GB2600494A - A straw fiber adsorption material, its preparation methods and applications - Google Patents

A straw fiber adsorption material, its preparation methods and applications Download PDF

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GB2600494A
GB2600494A GB2018479.2A GB202018479A GB2600494A GB 2600494 A GB2600494 A GB 2600494A GB 202018479 A GB202018479 A GB 202018479A GB 2600494 A GB2600494 A GB 2600494A
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adsorption material
straw fiber
fiber adsorption
adsorption
heavy metals
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GB202018479D0 (en
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Zheng Liuchun
Zhang Tao
Jiang Xuemin
Zou leyan
Li Yating
He Jinping
Huang Yanan
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South China Normal University
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    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
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    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur

Abstract

A preparation method for a straw fiber adsorption material capable of efficiently adsorbing heavy metal and antibiotic composite pollutants is described. The method includes pretreating corn straw cellulose, etherification with epichlorohydrin, crosslinking with ethylenediamine, and grafting of diethylenetriamine pentaacetic acid. Preferably the pretreatment includes crushing and sieving corn straws, soaking in 1mol/L NaOH solution for 24hours, respectively filtering and washing to neutrality, and drying. Etherification may include etherifying 2-5g of pre-treated corn straw with 70-100ml of epichlorohydrin and 60-100ml of N-N dimethylformamide at 70-100ºC for 1-3hours. Crosslinking can include adding 8-15ml ethylenediamine after the etherification has finished, then carrying out crosslinking at 70-100ºC for 1-3hours. Preferably, grafting includes adding 5-15g of diethylenetriamine pentaacetic acid after crosslinking has finished, then grafting at 70-100 ºC for 1-3hours. After grafting, the material can be washed with N-N dimethylformamide, deionized water, saturated sodium bicarbonate and deionized water in turn to neutrality, and then dried. The adsorption material has amino, carboxyl and hydroxyl groups which have been introduced into the fiber surface, as evidenced by SEM-EDS and FTIR. Adsorption experiments show that the modified materials have strong adsorption performance for single and mixed systems of heavy metal cadmium (Cd) and sulfamethoxazole (SMZ) in water.

Description

A straw fiber adsorption material, its preparation methods and applications
Technical field
The invention relates to the technical field of fiber adsorption materials, in particular to a preparation method of a straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants, as well as to the simultaneous adsorption of antibiotics and heavy metals.
Background technology
In recent years, the combined pollution of heavy metals and antibiotics in water has attracted great attention, because it truly reflects the real environmental situation. More and more evidences show that the complex toxicity of antibiotics and heavy metals is often greater than their single toxicity. Therefore, in recent years, many technologies have been used to remove the complex pollutants of heavy metals and antibiotics, such as hydrothermal treatment, aquatic plant remediation and electrochemical methods. Among them, adsorption method has been proved to be one of the most promising methods because of its low price, simple operation and reusability. In particular, corn straw cellulose, as an environmentally friendly natural carbonaceous biomass materials with the largest existing reserves, can introduce various groups through chemical modification to change its physical and chemical properties, so that it exhibits better adsorption performance. However, at present, the research on straw-based cellulose materials is almost focused on a single pollution system, and there are some shortcomings such as poor adsorption capacity, difficulty in adapting to complex environmental conditions and low efficiency, all of which greatly limit the large-scale application of straw-based cellulose materials.
In addition, the composite adsorption system of heavy metals and antibiotics is quite different from its single adsorption system, which is mainly composed of the following aspects: firstly, most modified materials are usually limited by their own structures, and it is difficult to provide enough adsorption sites for antibiotics and heavy metals. Secondly, heavy metals and antibiotics often interact in the adsorption process, for example, competition for adsorption sites (most studies show that heavy metals tend to exert stronger force on hydrophilic sites than antibiotics) and key-bridge cooperation, etc. All these increase the complexity of multi-pollutant adsorption system and the difficulty of designing adsorption materials.
Therefore, how to provide a straw fiber adsorption material which can efficiently adsorb heavy metal and antibiotic compound pollutants and its preparation method is an urgent problem for technicians in this field.
Summary of this invention
One purpose of this invention is to provide a preparation method of straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants, which is environmentally friendly, efficient, low in price and reusable, and has a good removal effect on heavy metals and antibiotic pollutants at the same time.
