CN105413662A - Heavy-metal macromolecule capture agent and preparation method and application thereof - Google Patents
Heavy-metal macromolecule capture agent and preparation method and application thereof Download PDFInfo
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- CN105413662A CN105413662A CN201511033887.5A CN201511033887A CN105413662A CN 105413662 A CN105413662 A CN 105413662A CN 201511033887 A CN201511033887 A CN 201511033887A CN 105413662 A CN105413662 A CN 105413662A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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Abstract
The invention discloses a heavy-metal macromolecule capture agent and a preparation method and application thereof. The heavy-metal macromolecule capture agent is polyvinyl alcohol modified by phthalahydroxamic acid; the polyvinyl alcohol modified by the phthalahydroxamic acid is modified hydroxamic acid type macromolecule polymer, the polyvinyl alcohol and heavy-metal ions can be quickly chelated into stable chelate, high adsorption capacity to the heavy-metal ions is achieved, the heavy-metal macromolecule capture agent can be used for treatment of heavy-metal pollution, and compared with a common traditional metal ion capture agent, the heavy-metal macromolecule capture agent can adsorb fine particles in sewage more effectively, has selective adsorption capacity and has quite good application prospect on the aspect of heavy metal ion sediment and separation; besides, the heavy-metal macromolecule capture agent can be further used for ore floatation, and high capture capacity is achieved for oxides of oxidized ores such as cassiterite, wolframite, cerusite and chrysocolla; besides, the heavy-metal macromolecule capture agent can be further widely applied to the fields of oilfield drilling, separation of red mud produced by aluminium oxide and the like.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to heavy metal species polymer chelating agent and its preparation method and application.
Background technology
Heavy Metals In Environment is a significant problem, and heavy metal pollution has involved in daily life, solves heavy metal pollution problem extremely urgent.The method of existing process heavy metal pollution comprises active carbon adsorption, shitosan method, flyash and Activated Zeolite Adsorption, microbial method, Electro Sorb method, de-isolation technics, coagulant sedimentation, membrane bioreactor, high molecular heavy metals trapping method etc.
Wherein the application of high molecular heavy metals trapping agent is very extensive, and such as, polyacrylamide, with the adsorption bridging mechanism of action, makes suspension micelle flocculate, and also can react with electronegative dissolved matter simultaneously and generate insoluble salt, flocculating effect is better; Natural macromolecule flocculating agent shitosan can form stable complex with transiting state metal ion generation complexation reaction, possesses the features such as easy degraded, nontoxic, aboundresources; Mercaptoacetyl shitosan MAC can remove heavy metal ion simultaneously and reduce turbidity of sewage, improves Industrial Wastewater Treatment feasibility; Macromolecule heavy metal flocculant PEX utilizes carbodithioic acid root (-C-S-) to carry out chelatropic reaction with coordinate bond and covalent bond form and metal ion, can generate the stable insoluble heavy metal chelating body with crosslinked space net structure; Phosphorus pentasulfide and alcohol effect obtain dialkyl dithiophosphate, can reach 99%, can reach discharging standards after process to the clearance of copper ion.
Hydroxamic acid; also known as acyl group azanol and hydroxamic acid; have two kinds of dynamic isomers, i.e. hydroxamic acid and hydroximic acid, hydroxamic acid is primary structure; it is the compound with-C (=O)-NH-OH structure; be a class organic sequestering agent, there is faintly acid, weak stability; wide complexing, poly-hydroxamic acid also has strong water-soluble.Due to hydroxamic acid and derivative energy thereof and Cu
2+, Mn
2+, Pb
2+, Cr
6+form stable metallo-chelate etc. heavy metal ion, hydroxamic acid is used for the flocculation treatment of heavy metal ion sewage by much research.But less about the research of poly-hydroxamic acid, the water soluble of poly-hydroxamic acid is large, and effective with complex, complexing product stable, has great prospects for development in adsorption of metal ions.
Summary of the invention
In view of this, the object of the present invention is to provide the polyvinyl alcohol that a heavy metal species polymer chelating agent phthalyl hydroxamic acid is modified, this trapping agent heavy metal has good flocculating effect, present invention also offers the preparation method of above-mentioned trapping agent and the application in heavy metal process.
The technical scheme that the present invention takes is as follows:
1, a heavy metal species polymer chelating agent, described heavy metal polymer chelating agent is that polyvinyl alcohol modified by phthalyl hydroxamic acid, and its structural formula is:
Wherein, 500≤n≤1200, n is integer.
