CN114524968B - Lignin amine macroporous anion exchange resin and preparation method and application thereof - Google Patents

Lignin amine macroporous anion exchange resin and preparation method and application thereof Download PDF

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CN114524968B
CN114524968B CN202210047972.0A CN202210047972A CN114524968B CN 114524968 B CN114524968 B CN 114524968B CN 202210047972 A CN202210047972 A CN 202210047972A CN 114524968 B CN114524968 B CN 114524968B
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lignin
anion exchange
exchange resin
amine
macroporous anion
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周明松
吴浩
邱学青
庞煜霞
杨东杰
钱勇
楼宏铭
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South China University of Technology SCUT
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Abstract

The invention discloses lignin amine macroporous anion exchange resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving lignin in water, and adjusting the pH value of the solution to 10-12; adding amine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 90-95 ℃, and then dropwise adding aldehyde for reaction; and then adding a cross-linking agent, taking water as a pore-forming agent, and carrying out curing reaction to obtain the lignin amine macroporous anion exchange resin. According to the method, the cross-linking agent is used in the aqueous solution to directly cross-link the lignin amine, on one hand, water can be used as a pore-forming agent to form the lignin amine macroporous anion exchange resin with a porous channel structure, so that the ion exchange efficiency and the desorption regeneration capacity are greatly improved; on the other hand, unreacted amine in the solution can be further crosslinked, the utilization rate of raw materials is improved, and the content of active groups in the lignin amine macroporous anion exchange resin is improved.

Description

Lignin amine macroporous anion exchange resin and preparation method and application thereof
Technical Field
The invention relates to modified lignin and application thereof, in particular to lignin amine macroporous anion exchange resin and a preparation method and application thereof.
Background
The lignin structure contains a large number of phenolic hydroxyl groups, and a large number of reaction sites are provided for amination modification of lignin, so that the lignin structure can be used as a natural raw material for preparing anion exchange resin. Not only can reduce the use of fossil energy, but also can realize the high-value utilization of lignin.
The ion exchange resin is a net-shaped high molecular polymer with active groups, mainly consists of a resin framework and the active groups fixed on the framework, has the functions of exchange, catalysis, adsorption and the like, and is widely applied to the fields of electroplating metallurgy, medicine and health, bioengineering and the like.
The anion exchange resin can dissociate hydroxyl in water and exchange with anions in the solution, thereby removing harmful anions in water, such as hexavalent chromium (Cr (VI)), sulfate ions, phosphate ions, cyanide ions, thiocyanate ions and the like.
Most of the currently commercially available anion exchange resins are anion exchange resins containing polyamino groups, which are obtained by reacting an acrylate with a polyamine or by polycondensation of an aromatic amine with formaldehyde. The synthesized resin has poor chemical stability and mechanical strength, and soluble substances often bleed out in use. Furthermore, with the decrease of fossil resources, the preparation of ion exchange resins from petrochemicals as raw materials will also face the problem of raw material shortage.
The pore size of the ion exchange resin can significantly affect the resin exchange rate and the anti-fouling capacity. Internationally, pore sizes are generally classified into three categories according to size: micropores are formed with the aperture not more than 2nm, mesopores are formed with the aperture not less than 2-50nm, and macropores are formed with the aperture not less than 50 nm. The gel type ion exchange resin only has 1-2nm molecular gaps, and large-volume ions or molecules are easy to cause resin poisoning and lose exchange capacity after entering the interior of the resin. Therefore, the characteristics of macroporous resin such as multiple pore channels and high porosity are required to be utilized to solve the problem of easy poisoning of resin and improve the resin exchange rate.
In the industrial process of preparing macroporous ion exchange resin, organic solvents such as toluene, xylene and hexane are often additionally added as pore-forming agents, so that a communicated pore channel structure is formed in the resin. However, the use of organic solvents often causes secondary pollution, and an additional process is required to remove the porogen, which affects the wide application of the macroporous ion exchange resin.