In order to achieve the above purpose, the technical scheme of this invention is as follows: The invention relates to a preparation method of a straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants, which is characterized in that the straw fiber adsorption material is prepared by pretreating corn straw cellulose, etherifying epichlorohydrin, crosslinking ethylenediamine and grafting diethylenetriamine pentaacetic acid.
The specific steps of preferred said pretreatment are as follows: crushing and sieving corn stalks (0.45mm), soaking in 1mol/L NaOH solution for 24 hours, respectively filtering, washing to neutrality, and drying.
The specific steps of preferred said etherification are as follows: etherification reaction of 2-5g pretreated corn stalks with 70-100 ml epichlorohydrin and 60-100m1 N-N dimethylformamide at 70-100°C for 1-3h.
The specific steps of preferred said crosslinking are as follows: after the etherification reaction is finished, 8-15m1 of ethylenediamine is added, and the crosslinking reaction is carried out for 1-3h at 70-100 DEG C..
The specific steps of preferred said grafting are as follows: after the crosslinking reaction is finished, 5-15g of diethylenetriamine pentaacetic acid is added, and graft reaction is carried out at 70-100 DEG C for 1-3h.
After the preferred grafting reaction is finished, it needs to be washed with N-N dimethylformamide, deionized water, saturated sodium bicarbonate and deionized water to be neutral, and then dried to obtain the straw fiber adsorption material.
The second purpose of this invention is to provide the straw fiber capable of efficiently adsorbing heavy metals and antibiotic pollutants.
The third purpose of this invention is to provide the straw fiber for efficiently adsorbing heavy metal and antibiotic compound pollutants for adsorbing antibiotics and heavy metals in water and simultaneously adsorbing heavy metal antibiotics.
In order to detect the adsorption performance of the straw fiber of this invention to heavy metal and antibiotic pollutants, this invention provides the following detection method: select sulfamethoxazole (SMZ) and heavy metal cadmium (Cd), which are commonly found in the environment, and explore the adsorption performance of modified materials to SMZ and Cd single and compound system.
In the adsorption experiment for this invention, the pH value is 7, the adsorption temperature is 25±1C, the adsorption time is 48h, the rotating speed of the shaking table is 180r/min, the SMZ concentration range is 10-50mg/L, and the Cd concentration range is 20-80mg/L.
As revealed in the technical schemes above, this invention has the following beneficial effects, as compared with existing technologies: 1. The technical scheme of this invention increases the number and diversity of hydrophilic adsorption sites (amino, carboxyl and hydroxyl) of modified materials, so as to meet the needs of different pollutant adsorption sites. On the one hand, it increases the spatial distance of hydrophilic adsorption sites, on the other hand, it increases the specific adsorption sites of antibiotics, such as hydrophobic and TI-T1 interaction. Therefore, the adsorption material of this invention has the characteristics of multi-groups, long chain and large space, thus reducing the direct competition of heavy metals and antibiotics on hydrophilic adsorption sites in the composite adsorption system, increasing the synergistic effect, and finally increasing the total adsorption amount of the composite pollution system.
2. The straw fiber adsorption material of this invention has good stability, high-efficient environmental protection and recyclable. Meanwhile, it has the characteristics of multi-groups (amino, carboxyl and hydroxyl), long chain and large space, thus making up for the defects of small specific surface area and few pores of straw fiber itself, and making it have better adsorption performance for heavy metal and antibiotic compound pollutants. In addition, the adsorption material of this invention has the advantages of high adsorption rate and strong selectivity, and has important reference value for high-value utilization of straw biomass materials and removal of heavy metal and antibiotic compound pollutants.
Description of figures
Fig.1 is the SEM-EDS figures of unmodified corn straw (RCS), HVUC, HVUC adsorbing single Cd(HVUC+Cd), HVUC adsorbing single SMZ(HVUC+SMZ), and HVUC adsorbing mixed solution of Cd and SMZ (HVUC+SMZ+Cd); Fig.2 is the FTIR figures of corn straw material before and after modification; Fig.3 shows the adsorption kinetics of Cd by HVUC in single and SMZ mixed 10 systems; Fig.4 shows the adsorption kinetics of HVUC to SMZ in single and Cd mixed systems; Fig.5 shows the adsorption isotherm of HVUC for Cd in single and SMZ mixed systems; Fig.6 shows the adsorption isotherm of HVUC on SMZ in single and Cd mixed systems; Fig.7 shows the adsorption-desorption cycle test results of Cd and HVUC to SMZ in mixed system.
