阅读说明：本技术 一种含铜工业废水制备金属-有机框架材料hkust-1的方法 (Method for preparing metal-organic framework material HKUST-1 from copper-containing industrial wastewater ) 是由 丁琳 王鹏翔 侯杨焱 任伟 邵鹏辉 罗旭彪 于 2021-10-08 设计创作，主要内容包括：本发明提供了一种含铜工业废水制备金属-有机框架材料HKUST-1的方法,属于废水利用技术领域,包括以下步骤：将含铜工业废水与均苯三甲酸混合,进行配位反应,得到反应粗品；所述含铜工业废水的pH值为0.4～1.5；将得到的反应粗品与活化剂混合,进行活化处理,得到金属-有机框架材料HKUST-1。本发明采用含铜工业废水制备金属-有机框架材料HKUST-1,不仅成本低廉,同时能够去除工业废水中的铜离子,减少环境污染。实施例的结果显示,本发明成功制备了HKUST-1。(The invention provides a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater, which belongs to the technical field of wastewater utilization and comprises the following steps: mixing copper-containing industrial wastewater with trimesic acid, and performing a coordination reaction to obtain a reaction crude product; the pH value of the copper-containing industrial wastewater is 0.4-1.5; and mixing the obtained reaction crude product with an activating agent, and performing activation treatment to obtain the metal-organic framework material HKUST-1. The invention adopts the copper-containing industrial wastewater to prepare the metal-organic framework material HKUST-1, has low cost, can remove copper ions in the industrial wastewater and reduce environmental pollution. The results of the examples show that HKUST-1 was successfully prepared by the present invention.)

1. A method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater comprises the following steps:

(1) mixing copper-containing industrial wastewater with trimesic acid, and performing a coordination reaction to obtain a reaction crude product; the pH value of the copper-containing industrial wastewater is 0.4-1.5;

(2) and (2) mixing the reaction crude product obtained in the step (1) with an activating agent, and performing activation treatment to obtain the metal-organic framework material HKUST-1.

2. The method according to claim 1, wherein the concentration of copper ions in the copper-containing industrial wastewater in the step (1) is 6-11 g/L, and the concentration of other metal ions is less than 5 g/L; the COD value of the copper-containing industrial wastewater is 0.07-0.1 mg/L.

3. The method according to claim 1, wherein the ratio of the amount of copper ions to the amount of trimesic acid in the copper-containing industrial wastewater in the step (1) is (1.5-2.7): 1.

4. the method according to claim 1, wherein the time of the coordination reaction in the step (1) is 6-24 h.

5. The method according to claim 1 or 4, wherein the temperature of the coordination reaction in the step (1) is 20 to 30 ℃.

6. The method according to claim 1, wherein the copper-containing industrial wastewater in step (1) is filtered before use.

7. The method of claim 1, wherein the activating agent in step (2) comprises N, N-dimethylformamide or dimethylsulfoxide.

8. The method as claimed in claim 1, wherein the ratio of the mass of the crude reaction product to the volume of the activating agent in the step (2) is 0.9846g (10-30) mL.

9. The method according to claim 1, wherein the time of the activation treatment in the step (2) is 24-120 h.

10. The method according to claim 1 or 9, wherein the temperature of the activation treatment in the step (2) is 20 to 25 ℃.

Technical Field

The invention relates to the technical field of wastewater utilization, in particular to a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater.

Background

Metal-organic frameworks (MOFs) are complexes of metal ions with heterogeneous organic compounds by coordination chemistryThe porous structure, large specific surface area and regular crystal structure of the reticular skeleton material are combined together, and compared with the traditional porous material, the reticular skeleton material has the porosity of up to 90 percent and the specific surface area of more than 6000m²The characteristics of the ligand are changed, and the structure of the ligand can be adjusted by adjusting the pore diameter and changing the types of the organic ligand, so that the ligand can be applied to hydrogen storage, drug carriers, catalysis, fluorescence, biosensors, gas adsorption and separation, supercapacitors and other fields, and the ligand can show excellent performance.

HKUST-1 is a typical metal-organic framework material, and the traditional preparation method comprises the step of reacting a copper salt precursor with trimesic acid in an organic solvent, wherein the copper salt precursor and the organic solvent are expensive and can not be reused, so that the cost is high, and the development and the application of the copper salt precursor and the organic solvent are hindered.

Therefore, how to reduce the production cost of HKUST-1 becomes a problem in the prior art.