It can be seen that the following problems still exist with the current macroporous anion exchange resins:
(1) The macroporous anion exchange resin is prepared by taking petrochemicals as raw materials, an organic solvent is required to be added as a pore-forming agent in the preparation process, a process for removing the pore-forming agent is required, a large amount of energy is consumed, and the preparation method is not environment-friendly.
(2) The anion exchange resin prepared by taking biomass as a raw material can reduce the use of fossil energy and reduce the cost. However, the pore channels of the product are mostly microporous, even have no pore channel structure, which is not favorable for the dynamic process of ion exchange, and is easy to cause resin poisoning and difficult in resin regeneration.
Disclosure of Invention
Aiming at the defects and shortcomings of the existing macroporous anion exchange resin, the invention aims to provide the lignin amine macroporous anion exchange resin and the preparation method and application thereof, after amination modification of lignin, water is used as a pore-forming agent, cross-linking and curing are carried out, tree particles are dried and water is removed to prepare the macroporous anion exchange resin, the diameter of a pore passage in the obtained macroporous anion exchange resin can reach 615nm, the porosity reaches 67.5%, the content of the lignin can reach 52.47 at most, and the lignin can be used for removing harmful anions in a water body, such as hexavalent chromium (Cr (VI)), sulfate ions, phosphate ions, cyanide ions, thiocyanate ions and the like.
The purpose of the invention is realized by the following technical scheme:
a preparation method of lignin amine macroporous anion exchange resin comprises the following steps:
dissolving 10-20 parts of lignin in water by mass, and adjusting the pH value of the solution to 10-12; adding 4-10 parts of amine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 90-95 ℃, and then dropwise adding 5-15 parts of aldehyde; after the dropwise addition is finished, the reaction is carried out for 1 to 3 hours at the temperature of between 90 and 95 ℃; then adding 5-10 parts of cross-linking agent, taking solvent water as pore-forming agent in the curing stage, curing and reacting for 6-12 hours at 70-90 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain powder or granular lignin amine macroporous anion exchange resin;
preferably, the lignin is more than one of alkali lignin, enzymolysis lignin, high-boiling alcohol lignin or organic solvent lignin;
preferably, the amine is more than one of ethylenediamine, hydroxyethyl ethylenediamine, diethylenetriamine, tetraethylenepentamine, polyether amine or polyethyleneimine;
preferably, the aldehyde is more than one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde or furfural;
preferably, the crosslinking agent is more than one of epichlorohydrin, dibromopropane or dibromohexane.
The macroporous anion exchange resin prepared by the method has the pore canal diameter of 474-615nm, the porosity of 46.8-67.5 percent and the lignin content of 39.53-52.47 percent, and can be used for removing harmful anions in water, such as hexavalent chromium (Cr (VI)), sulfate ions, phosphate ions, cyanide ions, thiocyanate ions and the like.
The hexavalent chromium (Cr (VI)) includes Cr 2 O 7 2- And CrO 4 2- (both Cr are hexavalent, which is commonly called hexavalent Cr (VI)), and Cr is mainly used in the acidic solution 2 O 7 2- Present in alkaline solution predominantly as CrO 4 2- Presence);
the dry-based exchange capacity of the macroporous anion exchange resin to Cr (VI) is 410.4-634.9mg/g, and to SO 4 2- Has a dry basis exchange capacity of 182.4-282.3mg/g for PO 4 3- The dry-based exchange capacity of (B) is 120.4-186.2mg/g.
Compared with the prior art, the invention has the following advantages and effects:
1. the lignin used in the preparation method of the invention does not need to be treated firstly, can directly participate in the reaction to prepare the lignin amine macroporous anion exchange resin, and has simple process,
2. According to the preparation method, the cross-linking agent is used in the aqueous solution to directly cross-link the lignin amine, on one hand, water can be used as a pore-forming agent to form the lignin amine macroporous anion exchange resin with a porous channel structure, so that the ion exchange efficiency and the desorption regeneration capacity are greatly improved; on the other hand, unreacted amine in the solution can be further crosslinked, the utilization rate of raw materials is improved, and the content of active groups in the lignin amine macroporous anion exchange resin is improved.
