CN115286812B - Lignin-based metal organic complex and preparation method and application thereof - Google Patents
Lignin-based metal organic complex and preparation method and application thereof Download PDFInfo
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- CN115286812B CN115286812B CN202211122089.XA CN202211122089A CN115286812B CN 115286812 B CN115286812 B CN 115286812B CN 202211122089 A CN202211122089 A CN 202211122089A CN 115286812 B CN115286812 B CN 115286812B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a lignin-based metal organic complex, and a preparation method and application thereof, wherein the lignin-based metal organic complex comprises the following components: reacting lignin with phenol to obtain phenolized lignin under the action of a catalyst; zirconium chloride, 2-amino terephthalic acid and phenolized lignin are dissolved in a solvent and reacted in a hydrothermal reaction kettle to obtain the lignin-based metal organic complex. The preparation method provided by the invention is simple, the reaction condition is mild, the obtained lignin-based metal organic complex has excellent adsorption capacity on methyl orange, methyl orange/methylene blue mixed solution and the like in wastewater, and the lignin-based metal organic complex has the advantages of small dosage and large adsorption capacity, and is suitable for industrial production.
Description
Technical Field
The invention relates to a lignin-based metal organic complex, a preparation method and application thereof, belonging to the technical field of development and application of adsorbents.
Background
The contradiction of current Chinese water resource shortage is more and more prominent, and the waste and pollution of water resources coexist. The water pollution phenomenon in China is serious, and dye wastewater becomes a prominent problem because of extremely dangerous ecological environment and human health. Dye wastewater is difficult to degrade under the action of light or organisms, has the threat of cancerogenesis, teratogenesis and mutation to human bodies, has the characteristics of high chromaticity, unstable pH, containing a large amount of organic pollutants, complex components and the like, and needs to be treated to reduce the risk after the discharge of the dye wastewater.
Lignin is a second most general polymer application material next to cellulose in the nature at present, and is also waste generated in the paper industry, wherein only 5% of lignin is recycled, and most lignin is directly burnt or directly discharged into the environment, so that resources are wasted and environmental pollution is caused. Lignin has excellent properties such as degradability and regenerability, can be modified, improves the performance and has important significance in developing the application.
The metal organic framework material is a porous material and takes metal ions or metal clusters as the center, and is a periodic network structure formed by self-assembly with organic ligands through coordination. Because the porous ceramic material has the characteristics of high specific surface area, high porosity, uniform pore size distribution, various and adjustable structure compositions, multiple special metal saturated or unsaturated active sites and the like, the porous ceramic material can be widely applied to the fields of adsorption separation, catalysis and the like. While UiO-66 is a first generation zirconium-based MOF consisting of Zr 6 O 4 (OH) 4 The octahedron assembled with terephthalic acid has ultrahigh specific surface area and water and heat stability, and is one of the most potential MOFs. Therefore, the modification of the UIO-66 and the reaction with lignin have a certain prospect.
Disclosure of Invention
The lignin-based metal organic complex prepared by using lignin as a raw material through a simple preparation method has excellent adsorption capacity on methyl orange and methyl orange/methylene blue mixed solution in wastewater.
In order to solve the technical problems, the invention provides a lignin-based metal organic complex, which has the structural formula:
wherein, R is selected from the group consisting of-OCH 3 or-OH.
In the above formula, lignin is lignin.
The invention also provides a preparation method of the lignin-based metal organic ligand, which comprises the following steps:
s1, reacting lignin with phenol to obtain phenolized lignin under the action of a catalyst;
s2, dissolving zirconium chloride, 2-amino terephthalic acid and phenolized lignin in a solvent, and reacting in a hydrothermal reaction kettle to obtain the lignin-based metal-organic complex.
Preferably, in step S1, the catalyst is concentrated sulfuric acid, the reaction temperature is 80-120 ℃, and the reaction time is 1-4 hours.
Preferably, in step S2, the zirconium chloride: phenolized lignin: the mass ratio of the 2-amino terephthalic acid is 1:1-4:1, the solvent is N, N-dimethylformamide, the reaction temperature is 100-150 ℃, and the reaction time is 18-30h.
Meanwhile, the invention provides application of the lignin-based metal organic complex prepared by the preparation method of the lignin-based metal organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater.
Preferably, the application of the lignin-based metal organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater comprises the following steps:
adding the lignin-based metal organic complex into methyl orange wastewater or methyl orange/methylene blue wastewater, carrying out adsorption treatment at 20-45 ℃, and calculating the removal rate.
Preferably, the lignin-based metal organic complex is used in an amount of 50-500mg/L, and the adsorption treatment time is 16-24 hours.
Preferably, the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-11.
Preferably, the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-7.
The technology not mentioned in the present invention refers to the prior art.