Disclosure of Invention

The invention aims to provide a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater. The preparation method provided by the invention adopts the copper-containing industrial wastewater to prepare the metal-organic framework material HKUST-1, has low cost, and can remove copper ions in the industrial wastewater and reduce environmental pollution.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater, which comprises the following steps:

(1) mixing copper-containing industrial wastewater with trimesic acid, and performing a coordination reaction to obtain a reaction crude product; the pH value of the copper-containing industrial wastewater is 0.4-1.5;

(2) and (2) mixing the reaction crude product obtained in the step (1) with an activating agent, and performing activation treatment to obtain the metal-organic framework material HKUST-1.

Preferably, the concentration of copper ions in the copper-containing industrial wastewater in the step (1) is 6-11 g/L, and the concentration of other metal ions is less than 5 g/L; the COD value of the copper-containing industrial wastewater is 0.07-0.1 mg/L.

Preferably, the ratio of the amount of copper ions to the amount of trimesic acid in the copper-containing industrial wastewater in the step (1) is (1.5-2.7): 1.

preferably, the time of the coordination reaction in the step (1) is 6-24 h.

Preferably, the temperature of the coordination reaction in the step (1) is 20-30 ℃.

Preferably, the copper-containing industrial wastewater in the step (1) is filtered before being used.

Preferably, the activating agent in the step (2) comprises N, N-dimethylformamide or dimethyl sulfoxide.

Preferably, the volume ratio of the mass of the crude reaction product to the volume of the activating agent in the step (2) is 0.9846g (10-30) mL.

Preferably, the time of the activation treatment in the step (2) is 24-120 h.

Preferably, the temperature of the activation treatment in the step (2) is 20-25 ℃.

The invention provides a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater, which comprises the following steps: mixing copper-containing industrial wastewater with trimesic acid, and performing a coordination reaction to obtain a reaction crude product; the pH value of the copper-containing industrial wastewater is 0.4-1.5; and mixing the obtained reaction crude product with an activating agent, and performing activation treatment to obtain the metal-organic framework material HKUST-1. According to the invention, copper ions in the copper-containing industrial wastewater are reacted with trimesic acid to prepare the metal-organic framework material HKUST-1, the pH value of the copper-containing industrial wastewater is controlled, expensive copper ion precursors and organic solvents are not required, the cost is low, and meanwhile, the copper ions in the industrial wastewater can be removed, and the environmental pollution is reduced.

Drawings

FIG. 1 is a graph showing the removal rate of copper ions in copper-containing industrial wastewater after the reaction of step (2) in examples 1 to 5 and 7 to 46 of the present invention is completed;

FIG. 2 is a graph showing the removal rate of copper ions from copper-containing industrial wastewater after the completion of the reaction of step (2) in examples 25 to 29 and 47 to 86 of the present invention;

FIG. 3 is an XRD pattern of HKUST-1 prepared by examples 76, 87-90 of the present invention;

FIG. 4 is an XRD pattern of HKUST-1 prepared by examples 91-95 of the present invention;

FIG. 5 is an XRD pattern of HKUST-1 prepared in example 93 of the present invention, comparative example 1 and comparative example 2.

Detailed Description

The invention provides a method for preparing a metal-organic framework material HKUST-1 from copper-containing industrial wastewater, which comprises the following steps:

(1) mixing copper-containing industrial wastewater with trimesic acid, and performing a coordination reaction to obtain a reaction crude product; the pH value of the copper-containing industrial wastewater is 0.4-1.5;

(2) and (2) mixing the reaction crude product obtained in the step (1) with an activating agent, and performing activation treatment to obtain the metal-organic framework material HKUST-1.

In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.

The invention mixes the copper-containing industrial wastewater with trimesic acid to carry out coordination reaction, and obtains a reaction crude product.

In the invention, the pH value of the copper-containing industrial wastewater is 0.4-1.5, preferably 0.6-1.5, and more preferably 0.7-1.4. The pH value of the copper-containing industrial wastewater is limited within the range, so that the trimesic acid can be well dissolved and can fully react with copper ions. In the present invention, when the pH of the copper-containing industrial wastewater is not within the above range, it is preferable that the copper-containing industrial wastewater is diluted or nitric acid is added. In the present invention, the dilution is preferably performed with deionized water. The invention has no special limit on the dosage of the deionized water or the dosage of the nitric acid during the dilution, and can ensure that the pH value of the copper-containing industrial wastewater is within the range.

In the invention, the concentration of copper ions in the copper-containing industrial wastewater is preferably 6-11 g/L, more preferably 7-10 g/L, and even more preferably 8-9 g/L. When the concentration of copper ions in the copper-containing industrial wastewater is higher than the above range, the present invention preferably dilutes the copper-containing industrial wastewater. In the present invention, the dilution is preferably performed with deionized water. The invention has no special limit on the dosage of the deionized water during the dilution, and can ensure that the concentration of copper ions in the copper-containing industrial wastewater is within the range.

