keep 90% or more than.
CN201610550185.2A 2016-07-12 2016-07-12 The preparation method and applications of pomelo peel modified amido functionalization adsorbent Pending CN106179239A (en)

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CN106582585A (en) * 2016-12-27 2017-04-26 常州大学 Preparation method of adsorbent material capable of removing mercurial ions in waste water
CN106582557A (en) * 2016-12-16 2017-04-26 常州市好利莱光电科技有限公司 Preparation method for grapefruit peel-based low-concentration chromium-containing wastewater adsorbent
CN106622157A (en) * 2016-12-20 2017-05-10 华南理工大学 Modified beet pulp fiber adsorbent as well as preparation method and application thereof
CN108499536A (en) * 2018-04-10 2018-09-07 浙江农林大学 A kind of efficient absorption anionic dye hydro-thermal bamboo charcoal preparation method
CN109721117A (en) * 2018-12-07 2019-05-07 南京林业大学 A kind of method of syringaldehyde functional modification and its product and the application of acquisition
CN111871390A (en) * 2020-07-08 2020-11-03 北部湾大学 Preparation of amino modified biological sponge and application of amino modified biological sponge in toxic metal wastewater treatment
CN112108126A (en) * 2020-10-15 2020-12-22 桂林理工大学 Passion fruit peel biological adsorbent for adsorbing anionic dye and preparation method and application thereof
CN112108127A (en) * 2020-10-15 2020-12-22 桂林理工大学 Passion fruit peel adsorption material and preparation method and application thereof
CN112892478A (en) * 2021-01-17 2021-06-04 桂林理工大学 Preparation method and application of biomass dye adsorbent
CN113210023A (en) * 2021-04-29 2021-08-06 黄山学院 Biochar-based anion exchanger and preparation method and application thereof

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CN106582557A (en) * 2016-12-16 2017-04-26 常州市好利莱光电科技有限公司 Preparation method for grapefruit peel-based low-concentration chromium-containing wastewater adsorbent
CN106622157A (en) * 2016-12-20 2017-05-10 华南理工大学 Modified beet pulp fiber adsorbent as well as preparation method and application thereof
CN106582585A (en) * 2016-12-27 2017-04-26 常州大学 Preparation method of adsorbent material capable of removing mercurial ions in waste water
CN108499536A (en) * 2018-04-10 2018-09-07 浙江农林大学 A kind of efficient absorption anionic dye hydro-thermal bamboo charcoal preparation method
CN108499536B (en) * 2018-04-10 2021-02-12 浙江农林大学 Preparation method of hydrothermal bamboo charcoal capable of efficiently adsorbing anionic dye
CN109721117A (en) * 2018-12-07 2019-05-07 南京林业大学 A kind of method of syringaldehyde functional modification and its product and the application of acquisition
CN111871390A (en) * 2020-07-08 2020-11-03 北部湾大学 Preparation of amino modified biological sponge and application of amino modified biological sponge in toxic metal wastewater treatment
CN112108126A (en) * 2020-10-15 2020-12-22 桂林理工大学 Passion fruit peel biological adsorbent for adsorbing anionic dye and preparation method and application thereof
CN112108127A (en) * 2020-10-15 2020-12-22 桂林理工大学 Passion fruit peel adsorption material and preparation method and application thereof
CN112892478A (en) * 2021-01-17 2021-06-04 桂林理工大学 Preparation method and application of biomass dye adsorbent
CN113210023A (en) * 2021-04-29 2021-08-06 黄山学院 Biochar-based anion exchanger and preparation method and application thereof

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