CN115505130A - 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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- 229920005610 lignin Polymers 0.000 title claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000010668 complexation reaction Methods 0.000 title description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 55
- 229940012189 methyl orange Drugs 0.000 claims abstract description 55
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005303 weighing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a lignin-based metal organic complex and a preparation method and application thereof, comprising the steps of reacting lignin with phenol to obtain phenolated lignin under the action of a catalyst; reacting phenolated lignin with polyethyleneimine and formaldehyde in water to obtain aminated lignin; reacting zirconium chloride and 2-amino terephthalic acid in a solvent to obtainUIO‑66‑NH 2 (ii) a Reacting UIO-66-NH 2 Reacting with glutaraldehyde in a solvent to obtain HO-UIO-66-NH 2 (ii) a HO-UIO-66-NH 2 And dissolving aminated lignin in a solvent for reaction to obtain the lignin-based metal organic complex. The preparation method is simple, the reaction conditions are mild, the obtained lignin-based metal organic complex has adsorbability on methyl orange and methylene blue in wastewater, and meanwhile, the lignin-based metal organic complex has an obvious adsorption effect on the methyl orange in a methyl orange/methylene blue mixed solution.
Description
Technical Field
The invention relates to a lignin-based metal organic complex and a preparation method and application thereof, belonging to the technical field of development and application of adsorbents.
Background
Waste and pollution of water resources coexist. Dye wastewater is a prominent problem due to the great danger to the ecological environment and human health. The dye wastewater is difficult to degrade under the action of light or organisms, has the threats of carcinogenesis, teratogenesis and mutagenesis to human bodies, has the characteristics of high chromaticity, unstable pH, large amount of organic pollutants, complex components and the like, and has to be treated to reduce the danger after the discharge.
The lignin is the second major polymer application material which is second only to cellulose in nature at present, and is also waste generated in the paper industry, wherein only 5% of the lignin is recycled, most of the lignin is directly burned or directly discharged into the environment, and not only resources are wasted, but also environmental pollution is caused. The lignin has excellent properties such as degradability and renewability, can be modified, and has important significance in improving the performance and developing the application of the lignin.
The metal organic framework material is a porous material, and is a periodic network structure formed by self-assembly of metal ions or metal clusters serving as centers and organic ligands through coordination. Because the catalyst has the characteristics of high specific surface area, high porosity, uniform pore size distribution, various and adjustable structural compositions, more special metal saturated or unsaturated active sites and the like, the catalyst is widely applied to the fields of adsorption separation, catalysis and the like. While UiO-66 is a first generation zirconium-based MOF made from Zr 6 O 4 (OH) 4 The octahedron assembled with terephthalic acid has ultrahigh specific surface area, water and thermal stability, and is one of the most potential MOFs. Thus, UIO-66 is modified and reacted withThe lignin has a certain prospect in reaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a lignin-based metal organic complex and a preparation method and application thereof.
In order to solve the technical problems, the invention provides a lignin-based metal organic complex which is characterized in that the structural formula is as follows:
in the above formula, lignin is lignin.
The invention also provides a preparation method of the lignin-based metal organic complex, which comprises the following steps:
s1, reacting lignin with phenol to obtain phenolated lignin under the action of a catalyst;
s2, reacting the phenolated lignin with polyethyleneimine and formaldehyde in water to obtain aminated lignin;
s3, reacting zirconium chloride with 2-aminoterephthalic acid in a solvent to obtain UIO-66-NH 2 ；
S4, reacting UIO-66-NH 2 Reacting with glutaraldehyde in a solvent to obtain HO-UIO-66-NH 2 ；
S5, mixing HO-UIO-66-NH 2 And dissolving aminated lignin in a solvent for reaction 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 1-4h.
Preferably, in step S2, the phenolized lignin: formaldehyde: the mass ratio of the polyethyleneimine to the raw materials is 1-3.
Preferably, in the step S3, the reaction temperature is 100-150 ℃ and the reaction time is 18-30h;
in the step S4, the reaction temperature is 60-100 ℃, and the reaction time is 18-30h;
in the step S5, the reaction temperature is 60-100 ℃, and the reaction time is 18-30h.
Preferably, the solvent is N, N-dimethylformamide.
Meanwhile, the invention provides an application of the lignin-based metal organic complex prepared by the preparation method of the lignin-based metal organic complex in treatment of methyl orange wastewater or methyl orange/methylene blue wastewater.