In the present invention, the concentration of other metal ions in the copper-containing industrial wastewater is preferably < 5g/L, more preferably < 1g/L, and most preferably < 500mg/L, the smaller the better. In the invention, the COD value of the copper-containing industrial wastewater is preferably 0.07-0.1 mg/L, and the smaller the COD value, the better the COD value.

According to the invention, each parameter of the copper-containing industrial wastewater is limited in the range, the copper ion content of the wastewater is higher, and the wastewater can better react with the trimesic acid, so that the metal-organic framework material HKUST-1 is obtained, and the copper ions in the wastewater are better removed; the content of other metal ions is low, and the adverse effect on the coordination reaction can be avoided.

In the present invention, the copper-containing industrial waste water is preferably filtered before use. The operation of the filtration is not particularly limited in the present invention, and a filtration technical scheme known to those skilled in the art may be adopted.

In the present invention, the ratio of the amount of copper ions to the amount of trimesic acid in the copper-containing industrial wastewater is preferably (1.5 to 2.7): 1, most preferably 1.8: 1. in the invention, the trimesic acid is used as a ligand and reacts with copper ions to generate HKUST-1. According to the invention, the ratio of the amount of copper ions in the copper-containing industrial wastewater to the amount of trimesic acid is limited within the range, so that the copper ions in the copper-containing industrial wastewater can fully react, and the removal rate of the copper ions is improved.

The operation of mixing the copper-containing industrial wastewater and the trimesic acid is not particularly limited, and the technical scheme of mixing materials, which is well known by the technical personnel in the field, is adopted.

In the present invention, the temperature of the coordination reaction is preferably room temperature, more preferably 25 ℃; the time of the coordination reaction is preferably 6-24 h, more preferably 16-20 h, and most preferably 18 h. In the invention, the coordination reaction is preferably carried out under a stirring condition, the stirring is preferably mechanical stirring, and the stirring speed is preferably 400-410 rpm. The invention limits the temperature and time of the coordination reaction within the range, can fully carry out the coordination reaction, and improves the removal rate of copper ions in the copper-containing industrial wastewater. In the invention, in the coordination reaction process, copper ions and trimesic acid are subjected to coordination reaction to generate a reaction crude product.

After the coordination reaction is finished, the invention preferably carries out suction filtration, water washing and drying on the product of the coordination reaction in sequence to obtain a reaction crude product.

The operation of the suction filtration is not particularly limited in the invention, and the technical scheme of suction filtration known to those skilled in the art can be adopted.

In the present invention, the number of times of the water washing is preferably 3. The invention has no special limitation on the using amount of water in each water washing, and the technical scheme of water washing, which is well known by the technical personnel in the field, can be adopted.

The drying operation is not particularly limited in the present invention, and a drying technical scheme known to those skilled in the art may be adopted.

After the reaction crude product is obtained, the reaction crude product is mixed with an activating agent for activation treatment to obtain the metal-organic framework material HKUST-1.

In the present invention, the activating agent preferably includes N, N-dimethylformamide or dimethylsulfoxide. In the invention, the activating agent can remove the residual raw materials on the surface of the reaction crude product and in the pore structure, improve the porosity and the specific surface area of the product, and remove the end-capping effect caused by the coordination of water molecules and copper ions to obtain the regular octahedral three-dimensional crystal.

In the invention, the ratio of the mass of the crude reaction product to the volume of the activating agent is preferably 0.9846g (10-30) mL, and most preferably 0.9846g:10 mL. The invention limits the mass of the reaction crude product and the volume ratio of the activating agent in the range, can fully remove impurities in the reaction crude product, and improves the specific surface area and the total pore volume of the reaction crude product.

The operation of mixing the crude reaction product and the activating agent is not particularly limited in the present invention, and the technical scheme of mixing materials, which is well known to those skilled in the art, can be adopted. In the present invention, the mixing is preferably performed under stirring conditions. The invention has no special limit on the stirring speed and time, and the crude reaction product is ensured to be dissolved.

In the invention, the temperature of the activation treatment is preferably 20-25 ℃; the activation treatment time is preferably 24-120 h, and most preferably 72 h; the activation treatment is preferably performed under a standing condition. The invention limits the temperature and time of the activation treatment within the range, can fully remove impurities in the reaction crude product, and improves the specific surface area and the total pore volume.

After the activation treatment is completed, the invention preferably carries out centrifugation, washing, drying and grinding on the activation treated product in sequence to obtain the metal-organic framework material HKUST-1.

