CN103933956A - Method for preparing coal-based composite chelated material from ethidene diamine as raw material - Google Patents
Method for preparing coal-based composite chelated material from ethidene diamine as raw material Download PDFInfo
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Abstract
The invention relates to a method for preparing a coal-based composite chelated material from ethidene diamine as a raw material. The method comprises the following steps: adding gamma-aminopropyl triethoxysilane into a raw coal powder solution, and carrying out coupled reaction for 2-5 hours, so as to obtain coupled modified coal powder; adding the ethidene diamine into the coupled modified coal powder, and carrying out amination for 1-5 hours, so as to obtain aminated coal powder; adding sodium hydroxide and carbon disulfide into the aminated coal powder, and carrying out reaction for 1-4 hours, so as to obtain the coal-based composite chelated material. The method has the beneficial effects that dithiocarbamate with the strong chelating performance can be generated on the surface of the coal powder; a preparation process is simple, and sources of the raw material is wide; the prepared coal-based composite chelated material has the characteristics of good adsorption performance, excellent physical-chemical stability, easiness in solid-liquid separation, wide application range and the like, has a good adsorbing effect on heavy metal ions and can be widely applied to the industrial wastewater treatment.
Description
Technical field
The invention belongs to contaminated wastewater and process the studying technological domain of chelate sorbent used, particularly a kind of preparation method of the coal-based composite chelate material taking ethylenediamine as raw material.
Background technology
Heavy metal pollution of water body is mainly that mankind's activity causes, reason is the discharge of industrial heavy metal wastewater thereby, the industry such as mining, ore dressing, chemical industry, plating, metallurgy, process hides and papermaking aborning, all can produce the waste water of heavy metals such as being rich in mercury (Hg), plumbous (Pb), chromium (Cr), cadmium (Cd), nickel (Ni), iron (Fe), zinc (Zn).Heavy metal pollution of water body processing method conventional in practice has: the means of the precipitation method, ion-exchange, membrane separation process technology, extraction, biological treatment, chelating absorption method etc.Chelating absorption method is because having lot of advantages, and such as high-molecule chelated adsorbent is due to polymer effect, it is synthetic easy, cheap, adsorption capacity is disturbed less with good stability etc., and is widely used.
In chelating absorption method, the performance of chelate sorbent directly affects the treatment effect of heavy metal ions in wastewater, increasing experts and scholars are devoted to chelate sorbent preparation method's research, spy is standby is, by methods such as chemical grafts, chelating functional group is fixed on to some particle surface, thereby forms the good chelate sorbent of adsorption effect.
But the matrix that most people selects is to adopt macromolecule resin, aerosil particles, nano-metal-oxide etc., the control of the higher and method of modifying of its manufacturing cost, condition is also comparatively complicated, therefore, select the focus that a kind of cost performance matrix high and that self-characteristic is excellent is current research.
Summary of the invention
The object of the present invention is to provide that technique is simple, condition is controlled, with low cost, prepared coal-based composite chelate materials chemistry character is stable, non-secondary pollution, has the preparation method of a kind of coal-based composite chelate material taking ethylenediamine as raw material of good effect to processing heavy metal.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
(1) take the former coal dust that particle diameter is 0.075～0.113mm, be dissolved in distilled water according to the amount that adds the former coal dust of 10g in the distilled water of every 100mL, in coal dust solution, add gamma-aminopropyl-triethoxy-silane, the mass ratio of coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.01～1, preferably 1:0.1～0.5,50～90 DEG C are stirred coupling reaction 2～5 hours, and preferably 60～80 DEG C are stirred coupling reaction 3 hours, obtain coupling modification coal dust;
(2) in coupling modification coal dust, add ethylenediamine, the mass ratio that makes former coal dust and ethylenediamine is 1:0.45～1.5, and preferably 50～90 DEG C of aminating reactions 1～5 hour, obtain amination coal dust;
(3) in amination coal dust, add NaOH and carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:0.8～1.2:0.75～1.76, and 35 DEG C are reacted 1～4 hour, obtain coal-based composite chelate material.
Preferred 1:0.8～1.3 of mass ratio of above-mentioned steps (2) Central Plains coal dust and ethylenediamine, 1:1.2 is best, preferably 60～80 DEG C of aminating reactions 2～4 hours, 70 DEG C of aminating reactions 3 hours be the best, obtain amination coal dust.
Preferred 1:1.0～1.2:0.5～1.5 of mass ratio of above-mentioned steps (3) Central Plains coal dust and NaOH, carbon disulfide, 1:1.0:1.25 is best, and 35 DEG C are reacted 1～4 hour, and it 2 hours is good reacting, and obtains coal-based composite chelate material.