3. The diameter of the pore channel in the lignin amine macroporous anion exchange resin prepared by the invention can reach 615nm, and the porosity reaches 67.5%.
4. The lignin amine macroporous anion exchange resin prepared by the invention has the highest lignin content of 52.47 percent. The high lignin content can reduce the dosage of petrochemicals, reduce the preparation cost, is environment-friendly and renewable, and accords with the development direction of green chemistry.
5. The lignin amine macroporous anion exchange resin prepared by the invention can be applied to the removal of anions such as Cr (VI) in water.
Drawings
FIG. 1 is an infrared spectrum of the lignin amine macroporous anion exchange resin obtained in example 1.
FIG. 2 is a graph comparing the dry-based exchange capacity of lignin amine macroporous anion exchange resins obtained in examples 1, 2, 3, and 4 and commercial anion exchange resins for Cr (VI).
FIG. 3 is a graph comparing the dry-based exchange capacity of lignin amine macroporous anion exchange resins obtained in examples 1, 2, 3 and 4 and the dry-based exchange capacity of biomass ion exchange resins in the literature for Cr (VI).
FIG. 4 is an appearance diagram of the lignin amine macroporous anion exchange resin obtained in example 3.
FIG. 5 is a scanning electron micrograph of the lignin amine macroporous anion exchange resin obtained in example 1, example 2, example 3, and example 4.
FIG. 6 is a graph of mass loss of lignin amine macroporous anion exchange resin obtained in example 3 in strong acid, strong base, deionized water.
FIG. 7 is a thermogravimetric analysis of the lignin amine macroporous anion exchange resin with alkali lignin obtained in example 3.
FIG. 8 is a graph of the regeneration efficiency of the lignin amine macroporous anion exchange resin obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
Dissolving 10g of alkali lignin (raw material is Hungjiang alkali lignin provided by Hungjiang paper industry, ltd., yongzhou, hunan province, the same below) in 20 parts of water, and adjusting the pH to be =12 by using a sodium hydroxide solution; adding 4g of diethylenetriamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 95 ℃, and then dropwise adding 5g of formaldehyde; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then 5g of epoxy chloropropane is added, solvent water is taken as a pore-foaming agent in the curing stage, the curing reaction is carried out for 12 hours at the temperature of 80 ℃, blocky lignin amine macroporous anion exchange resin is obtained, and the lignin amine macroporous anion exchange resin with the particle size of 0.5mm can be obtained after the crushing.
The lignin amine macroporous anion exchange resin prepared in example 1 was named DAL 1 . DAL in this example 1 Has an average pore diameter of 520nm, a porosity of 54.8%, a lignin content of 46.0%, a dry-based exchange capacity for Cr (VI) of 410.4mg/g and for SO 4 2- Has a dry basis exchange capacity of 182.4mg/g for PO 4 3- The dry exchange capacity of (b) was 120.4mg/g.
Example 2
Dissolving 10g of alkali lignin in 20 parts of water, and adjusting the pH =12 with sodium hydroxide solution; adding 6g of diethylenetriamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 95 ℃, and then dropwise adding 7g of formaldehyde; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then 5g of epoxy chloropropane is added, solvent water is taken as a pore-foaming agent in the curing stage, the curing reaction is carried out for 12 hours at the temperature of 80 ℃, blocky lignin amine macroporous anion exchange resin is obtained, and the lignin amine macroporous anion exchange resin with the particle size of 0.5mm can be obtained after the crushing.
The lignin amine macroporous anion exchange resin prepared in example 2 was named DAL 2 . DAL in this example 2 The average pore diameter of the catalyst is 482nm, the porosity is 50.2 percent, the lignin content is 52.47 percent, the dry-based exchange capacity for Cr (VI) reaches 460.7mg/g, and the dry-based exchange capacity for SO 4 2- Has a dry basis exchange capacity of 201.8mg/g for PO 4 3- The dry basis exchange capacity of (b) was 132.8mg/g.