In the invention, the speed of centrifugation is preferably 9000-10000 rpm, and more preferably 10000 rpm; the time for centrifugation is preferably 3-6 min, and more preferably 4-5 min.

In the present invention, the washing is preferably carried out with an activating agent; the number of washing is preferably 3. The amount of the activator used per washing in the present invention is not particularly limited, and may be an amount well known to those skilled in the art.

In the invention, the drying temperature is preferably 30-50 ℃, and more preferably 40 ℃; the drying time is preferably 12-36 h, and more preferably 24 h.

The grinding operation is not particularly limited in the present invention, and a grinding technical scheme known to those skilled in the art may be adopted.

The invention adopts the reaction of copper ions in the copper-containing industrial wastewater and trimesic acid to prepare the metal-organic framework material HKUST-1, controls the process parameters such as the content of each metal ion, the pH value and the like in the copper-containing industrial wastewater, does not need to use expensive copper ion precursors and organic solvents, has low cost, can remove the copper ions in the industrial wastewater, reduces the environmental pollution, controls the process parameters such as the consumption of the copper ions and the trimesic acid in the copper-containing industrial wastewater, the reaction temperature, the reaction time, the activation time and the like, improves the specific surface area and the total pore volume of the product, and improves the removal rate of the copper ions in the wastewater.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

(1) Taking copper-containing industrial wastewater of Ningbo factory, filtering, removing solid residue, and testing the content of each metal ion, pH value and COD value of the wastewater, wherein Cu is²⁺213.7g/L、Co²⁺0.01584g/L、Ni⁺1.144g/L、Zn²⁺0.3154g/L、Fe^2+/3+3.634g/L、Na⁺98.3g/L、Mg²⁺0.1034g/L and Cr^3+/6+0.055 g/L; the pH value is-0.87; COD value of 2X 10^-3g/L；

(2) Adding 152mL of deionized water into 8mL of copper-containing industrial wastewater to dilute the wastewater by 20 times (Cu after dilution)²⁺10.685g/L、Co²⁺0.000792g/L、Ni⁺0.0572g/L、Zn²⁺0.01577g/L、Fe^2+/3+0.1817g/L、Na⁺4.915g/L、Mg²⁺0.00517g/L and Cr^3+/6+0.00275 g/L; the pH value is 0.43; COD value of 0.1X 10^-3g/L) is placed in a beaker, then 2.75g of trimesic acid (the mass ratio of copper ions in the copper-containing industrial wastewater to the trimesic acid is 2.0:1) is added, the beaker is placed on a constant-temperature stirrer, the rotating speed is controlled to be 410rpm, the temperature is 25 ℃ for reaction for 6 hours, the reaction product is filtered, washed for 3 times and then placed in an oven for drying for 12 hours, and a reaction crude product is obtained;

(3) placing 0.9846g of weighed reaction crude product into a centrifugal tube, adding 10mLN, N-dimethylformamide, stirring and dissolving (the mass ratio of the reaction crude product to the volume of the N, N-dimethylformamide is 0.9846g:10mL), standing for 60h at 25 ℃, then centrifuging for 5min at 10000rpm, washing for 3 times by adopting the N, N-dimethylformamide, drying for 24h at 40 ℃, and grinding to obtain the metal-organic framework material HKUST-1.

Example 2

168mL of deionized water was added to 8mL of copper-containing industrial wastewater obtained in example 1 and diluted 22 times (diluted Cu)²⁺9.714g/L、Co²⁺0.00072g/L、Ni⁺0.052g/L、Zn²⁺0.01434g/L、Fe^2+/3+0.1652g/L、Na⁺4.468g/L、Mg²⁺0.0047g/L and Cr^3+/6+0.0025 g/L; the pH value is 0.47; COD value of 0.09X 10^-3g/L), the other parameters are the same as in example 1.

Example 3

192mL of deionized water was added to 8mL of the copper-containing industrial wastewater obtained in example 1 to dilute the wastewater by a factor of 25 (Cu after dilution)²⁺8.548g/L、Co²⁺0.0006g/L、Ni⁺0.046g/L、Zn²⁺0.0126g/L、Fe^2+/3+0.1454g/L、Na⁺3.932g/L、Mg^{2 +}0.0041g/L and Cr^3+/6+0.0022 g/L; the pH value is 0.53; COD value of 0.08X 10^-3g/L), the other parameters are the same as in example 1.