The invention has the beneficial effects that:
(1) According to the lignin-based metal organic complex, the lignin which is a natural product is taken as a raw material, amine groups are introduced, so that the adsorption activity of lignin monomers is increased, and meanwhile, a metal organic complex system is used, so that the specific surface area of the lignin-based metal organic complex is increased, and the adsorption point of lignin monomers is increased;
(2) The lignin-based metal organic complex has the advantages of simple preparation method, mild reaction conditions, excellent adsorption capacity to methyl orange, methyl orange/methylene blue mixed solution and the like in wastewater, small dosage and large adsorption capacity, and is suitable for industrial production;
(3) The lignin-based metal organic complex and the preparation method and application thereof improve the utilization rate and the added value of lignin, realize the recycling of lignin as a natural resource, achieve the effect of treating waste with waste, and have wide practical application prospect.
Drawings
FIG. 1 is a technical scheme for preparing lignin-based metal organic complexes according to the present invention;
FIG. 2 is an infrared spectrum of lignin, phenolized lignin, lignin-based metal organic complexes obtained in example 1;
FIG. 3 is an XPS diagram of the lignin-based metal organic complex obtained in example 1;
FIG. 4 is a graph showing the comparison of the lignin-based metal organic complex obtained in example 1 before and after absorption of methyl orange solution, wherein: a is methyl orange solution before adsorption, b is methyl orange solution after adsorption;
FIG. 5 is a graph showing the comparison of the lignin-based metal organic complex obtained in example 1 before and after adsorption of methyl orange/methylene blue mixed solution, wherein: a is methyl orange/methylene blue mixed solution before adsorption, and b is methyl orange/methylene blue mixed solution after adsorption;
FIG. 6 shows the adsorption effect of lignin-based metal organic complex obtained in example 1 on methyl orange at different pH values.
FIG. 7 shows the adsorption effect of lignin-based metal organic complex obtained in example 1 of the present invention on methyl orange/methylene blue mixed solution at different pH values.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
The removal rate in each example was calculated from the difference in methyl orange concentration between before and after adsorption in the methyl orange aqueous solution, compared with the methyl orange concentration before adsorption. The removal rate in each example was calculated from the difference in methylene blue concentration between before and after adsorption in the aqueous methylene blue solution, compared with the methylene blue concentration before adsorption. Calculation methods are referred to (Omid, M., iman, D.S.,2022,Separation of organic contaminant (dye) using the modified porous metal-organic framework (MIL), environmental Research, volume 214 (3): 114006).
Example 1
15g of lignin is weighed, 30g of phenol is reacted for 2 hours at 120 ℃ under the catalysis of 0.33mL of 12% concentrated sulfuric acid to obtain 26.32g of phenolized lignin.
0.2g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 24 hours at 120 ℃ to obtain 0.22g of lignin-based metal organic complex.
The technical scheme is shown in fig. 1.
The infrared spectrum and XPS of the obtained lignin-based metal organic complex are respectively shown in fig. 2 and 3, and the successful preparation of the lignin-based metal organic complex can be seen from fig. 2 and 3.
Example 2
The phenolated lignin was prepared as in example 1.
0.1g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 24 hours at 120 ℃ to obtain 0.24g of lignin-based metal organic complex.
Example 3
The phenolated lignin was prepared as in example 1.
0.3g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 24 hours at 120 ℃ to obtain 0.29g of lignin-based metal organic complex.
Example 4
The phenolated lignin was prepared as in example 1.
0.4g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 24 hours at 120 ℃ to obtain 0.44g of lignin-based metal-organic complex.
Example 5
The phenolated lignin was prepared as in example 1.
0.2g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 30 hours at 100 ℃ to obtain 0.19g of lignin-based metal organic complex.
Example 6
The phenolated lignin was prepared as in example 1.
0.2g of phenolized lignin, 0.12g of zirconium chloride, 0.25g of 2-amino terephthalic acid and 1mL of concentrated hydrochloric acid are dissolved in 15mL of N, N-dimethylformamide, and the mixture is placed in a hydrothermal reaction kettle to react for 18 hours at 150 ℃ to obtain 0.18g of lignin-based metal-organic complex.
Application example 1
8mg, 10mg and 12mg of the lignin-based metal organic complex prepared in example 1 are weighed and respectively added into 10mL of 100mg/L methyl orange aqueous solution, the pH is 6.8-7.5, the lignin-based metal organic complex is adsorbed for 24 hours at 30 ℃, and the removal rates of methyl orange are 82.69%, 89.01% and 90.19%, respectively.
TABLE 1 influence of the addition amount of lignin-based Metal organic Complex on methyl orange adsorption Effect
The effect diagram of the lignin-based metal organic complex for adsorbing methyl orange is shown in fig. 4, and the color change before and after methyl orange adsorption can be seen, so that the obvious effect of the lignin-based metal organic complex on methyl orange adsorption is further illustrated.
Application example 2
40mg of the lignin-based metal organic complex prepared in example 1 is weighed and added into 50mL of 100mg/L methyl orange aqueous solution, the pH is 6.5-7.5, the lignin-based metal organic complex is adsorbed for 24 hours at the temperature of 25 ℃ and 30 ℃ and 35 ℃ and the removal rate of methyl orange is 85.07%, 91.77%, 80.55% and 71.47% respectively.