Example 3
Dissolving 10g of alkali lignin in 20 parts of water, and adjusting the pH value to be =12 by using a sodium hydroxide solution; adding 8g of diethylenetriamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 95 ℃, and then dropwise adding 9.3g of formaldehyde; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then 5g of epoxy chloropropane is added, solvent water is taken as a pore-foaming agent in the curing stage, the curing reaction is carried out for 12 hours at the temperature of 80 ℃, blocky lignin amine macroporous anion exchange resin is obtained, and the lignin amine macroporous anion exchange resin with the particle size of 0.5mm can be obtained after the crushing.
The lignin amine macroporous anion exchange resin prepared in example 3 was named DAL 3 . DAL in this example 3 Has an average pore diameter of 615nm, a porosity of 67.5%, a lignin content of 46.15%, a dry-based exchange capacity for Cr (VI) of 634.9mg/g and for SO 4 2- Has a dry basis exchange capacity of 186.2mg/g for PO 4 3- The dry exchange capacity of (b) was 282.3mg/g.
Example 4
Dissolving 10g of alkali lignin in 20 parts of water, and adjusting the pH (potential of Hydrogen) to be 12 by using a sodium hydroxide solution; adding 10g of diethylenetriamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 95 ℃, and then dropwise adding 11.7g of formaldehyde; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then adding 5g of epoxy chloropropane, taking solvent water as a pore-foaming agent at a curing stage, curing and reacting for 12 hours at 80 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 0.5 mm.
The lignin amine macroporous anion exchange resin prepared in example 4 was named DAL 4 . DAL in this example 4 Has an average pore diameter of 474nm, a porosity of 46.8 percent and a lignin content of 39.53 percent, and has a dry-based exchange capacity for Cr (VI) of 503.1mg/g and for SO 4 2- The dry basis exchange capacity of 228.1mg/g for PO 4 3- The dry basis exchange capacity of (2) was 150.5mg/g.
Example 5
Dissolving 20g of alkali lignin in 40 parts of water, and adjusting the pH =10 with a sodium hydroxide solution; adding 10g of ethylenediamine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 95 ℃, and then dropwise adding 15g of acetaldehyde; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then 10g of epoxy chloropropane is added, solvent water is taken as a pore-foaming agent in the curing stage, curing reaction is carried out for 12 hours at 90 ℃, blocky lignin amine macroporous anion exchange resin is obtained, and the lignin amine macroporous anion exchange resin with the particle size of 1mm can be obtained after crushing.
The lignin amine macroporous anion exchange resin prepared in the embodiment has the average pore diameter of 546nm, the porosity of 62.8 percent and the lignin content of 43.2 percent, and has the dry-based exchange capacity for Cr (VI) of 522.3mg/g and SO of 522.3mg/g 4 2- Has a dry basis exchange capacity of 241.5mg/g for PO 4 3- The dry exchange capacity of (b) was 163.2mg/g.
Example 6
Dissolving 10g of organic solvent lignin (extraction method references: tian Yigong, li Dachen, gong Dachun. Process for extracting lignin from wheat straw by organic solvent [ J ]. Hubei agricultural science, 2012,51 (06): 1228-1231.) in 50 parts of water, and adjusting pH =10 by using sodium hydroxide solution; adding 10g of tetraethylenepentamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 90 ℃, and then dropwise adding 9g of propionaldehyde; after the dropwise addition, the reaction was carried out at 90 ℃ for 1 hour. Then adding 10g of dibromopropane, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 6 hours at 90 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 1 mm.
The lignin amine macroporous anion exchange resin prepared in the embodiment has the average pore diameter of 488nm, the porosity of 53.8 percent and the lignin content of 47 percent, and has the dry-based exchange capacity of 576.4mg/g for Cr (VI) and SO (sulfur oxide) 4 2- The dry basis exchange capacity of 235.3mg/g for PO 4 3- The dry exchange capacity of (b) was 155.8mg/g.
Example 7
Dissolving 10g of alkali lignin in 40 parts of water, and adjusting the pH =12 with a sodium hydroxide solution; adding 4g of polyethyleneimine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 92 ℃, and then dropwise adding 5g of glyoxal; after the completion of the dropwise addition, the reaction was carried out at 92 ℃ for 1.5 hours. Then adding 5g of dibromohexane, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 12 hours at 70 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 1 mm.