Preferably, the application of the lignin-based metal organic complex in methyl orange wastewater or methyl orange/methylene blue wastewater treatment comprises the following steps:
adding the lignin-based metal organic complex into methyl orange wastewater or methyl orange/methylene blue wastewater, performing adsorption treatment at 20-45 ℃, and calculating the removal rate.
Preferably, the dosage of the lignin-based metal organic complex is 50-500mg/L, the adsorption treatment time is 16-24h, and the pH of the methyl orange wastewater or the methyl orange/methylene blue wastewater is 3-11.
Preferably, the pH of the methyl orange wastewater or the methyl orange/methylene blue wastewater is 3 to 7.
The technology not mentioned in the present invention is referred to the prior art.
The invention achieves the following beneficial effects:
(1) The invention relates to a lignin-based metal organic complex and a preparation method and application thereof, wherein natural product lignin is used as a raw material, phenolic lignin and aminated lignin are obtained in sequence by modifying the lignin, and the phenolic lignin and the aminated lignin are reacted with HO-UIO-66-NH 2 The lignin-based metal organic complex is obtained through further reaction, the adsorption activity of a lignin monomer is increased while an amine group is introduced, and meanwhile, the specific surface area of the lignin-based metal organic complex is increased and the adsorption point position of the lignin monomer is increased by using a metal organic complex system;
(2) The lignin-based metal organic complex and the preparation method and application thereof have the advantages that the preparation method is simple, the reaction conditions are mild, the obtained lignin-based metal organic complex has adsorbability on methyl orange and methylene blue in wastewater, meanwhile, in a methyl orange/methylene blue mixed solution, the lignin-based metal organic complex has an obvious adsorption effect on the methyl orange, and meanwhile, when the wastewater is treated, the lignin-based metal organic complex is small in using amount and large in adsorption amount, and is suitable for industrial production;
(3) According to the lignin-based metal organic complex and the preparation method and application thereof, the utilization rate and the additional value of lignin are improved, the recycling of natural resource lignin is realized, the effect of treating wastes with wastes is achieved, and the lignin-based metal organic complex has a wide practical application prospect.
Drawings
FIG. 1 is a schematic diagram of a preparation technique of the lignin-based metal-organic complex of the present invention;
FIG. 2 shows aminated lignin, UIO-66-NH 2 、HO-UIO-66-NH 2 An infrared spectrum of the lignin-based metal-organic complex obtained in example 1;
FIG. 3 is an XPS plot of the lignin-based metal-organic complex obtained in example 1;
fig. 4 is a comparison of lignin-based metal-organic complexes obtained in example 1 before and after adsorption of methyl orange solution, wherein: a is a methyl orange solution before adsorption, and b is a methyl orange solution after adsorption;
fig. 5 is a graph comparing the lignin-based metal-organic complex obtained in example 1 before and after adsorbing the methyl orange/methylene blue mixed solution, wherein: a is a methyl orange/methylene blue mixed solution before adsorption, and b is a methyl orange/methylene blue mixed solution after adsorption;
fig. 6 shows the adsorption effect of the lignin-based metal-organic complex obtained in example 1 on methyl orange at different pH.
Fig. 7 shows the adsorption effect of the lignin-based metal-organic complex obtained in example 1 of the present invention on a methyl orange/methylene blue mixed solution at different pH values.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The removal rate in each example was calculated from the difference between the methyl orange concentration 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 ratio of the difference in methylene blue concentration before and after adsorption in the methylene blue aqueous solution to the methylene blue concentration before adsorption. Reference is made to the calculation method (Omid, M., iman, D.S.,2022, separation of organic reagents (dye) using the modified porous metal-organic frame (MIL), environmental Research, volume 214 (3): 114006).
Example 1
Weighing 15g of lignin and 30g of phenol, and reacting for 2h at 120 ℃ under the catalysis of 0.33mL of 12% concentrated sulfuric acid to obtain 26.32g of phenolated lignin.
At 50 ℃, phenolized lignin: formaldehyde: polyethyleneimine was dissolved in 200mL of water at a mass ratio of 2.
1.20g of zirconium chloride, 2.50g of 2-aminoterephthalic acid and 1mL of concentrated hydrochloric acid were weighed and dissolved in 150mL of N, N-dimethylformamide and reacted at 120 ℃ for 24 hours to obtain 1.60g of UIO-66-NH 2 。
Weighing 1g of UIO-66-NH 2 1g of glutaraldehyde was dissolved in 150mL of N, N-dimethylformamide solution and reacted at 80 ℃ for 24 hours to obtain 1.12g of HO-UIO-66-NH 2 。
Weighing 1g of aminated lignin and 1g of HO-UIO-66-NH 2 Dissolving in 150mL of N, N-dimethylformamide, reacting at 80 ℃ for 24h, and filtering to obtain yellow solid powder, namely 0.9844g of lignin-based metal organic complex.