The preparation method of a kind of coal-based composite chelate material taking ethylenediamine as raw material provided by the present invention, it is taking pulverized coal particle as matrix, adopt coupling agent gamma-aminopropyl-triethoxy-silane that ethylenediamine coupling is grafted to pulverized coal particle surface, again by modification coal dust and NaOH, carbon disulfide reacts, there is the dithiocar-bamate of strong chelating ability at coal dust Surface Creation, be prepared into coal-based composite chelate material, it provides a kind of preparation method of novel coal-based composite chelate material, its preparation technology is simple, raw material sources are wide, prepared coal-based composite chelate material has absorption property that coal-based body is good and excellent physical and chemical stability concurrently, be easy to Separation of Solid and Liquid, the features such as applied range, to the advantages of good adsorption effect of heavy metal ion, applicable to Industrial Wastewater Treatment.
Brief description of the drawings
Fig. 1 is that ethylenediamine dosage is to Ni
2+the influence curve of clearance;
Fig. 2 is that reaction time of ethylenediamine is to Ni
2+clearance affect comparison diagram;
Fig. 3 is that the reaction temperature of ethylenediamine is to Ni
2+the influence curve of clearance;
Fig. 4 is that NaOH consumption is to Ni
2+the influence curve of clearance;
Fig. 5 is CS
2consumption is to Ni
2+clearance affect comparison diagram;
Fig. 6 is the infrared spectrogram of coupling modification coal dust, amination coal dust, coal-based composite chelate material.
Detailed description of the invention
Now in conjunction with experiment, technical scheme of the present invention is further described, but the present invention is not limited only to the situation of following enforcement.
Embodiment 1
The present embodiment is taking 10g coal dust as example, and the method for the coal-based composite chelate material of preparation taking ethylenediamine as raw material is realized by following steps:
(1) take the former coal dust 10g that particle diameter is 0.075～0.113mm, add in the distilled water of 100mL, mix, taking 0.3g gamma-aminopropyl-triethoxy-silane adds in coal dust solution, the mass ratio that makes former coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.03,70 DEG C are stirred coupling reaction 3 hours, obtain coupling modification coal dust.
(2) measure the ethylenediamine of 12g, add in coupling modification coal dust, the mass ratio that makes former coal dust and ethylenediamine is 1:1.2,70 DEG C of aminating reactions 3 hours, obtains amination coal dust;
(3) in the amination coal dust of step (2), add 10g NaOH and 12.5g carbon disulfide, the mass ratio of former coal dust and NaOH, carbon disulfide is 1:1:1.25, and 35 DEG C are reacted 2 hours, obtain coal-based composite chelate material.
Embodiment 2
The present embodiment is taking 10g coal dust as example, and the method for the coal-based composite chelate material of preparation taking ethylenediamine as raw material is realized by following steps:
(1) take the former coal dust 10g that particle diameter is 0.075～0.113mm, add in the distilled water of 100mL, mix, taking 1g gamma-aminopropyl-triethoxy-silane adds in coal dust solution, the mass ratio that makes former coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.1,60 DEG C are stirred coupling reaction 4 hours, obtain coupling modification coal dust.
(2) measure the ethylenediamine of 8g, add in coupling modification coal dust, the mass ratio that makes former coal dust and ethylenediamine is 1:0.8,60 DEG C of aminating reactions 3 hours, obtains amination coal dust;
(3) in the amination coal dust of step (2), add 10g NaOH and 5g carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:1.0:0.5, and 35 DEG C are reacted 1 hour, obtain coal-based composite chelate material.
Embodiment 3
The present embodiment is taking 10g coal dust as example, and the method for the coal-based composite chelate material of preparation taking ethylenediamine as raw material is realized by following steps:
(1) take the former coal dust 10g that particle diameter is 0.075～0.113mm, add in the distilled water of 100mL, mix, taking 5g gamma-aminopropyl-triethoxy-silane adds in coal dust solution, the mass ratio that makes former coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.5,80 DEG C are stirred coupling reaction 3 hours, obtain coupling modification coal dust.
(2) measure the ethylenediamine of 13g, add in coupling modification coal dust, the mass ratio that makes former coal dust and ethylenediamine is 1:1.3,80 DEG C of aminating reactions 2 hours, obtains amination coal dust;
(3) in the amination coal dust of step (2), add 12g NaOH and 15g carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:1.2:1.5, and 35 DEG C are reacted 4 hours, obtain coal-based composite chelate material.