The lignin amine macroporous anion exchange resin prepared in the embodiment has the average pore diameter of 566nm, the porosity of 54.8 percent and the lignin content of 41.5 percent, and has the dry-based exchange capacity for Cr (VI) of 465.4mg/g and SO (sulfur oxide) 4 2- Has a dry basis exchange capacity of 198.0mg/g for PO 4 3- The dry basis exchange capacity of (b) was 131.2mg/g.
Example 8
Dissolving 10g of enzymatic hydrolysis lignin (the raw material is from Nanyang enzymatic hydrolysis lignin provided by Henan Tian Guang Enterprise group) in 20 parts of water, and adjusting pH =12 with sodium hydroxide solution; adding 4g of hydroxyethyl ethylenediamine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 92 ℃, and then dropwise adding 5g of malondialdehyde; after the completion of the dropwise addition, the reaction was carried out at 92 ℃ for 1 hour. Then adding 5g of dibromohexane, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 12 hours at 70 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 1 mm.
The lignin amine macroporous anion exchange resin prepared in the embodiment has the average pore diameter of 568nm, the porosity of 59.7 percent and the lignin content of 47.8 percent, and has the dry-based exchange capacity for Cr (VI) of 550.8mg/g and SO (sulfur oxide) 4 2- Has a dry basis exchange capacity of 221.3mg/g for PO 4 3- The dry basis exchange capacity of (2) was 147.5mg/g.
Example 9
Dissolving 10g of high boiling alcohol lignin (raw material is high boiling alcohol lignin provided by Nanpingsen metallocene Fine chemical assistant Co., ltd., the same applies hereinafter) in 20 parts of water, and adjusting pH =12 by using sodium hydroxide solution; adding 4g of polyetheramine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 95 ℃, and then dropwise adding 5g of succinaldehyde; after the completion of the dropwise addition, the reaction was carried out at 95 ℃ for 1 hour. Then adding 5g of dibromopropane, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 10 hours at 80 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 0.5 mm.
The lignin amine macroporous anion exchange resin prepared in the embodiment has the average pore diameter of 612nm, the porosity of 60.4 percent and the lignin content of 49.3 percent, and has the dry-based exchange capacity for Cr (VI) of 604.1mg/g and SO 4 2- Has a dry basis exchange capacity of 177.4mg/g for PO 4 3- The dry exchange capacity of (b) was 268.9mg/g.
Example 10
Dissolving 10g of high boiling alcohol lignin in 20 parts of water, and adjusting the pH value to be =12 by using a sodium hydroxide solution; adding 4g of tetraethylenepentamine, stirring and dissolving the mixture evenly at room temperature under the protection of nitrogen, heating the mixture to 95 ℃, and then dropwise adding 5g of furfural; after the dropwise addition, the reaction was carried out at 95 ℃ for 3 hours. Then adding 5g of dibromohexane, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 6 hours at 80 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain the lignin amine macroporous anion exchange resin with the particle size of 0.5 mm.
Average of Lignin amine macroporous anion exchange resins prepared in this exampleThe pore diameter is 553nm, the porosity is 51.8 percent, the lignin content is 43.6 percent, the dry-base exchange capacity for Cr (VI) reaches 587.6mg/g, and for SO 4 2- Has a dry basis exchange capacity of 168.2mg/g for PO 4 3- Has a dry basis exchange capacity of 257.5mg/g.
Description of the effects of the embodiments
The lignin amine macroporous anion exchange resin DAL prepared in example 1 1 Infrared spectroscopic analysis was performed while using Alkali Lignin (AL) (raw material from xiangjiang alkali lignin provided by xiangjiang paper industry llc, yongzhou, hu) and Diethylenetriamine (DETA) as a control, and the results are shown in fig. 1. As can be seen from the IR contrast chart, DAL 1 Compared with AL at 1461cm -1 A new absorption peak appears at the wavelength, whereas the alkali lignin raw material is absent, which is caused by the secondary amine C-N internal bending vibration. At the same time, 1597 cm and 1661cm -1 The absorption peak of N-H appears at the wavelength, which indicates that the diethylenetriamine is successfully accessed into the lignin to prepare the DAL 1 In which amine groups are present as reactive ion exchange groups.