Example 4

To 8mL of the copper-containing industrial wastewater obtained in example 1, 216mL of deionized water was added to dilute the wastewater by 28 times (diluted Cu)²⁺7.632g/L、Co²⁺0.00057g/L、Ni⁺0.041g/L、Zn²⁺0.011g/L、Fe^2+/3+0.1298g/L、Na⁺3.511g/L、Mg^{2 +}0.0037g/L and Cr^3+/6+0.0020 g/L; the pH value is 0.58; COD value of 0.07X 10^-3g/L), the other parameters are the same as in example 1.

Example 5

To 8mL of the copper-containing industrial wastewater obtained in example 1, 232mL of deionized water was added to dilute the wastewater by 30 times (Cu after dilution)²⁺7.123g/L、Co²⁺0.00053g/L、Ni⁺0.038g/L、Zn²⁺0.0105g/L、Fe^2+/3+0.1211g/L、Na⁺3.277g/L、Mg²⁺0.0034g/L and Cr^3+/6+0.0018 g/L; the pH value is 0.61; COD value of 0.067X 10^-3g/L), the other parameters are the same as in example 1.

Example 6

272mL of deionized water was added to 8mL of copper-containing industrial wastewater obtained in example 1Release 35 times (Cu after dilution)²⁺6.106g/L、Co²⁺0.00045g/L、Ni⁺0.033g/L、Zn²⁺0.009g/L、Fe^2+/3+0.1038g/L、Na⁺2.8086g/L、Mg²⁺0.0029g/L and Cr^3+/6+0.0016 g/L; the pH value is 0.67; COD value of 0.057X 10^-3g/L), the other parameters are the same as in example 1.

Example 7

The reaction time in step (2) of example 1 was replaced with 8 hours, and the other parameters were the same as in example 1.

Example 8

The reaction time in step (2) of example 1 was replaced with 10 hours, and the other parameters were the same as in example 1.

Example 9

The reaction time in step (2) of example 1 was replaced with 12 hours, and the other parameters were the same as in example 1.

Example 10

The reaction time in step (2) of example 1 was replaced with 14h, and the other parameters were the same as in example 1.

Example 11

The reaction time in step (2) of example 1 was replaced with 16h, and the other parameters were the same as in example 1.

Example 12

The reaction time in step (2) of example 1 was replaced with 18h, and the other parameters were the same as in example 1.

Example 13

The reaction time in step (2) of example 1 was replaced with 20 hours, and the other parameters were the same as in example 1.

Example 14

The reaction time in step (2) of example 1 was replaced with 24 hours, and the other parameters were the same as in example 1.

Example 15

The reaction time in step (2) of example 2 was replaced with 8 hours, and the other parameters were the same as in example 2.

Example 16

The reaction time in step (2) of example 2 was replaced with 10 hours, and the other parameters were the same as in example 2.

Example 17

The reaction time in step (2) of example 2 was replaced with 12 hours, and the other parameters were the same as in example 2.

Example 18

The reaction time in step (2) of example 2 was replaced with 14h, and the other parameters were the same as in example 2.

Example 19

The reaction time in step (2) of example 2 was replaced with 16h, and the other parameters were the same as in example 2.

Example 20

The reaction time in step (2) of example 2 was replaced with 18h, and the other parameters were the same as in example 2.

Example 21

The reaction time in step (2) of example 2 was replaced with 20 hours, and the other parameters were the same as in example 2.

Example 22

The reaction time in step (2) of example 2 was replaced with 24 hours, and the other parameters were the same as in example 2.

Example 23

The reaction time in step (2) of example 3 was replaced with 8 hours, and the other parameters were the same as in example 3.

Example 24

The reaction time in step (2) of example 3 was replaced with 10 hours, and the other parameters were the same as in example 3.

Example 25

The reaction time in step (2) of example 3 was replaced with 12 hours, and the other parameters were the same as in example 3.

Example 26

The reaction time in step (2) of example 3 was replaced with 14h, and the other parameters were the same as in example 3.

Example 27

The reaction time in step (2) of example 3 was replaced with 16h, and the other parameters were the same as in example 3.

Example 28

The reaction time in step (2) of example 3 was replaced with 18 hours, and the other parameters were the same as in example 3.

Example 29

The reaction time in step (2) of example 3 was replaced with 20 hours, and the other parameters were the same as in example 3.

Example 30

The reaction time in step (2) of example 3 was replaced with 24 hours, and the other parameters were the same as in example 3.

Example 31

The reaction time in step (2) of example 4 was replaced with 8 hours, and the other parameters were the same as in example 4.

Example 32

The reaction time in step (2) of example 4 was replaced with 10 hours, and the other parameters were the same as in example 4.

Example 33

The reaction time in step (2) of example 4 was replaced with 12 hours, and the other parameters were the same as in example 4.