A technical roadmap is shown in fig. 1.
Aminated lignin, UIO-66-NH 2 、HO-UIO-66-NH 2 The obtained woodThe infrared spectrum of the lignin-based metal-organic complex is shown in fig. 2, the XPS spectrum of the obtained lignin-based metal-organic complex is shown in fig. 3, and the successful preparation of the lignin-based metal-organic complex can be seen from fig. 2 and fig. 3.
Example 2
Weighing 15g of lignin and 30g of phenol, and reacting at 80 ℃ for 1h under the catalysis of 0.33mL of 12% concentrated sulfuric acid to obtain 23.60g of phenolated lignin.
At 40 ℃, phenolized lignin: formaldehyde: polyethyleneimine was dissolved in 200mL of water in a mass ratio of 1.
1.20g of zirconium chloride, 2.50g of 2-aminoterephthalic acid and 1mL of concentrated hydrochloric acid were weighed and dissolved in 150mL of N, N-dimethylformamide and reacted at 100 ℃ for 18 hours to obtain 1.50g of UIO-66-NH 2 。
Weighing 1g of UIO-66-NH 2 1g of glutaraldehyde was dissolved in 150mL of N, N-dimethylformamide solution and reacted at 60 ℃ for 18 hours to obtain 1.05g of HO-UIO-66-NH 2 。
Weighing 1g of aminated lignin, 1g of HO-UIO-66-NH 2 Dissolving in 150mL of N, N-dimethylformamide, reacting at 60 ℃ for 18h, and filtering to obtain yellow solid powder, namely 0.8362g of lignin-based metal organic complex.
Example 3
Weighing 15g of lignin and 30g of phenol, and reacting for 4h at 100 ℃ under the catalysis of 0.33mL of 12% concentrated sulfuric acid to obtain 25.62g of phenolated lignin.
At 60 ℃, phenolized lignin: formaldehyde: polyethyleneimine was dissolved in 200mL of water at a mass ratio of 3.
1.20g of zirconium chloride, 2.50g of 2-aminoterephthalic acid and 1mL of concentrated hydrochloric acid were weighed and dissolved in 150mL of N, N-dimethylformamide and reacted at 150 ℃ for 30 hours to obtain 1.56g of UIO-66-NH 2 。
1g of UIO-66-NH was weighed 2 1g of glutaraldehyde was dissolved in 150mL of N, N-dimethylformamide solution and reacted at 100 ℃ for 30 hours to obtain 1.08g of HO-UIO-66-NH 2 。
Weighing 1g of aminated lignin and 1g of HO-UIO-66-NH 2 Dissolving in 150mL of N, N-dimethylformamide, reacting at 100 deg.C for 30h, and filtering to obtain yellow solid powder, i.e. 0.9634g lignin-based metal organic complex.
Application example 1
2mg, 4mg, 6mg, 8mg and 10mg of the lignin-based metal-organic complex prepared in example 1 were weighed and added to 10mL of a 100mg/L aqueous solution of methyl orange, and the mixture was adsorbed at 30 ℃ for 24 hours at pH 6.5-7.0, and the methyl orange removal rates were 42.92%,92.43%, 97.24%, 93.96% and 98.73%, respectively.
The adsorption effect of the lignin-based metal-organic complex is shown in fig. 4, and the color change before and after methyl orange adsorption can be seen, which further shows that the lignin-based metal-organic complex has a remarkable adsorption effect on methyl orange.
Application example 2
30mg of the lignin-based metal organic complex prepared in example 1 was weighed and added into 50mL of a 100mg/L methyl orange aqueous solution, and the mixture was adsorbed at 30 ℃, 35 ℃ and 40 ℃ for 24 hours at a pH of 6.5-7.0, with methyl orange removal rates of 95.51%, 98.82% and 98.02%, respectively.
Application example 3
10mg of the lignin-based metal-organic complex prepared in example 1 was weighed and added to 10mL of a 100mg/L methyl orange aqueous solution. Adsorbing at 30 deg.C for 18h at pH of 3-11. As shown in fig. 6, the removal rates of methyl orange were 96.09%, 96.08%, 98.55%, 97.61%, 98.73%, 91.42%, 98.52%, 98.83%, and 92.14% at pH =3,4,5,6,7,8,9,10, and 11, respectively.