Embodiment 4
The present embodiment is taking 10g coal dust as example, and the method for the coal-based composite chelate material of preparation taking ethylenediamine as raw material is realized by following steps:
(1) take the former coal dust 10g that particle diameter is 0.075～0.113mm, add in the distilled water of 100mL, mix, taking 0.1g gamma-aminopropyl-triethoxy-silane adds in coal dust solution, the mass ratio that makes former coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.01,50 DEG C are stirred coupling reaction 5 hours, obtain coupling modification coal dust.
(2) measure the ethylenediamine of 4.5g, add in coupling modification coal dust, the mass ratio that makes former coal dust and ethylenediamine is 1:0.45,50 DEG C of aminating reactions 5 hours, obtains amination coal dust;
(3) in the amination coal dust of step (2), add 8g NaOH and 7.5g carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:0.8:0.75, and 35 DEG C are reacted 1 hour, obtain coal-based composite chelate material.
Embodiment 5
The present embodiment is taking 10g coal dust as example, and the method for the coal-based composite chelate material of preparation taking ethylenediamine as raw material is realized by following steps:
(1) take the former coal dust 10g that particle diameter is 0.075～0.113mm, add in the distilled water of 100mL, mix, taking 10g gamma-aminopropyl-triethoxy-silane adds in coal dust solution, the mass ratio that makes former coal dust and gamma-aminopropyl-triethoxy-silane is 1:1,90 DEG C are stirred coupling reaction 2 hours, obtain coupling modification coal dust.
(2) measure the ethylenediamine of 15g, add in coupling modification coal dust, the mass ratio that makes former coal dust and ethylenediamine is 1:1.5,90 DEG C of aminating reactions 1 hour, obtains amination coal dust;
(3) in the amination coal dust of step (2), add 12g NaOH and 17.6g carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:1.2:1.76, and 35 DEG C are reacted 4 hours, obtain coal-based composite chelate material.
In order to verify optimum process condition of the present invention, inventor has carried out a large amount of experimental verifications, by single factor experiment, the process conditions of amination coal dust is optimized, specific as follows:
The coal dust that this experiment adopts stems from Shenfu Coal Powder.
1) ethylenediamine consumption is inhaled the impact of material property on coal-based composite chelate
Get 5 three mouthfuls of round-bottomed flasks, add respectively 10g coal dust, be fully dissolved in 100mL distilled water, add 0.3g gamma-aminopropyl-triethoxy-silane, at 70 DEG C, react 3 hours, obtain coupling modification coal dust; Add respectively the ethylenediamine of 4.5g, 6g, 9g, 12g, 15g, 70 DEG C of reactions 3 hours, obtain amination coal dust; To adding respectively in amination coal dust the carbon disulfide, NaOH of equivalent 35 DEG C of reactions 2 hours, respectively with distilled water washing for several times, suction filtration separates, vacuum drying, can obtain coal-based composite chelate material, by the coal-based composite chelate material obtaining respectively to Ni
2+concentration is that the simulated wastewater 100mL of 100mg/L adsorbs, and calculates separately to Ni
2+clearance, the results are shown in Figure 1.
As shown in Figure 1, add composite chelate adsorbent that the ethylenediamine of different quality obtains to Ni
2+clearance also different, and the consumption of ethylenediamine is larger for the grafting amount impact of coal-based composite chelate material, when ethylenediamine is increased to 12g from 4.5g, Ni
2+clearance constantly increases, in the time that ethylenediamine quality continues to increase, and Ni
2+clearance substantially no longer changes, and the best that therefore can determine ethylenediamine is 12g, and the optimum quality ratio of former coal dust and ethylenediamine is 1:1.2.
2) reaction time of ethylenediamine is inhaled impact prepared by material to coal-based composite chelate
Get 5 three mouthfuls of round-bottomed flasks, add respectively 10g coal dust, be fully dissolved in 100mL distilled water, add 0.3g gamma-aminopropyl-triethoxy-silane, at 70 DEG C, react 3 hours, obtain coupling modification coal dust; Add respectively 12g ethylenediamine, react respectively 2 hours, 3 hours, 4 hours, 5 hours at 70 DEG C, obtain amination coal dust; To adding respectively in amination coal dust the carbon disulfide, NaOH of equivalent 35 DEG C of reactions 2 hours, respectively with distilled water washing for several times, suction filtration separates, vacuum drying, can obtain composite chelate adsorbent, by the coal-based composite chelate material obtaining respectively to Ni
2+concentration is that the simulated wastewater 100mL of 100mg/L adsorbs, and calculates separately to Ni
2+clearance, the results are shown in Figure 2.