2, the preparation method of heavy metal polymer chelating agent, comprises the following steps:
(1) preparation of 2-carboxyl benzoic acid polyvinyl ester: in molar ratio for the ratio of 1:1 ~ 2 gets polyvinyl alcohol and phthalic anhydride, be dissolved in N respectively, in dinethylformamide, then phthalic anhydride is added drop-wise in polyvinyl alcohol, reacts under 100 ± 2 DEG C of conditions and within 5 hours, obtain liquid 2-carboxyl benzoic acid polyvinyl ester;
(2) preparation of polyvinyl alcohol modified by phthalyl hydroxamic acid: get the cooled liquid 2-carboxyl benzoic acid polyvinyl ester that step (1) obtains, be the ratio of 1:0.3:1:0.1:1.1 in molar ratio, add melamine, N-methylmorpholine, DMAP and hydroxylamine hydrochloride, Keep agitation 12 hours under 18 ~ 25 DEG C of conditions, add salt acid for adjusting pH to 5 ~ 6 again, stir 5min cessation reaction, distillation, ethyl acetate precipitates, suction filtration, drying, obtains white gum phthalyl hydroxamic acid and modifies polyvinyl alcohol.
Preferably, described in described step (1), the mol ratio of polyvinyl alcohol and phthalic anhydride is 1:1.2 or 1:1.5.
3, the application of heavy metal polymer chelating agent in heavy metal accumulation.
Preferably, described heavy metal ion is Cu
2+, Cr
6+, Pb
2+or Mn
2+in one or more.
Preferably, described Cu
2+concentration is 5mg/L, Cr
6+and/or Pb
2+concentration is 40mg/L, Mn
2+concentration is 15mg/L.
Preferably, described heavy metal polymer chelating agent operative temperature 25 ~ 45 DEG C, action time is 3h, and addition is 2 ~ 4g/L.
Preferably, described heavy metal accumulation comprises the heavy metal accumulation in sewage disposal or ore floatation process.
Beneficial effect of the present invention is: the hydroxamic acid polymer polymer that polyvinyl alcohol is modification modified by phthalyl hydroxamic acid, stable chelate can be become with the rapid chelating of heavy metal ion, heavy metal ion has strong adsorption capacity, can be used for heavy metal pollution process aspect, trapped heavy metal ion can also be reclaimed while purifying waste water, hydroxamic acid polymer metallic ion trapping agent is different from conventional metals ion-trapping agent, it contains a large amount of hydroxamic acid functional group, heavy metal ion has very strong affinity, stable absorption can be formed with heavy metal ion.Compare conventional conventional metals ion-trapping agent, fine particle in the more effective absorption effluent of its energy, also has selective adsorption capacity, very promising in heavy metal ion sedimentation separation.In addition, ore floatation aspect can also be used for, to the oxide etc. of oxide ore as cassiterite, wolframite, cerussite, chrysocolla, all there is higher trapping ability.In addition, also extensive utilization can be had in the field such as red-mud separation of oil drilling, alumina producing.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing:
The infrared spectrum of Fig. 1 product 2-carboxyl benzoic acid polyvinyl ester;
Polyvinyl alcohol infrared spectrum modified by Fig. 2 phthalyl hydroxamic acid;
Fig. 3 Cu
2+different time adsorption effect figure;
Fig. 4 Cr
6+different time adsorption effect figure;
Fig. 5 Pb
2+different time adsorption effect figure;
Fig. 6 Mn
2+different time adsorption effect figure;
Fig. 7 Cu
2+adsorption effect figure under different temperatures;
Fig. 8 Cr
6+adsorption effect figure under different temperatures;
Fig. 9 Pb
2+adsorption effect figure under different temperatures;
Figure 10 Mn
2+adsorption effect figure under different temperatures;
Figure 11 Cu
2+adsorption effect figure under variable concentrations;
Figure 12 Cr
6+adsorption effect figure under variable concentrations;
Figure 13 Pb
2+adsorption effect figure under variable concentrations;
Figure 14 Mn
2+adsorption effect figure under variable concentrations;
Figure 15 Cu
2+adsorption effect figure under variable concentrations;
Figure 16 Cr
6+adsorption effect figure under variable concentrations;
Figure 17 Pb
2+adsorption effect figure under variable concentrations;
Figure 18 Mn
2+adsorption effect figure under variable concentrations;
The different PVA of Figure 19 and phthalic anhydride mol ratio are to Cu
2+adsorption effect figure;
The different PVA of Figure 20 and phthalic anhydride mol ratio are to Cr
6+adsorption effect figure;
The different PVA of Figure 21 and phthalic anhydride mol ratio are to Pb
2+adsorption effect figure;
The different PVA of Figure 22 and phthalic anhydride mol ratio are to Mn
2+adsorption effect figure.