Mode of carrying out this invention: The technical scheme in the embodiments of this invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of this invention, not all of them. Based on the embodiments of this invention, all other embodiments obtained by ordinary technicians in the field without creative labor belong to the scope of protection of this invention.
Embodiment 1 (1) Pretreatment: Weigh lOg of crushed and sieved corn stalks (0.45mm) into a beaker, add 1mol/L NaOH solution, immerse them for 24h, filter, wash them to neutrality, and dry them for later use.
(2) Etherification reaction: put 2g pretreated straw, 70m1 N-N dimethylformamide and 70m1epichlorohydrin in a 250m1 three flasks and stirred at 70°C for 2h.
(3) Crosslinking reaction: slowly add 8m1 ethylenediamine and react at 70°C for 1h.
(4) Grafting reaction: after 5g diethylenetriamine pentaacetic acid is dissolved in NaOH solution until the solution is weakly alkaline, add it into the above reaction system, and keep the reaction temperature at 70°C for 1h.
(5) Flushing, filtering and drying: washing with N-N dimethylformamide, deionized 5 water, washed saturated sodium bicarbonate and deionized water to neutrality, and then drying at 60°C to prepare the modified adsorbent.
Embodiment 2 (1) Pretreatment: Weigh lOg of crushed and sieved corn stalks (0.45mm) into a beaker, add lmol/L NaOH solution, immerse them for 24h, filter, wash them to neutrality, and dry them for later use.
(2) Etherification reaction: put 3g pretreated straw, 85m1 N-N dimethylformamide and 85m1 epichlorohydrin in a 250m1 three flasks and stirred at 85°C for lh.
(3) Crosslinking reaction: slowly add 10.5 ml ethylenediamine and react at 85°C for 1h.
(4) Grafting reaction: after 10g diethylenetriamine pentaacetic acid is dissolved in NaOH solution until the solution is weakly alkaline, add it into the above reaction system, and keep the reaction temperature at 85°C for 2h.
(5) Flushing, filtering and drying: washing with N-N dimethylformamide, deionized water, washed saturated sodium bicarbonate and deionized water to neutrality, and 20 then drying at 60°C to prepare the modified adsorbent.
Embodiment 3 (1) Pretreatment: Weigh lOg of crushed and sieved corn stalks (0.45mm) into a beaker, add 1mol/L NaOH solution, immerse them for 24h, filter, wash them to neutrality, and dry them for later use.
(2) Etherification reaction: put 5g pretreated straw, 100m1N-N dimethylformamide and 100m1 epichlorohydrin in a 250m1 three flasks and stirred at 100°C for 3h.
(3) Crosslinking reaction: slowly add 15m1 ethylenediamine and react at 100°C for 3h (4) Grafting reaction: after 15g diethylenetriamine pentaacetic acid is dissolved in NaOH solution until the solution is weakly alkaline, add it into the above reaction system, and keep the reaction temperature at 100°C for 3h.
(5) Flushing, filtering and drying: washing with N-N dimethylformamide, deionized water, washed saturated sodium bicarbonate and deionized water to neutrality, and then drying at 60°C to prepare the modified adsorbent.
Embodiment 4 HVUCs obtained from Embodiments 1-3 are all well surface modified, and can achieve good adsorption effects on Cd and SMZ. the hvucs obtained in example 2 are characterized as follows: Refer to Fig.1 for SEM-EDS figures of RCS, HVUC, HVUC-'-Cd, HVUC+SMZ and HVUC+SMZ+Cd; and refer to Fig.2 for FTIR figures of corn straw materials before and after modification.
The result shows that: SEM atlas show that, HVUC is more irregular and rough than RCS with smooth surface, and has hollow and spongy surface structure. EDS atlas show that, compared with RCS, the nitrogen content in HVUC increased by 11.77%, but the oxygen content in HVUC decreased to some extent. This is mainly because the hydrogen bonds formed by hydroxyl groups in cellulose are destroyed greatly after modification, thus introducing carboxyl groups and hydroxyl groups with adsorption activity. The above result shows that that specific surface area of HVUC is greatly increased, and a large number of groups (amino, carboxyl and hydroxyl) are introduced into the surface. In addition, HUUC SEM has little change before and after single adsorption and mixed Cd and SMZ, which proves that it has high mechanical strength and can be reused. EDS result shows that the contents of Cd and SEM before and after HVUC adsorption also increase correspondingly, which proves that hviac has strong adsorption capacity for Cd and SMZ.