As shown in Figure 2, reacting ethylenediamine asynchronism(-nization) is to Ni
2+clearance affects relative dosage, is not clearly, and the reaction time is while being increased to 3h from 1h, Ni
2+it is the highest that clearance reaches, and continues to increase clearance and slightly reduce.Therefore the optimum reacting time that can determine ethylenediamine is 3h.
3) reaction temperature of ethylenediamine is inhaled impact prepared by material to coal-based composite chelate
Get 5 three mouthfuls of round-bottomed flasks, add respectively 10g coal dust, be fully dissolved in 100mL distilled water, add 0.3g gamma-aminopropyl-triethoxy-silane, at 70 DEG C, react 3 hours, obtain coupling modification coal dust; Add respectively 12g ethylenediamine, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C reactions 3 hours, obtain amination coal dust; To adding respectively in amination coal dust the carbon disulfide, NaOH of equivalent 35 DEG C of reactions 2 hours, respectively with distilled water washing for several times, suction filtration separates, vacuum drying, can obtain coal-based composite chelate material, by the coal-based composite chelate material obtaining respectively to Ni
2+concentration is that the simulated wastewater 100mL of 100mg/L adsorbs, and calculates separately to Ni
2+clearance, the results are shown in Figure 3.
As shown in Figure 3, along with the rising of reaction temperature, chelate sorbent is removed Ni
2+effect also constantly increases, in the time that temperature continues to be elevated to 70 DEG C, and Ni
2+clearance slightly reduces.Therefore the optimal reaction temperature that can determine ethylenediamine is 70 DEG C.
4) NaOH dosage is inhaled the impact of material on coal-based composite chelate
Get 5 three mouthfuls of round-bottomed flasks, add respectively 10g coal dust, be fully dissolved in 100mL distilled water, add 0.3g gamma-aminopropyl-triethoxy-silane, at 70 DEG C, react 3 hours, obtain coupling modification coal dust; Add respectively 12g ethylenediamine, 70 DEG C of reactions 3 hours, obtain amination coal dust; In amination coal dust, add respectively the NaOH of 8g, 9g, 10g, 11g, 12g to add again the carbon disulfide of same amount, 35 DEG C of reactions 2 hours, respectively with distilled water washing several, suction filtration separates, vacuum drying, can obtain composite chelate adsorbent, by the coal-based composite chelate material obtaining respectively to Ni
2+concentration is that the simulated wastewater 100mL of 100mg/L adsorbs, and calculates separately to Ni
2+clearance, the results are shown in Figure 4.
As shown in Figure 4, the NaOH of different dosages is to Ni
2+clearance impact is different, along with the increase of NaOH consumption, Ni
2+clearance increases to some extent, in the time that the amount of NaOH is increased to 10g, and Ni
2+clearance maximum, optimum dosage is 10g, the mass ratio of former coal dust and NaOH is 1:1.
5) carbon disulfide dosage is inhaled the impact of material property on coal-based composite chelate
Get 5 three mouthfuls of round-bottomed flasks, add respectively 10g coal dust, be fully dissolved in 100mL distilled water, add 0.3g gamma-aminopropyl-triethoxy-silane, at 70 DEG C, react 3 hours, obtain coupling modification coal dust; Add respectively 12g ethylenediamine, 70 DEG C of reactions 3 hours, obtain amination coal dust; To adding the carbon disulfide that adds respectively again 7.5g, 10g, 12.5g, 15,17.6g after the NaOH of same amount in amination coal dust, 35 DEG C of reactions 2 hours, respectively with distilled water washing several, suction filtration separates, vacuum drying, can obtain coal-based composite chelate material, by the coal-based composite chelate material obtaining respectively to Ni
2+concentration is that the simulated wastewater 100mL of 100mg/L adsorbs, and calculates separately to Ni
2+clearance, the results are shown in Figure 5.
As shown in Figure 5, when the addition of carbon disulfide is increased to 12.5g from 7.5g, Ni
2+clearance increases gradually, tends to be steady when being increased to after 12.5g, and therefore, the optimization consumption of carbon disulfide is 12.5g.The mass ratio that is former coal dust and carbon disulfide is 1:1.25.
In sum, the preferred plan that draws preparation coal-based composite chelate material of the present invention by above-mentioned experiment of single factor is: the mass ratio of former coal dust and ethylenediamine is 1:1.2, temperature is 70 DEG C, reaction time is 3h, add 10g NaOH at amination coal dust, 12.5g carbon disulfide, 35 DEG C of reaction 2h, obtain coal-based composite chelate material.