Detailed description of the invention
Below the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
The preparation of embodiment 12-carboxyl benzoic acid polyvinyl ester
Table 1PVA and phthalic anhydride esterification react each material amounts
According to the various consumptions of table 1, first PVA is dropped in the round-bottomed flask of 250mL drying, add 50mLDMF, fully shake up, put into stirrer, start stir and temperature programming to 140 DEG C (about 1h), after polyvinyl alcohol dissolves completely (about 1.5h) be cooled to 100 DEG C (about 0.5h) now reactant liquor be water white transparency shape.Then the phthalic anhydride being dissolved in 50mLDMF is in advance added drop-wise in reaction bulb, drips off in 2min, in dropping process, have a small amount of white cigarette to emerge.Maintaining reaction temperature is 100 ± 2 DEG C, reacts 5 hours, then pours into 1/4 of reactant liquor while hot in the about 150mL carrene that stirred and precipitate, topple over solution, product precipitating reagent washing 2 ~ 3 times, finally uses suction filtration after precipitating reagent soaked overnight, dry in vacuum drying chamber.Products therefrom is white fluffy solid, has stronger viscosity, is orange-yellow clear gummy solid after dry.
Reaction equation:
After the product of preparation is made film, (see embodiment 2) carries out infrared spectrum characterization, and infrared results is shown in Fig. 1.As shown in Figure 1, in IR spectrum, product 2-carboxyl benzoic acid polyvinyl ester is at 3300cm
-1near there is v
oHbroad peak may be the reason that polymer-OH functional group associates, 1700cm
-1neighbouring sharp-pointed absworption peak belongs to the stretching vibration of C=O, 1600cm
-1~ 1430cm
-1aromatic ring frame vibration absorption peak, 770cm
-1~ 730cm
-1strong peak illustrate that phenyl ring is adjacent two replacements.
The preparation of polyvinyl alcohol modified by embodiment 2 phthalyl hydroxamic acid
Table 2 oximation reaction each reactant consumption mol ratio
Liquid 2-carboxyl benzoic acid polyvinyl ester prepared by Example 1,1.106g melamine is added by material ratio described in table 2,1.78mLN-methyl morpholine, the DMAP of 0.245g makes catalyst, 1.529g hydroxylamine hydrochloride, at ambient temperature Keep agitation 12 hours, until carboxylic acid transforms completely, add salt acid for adjusting pH to 5 ~ 6 again, stir 5min cessation reaction, reactant liquor becomes light yellow transparent liquid from milky.Then reaction bulb is gone to Rotary Evaporators 90 DEG C and distill about 1.5h, the impurity such as solvent are distilled out, remaining product ethyl acetate precipitating reagent precipitation, then suction filtration, dry.Products therefrom is white gummy solid, has very strong viscosity and water-soluble.
Reaction equation:
The product of preparation is carried out infrared spectrum characterization, get 2g to gather hydroxamic acid product and be dissolved in 20mL1, in 4-dioxane alkane, to be dissolved complete after, with glass bar the thick liquid of dissolving is layered on surface plate gently and makes film, after drying, take off film can survey infrared.Infared spectrum is shown in Fig. 2.As shown in Figure 2, poly-hydroxamic acid is at 3400cm
-1~ 3000cm
-1overlapping broad peak is v
o-Hwith the superposition of vN-H vibration peak, and formed caused by intermolecular hydrogen bonding, near 3400cm
-1v
o-H, near 3000cm
-1v
n-H, this is the characteristic absorption of hydroxamic acid; 1730cm
-1the neighbouring absworption peak occurred is the stretching vibration of ester carbonyl group (C=O), 1650cm
-1the neighbouring absworption peak occurred is poly-hydroxamic acid amide v
c=Othe absworption peak that stretching vibration causes, because the above-mentioned absworption peak of conjugation moves to lower wave number direction, 1500cm
-1for being aromatic ring frame vibration absorption peak, 1050cm
-1near be the out-of-plane bending vibration of olefine=C-H.
Embodiment 3 heavy metal ion flocculating experiment
This experiment mainly have studied the flocculating effect that phthalyl hydroxamic acid heavy metal ion modified by polyvinyl alcohol.Choose four common heavy metal species ion Cu
2+, Cr
6+, Pb
2+, Mn
2+for representative, the flocculation of the poly-hydroxamic acid heavy metal ion waste water of research, the selective analysis factors such as flocculation time, temperature, concentration of metal ions, flocculant dose and material ratio are on the impact of flocculating effect, find out optimum flocculating condition, then under concentration of metal ions permanence condition, compared for the flocculation activity of first step reaction esterification products and flocculant, explore material ratio and the flocculation activity of flocculant synthesis and optionally contact.
