CN103586007B - Metal ion carbonized adsorption material and preparation method thereof - Google Patents
Metal ion carbonized adsorption material and preparation method thereof Download PDFInfo
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- CN103586007B CN103586007B CN201310585082.6A CN201310585082A CN103586007B CN 103586007 B CN103586007 B CN 103586007B CN 201310585082 A CN201310585082 A CN 201310585082A CN 103586007 B CN103586007 B CN 103586007B
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 title abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 25
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- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
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- 229910001385 heavy metal Inorganic materials 0.000 abstract description 21
- 239000002351 wastewater Substances 0.000 abstract description 9
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- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
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- 238000010000 carbonizing Methods 0.000 abstract 1
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- 238000010521 absorption reaction Methods 0.000 description 24
- 239000010949 copper Substances 0.000 description 19
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical group Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910020820 NaAc-HAc Inorganic materials 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a metal ion carbonized adsorption material and a preparation method thereof, belongs to the technical field of functional adsorption materials and solves the problem that polymine can not be reclaimed while being used for treating heavy metal wastewater. The metal ion carbonized adsorption material is prepared by crosslinking polymine with epichlorohydrin to modify polymine, and carbonizing, wherein the mass ratio of polymine to epichlorohydrin is 1: (0.5 to 0.6). The metal ion carbonized adsorption material provided by the invention is an adsorbent containing an active amino functional group and possessing a portion of properties of carbon materials, so that the metal ion carbonized adsorption material has a higher adsorption rate to metal ions and a higher removal rate, and can be reutilized.
Description
Technical field
The invention belongs to functional charing sorbing material technical field, be specifically related to charing sorbing material of a kind of metal ion be mainly used in absorption waste water and preparation method thereof.
Background technology
The pollutant that heavy metal in water ionic soil refers to containing heavy metal ion enters the pollution that water body causes water body, be the most serious to water pollution and one of maximum pollution is endangered to the mankind, pollution sources are mainly derived from the heavy metal wastewater thereby produced in the industrial processes such as mining and metallurgy, machine-building, chemical industry, electronics, instrument, general containing heavy metal ion such as chromium, cadmium, copper, mercury, nickel, zinc in waste water.
Heavy metal ion in entered environment or the ecosystem, mainly exists with the form of compound, and can not by natural degradation, and retaining, accumulate and moving by biology, slowly enrichment causes serious harm.And most metal ions and compound thereof to be easy to adsorb by suspended particulate in water and be deposited in water-bed sedimentary deposit, long-term pollution water body; Some heavy metal and compound thereof can in fish and other aquatic organisms and enrichment in crops tissue, accumulation participate in the wider harm of biosphere circulation forming range.The processing method of heavy metal wastewater thereby is a lot, can be divided into two large classes: a class makes deliquescent heavy metal change metallic compound that is insoluble or indissoluble into, thus it removed from water; Another kind of is carry out concentrating and separating when not changing Chemical Forms of Heavy Metals.Process heavy metal wastewater thereby method conventional at present has: chemical precipitation method, oxidation-reduction method, ion-exchange, electrolysis, bioanalysis and absorption method.In these methods, absorption method is a kind of not only efficient but also the method for easy economy.
Have developed many synthetic adsorbents with stronger adsorption capacity both at home and abroad to be at present used for purifying liquid waste, wherein polymine (Polyethyleneimine, PEI) be a kind of novel heavy metal capturing agent, be divided into linear and branched two kinds, have a large amount of amido atom N in its linear macromolecule chain, heavy metal ion can produce very strong chelation.But, because polymine belongs to water-soluble polyamine, can not reclaim when processing heavy metal wastewater thereby, not meet the epoch demand of current high-efficiency environment friendly.
Therefore, how to utilize the chelation of polymine heavy metal ion, preparation one can metal ion, water insoluble, callable sorbing material in efficient adsorption waste water, is a current study hotspot.