Example 34

The reaction time in step (2) of example 4 was replaced with 14h, and the other parameters were the same as in example 4.

Example 35

The reaction time in step (2) of example 4 was replaced with 16h, and the other parameters were the same as in example 4.

Example 36

The reaction time in step (2) of example 4 was replaced with 18 hours, and the other parameters were the same as in example 4.

Example 37

The reaction time in step (2) of example 4 was replaced with 20 hours, and the other parameters were the same as in example 4.

Example 38

The reaction time in step (2) of example 4 was replaced with 24 hours, and the other parameters were the same as in example 4.

Example 39

The reaction time in step (2) of example 5 was replaced with 8 hours, and the other parameters were the same as in example 5.

Example 40

The reaction time in step (2) of example 5 was replaced with 10 hours, and the other parameters were the same as those of example 5.

EXAMPLE 41

The reaction time in step (2) of example 5 was replaced with 12 hours, and the other parameters were the same as those of example 5.

Example 42

The reaction time in step (2) of example 5 was replaced with 14h, and the other parameters were the same as in example 5.

Example 43

The reaction time in step (2) of example 5 was replaced with 16h, and the other parameters were the same as in example 5.

Example 44

The reaction time in step (2) of example 5 was replaced with 18h, and the other parameters were the same as in example 5.

Example 45

The reaction time in step (2) of example 5 was replaced with 20 hours, and the other parameters were the same as those of example 5.

Example 46

The reaction time in step (2) of example 5 was replaced with 24 hours, and the other parameters were the same as in example 5.

Example 47

The reaction time in step (2) of example 25 was replaced with 13h, and the other parameters were the same as in example 25.

Example 48

The reaction time in step (2) of example 25 was replaced with 15 hours, and the other parameters were the same as in example 25.

Example 49

The reaction time in step (2) of example 25 was replaced with 17h, and the other parameters were the same as in example 25.

Example 50

The reaction time in step (2) of example 25 was replaced with 19h, and the other parameters were the same as in example 25.

Example 51

The amount of trimesic acid added in step (2) of example 25 was replaced with 2.0625g (the ratio of copper ions to the amount of trimesic acid in the copper-containing industrial wastewater was 2.6: 1), and the other parameters were the same as in example 25.

Example 52

The amount of trimesic acid added in step (2) of example 25 was replaced with 2.4750g (the ratio of copper ions to the amount of trimesic acid in the copper-containing industrial wastewater was 2.2: 1), and the other parameters were the same as in example 25.

Example 53

The amount of trimesic acid added in step (2) of example 25 was replaced with 3.0250g (the ratio of copper ions in the copper-containing industrial wastewater to the amount of trimesic acid was 1.8: 1), and the other parameters were the same as in example 25.

Example 54

The amount of trimesic acid added in step (2) of example 25 was replaced with 3.4375g (the ratio of copper ions in the copper-containing industrial wastewater to the amount of trimesic acid was 1.6: 1), and the other parameters were the same as in example 25.

Example 55

The reaction time in step (2) of example 51 was changed to 13h, and the other parameters were the same as in example 51.

Example 56

The reaction time in step (2) of example 51 was replaced with 14h, and the other parameters were the same as in example 51.

Example 57

The reaction time in step (2) of example 51 was replaced with 15h, and the other parameters were the same as in example 51.

Example 58

The reaction time in step (2) of example 51 was replaced with 16h, and the other parameters were the same as in example 51.

Example 59

The reaction time in step (2) of example 51 was replaced with 17h, and the other parameters were the same as in example 51.

Example 60

The reaction time in step (2) of example 51 was changed to 18 hours, and the other parameters were the same as in example 51.

Example 61

The reaction time in step (2) of example 51 was replaced with 19h, and the other parameters were the same as in example 51.

Example 62

The reaction time in step (2) of example 51 was changed to 20 hours, and the other parameters were the same as those of example 51.

Example 63

The reaction time in step (2) of example 52 was changed to 13h, and the other parameters were the same as in example 52.

Example 64

The reaction time in step (2) of example 52 was replaced with 14h, and the other parameters were the same as in example 52.

Example 65

The reaction time in step (2) of example 52 was replaced with 15 hours, and the other parameters were the same as in example 52.

Example 66

The reaction time in step (2) of example 52 was replaced with 16h, and the other parameters were the same as in example 52.

Example 67

The reaction time in step (2) of example 52 was replaced with 17h, and the other parameters were the same as in example 52.

Example 68

The reaction time in step (2) of example 52 was replaced with 18h, and the other parameters were the same as in example 52.