In order to verify performance, the adsorption effect etc. of the prepared product of the present invention, inventor has carried out a large amount of experimental verifications, specific as follows:
Pass through infrared spectrum, coupling modified coal powder, amination coal dust and the synthetic coal-based composite chelate material taking ethylenediamine as raw material (being called for short coal-based composite chelate material) are measured respectively to their infrared absorption spectroscopy, to determine the variation of coal dust structure in the preparation process of the coal-based composite chelate material taking ethylenediamine as raw material, specifically as shown in Figure 6, in figure: the infrared spectrogram that curve (1) is coupling modification coal dust, curve (2) is amination coal dust infrared spectrogram, and curve (3) is coal-based composite chelate material infrared spectrogram.
As seen from Figure 6, curve (2) compared with curve (1), 3649cm
-1place's absworption peak is that N-H (hydrogen bond association) stretching vibration Absorption Characteristics peak is strengthened, 1618cm
-1with 1553cm
-1near the vibration absorption peak for C-N-H is obviously better than the vibration absorption peak in (1), and weakened-CH
2absworption peak, in the infrared spectrogram (3) of composite chelate adsorbent, 1503cm
-1there is the special absworption peak of N-C=S, 1316cm in place
-1there is the stretching vibration absworption peak of N-C-S in place, result proves that dithiocar-bamate chelation group is successfully grafted to coal particle surface.
Claims (6)
1. a preparation method for the coal-based composite chelate material taking ethylenediamine as raw material, is characterized in that being realized by following steps:
(1) take the former coal dust that particle diameter is 0.075～0.113mm, be dissolved in distilled water according to the amount that adds the former coal dust of 10g in the distilled water of every 100mL, in coal dust solution, add gamma-aminopropyl-triethoxy-silane, the mass ratio of coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.01～1,50～90 DEG C are stirred coupling reaction 2～5 hours, obtain coupling modification coal dust;
(2) in coupling modification coal dust, add ethylenediamine, the mass ratio that makes former coal dust and ethylenediamine is 1:0.45～1.5, and 50～90 DEG C of aminating reactions 1～5 hour, obtain amination coal dust;
(3) in amination coal dust, add NaOH and carbon disulfide, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:0.8～1.2:0.75～1.76, and 35 DEG C are reacted 1～4 hour, obtain coal-based composite chelate material.
2. the preparation method of the coal-based composite chelate material taking ethylenediamine as raw material according to claim 1, it is characterized in that: described step (1) is to take the former coal dust that particle diameter is 0.075～0.113mm, be dissolved in distilled water according to the amount that adds the former coal dust of 10g in the distilled water of every 100mL, in coal dust solution, add gamma-aminopropyl-triethoxy-silane, the mass ratio of former coal dust and gamma-aminopropyl-triethoxy-silane is 1:0.1～0.5,60～80 DEG C are stirred coupling reaction 3 hours, obtain coupling modification coal dust.
3. the preparation method of the coal-based composite chelate material taking ethylenediamine as raw material according to claim 1, it is characterized in that: described step (2) is to add ethylenediamine in coupling modification coal dust, the mass ratio of former coal dust and ethylenediamine is 1:0.8～1.3,60～80 DEG C of aminating reactions 2～4 hours, obtain amination coal dust.
4. the preparation method of the coal-based composite chelate material taking ethylenediamine as raw material according to claim 3, it is characterized in that: described step (2) is to add ethylenediamine in coupling modification coal dust, the mass ratio of former coal dust and ethylenediamine is 1:1.2,70 DEG C of aminating reactions 3 hours, obtain amination coal dust.
5. the preparation method of the coal-based composite chelate material taking ethylenediamine as raw material according to claim 1, it is characterized in that: described step (3) adds and first adds NaOH, adds carbon disulfide again in amination coal dust, the mass ratio that makes former coal dust and NaOH, carbon disulfide is 1:1.0～1.2:0.5～1.5,35 DEG C are reacted 1～4 hour, obtain coal-based composite chelate material.
6. the preparation method of the coal-based composite chelate material taking ethylenediamine as raw material according to claim 1, it is characterized in that: described step (3) adds and first adds NaOH, adds carbon disulfide again in amination coal dust, the mass ratio of former coal dust and NaOH, carbon disulfide is 1:1.0:1.25,35 DEG C are reacted 2 hours, obtain coal-based composite chelate material.
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| CN106925221A (en) * | 2017-04-25 | 2017-07-07 | 河海大学 | Biradical method of modifying of charcoal amine sulphur |
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