Summary of the invention
The present invention is to solve polymine unrenewable problem when processing heavy metal wastewater thereby, and provides metal ion species charing sorbing material and preparation method thereof.
The present invention is achieved by the following technical solutions:
One metal ion species charing sorbing material, be use epoxychloropropane to carry out cross-linking modified to polymine, then charing is formed, and wherein the mass ratio of polymine and epoxychloropropane is 1: 0.5 ~ 0.6.
The preparation method of above-mentioned metal ion charing sorbing material, step is:
(1) ethanolic solution of epoxychloropropane ECH is added dropwise in the aqueous solution of polymine PEI, regulate solution system pH=7 ~ 8, stirring reaction 1 ~ 2h obtains cross-linking modified polymine CPEI, and wherein the mass ratio of aziridine and epoxychloropropane is 1: 0.5 ~ 0.6;
(2) be placed in retort by cross-linking modified polymine CPEI, be warming up to 200 ~ 300 DEG C, charing 2 ~ 3h, get product CCPEI.
Further, the mass concentration of the aq. polyethyleneimine described in step (1) is 40 ~ 60%, and the mass concentration of described epoxychloropropane ethanolic solution is 40 ~ 60%.
Epoxychloropropane ethanolic solution described in step (1) and aq. polyethyleneimine stirring reaction 1 ~ 2h under 30 ~ 40 DEG C of conditions.
Step heats up in (2) under nitrogen protection, and heating rate is 3 ~ 5 DEG C/min.
Invention thinking of the present invention is, polymine is fully swelling in aqueous medium, after adding crosslinking agent epoxychloropropane, under the amido effect of polymine, first there is the ring-opening reaction of epoxychloropropane epoxy bond, there is de-HCl and react in the amido on epoxychloropropane and polymine, and with another polymine macromolecular chain generation cross-linking reaction, then by cross-linking products high temperature sintering, short molecular chain is removed and part carbochain is carbonized, form loose porous physical arrangement, synthesis nano microcellular structure Carbon Materials, product can possess the chelation of polymine to metal ion simultaneously, the porous suction-operated of active carbon.
Metal ion charing sorbing material of the present invention is the adsorbent containing active amino functional group, and possess part Carbon Materials character, respectively 71.98mg/g, 47.65mg/g, 37.51mg/g are reached to the maximum saturation adsorption capacity of copper ion, iron ion, lead ion, and to three heavy metal species ions, all there is good clearance, when leaching regeneration is carried out to sorbing material acid, can again be applied in heavy metal containing wastewater treatment.
Metal ion charing sorbing material of the present invention is as follows to metal biosorption the performance test results:
One, according to the principle of static capacity method and nitrogen absorption under low temperature, carried out testing characterizing to the BET specific surface of product, pore volume and pore-size distribution by static n2 absorption apparatus, result is as table 1
Table 1 CCPEI surface nature characterization result
| BET specific surface m2/g | Total pore volume cm3/g | HK method micropore can and aperture nm |
| 4.9—8.5 | 0.01—0.3 | 1.1—3.5 |
Two, the Staticadsorption experiment of CCPEI heavy metal ion, main test is as follows:
(1) mensuration of curve of adsorption kinetics: pipette 100mL concentration 100mgL with pipette
-1metal ion solution, be placed in tool plug conical flask, add the CCPEI of about 0.1g again, then constant temperature oscillation in gas bath constant temperature oscillator, separated in time takes out solution, after centrifugal with supercentrifuge, measure the concentration of metal ion in supernatant, calculate CCPEI to metal biosorption amount, draw the relation curve of adsorbance-time, investigate CCPEI to metal biosorption speed, determine to adsorb the time reaching balance.