First the CuCl of 100mg/L is prepared
2, K
2cr
2o
7, PbNO
3and MnSO
4female mark liquid, then prepares the titer of each concentration with female mark liquid, draw the calibration curve of each solution simultaneously.CuCl
2concentration of standard solution and each strength solution absorbance are as table 3.
Table 3Cu
2+absorbance
Cu is obtained according to table 3
2+calibration curve equation is y=0.0062x-0.0010, R
2=0.9998.
K
2cr
2o
7concentration of standard solution and each strength solution absorbance are as table 4.
Table 4Cr
6+absorbance
| Cr 6+Concentration (mg/L) | 0 | 5 | 10 | 15 | 20 | 25 |
| Absorbance (Abs) | 0.0002 | 0.0321 | 0.0470 | 0.0758 | 0.1146 | 0.1458 |
Cr is obtained according to table 4
6+calibration curve equation is y=0.0057x-0.0025, R
2=0.9867.
PbNO
3concentration of standard solution and each strength solution absorbance are as table 5.
Table 5Pb
2+absorbance
Pb is obtained according to table 5
2+calibration curve equation is y=0.0027x-0.0005, R
2=0.9995.
MnSO
4concentration of standard solution and each strength solution absorbance are as table 6.
Table 6Mn
2+absorbance
| Mn 2+(concentration) mg/L | 0 | 2 | 4 | 6 | 8 | 10 |
| Absorbance (Abs) | 0.0005 | 0.0432 | 0.0832 | 0.1238 | 0.1601 | 0.2047 |
Mn is obtained according to table 6
2+calibration curve equation is y=0.0202x+0.0017, R
2=0.9995.
1, the time affects the flocculation of metal ion
With the CuCl of 100mg/L
2, K
2cr
2o
7, PbNO
3and MnSO
4female mark liquid is respectively mixed with the solution of 10mg/L, respectively get 50mL, then the phthalyl hydroxamic acid obtained in the ratio of PVA and phthalic anhydride mol ratio 1:1 is modified polyvinyl alcohol and is weighed 4 parts, every part of 0.2g, join in each solution, 25 DEG C of shaking table vibrations, measure absorbance every 30min Aspirate supernatant 8 ~ 10mL in colorimetric cylinder, measure 8 times altogether, the results are shown in Table 7-10.
Table 7Cu
2+different time absorbance
Table 8Cr
6+different time absorbance
Table 9Pb
2+different time absorbance
Table 10Mn
2+different time absorbance
Absorbance according to table 7-10 calculates heavy metal ion adsorbed amount and clearance, and formula is as follows:
(1) calculating of adsorbance q
Adsorbance q is calculated as follows:
In formula: the absorption weight mg/g of Adsorption of Heavy Metal Ions when q represents adsorption equilibrium; V represents heavy metal ion liquor capacity L; C
0represent the absorption initial concentration of heavy metal ion respectively with C and stop concentration, unit is mg/L; M represents adsorbent mass g.
(2) calculating of clearance
(formula 2)
In formula: C
0represent heavy metal ion initial concentration, unit mg/L; C represents the concentration of heavy metal ion after absorption, unit mg/L.
The result of calculation of each heavy metal ion is respectively in Table 11-14.
Table 11Cu
2+the result of calculation of different time
Cu
2+different time adsorption effect is shown in Fig. 3.From table 11 and Fig. 3, adsorption time is longer, and adsorbance is larger, but can be found out by clearance, and when 180min, it is more obvious that other times are compared in clearance change, and phthalyl hydroxamic acid now modifies polyvinyl alcohol to Cu
2+adsorption effect best.
Table 12Cr
6+the result of calculation of different time
Cr
6+different time adsorption effect figure is shown in Fig. 4, and from table 12 and Fig. 4, adsorption time is longer, adsorbance is larger, but can be found out by clearance, when 180min, clearance change is relatively more obvious, and therefore, now phthalyl hydroxamic acid modifies polyvinyl alcohol to Cr
6+adsorption effect best.
Table 13Pb
2+the result of calculation of different time
Pb
2+the adsorption effect figure of different time is shown in Fig. 5, and from table 13 and Fig. 5, adsorption time is longer, adsorbance is larger, but can be found out by clearance, when 180min, clearance change is relatively more obvious, and therefore, now phthalyl hydroxamic acid modifies polyvinyl alcohol to Pb
2+adsorption effect best.