Table 1: AL, DAL 1 、DAL 2 、DAL 3 、DAL 4 Result of elemental analysis of
Figure BDA0003473180690000081
As is clear from the data in Table 1, the sulfur content in AL is 1.38%, and DAL can be obtained by calculation 1 、DAL 2 、DAL 3 、DAL 4 The Al content in (1) is 46%, 52.47%, 46.15% and 39.53%, respectively. With the increase of the proportion of the amine and the lignin, the nitrogen content in the product shows a trend of increasing firstly and then decreasing, and the maximum nitrogen content is 6.74 percent.
Will prepare DAL 1 、DAL 2 、DAL 3 、DAL 4 Carrying out ion exchange performance test, wherein the detection method comprises the following steps: 20mg of resin was added to an Erlenmeyer flask containing 50ml of K 2 Cr 2 O 7 The concentration of Cr (VI) in the water solution is 1000mg/L, and the pH value of the system is adjusted to be 2.After 24h of exchange in a shaking table at 30 ℃ and 150rpm/min, the capacity for Cr (VI) ion exchange was measured and compared to commercial lignin amine macroporous anion exchange resin type D301 and strongly basic anion exchange resin type 717, and the results are shown in FIG. 2.
As can be seen in FIG. 2, DAL 1 、DAL 2 、DAL 3 、DAL 4 The dry-based exchange capacity for Cr (VI) ranges from 410.4 to 634.9mg/g, both greater than the dry-based exchange capacity of commercial D301 lignin amine macroporous anion exchange resins and 717 strongly basic anion exchange resins, wherein DAL 3 The dry-based exchange capacity is the highest, and is 634.9mg/g. The experimental results show that the prepared DAL has excellent ion exchange capacity.
As can be seen from FIG. 3, the dry-based exchange capacity of the biomass ion exchange material for Cr (VI) in the current literature ranges from 57.7 to 183.7mg/g, DAL 1 、DAL 2 、DAL 3 、DAL 4 The dry-based exchange capacity for Cr (VI) is significantly higher than that of the document 1 (Song ZX, li W, liu WT, et al. Novel magnetic lipid composition for chromium (VI) adsorption [ J]Rsc Advances,2015,5, 13028-13035.), document 2 (El-Sayed M, nada. Polyethylene-functionalized Amorphous carbon fibrous membranes as a novel adsorbent for Cr (VI) and Pb (II) from aqueous solution [ J (II) ]]Journal of Water Process Engineering,2017,16]Scientific Reports,2018, 1438), literature 4 (Liang FB, song YL, huang CP, et al. Adsorption of hexavalve chromium on a magnet-based resin: equilibrium, thermodynamics, and kinetics [ J ]]Journal of Environmental Chemical Engineering,2013, 1. Indicating that the prepared DAL has excellent ion exchange capacity.
FIG. 4 is DAL 3 The appearance of (D) is brownish yellow. FIG. 5 is DAL 1 、DAL 2 、DAL 3 、DAL 4 As can be seen from fig. 5, a large number of connected pores are present in the resin particles. The existence of the pore canal is beneficial to the ion exchange and desorption regeneration processAnd (6) rows.
Table 2: DAL 1 、DAL 2 、DAL 3 、DAL 4 Pore structure data sheet of
Figure BDA0003473180690000101
As can be seen from the data in Table 2, DAL 1 、DAL 2 、DAL 3 、DAL 4 The diameter of the pore channel is distributed between 474nm and 615nm, and the porosity is 46.8 percent to 67.5 percent. Has a macroporous structure and high porosity. And the total aperture area is greater than 9.82m 2 The high surface area facilitates the resin to contact with ions in solution, submitting to ion exchange capacity.