Test records CCPEI to Cu
2+, Fe
3+, Pb
2+curve of adsorption kinetics as Fig. 3, wherein temperature 25 DEG C, pH (Cu
2+)=6; PH (Fe
3+)=2.5; PH (Pb
2+)=4.As can be seen from the figure, compound chelate adsorption CCPEI-1 is to Cu
2+, Fe
3+, Pb
2+absorption all quickly, 30 ~ 40min just reaches balance, and this is mainly chelation power due to the adsorption of CCPEI heavy metal ion, occurs a large amount of loose structure after adding sintering, chemisorbed and physical absorption acting in conjunction, thus cause above-mentioned good adsorption dynamics adsorption kinetics behavior.And material is to Cu
2+, Fe
3+, Pb
2+maximum adsorption capacity reach 63.776mg/g, 47.648mg/g, 37.506mg/g respectively, can find out that wherein material is for Cu
2+adsorption capacity obviously exceed both all the other.
(2) mensuration of absorption isotherm: the metal ion solution pipetting the change of 100mL concentration series is placed in several tool plug conical flasks, the pH of fixed solution, add the CCPEI of about 0.1g again, then constant temperature oscillation certain hour at a certain temperature, absorption is made to reach balance, centrifugation, measures the equilibrium concentration of heavy metal in supernatant, calculates CCPEI to the equilibrium adsorption capacity of metal ion
, draw equilibrium adsorption capacity ~ equilibrium concentration relation curve.
CCPEI is to Cu
2+absorption isotherm as shown in Figure 4, as can be seen from the figure, when concentration reaches certain value, equilibrium adsorption capacity almost no longer changes, and absorption reaches capacity, and is typical Langmuir type monolayer absorption isotherm.
Fig. 5 is Lang Gemiaoer fitting a straight line, and the linear relationship of obvious straight line is fine, absolutely proves that Cu2+ is adsorbed on CCPEI with coordination mode, monolayer state chemistry, and absorption behavior and Langmuir isothermal adsorption coincide.
(3) various factors is on the impact of absorption property: use hydrochloric acid, NH
4nO
3-NH
3h
2the pH of O and NaAc-HAc cushioning liquid adjusting sample solution, investigates pH value of solution to the impact of absorption property; Change the temperature of constant temperature oscillator, investigate temperature to the impact of CCPEI absorption property.
Fig. 6 be under different pH CCPEI-1 to Cu
2+adsorption capacity, as can be seen from the figure, when pH < 7, along with the increase of pH, adsorbance increases, and during pH=7, adsorbance is the highest can reach 136mg/g; As pH > 7, adsorbance declines again.This is because in an acidic solution, in polymine strand, amido atom N is in protonation state, there is hydrionic competitive effect; Along with the reduction of acidity, amido atom N protonation reduces, and hydrionic competitive effect weakens, and strengthens the mating reaction of metal ion, therefore along with the increase of pH, adsorbance increases; As pH > 7, metal ion Cu
2+hydrolysis can occur, therefore adsorbance declines again.
Fig. 7 be under different temperatures CCPEI-1 to Cu
2+adsorbance, as can be seen from the figure, along with the rising of temperature, adsorbance increase, this is because CCPEI-1 is to Cu
2+chelating be adsorbed as chemisorbed, and chemisorbed is endothermic process, and temperature raises the carrying out being conducive to chelating absorption, and therefore adsorbance raises with temperature and increases.
Product of the present invention contains the adsorbent of active amino functional group and possesses part Carbon Materials character, has higher adsorption rate, and has good clearance, can reuse metal ion.
Accompanying drawing explanation
Fig. 1 is chemical reaction process of the present invention;
Fig. 2 is that polymine contrasts figure with the infrared absorption spectroscopy of cross-linking modified polymine;
Fig. 3 is that embodiment 1 sorbing material is to Cu
2+, Fe
3+, Pb
2+curve of adsorption kinetics;
Fig. 4 is that sorbing material is to Cu
2+absorption isotherm;
Fig. 5 is Lang Gemiaoer fitting a straight line;
Fig. 6 is to Cu under different pH
2+adsorbance;
Fig. 7 is different temperatures Cu
2+saturated extent of adsorption.