Table 14Mn
2+the result of calculation of different time
Mn
2+the adsorption effect figure of different time is shown in Fig. 6, and from table 14 and Fig. 6, adsorption time is longer, adsorbance is larger, but can be found out by clearance, when 180min, clearance change is relatively more obvious, and therefore, now phthalyl hydroxamic acid modifies polyvinyl alcohol to Mn
2+adsorption effect best.
2, temperature affects metal biosorption
With the CuCl of 100mg/L
2, K
2cr
2o
7, PbNO
3and MnSO
4the solution that female mark liquid is respectively mixed with 20mg/L is triplicate, every part of 50mL, the phthalyl hydroxamic acid obtained in the ratio of PVA and phthalic anhydride mol ratio 1:1 is modified polyvinyl alcohol and is respectively added 0.1g, respectively at 25 DEG C, 35 DEG C and 45 DEG C of shaking table vibration 3h, finally survey absorbance, the results are shown in Table 15-18.
Table 15Cu
2+the absorbance of different temperatures
| Temperature/DEG C | 25 | 35 | 45 |
| Absorbance/Abs | 0.1033 | 0.1055 | 0.1117 |
Table 16Cr
6+absorbance under different temperatures
| Temperature/DEG C | 25 | 35 | 45 |
| Absorbance/Abs | 0.0874 | 0.0917 | 0.0957 |
Table 17Pb
2+absorbance under different temperatures
| Temperature/DEG C | 25 | 35 | 45 |
| Absorbance/Abs | 0.0445 | 0.0451 | 0.488 |
Table 18Mn
2+absorbance under different temperatures
| Temperature/DEG C | 25 | 35 | 45 |
| Absorbance/Abs | 0.5428 | 0.5520 | 0.6639 |
The adsorbance of the formulae discovery flocculation of employing formula 1 and 2 and clearance, the results are shown in Table 19-22 and Fig. 7-10.
Table 19Cu
2+result of calculation under different temperatures
Cu
2+adsorption effect figure under different temperatures is shown in Fig. 7.From table 19 and Fig. 7, when ion concentration one timing, temperature is lower, and adsorbance is larger, and clearance is also higher, to Cu 25 DEG C time
2+clearance maximum.
Table 20Cr
6+result of calculation under different temperatures
Cr
6+adsorption effect figure under different temperatures is shown in Fig. 8.From table 20 and Fig. 8, when concentration is constant, temperature is higher, and adsorbance is less, and clearance also reduces, by compare clearance known 25 DEG C time to Cr
6+adsorption effect best.
Table 21Pb
2+result of calculation under different temperatures
Pb
2+adsorption effect figure under different temperatures is shown in Fig. 9.From table 21 and Fig. 9, when concentration is certain, temperature is lower, and adsorbance is also larger, and clearance also becomes large thereupon, and compare clearance known, 25 DEG C time, product is to Pb
2+clearance the highest.
Table 22Mn
2+result of calculation under different temperatures
Mn
2+adsorption effect figure under different temperatures is shown in Figure 10.From table 22 and Figure 10, work as Mn
2+when concentration is constant, temperature is higher, and adsorbance reduces on the contrary, and clearance also reduces, and finds that product is to Mn 25 DEG C time by comparing clearance
2+adsorption effect best.
3, the concentration of heavy metal ion is to Adsorption Effect
With the CuCl of 100mg/L
2, K
2cr
2o
7, PbNO
3and MnSO
4female mark liquid prepares each solution of 10mg/L, 20mg/L, 30mg/L, 40mg/L tetra-concentration gradients respectively, every part of 50mL, respectively add the phthalyl hydroxamic acid that PVA and phthalic anhydride mol ratio 1:1 obtains and modify polyvinyl alcohol 0.1g, 25 DEG C of shaking table vibration 3h, survey absorbance, the results are shown in Table 23-26.
Table 23Cu
2+absorbance under variable concentrations
Table 24Cr
6+absorbance under variable concentrations
| Chromium ion concentration mg/L | 10 | 20 | 30 | 40 |
| Absorbance A bs | 0.0368 | 0.0718 | 0.0909 | 0.1072 |
Table 25Pb
2+absorbance
Table 26Mn
2+absorbance
The adsorbance of the formulae discovery flocculation of employing formula 1 and 2 and clearance, the results are shown in Table 27-30 and Figure 11-14.