Example 69

The reaction time in step (2) of example 52 was replaced with 19h, and the other parameters were the same as in example 52.

Example 70

The reaction time in step (2) of example 52 was changed to 20 hours, and the other parameters were the same as those of example 52.

Example 71

The reaction time in step (2) of example 53 was changed to 13h, and the other parameters were the same as in example 53.

Example 72

The reaction time in step (2) of example 53 was replaced with 14h, and the other parameters were the same as in example 53.

Example 73

The reaction time in step (2) of example 53 was replaced with 15h, and the other parameters were the same as in example 53.

Example 74

The reaction time in step (2) of example 53 was changed to 16h, and the other parameters were the same as in example 53.

Example 75

The reaction time in step (2) of example 53 was replaced with 17h, and the other parameters were the same as in example 53.

Example 76

The reaction time in step (2) of example 53 was changed to 18 hours, and the other parameters were the same as in example 53.

Example 77

The reaction time in step (2) of example 53 was replaced with 19h, and the other parameters were the same as in example 53.

Example 78

The reaction time in step (2) of example 53 was changed to 20 hours, and the other parameters were the same as in example 53.

Example 79

The reaction time in step (2) of example 54 was changed to 13h, and the other parameters were the same as in example 54.

Example 80

The reaction time in step (2) of example 54 was replaced with 14h, and the other parameters were the same as in example 54.

Example 81

The reaction time in step (2) of example 54 was replaced with 15h, and the other parameters were the same as in example 54.

Example 82

The reaction time in step (2) of example 54 was replaced with 16h, and the other parameters were the same as in example 54.

Example 83

The reaction time in step (2) of example 54 was replaced with 17h, and the other parameters were the same as in example 54.

Example 84

The reaction time in step (2) of example 54 was changed to 18 hours, and the other parameters were the same as in example 54.

Example 85

The reaction time in step (2) of example 54 was replaced with 19h, and the other parameters were the same as in example 54.

Example 86

The reaction time in step (2) of example 54 was changed to 20 hours, and the other parameters were the same as in example 54.

Example 87

The volume of N, N-dimethylformamide in step (3) of example 76 was replaced with 15mL (the ratio of the mass of the crude reaction product to the volume of N, N-dimethylformamide was 0.9846g:15mL), and the other parameters were the same as in example 76.

Example 88

The volume of N, N-dimethylformamide in step (3) of example 76 was replaced with 20mL (the ratio of the mass of the reaction crude product to the volume of N, N-dimethylformamide was 0.9846g:20mL), and the other parameters were the same as in example 76.

Example 89

The volume of N, N-dimethylformamide in step (3) of example 76 was replaced with 25mL (the ratio of the mass of the crude reaction product to the volume of N, N-dimethylformamide was 0.9846g:25mL), and the other parameters were the same as in example 76.

Example 90

The volume of N, N-dimethylformamide in step (3) of example 76 was replaced with 30mL (the ratio of the mass of the crude reaction product to the volume of N, N-dimethylformamide was 0.9846g:30mL), and the other parameters were the same as in example 76.

Example 91

The standing time in step (3) of example 76 was replaced with 24 hours, and the other parameters were the same as in example 76.

Example 92

The standing time in step (3) of example 76 was replaced with 48 hours, and the other parameters were the same as in example 76.

Example 93

The standing time in step (3) of example 76 was replaced with 72 hours, and the other parameters were the same as those in example 76 and labeled Green-25 ℃ to HK.

Example 94

The standing time in step (3) of example 76 was replaced with 96 hours, and the other parameters were the same as in example 76.

Example 95

The standing time in step (3) of example 76 was replaced with 120 hours, and the other parameters were the same as in example 76.

Comparative example 1

HKUST-1 prepared by Muhammadrizwanazhar et al: 1.087g of Cu (NO)₃)₂·3H₂O was dissolved in 15ml of absolute ethanol, and 0.525g of BTC was dissolved in 15ml of absolute ethanol. The two solutions were then transferred to an autoclave and reacted in an oven at 393K for 12 hours, the synthesized blue crystals were filtered under vacuum, dried overnight at 418K, the synthesized MOF was soaked in methanol for 2days and then dried at 418K to give the metal-organic framework material HKUST-1, noted Science-180 deg.C-HK.

Comparative example 2

HKUST-1 prepared by Ayako Umemura et al: 41.0mg of Cu (NO)₃)₂·3H₂O and lauric acid were dissolved in 10mL of butanol in a 20mL microwave vial, the mixed solution was heated with a hot air gun until a clear solution was obtained, 20mg of trimesic acid was added, the mixture was heated at 413K for 60 minutes by microwave irradiation, the resulting blue powder was centrifuged and washed with ethanol (3X 10mL) to give a metal-organic framework material HKUST-1, designated Jacs-80 deg.C-HK.