Detailed description of the invention
below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The preparation method of one metal ion species charing sorbing material, step is:
(1) 20g 50% polymine monomer solution is got, Keep agitation makes system fully swelling, dropwise adds 12g 50% epoxychloropropane ethanolic solution at 30 DEG C, and with the pH value to 8 of 0.1mol/l sodium hydroxide solution regulation system, stirring reaction 1h, until product all becomes gel, leave standstill 3h, suction filtration, product is first with ethanol washing several, use distilled water cyclic washing again, vacuum drying, obtained cross-linking modified polymine;
(2) get the cross-linking modified polymine of 5g and be placed in reactor; reactor is placed in airtight retort; 200 DEG C are warming up to the heating rate of 3 DEG C/min under nitrogen protection; constant temperature 2h; take out after naturally cooling, with distilled water cyclic washing to pH=6 ~ 7, suction filtration isolates product particles; vacuum drying, to constant weight, obtains charing sorbing material product.
Above-mentioned course of reaction as shown in Figure 1.
Fig. 2 gives the infrared spectrogram of polymine, cross-linking modified polymine, as seen from the figure, after cross-linking modified to polymine enforcement, and 1098cm
-1the vibration absorption peak of place tertiary amine groups C-N key obviously strengthens, and original 3625cm
-1amido N-H stretching vibration absworption peak and 2135, the 784cm at place
-1the deformation vibration absworption peak at place all disappears, the H atom that primary amine groups in polymine macromolecular chain and secondary amine N-H key be described all replace by the methylene of epoxychloropropane the ring-opening reaction of epoxy bond (reacted by de-HCl and), namely primary, secondary amido becomes tertiary amine groups all; And 3409cm
-1the hydroxyl O-H vibration absorption peak that place occurs illustrates that epoxychloropropane there occurs ring-opening reaction, more than analyze and absolutely prove, reacted and ring-opening reaction by de-HCl, epoxychloropropane and the large molecule of polymine there occurs cross-linking reaction, define cross-linking modified polymine.
Product sintering weight-loss ratio 3.85%, static n2 absorption apparatus records product B ET specific area 8.319m
2/ g; Most probable pore size 3.465nm, total pore volume 0.012cm
2/ g.
To Cu
2+, Fe
3+, Pb
2+maximum saturation adsorption capacity reach 71.98mg/g, 47.65mg/g, 37.51mg/g respectively,
Embodiment 2
The preparation method of one metal ion species charing sorbing material, step is:
(1) 20g 40% polymine monomer solution is got, Keep agitation makes system fully swelling, dropwise adds 10g 60% epoxychloropropane ethanolic solution at 35 DEG C, and with the pH value to 7.5 of 0.1mol/l sodium hydroxide solution regulation system, stirring reaction 1.5h, until product all becomes gel, leave standstill 2h, suction filtration, product is first with ethanol washing several, use distilled water cyclic washing again, vacuum drying, obtained cross-linking modified polymine;
(2) get the cross-linking modified polymine of 5g and be placed in reactor; reactor is placed in airtight retort; 300 DEG C are warming up to the heating rate of 4 DEG C/min under nitrogen protection; constant temperature 3h; take out after naturally cooling, with distilled water cyclic washing to pH=6 ~ 7, suction filtration isolates product particles; vacuum drying, to constant weight, obtains charing sorbing material product.
Product sintering weight-loss ratio 44.9%, static n2 absorption apparatus records product B ET specific area 4.952m
2/ g; Most probable pore size 1.767nm, total pore volume 0.351cm
2/ g.
Material is to Cu
2+, Fe
3+, Pb
2+maximum adsorption capacity reach 71.98mg/g, 43.28mg/g, 30.52mg/g respectively.