Table 27Cu
2+absorbance under variable concentrations
Cu
2+under variable concentrations, adsorption effect figure is shown in Figure 11, from table 27 and Figure 11, Cu
2+concentration is larger, and adsorbance is larger, but clearance is less, can be found out by clearance, and when 5mg/L, phthalyl hydroxamic acid modifies polyvinyl alcohol to Cu
2+adsorption effect best.
Table 28Cr
6+absorbance under variable concentrations
Cr
6+under variable concentrations, adsorption effect figure is shown in Figure 12, from table 28 and Figure 12, along with Cr
6+the increase of concentration, adsorbance also increases thereupon, and clearance is also larger, can be found out by clearance, and when 40mg/L, phthalyl hydroxamic acid modifies polyvinyl alcohol to Cr
6+adsorption effect the most obvious.
Table 29Pb
2+absorbance under variable concentrations
Pb
2+under variable concentrations, adsorption effect figure is shown in Figure 13, from table 29 and Figure 13, Pb
2+concentration is larger, and adsorbance also constantly increases, and clearance is also thereupon higher, can be found by the situation of change of observing adsorbance and clearance, and when 40mg/L, phthalyl hydroxamic acid modifies polyvinyl alcohol to Pb
2+adsorption effect best.
Table 30Mn
2+absorbance under variable concentrations
Mn
2+under variable concentrations, adsorption effect figure is shown in Figure 14, from table 30 and Figure 14, Mn
2+concentration is larger, and adsorbance also becomes large, can be found out by clearance, and when 15mg/L, phthalyl hydroxamic acid modifies polyvinyl alcohol to Mn
2+adsorption effect best.
4, adsorbent amount affects the flocculation of metal ion
Prepare 5mg/LCuCl respectively
2solution, 40mg/LK
2cr
2o
7solution, 40mg/LPbNO
3solution and 15mg/LMnSO
4solution, parallel 4 groups of often kind of solution, often group gets 50mL, take phthalyl hydroxamic acid respectively and modify each four parts of polyvinyl alcohol (PVA and phthalic anhydride mol ratio 1:1 obtains) 0.1g, 0.2g, 0.3g and 0.4g, add in each solution respectively, 25 DEG C of shaking table vibration 3h, survey its absorbance, the results are shown in Table 31-34.
Table 31Cu
2+absorbance under various dose
| Adsorbent dosage/g | 0.1 | 0.2 | 0.3 | 0.4 |
| Absorbance A bs | 0.0123 | 0.0047 | 0.0024 | 0.0071 |
Table 32Cr
6+absorbance under various dose
| Adsorbent dosage/g | 0.1 | 0.2 | 0.3 | 0.4 |
| Absorbance A bs | 0.1310 | 0.1289 | 0.1107 | 0.1039 |
Table 33Pb
2+absorbance under various dose
| Adsorbent dosage/g | 0.1 | 0.2 | 0.3 | 0.4 |
| Absorbance A bs | 0.0996 | 0.0722 | 0.0573 | 0.0580 |
Table 34Mn
2+absorbance under various dose
| Adsorbent dosage/g | 0.1 | 0.2 | 0.3 | 0.4 |
| Absorbance A bs | 0.4650 | 0.4637 | 0.4195 | 0.3786 |
The adsorbance of the formulae discovery flocculation of employing formula 1 and 2 and clearance, the results are shown in Table 35-38 and Figure 15-18.
Table 35Cu
2+absorbance under different quantity of sorbent
Cu
2+under variable concentrations, adsorption effect figure is shown in Figure 15, and from table 35 and Figure 15, the dosage of adsorbent is larger, adsorbance reduces on the contrary, but adsorption rate is larger, and comprehensive adsorbance and adsorption rate can draw, when adsorbent dosage 0.1g, phthalyl hydroxamic acid modifies polyvinyl alcohol to Cu
2+adsorption effect best.
Table 36Cr
6+absorbance under different quantity of sorbent
Cr
6+under variable concentrations, adsorption effect figure is shown in Figure 16, from table 36 and Figure 16, along with the increase of adsorbent dosage, adsorbance but reduces on the contrary, and clearance increasing degree is little, comprehensive adsorbance and clearance can find, when adsorbent dosage 0.1g, phthalyl hydroxamic acid modifies polyvinyl alcohol to Cr
6+adsorption effect best.