Mixing DAL 3 And (3) carrying out acid and alkali resistance test, wherein the detection method comprises the following steps: 0.5g of sample is soaked in 25ml of 5M hydrochloric acid (strong acid), deionized water and 5M sodium hydroxide (strong base) solution for 24 hours, and the soaked sample is washed clean by deionized water for multiple times, and weighed after being fully dried, and the mass loss of the sample is calculated. The results are shown in FIG. 6.
As can be seen from FIG. 6, DAL 3 The mass loss in strong acid and strong base is less and less than 5%, which shows that the prepared lignin amine macroporous anion exchange resin has good acid and alkali resistance and is suitable for complex water body environment.
For the prepared DAL 3 Thermogravimetric analysis was performed and compared to AL, and the results are shown in fig. 7. From the thermogravimetric analysis chart of FIG. 7, DAL 3 The mass loss curve of (D) is substantially consistent with AL, which indicates that DAL 3 The heat-resistant characteristic of the lignin is retained. Except for water evaporation loss at 25-100 ℃, the mass loss at 100-200 ℃ is only 2.03%, and the thermal stability is better.
Will be paired with the prepared DAL 3 Regeneration experiments were performed in 0.1M sodium hydroxide solution, the regeneration experiment method was as follows: and washing and filtering the resin after the first exchange by using deionized water, mixing the resin with 0.1M sodium hydroxide solution according to a mass ratio of 1. Washing and drying the regenerated resin, measuring the dry-based exchange capacity, repeating the cycle for five timesAs shown in fig. 8.
From figure 8, it can be seen that the prepared lignin amine macroporous anion exchange resin has high regeneration efficiency, the single regeneration efficiency reaches 80%, the 5-cycle regeneration efficiency is still kept above 56%, and the prepared lignin amine macroporous anion exchange resin can be used for a long time.
The lignin amine macroporous anion exchange resin has good pore structure and high ion exchange capacity, the dry-based exchange capacity range of Cr (VI) is 410.4-634.9mg/g, and the ion exchange effect is more than twice that of commercial ion exchange resin; meanwhile, the lignin content is high and is 39.53-52.47%, so that the thermal stability of the resin is ensured, and the cost is low. Can be widely applied to removing hexavalent chromium in electroplating wastewater and printing and dyeing wastewater, is also suitable for removing anions such as sulfate radicals, phosphate radicals and the like in water, and has wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (4)

1. A preparation method of lignin amine macroporous anion exchange resin is characterized by comprising the following steps:
dissolving 10 parts by mass of lignin in water, and adjusting the pH value of the solution to 12; adding 8 parts of amine, stirring and dissolving uniformly at room temperature under the protection of nitrogen, heating to 95 ℃, and then dropwise adding 9.3 parts of aldehyde; after the dropwise addition is finished, the reaction is carried out for 3 hours at the temperature of 95 ℃; then adding 5 parts of cross-linking agent, taking solvent water as a pore-foaming agent in a curing stage, curing and reacting for 12 hours at 80 ℃ to obtain blocky lignin amine macroporous anion exchange resin, and crushing to obtain powder or granular lignin amine macroporous anion exchange resin;
the amine is diethylenetriamine;
the aldehyde is formaldehyde;
the lignin is alkali lignin; the cross-linking agent is epichlorohydrin.
2. A lignin amine macroporous anion exchange resin is characterized in that: is prepared by the process of claim 1.
3. Use of the lignin amine macroporous anion exchange resin of claim 2 for removing harmful anions from a body of water.
4. Use according to claim 3, characterized in that: the anion comprises hexavalent chromium (Cr (VI)), sulfate ion, phosphate ion, cyanide ion and thiocyanate ion.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN109970936A (en) * 2019-03-21 2019-07-05 华南理工大学 A kind of cross-linking type sulfomethylated lignin acidic group cation exchange resin and the preparation method and application thereof

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CN109970936A (en) * 2019-03-21 2019-07-05 华南理工大学 A kind of cross-linking type sulfomethylated lignin acidic group cation exchange resin and the preparation method and application thereof

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