Embodiment 3
The preparation method of one metal ion species charing sorbing material, step is:
(1) 20g 60% polymine monomer solution is got, Keep agitation makes system fully swelling, dropwise adds 11g 40% epoxychloropropane ethanolic solution at 40 DEG C, and with the pH value to 7 of 0.1mol/l sodium hydroxide solution regulation system, stirring reaction 2h, until product all becomes gel, leave standstill 2.5h, suction filtration, product is first with ethanol washing several, use distilled water cyclic washing again, vacuum drying, obtained cross-linking modified polymine;
(2) get the cross-linking modified polymine of 5g and be placed in reactor; reactor is placed in airtight retort; 250 DEG C are warming up to the heating rate of 5 DEG C/min under nitrogen protection; constant temperature 2.5h; take out after naturally cooling, with distilled water cyclic washing to pH=6 ~ 7, suction filtration isolates product particles; vacuum drying, to constant weight, obtains charing sorbing material product.
Product sintering weight-loss ratio 10.2%, static n2 absorption apparatus records product B ET specific area 6.729m
2/ g; Most probable pore size 1.110nm, total pore volume 0.023cm
2/ g.
Material is to Cu
2+, Fe
3+, Pb
2+maximum adsorption capacity reach 52.78mg/g, 39.91mg/g, 26.72mg/g respectively.
Embodiment 4
The preparation method of one metal ion species charing sorbing material, step is:
(1) 20g 50% polymine monomer solution is got, Keep agitation makes system fully swelling, dropwise adds 11g 50% epoxychloropropane ethanolic solution at 40 DEG C, and with the pH value to 8 of 0.1mol/l sodium hydroxide solution regulation system, stirring reaction 1h, until product all becomes gel, leave standstill 3h, suction filtration, product is first with ethanol washing several, use distilled water cyclic washing again, vacuum drying, obtained cross-linking modified polymine;
(2) get the cross-linking modified polymine of 5g and be placed in reactor; reactor is placed in airtight retort; 300 DEG C are warming up to the heating rate of 5 DEG C/min under nitrogen protection; constant temperature 2h; take out after naturally cooling, with distilled water cyclic washing to pH=6 ~ 7, suction filtration isolates product particles; vacuum drying, to constant weight, obtains charing sorbing material product.
Product sintering weight-loss ratio 66.6%, static n2 absorption apparatus records product B ET specific area 3.76955m
2/ g; Most probable pore size 1.108nm, total pore volume 0.016cm
2/ g.
Material is to Cu
2+, Fe
3+, Pb
2+maximum adsorption capacity reach 57.63mg/g, 42.42mg/g, 28.02mg/g respectively.
Claims (1)
1. the preparation method of a metal ion species charing sorbing material, it is characterized in that, step is:
(1) ethanolic solution of epoxychloropropane ECH is added dropwise in the aqueous solution of polymine PEI, regulate solution system pH=7 ~ 8, under 30 ~ 40 DEG C of conditions, stirring reaction 1 ~ 2h obtains cross-linking modified polymine CPEI, and wherein the mass ratio of polymine and epoxychloropropane is 1: 0.5 ~ 0.6;
Wherein, the mass concentration of described aq. polyethyleneimine is 40 ~ 60%, and the mass concentration of described epoxychloropropane ethanolic solution is 40 ~ 60%;
(2) be placed in retort by cross-linking modified polymine CPEI, be warming up to 200 ~ 300 DEG C, heating rate is 3 ~ 5 DEG C/min, and charing 2 ~ 3h, get product CCPEI.
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|---|---|---|---|
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|---|---|
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| CN102179228A (en) * | 2011-04-15 | 2011-09-14 | 华东理工大学 | Method for preparing carbon adsorbing material used for efficiently removing harmful ions from waste water |
| CN102188957A (en) * | 2011-04-26 | 2011-09-21 | 湖南大学 | Polyethyleneimine modified magnetic porous adsorbent and preparation method and application thereof |
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| Dalia M.Saad et al.Development and application of cross-linked polyethylenimine for trace metal and metalloid removal from mining and industrial wastewaters.《Toxicological & * |
| Environmental Chemistry》.2011,第93卷(第5-6期),第914页摘要,第915页第3-4段和第916页第2.2-2.3节. * |
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