Sampling and testing the copper content in the residual industrial wastewater after the reaction in the step (2) of examples 1 to 5 and 7 to 46, wherein the sampling and testing method comprises the following steps: sampling by using a 2.5mL disposable needle, filtering by using a 0.45-micrometer filter head to obtain 2mL of clear liquid, adding the clear liquid into a 2.0mL volumetric tube, then taking 1mL of liquid into a 10mL colorimetric tube by using a liquid-transferring gun, diluting the clear liquid by 10000 times for each sample by using 1% nitric acid to fix the volume, diluting the sample by four times, taking 1mL of the sample each time, diluting the sample into the 10mL colorimetric tube, determining the content of copper ions by using an atomic absorption spectrometer, and recording the concentration of the copper ions in the initial solution as C₀And the concentration of copper ions in the residual industrial wastewater after the reaction is recorded as C₁Copper ionThe sub-removal rate was R% ([ (C))₀-C₁)/C₀]100%, the results are shown in figure 1. As can be seen from fig. 1, the adsorption rate of copper ions is in a state of continuously increasing within 10 hours of the reaction, and after 10 hours, the groups with relatively small dilution factor are properly decreased individually, but as a whole, the adsorption rate of copper ions is higher in the embodiment with the dilution factor of 25 than in other embodiments, and is lower in the range of 30-35%, and when the dilution factor is increased to 28 times and 30 times; in conclusion, when the dilution factor is 25 times, the reaction of copper ions and trimesic acid is facilitated.

In the same manner, the copper content in the industrial wastewater remained after the reaction in step (2) of examples 25 to 29 and 47 to 86 was sampled and tested, and the results are shown in FIG. 2. As can be seen from fig. 2, when the ratio of the amounts of the copper ions and the trimesic acid is too high or too low, the adsorption rate of the copper ions in the wastewater is low, and the copper ions fluctuate up and down properly with the increase of time, each group can reach a highest adsorption rate when the time is 18h, and the adsorption rate of the copper ions in the wastewater tends to decrease with the increase of time, for two reasons, the coordination binding force between the copper ions and the trimesic acid in the wastewater environment is not strong, and the copper ions can be resolved with continuous stirring, so that the copper ions which have been coordinated before are resolved into liquid again, or the copper ions are coordinated with the trimesic acid first, and divalent zinc, iron and magnesium ions in the solution occupy partial coordination sites with the lapse of time; in conclusion, when the mass ratio of the copper ions to the trimesic acid is 1.8, the removal rate of the copper ions in the wastewater is the highest, which is beneficial to the reaction.

The XRD patterns of HKUST-1 prepared in examples 76 and 87-90 were measured, and the results are shown in FIG. 3, wherein the crude reaction product is shown in FIG. 3, and the crude reaction product comprises 10mL of DMF purification volume, 15mL of DMF purification volume, 20mL of DMF purification volume, 25mL of DMF purification volume and 30mL of DMF purification volume from bottom to top. As can be seen from FIG. 3, when 10mLN, N-dimethylformamide is added, the height of the product peak is higher and the number of existing peaks is less, and as the N, N-dimethylformamide is added, the number of peaks is more and more, and the peak shape is unstable, which indicates that the shape and performance of the crude reaction product are changed to a certain extent by the activation treatment.

The XRD patterns of HKUST-1 prepared in examples 91 to 95 were measured, and the results are shown in FIG. 4, in which FIG. 4 shows the crude reaction product as it is, from bottom to top, 1day of DMF purification at room temperature, 2days of DMF purification at room temperature, 3days of DMF purification at room temperature, 4days of DMF purification at room temperature, and 5days of DMF purification at room temperature. As can be seen from FIG. 4, the crystal phase of the product did not undergo large transformation at 24h and 48h of activation, the difference between the original peak shape of the crude reaction product without purification was not large, the crystal phase transformation occurred at 72h of activation time, and the peak shape at 72h were comparable with each other as the activation time further increased, so that the activity at 72h was better.

The XRD patterns of HKUST-1 prepared in example 93, comparative example 1 and comparative example 2 were tested, and the results are shown in FIG. 5, in which the modulated-HK is the standard XRD pattern of the HKUST-1 material. As can be seen from FIG. 5, the peaks in the XRD patterns of the three products are comparable, thus demonstrating that HKUST-1 prepared by the present invention is consistent with the material prepared by the prior art, demonstrating that HKUST-1 is successfully prepared by the present invention.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.