Application example 3
10mg of the lignin-based metal organic complex prepared in example 1 was weighed and added to 10mL of 100mg/L methyl orange aqueous solution, and adsorbed at 30℃for 24 hours under the condition of pH 3-11. As shown in fig. 6, at ph=3, 4,5,6,7,8,9,10,11, the removal rates of methyl orange were 93.58%, 79.50%, 86.68%, 75.11%, 86.15%, 79.05%, 78.23%, 68.61%, 34.67%, respectively.
Application example 4
The lignin-based metal organic complex prepared in example 4 was weighed and added to 20mL of mixed solution of methyl orange and methylene blue with the concentration of 50mg/L and the concentration of 50mg/L respectively, the pH was 6.0-7.5, the mixture was adsorbed for 24 hours at 30 ℃, the removal rates of the methyl orange were 84.77%, 86.88% and 90.20% respectively, and the removal rates of the methylene blue were 85.59%, 72.73% and 82.22% respectively. The color change before and after the lignin-based metal organic complex adsorbs the methyl orange/methylene blue is shown in fig. 5, and the color change before and after the lignin-based metal organic complex adsorbs the methyl orange/methylene blue can be seen, so that the obvious adsorption effect of the lignin-based metal organic complex on the methyl orange/methylene blue is further demonstrated.
Application example 5
10mg of the lignin-based metal organic complex prepared in example 1 was weighed and added to 20mL of a mixed solution of methyl orange and methylene blue at a concentration of 50mg/L and 50mg/L, respectively, and adsorbed at 30℃for 24 hours under a pH of 3-11. As shown in fig. 7, at ph=3, 4,5,6,7,8,9,10,11, the removal rates of methyl orange were 95.83%, 87.07%, 96.29%, 90.27%, 92.22%, 94.96%, 87.83%, 90.53% and 50.97%, respectively, and the removal rates of methylene blue were 48.58%, 45.26%, 73.52%, 70.06%, 69.90%, 78.63%, 73.63%, 84.69% and 95.49%, respectively. In the mixed solution, the lignin-based metal organic complex has obvious adsorption effect on methyl orange and methylene blue.
Claims (7)
1. Lignin baseMetal materialThe preparation method of the organic complex is characterized by comprising the following steps:
s1, reacting lignin with phenol to obtain phenolized lignin under the action of a catalyst;
s2, dissolving zirconium chloride, 2-amino terephthalic acid and phenolized lignin in a solvent, and reacting in a hydrothermal reaction kettle to obtain a lignin-based metal organic complex;
in the step S1, the catalyst is concentrated sulfuric acid, the reaction temperature is 80-120 ℃, the reaction time is 1-4h, and the zirconium chloride is: phenolized lignin: the mass ratio of the 2-amino terephthalic acid is 1:1-4:1;
the concentration of the concentrated sulfuric acid is 12%.
2. The lignin-based according to claim 1Metal materialThe preparation method of the organic complex is characterized in that in the step S2, the solvent is N, N-dimethylformamide, the reaction temperature is 100-150 ℃, and the reaction time is 18-30h.
3. The lignin-based according to claim 1Metal materialLignin base prepared by preparation method of organic complexGold alloy Belonging to the genusThe application of the organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater.
4. A lignin-based according to claim 3Metal materialThe application of the organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater is characterized by comprising the following steps:
lignin-basedMetal materialThe organic complex is added into methyl orange wastewater or methyl orange/methylene blue wastewater, and is subjected to adsorption treatment at 20-45 ℃ to calculate the removal rate.
5. The lignin-based according to claim 4Metal materialThe use of an organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater, characterized in that the lignin-basedMetal materialThe dosage of the organic complex is 50-500mg/L, and the adsorption treatment time is 16-24h.
6. Lignin-based according to claim 4 or 5Metal materialThe use of an organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater, characterized in that the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-11.
7. The lignin-based according to claim 6Metal materialThe use of an organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater, characterized in that the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-7.
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| CN111229171A (en) * | 2020-01-19 | 2020-06-05 | 武汉工程大学 | Straw-loaded MOF material adsorbent and preparation method and application thereof |
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| CN113546606A (en) * | 2021-05-11 | 2021-10-26 | 华东理工大学 | Preparation and application of lignin-doped metal organic framework-derived carbon-iron composite material |
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| CN107511134A (en) * | 2017-06-29 | 2017-12-26 | 湖南大学 | A kind of mesoporous Zr polymerization of olefin using catalyst polymer and its preparation and application |
| WO2020089655A1 (en) * | 2018-11-02 | 2020-05-07 | Imperial College Of Science, Technology And Medicine | Adsorption of lignin |
| CN111229171A (en) * | 2020-01-19 | 2020-06-05 | 武汉工程大学 | Straw-loaded MOF material adsorbent and preparation method and application thereof |
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