FTIR atlas of corn straw before and after modification show that the peak value at 1577cm-1 and 1390cm-1 is the stretching vibration of -COOH, and the peak value at 1457cm-1 and 1317cm-1 is the stretching vibration of -NH, which indicates that HVUC successfully introduced amino and carboxyl groups.
Furthermore, the adsorption kinetics of Cd by HVUC in single and SMZ mixed systems: In case of single system, When adding lg HVUC into a 1L conical flask, the pH value of 500m1 Cd(70mg/L) solution is 7; In case of mixing the system, when adding lg HVUC into a 1L conical flask, the pH value of the mixed solution of 500m1 Cd(70mg/L) and SMZ(20mg/L) is 7; Then, seal the said conical flask and put it into a constant-temperature oscillating shaker, set the temperature at 25°C, shaking table rotation speed at 180r/min, take samples every 0.5h, 1h, 3h, 6h, 12h, 24h, 48h and 72h, and use atomic absorption spectrophotometer to determine its concentration.
Refer to Fig.3 for the adsorption kinetics of Cd by HVUC in single and SMZ mixed system The result shows that that adsorption of Cd by HVUC can almost reach equilibrium at 30min, whether in Cd single system or SMZ mixed system.
Furthermore, the adsorption kinetics of HVUC on SMZ in single and Cd mixed 10 systems: In case of single system, When adding 1g HVUC into a 1L conical flask, the pH value of 500m1 SMZ( 20mg/L) solution is 7; In case of mixing the system, when adding 1g HVUC into a 1L conical flask, the pH value of the mixed solution of 500mICd(70mg/L) and SMZ(20mg/L) is 7; Then, seal the said conical flask and put it into a constant-temperature oscillating shaker, set the temperature at 25 C, shaking table rotation speed at 180r/min, take samples every 0.5h, 1h, 3h, 6h, 12h, 24h, 48h 72h, and use high-efficient liquid chromatography to determine its concentration.
Refer to Fig.4 for the adsorption kinetics of HVUC to SMZ in single and Cd mixed 20 system The result shows that that adsorption of HVUC to SMZ can almost reach equilibrium at 30min, whether in Cd single system or Cd mixed system.
Furthermore, the adsorption isothermal of Cd by HVUC in single and SMZ mixed systems: Weigh 0.02gHVUC and put it into a 20m1 conical flask, and add a series of Cd solutions with concentration gradients of 20mg/L, 40mg/L, 60mg/L, 70mg/L and 80mg/L respectively. In Cd and SMZ coexistence system, SMZ concentration is 5mg/L and 20mg/L respectively, and Cd concentration gradient remains unchanged. In which, the solution dosage is 10m1, the solution pH is 7, the temperature of the constant-temperature shaking table is set up at 25°C, rotation speed 180r/min, and the adsorption equilibrium time is 48h. Three groups of parallel samples are provided for each concentration. Then take out the balanced solution and measure the residual concentration of Cd by atomic absorption spectrophotometer.
S
Refer to Fig.5 for the adsorption isothermal of Cd by HVUC in single and SMZ mixed system The results shows that HVUC has strong adsorption performance for Cd single and SMZ mixed systems, and the coexistence of SMZ can promote Cd to a certain extent, and the greater the concentration of coexisting SMZ, the more obvious the promotion effect is. The fitting results of adsorption isotherms show that the maximum adsorption capacities of HVUC for Cd in single, SMZ5mg/L mixed system and SMZ20mg/L mixed system are 26.620mg/g, 28.121mg/g and 28.385mg/g respectively.