Table 37Pb
2+absorbance under different quantity of sorbent
| Adsorbent dosage/g | Absorbance/Abs | C mg/L after flocculation | Adsorbance q mg/g | Clearance % |
| 0.1 | 0.0996 | 37.074 | 1.463 | 7.32 |
| 0.2 | 0.0722 | 26.926 | 3.269 | 32.69 |
| 0.3 | 0.0573 | 21.407 | 3.099 | 46.48 |
| 0.4 | 0.0580 | 21.667 | 2.292 | 45.83 |
Pb
2+under variable concentrations, adsorption effect figure is shown in Figure 17, and from table 37 and Figure 17, adsorbent dosage is larger, Pb
2+adsorbance first increases and then decreases, but clearance is all increasing trend always, considers adsorbance and clearance is known, and when adsorbent dosage 0.2g, phthalyl hydroxamic acid modifies polyvinyl alcohol to Pb
2+the adsorption effect of son is best.
Table 38Mn
2+absorbance under different quantity of sorbent
| Adsorbent dosage/g | Absorbance/Abs | C mg/L after flocculation | Adsorbance q mg/g | Clearance % |
| 0.1 | 0.4650 | 2.294 | 6.353 | 84.71 |
| 0.2 | 0.4637 | 2.287 | 3.178 | 84.75 |
| 0.3 | 0.4195 | 2.068 | 2.155 | 86.21 |
| 0.4 | 0.3786 | 1.866 | 1.642 | 87.56 |
Mn
2+under variable concentrations, adsorption effect figure is shown in Figure 18, and from table 38 and Figure 18, adsorbent dosage is larger, adsorbance is less on the contrary, and clearance growth trend is not obvious, considers adsorbance and clearance can be thought, when adsorbent 0.1g, phthalyl hydroxamic acid modifies polyvinyl alcohol to Mn
2+adsorption effect best.
5, PVA and phthalic anhydride mol ratio are on the impact of adsorbent performance
Prepare 5mg/LCuCl respectively
2solution, 40mg/LK
2cr
2o
7solution, 40mg/LPbNO
3solution and 15mg/LMnSO
4solution, parallel 4 groups of often kind of solution, often group gets 50mL, respectively adds the phthalyl hydroxamic acid that in embodiment 1 table 1, different PVA and phthalic anhydride mol ratio obtain and modifies polyvinyl alcohol 0.1g, and 25 DEG C of shaking tables vibration 3h, survey absorbance, the results are shown in Table 39.
Table 39 different proportion product is to four kinds of ion absorbances
The adsorbance of the formulae discovery flocculation of employing formula 1 and 2 and clearance, the results are shown in Table 40-43 and Figure 19-22.
Table 40 different proportion product is to Cu
2+adsorpting data
Different proportion product is to Cu
2+adsorption effect figure is shown in Figure 19, and from table 40 and Figure 19, different proportion product is to Cu
2+adsorbance and clearance be all more or less the same, consider, the adsorption effect of 1:1 product is better.
Table 41 different proportion product is to Cr
6+adsorpting data
Different proportion product is to Cr
6+adsorption effect figure is shown in Figure 20, and from table 41 and Figure 20, different proportion product is to Cr
6+adsorbance higher, adsorbance and clearance are all in rising trend, and 1:2 product adsorption capacity is best.
Table 42 different proportion product is to Pb
2+adsorpting data
Different proportion product is to Pb
2+adsorption effect figure is shown in Figure 21, and from table 42 and Figure 21, ratio is higher, and adsorption effect is relatively better, but overall adsorption amount is on the low side, and clearance is not high yet.
Table 43 different proportion product is to Mn
2+adsorpting data
Different proportion product is to Mn
2+adsorption effect figure is shown in Figure 22, and from table 43 and Figure 22, different proportion product is to Mn
2+adsorption effect fine, adsorbance is comparatively large, and adsorption rate is higher, but four ratios absorption difference are little, and the adsorption capacity considering 1:1 product is best.
To sum up each influence factor result can be drawn a conclusion:
Flocculation Best Times is 3h, and optimum temperature is 25 DEG C, and each ion optium concentration is Cu
2+5mg/L, Cr
6+40mg/L, Pb
2+40mg/L, Mn
2+15mg/L, optimum flocculent dosage is that 0.1g, PVA and phthalic anhydride mol ratio consider for 1:1 is comparatively suitable.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (8)
1. a heavy metal species polymer chelating agent, is characterized in that, described heavy metal polymer chelating agent is that polyvinyl alcohol modified by phthalyl hydroxamic acid, and its structural formula is:
Wherein, 500≤n≤1200, n is integer.