Application example 4
30mg of the lignin-based metal organic complex prepared in example 1 is weighed and respectively added into 100mL of mixed solution of methyl orange with the concentration of 50mg/L and methylene blue with the concentration of 50mg/L, the pH value is 6.8-7.5, the mixed solution is adsorbed for 24 hours at the temperature of 30 ℃, 35 ℃ and 40 ℃, the removal rates of the methyl orange are 93.19%, 85.72% and 87.42%, and the removal rates of the methylene blue are 58.36%, 6.44% and 5.76%, respectively. The color change of the lignin-based metal-organic complex before and after the adsorption of methyl orange/methylene blue is shown in fig. 5, and it can be seen that the lignin-based metal-organic complex can selectively adsorb methyl orange in the mixed solution.
Application example 5
Weighing 10mg of the lignin-based metal-organic complex prepared in example 1, adding into 20mL of a mixed solution of methyl orange with a concentration of 50mg/L and methylene blue with a concentration of 50mg/L, and adsorbing at 30 ℃ for 24h under the condition of pH 3-11. As shown in fig. 7, at pH =3,4,5,6,7,8,9,10 and 11, the removal rates of methyl orange were 92.25%, 84.72%, 92.87%, 91.90%, 93.57%, 93.28%, 93.60%, 89.23% and 89.11%, respectively, and the removal rates of methylene blue were 7.39%, 1.07%, 9.28%, 23.35%, 7.20%, 5.00%, 2.47%, 16.80% and 61.33%, respectively. It can be seen that the lignin-based metal organic complex has adsorbability to both methyl orange and methylene blue, and meanwhile, the lignin-based metal organic complex has an obvious adsorbability to methyl orange in a methyl orange/methylene blue mixed solution.
Claims (10)
1. A lignin-based metal-organic complex is characterized in that the structural formula is as follows:
2. the method for preparing a lignin-based metal-organic complex according to claim 1, comprising the steps of:
s1, reacting lignin with phenol to obtain phenolated lignin under the action of a catalyst;
s2, reacting the phenolated lignin with polyethyleneimine and formaldehyde in water to obtain aminated lignin;
s3, reacting zirconium chloride with 2-aminoterephthalic acid in a solvent to obtain UIO-66-NH 2 ；
S4, mixing UIO-66-NH 2 Reacting with glutaraldehyde in a solvent to obtain HO-UIO-66-NH 2 ；
S5, mixing HO-UIO-66-NH 2 And dissolving aminated lignin in a solvent for reaction to obtain the lignin-based metal organic complex.
3. The method for preparing lignin-based metal organic complex according to claim 2, wherein in step S1, the catalyst is concentrated sulfuric acid, the reaction temperature is 80-120 ℃ and the reaction time is 1-4h.
4. The method for producing a lignin-based metal organic complex according to claim 2, wherein in step S2, the phenolated lignin: formaldehyde: the mass ratio of the polyethyleneimine is 1-3, the reaction temperature is 40-60 ℃, and the reaction time is 2-8h.
5. The method for preparing lignin-based metal organic complexes according to claim 2, wherein in step S3, the reaction temperature is 100-150 ℃ and the reaction time is 18-30h;
in the step S4, the reaction temperature is 60-100 ℃, and the reaction time is 18-30h;
in the step S5, the reaction temperature is 60-100 ℃, and the reaction time is 18-30h.
6. The method for preparing a lignin-based metal organic complex according to any one of claims 2 to 5, wherein the solvent is N, N-dimethylformamide.
7. Use of the lignin-based metal-organic complex according to claim 1 or prepared by the method for preparing the lignin-based metal-organic complex according to any one of claims 2 to 6 in methyl orange wastewater or methyl orange/methylene blue wastewater treatment.
8. Use of a lignin-based metal organic complex according to claim 7 in methyl orange wastewater or methyl orange/methylene blue wastewater treatment, comprising the steps of:
adding the lignin-based metal organic complex into methyl orange wastewater or methyl orange/methylene blue wastewater, performing adsorption treatment at 20-45 ℃, and calculating the removal rate.
9. The use of lignin-based metal organic complex in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater according to claim 8, wherein the lignin-based metal organic complex is used in an amount of 50-500mg/L, the adsorption treatment time is 16-24h, and the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-11.
10. Use of the lignin-based metal organic complex according to claim 9 in the treatment of methyl orange wastewater or methyl orange/methylene blue wastewater, wherein the pH of the methyl orange wastewater or methyl orange/methylene blue wastewater is 3-7.
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