Furthermore, the adsorption isothermal of HVUC to SMZ in single and Cd mixed 10 systems: Weigh 0.02gHVUC and put it into a 20m1 conical flask, and add a series of difference SMZ solutions with concentration gradient 10mg/L, concentration gradient 20mg/L, 30mg/L, 40mg/L and 50mg/L respectively. In SMZ and Cd coexistence system, Cd concentration is 10mg/L and 70mg/L respectively, and SMZ concentration gradient remains unchanged. In which, the solution dosage is 10m1, the solution pH is 7, the temperature of the constant-temperature shaking table is set up at 25°C, rotation speed 180r/min, and the adsorption equilibrium time is 48h. Three groups of parallel samples are provided for each concentration. Then take out the balanced solution and measure the residual concentration of SMZ by high-efficient liquid chromatography Refer to Fig.6 for the adsorption isothermal of HVUC to SMZ in single and Cd mixed system The results show that HVUC has strong adsorption performance for SMZ single and Cd mixed systems, even in the case of high Cd coexistence concentration. The fitting results of adsorption isotherm shows that the maximum adsorption capacity of HVUC to SMZ in single, mixed system of Cd10mg/L and mixed system of Cd70mg/Lmg/L are 59.150mg/g, 40.887mg/g and 25.112mg/g respectively, all of which are stronger than those of most modified straw fiber materials.
Furthermore, HVUC reuses SMZ and Cd adsorption-desorption in mixed system: Afte every time when the mixed solution of HVUC and SMZ/Cd reaches adsorption equilibrium, use 0.1MNaOH and 0.1MHCI for desorption respectively, and test the stability of the mixture of SMZ and Cd after five adsorption-desorption of HVUC.
Refer to Fig.7 for the result of HVUC's resuse of SMZ/Cd adsorption-desorption in mixed system; The result shows that even after five adsorption-desorption times, HVUC has little effect on Cd adsorption, but only shows a slight decrease in SMZ, which proves that HVUC has strong adsorption stability.
To sum up, HVUC has strong adsorption performance for single and mixed systems of Cd and SMZ, and has the characteristics of fast adsorption rate and high stability.
Each embodiment in this Instruction is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. It is sufficient to refer to the same and similar parts between each embodiment.
The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Many modifications to these embodiments will be apparent to those skilled in this field, and the general principles defined herein may be realized in other embodiments without departing from the spirit or scope of this invention. Therefore, this invention shall not be limited to the embodiments as shown herein, but shall be applicable to the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

  1. CLAIMS: 1. A preparation method of straw fiber adsorption material for efficiently adsorbing heavy metals and antibiotic pollutants, which is characterized in that the straw fiber adsorption material is prepared by pretreating corn straw cellulose, etherifying epichlorohydrin, crosslinking ethylenediamine and grafting diethylenetriamine pentaacetic acid.
  2. 2. A preparation method of a straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants as described in Claim 1, which is characterized in that the specific steps of pretreatment are as follows: crushing and sieving corn straws, soaking in 1mol/L NaOH solution for 24 hours, respectively filtering, washing to neutrality, and drying.
  3. 3. A preparation method of straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants as described in Claim 1, which is characterized in that the specific step of etherification is to etherify 2-5g of pretreated corn straw with 70-100 ml of epichlorohydrin and 60-100m1 of N-N dimethylformamide at 70-100t for 1-3h.
  4. 4. A preparation method of straw fiber adsorption material for efficiently adsorbing heavy metals and antibiotic pollutants according to Claim 1, which is characterized in that the specific step of crosslinking is to add 8-15m1 ethylenediamine after the etherification reaction is finished, and carry out crosslinking reaction at 70-100'C for 1-3h.
  5. 5. A preparation method of a straw fiber adsorption material for efficiently adsorbing heavy metals and antibiotic pollutants as described in Claim 1, which is characterized in that the specific step of grafting is to add 5-15g of diethylenetriamine pentaacetic acid after the crosslinking reaction is finished, and graft reaction is carried out at 70-100'C for 1-3 hours.
  6. 6. The preparation method of the straw fiber adsorption material for efficiently adsorbing heavy metals and antibiotic pollutants as described in Claim 1, which is characterized in that after the grafting reaction is finished, the straw fiber adsorption material needs to be washed with N-N dimethylformamide, deionized water, saturated sodium bicarbonate and deionized water in turn to be neutral, and then dried to obtain the straw fiber adsorption material.
  7. 7. A straw fiber adsorption material prepared by the preparation method of the straw fiber adsorption material capable of efficiently adsorbing heavy metals and antibiotic pollutants as described in any one of Claims 1-6.
  8. 8. A straw fiber adsorption material as described in Claim 7 which is used adsorbing antibiotics and heavy metals in water.
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