2. the preparation method of heavy metal polymer chelating agent described in claim 1, is characterized in that, comprise the following steps:
(1) preparation of 2-carboxyl benzoic acid polyvinyl ester: in molar ratio for the ratio of 1:1 ~ 2 gets polyvinyl alcohol and phthalic anhydride, be dissolved in N respectively, in dinethylformamide, then phthalic anhydride is added drop-wise in polyvinyl alcohol, reacts under 100 ± 2 DEG C of conditions and within 5 hours, obtain liquid 2-carboxyl benzoic acid polyvinyl ester;
(2) preparation of polyvinyl alcohol modified by phthalyl hydroxamic acid: get the cooled liquid 2-carboxyl benzoic acid polyvinyl ester that step (1) obtains, be the ratio of 1:0.3:1:0.1:1.1 in molar ratio, add melamine, N-methylmorpholine, DMAP and hydroxylamine hydrochloride, Keep agitation 12 hours under 18 ~ 25 DEG C of conditions, add salt acid for adjusting pH to 5 ~ 6 again, stir 5min cessation reaction, distillation, ethyl acetate precipitates, suction filtration, drying, obtains white gum phthalyl hydroxamic acid and modifies polyvinyl alcohol.
3. the preparation method of heavy metal polymer chelating agent according to claim 2, it is characterized in that, described in described step (1), the mol ratio of polyvinyl alcohol and phthalic anhydride is 1:1.2 or 1:1.5.
4. the application of heavy metal polymer chelating agent in heavy metal accumulation described in claim 1.
5. the application of heavy metal polymer chelating agent in heavy metal accumulation according to claim 4, is characterized in that, described heavy metal ion is Cu
2+, Cr
6+, Pb
2+or Mn
2+in one or more.
6. the application of heavy metal polymer chelating agent in heavy metal accumulation according to claim 5, is characterized in that, described Cu
2+concentration is 5mg/L, Cr
6+and/or Pb
2+concentration is 40mg/L, Mn
2+concentration is 15mg/L.
7. the application of heavy metal polymer chelating agent in heavy metal accumulation according to any one of claim 4 ~ 6, is characterized in that, described heavy metal polymer chelating agent operative temperature 25 ~ 45 DEG C, and action time is 3h, and addition is 2 ~ 4g/L.
8. the application of heavy metal polymer chelating agent in heavy metal accumulation according to claim 4, is characterized in that, described heavy metal accumulation comprises the heavy metal accumulation in sewage disposal or ore floatation process.
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| CN105944656A (en) * | 2016-05-16 | 2016-09-21 | 成都信息工程大学 | Titanium-based heavy metal ion adsorbent as well as preparation method and application thereof |
| CN107442288A (en) * | 2017-08-14 | 2017-12-08 | 江西理工大学 | A kind of morpholine quaternary ammonium salt Gemini surface active for mineral floating |
| CN112500602A (en) * | 2020-12-04 | 2021-03-16 | 李桂云 | High-molecular preparation for detecting heavy metals in outdoor water source and preparation method thereof |
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| CN102250270A (en) * | 2010-05-19 | 2011-11-23 | 重庆市化工研究院 | Preparation method of novel metal ion trapping agent |
| CN102659231A (en) * | 2012-05-26 | 2012-09-12 | 江南大学 | Preparation and application of water-soluble macromolecule heavy-metal collector |
| CN103204963A (en) * | 2013-04-19 | 2013-07-17 | 重庆工商大学 | Synthetic method of hydroxamic acid polymer |
| CN103769062A (en) * | 2014-02-27 | 2014-05-07 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
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| CN102250270A (en) * | 2010-05-19 | 2011-11-23 | 重庆市化工研究院 | Preparation method of novel metal ion trapping agent |
| CN102659231A (en) * | 2012-05-26 | 2012-09-12 | 江南大学 | Preparation and application of water-soluble macromolecule heavy-metal collector |
| CN103204963A (en) * | 2013-04-19 | 2013-07-17 | 重庆工商大学 | Synthetic method of hydroxamic acid polymer |
| CN103769062A (en) * | 2014-02-27 | 2014-05-07 | 江南大学 | Functionalized polyvinyl alcohol hydrogel and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105944656A (en) * | 2016-05-16 | 2016-09-21 | 成都信息工程大学 | Titanium-based heavy metal ion adsorbent as well as preparation method and application thereof |
| CN107442288A (en) * | 2017-08-14 | 2017-12-08 | 江西理工大学 | A kind of morpholine quaternary ammonium salt Gemini surface active for mineral floating |
| CN107442288B (en) * | 2017-08-14 | 2019-08-06 | 江西理工大学 | A kind of morpholine quaternary ammonium salt Gemini surface active for mineral floating |
| CN112500602A (en) * | 2020-12-04 | 2021-03-16 | 李桂云 | High-molecular preparation for detecting heavy metals in outdoor water source and preparation method thereof |
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