WO2021022938A1 - Method for preparing metal-organic framework using solid waste from metallurgical mine - Google Patents

Method for preparing metal-organic framework using solid waste from metallurgical mine Download PDF

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WO2021022938A1
WO2021022938A1 PCT/CN2020/098654 CN2020098654W WO2021022938A1 WO 2021022938 A1 WO2021022938 A1 WO 2021022938A1 CN 2020098654 W CN2020098654 W CN 2020098654W WO 2021022938 A1 WO2021022938 A1 WO 2021022938A1
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organic
metal
solid waste
solution
metallurgical
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王丽君
吴顺
何晓波
谭博
王旗
侯云廷
冯晓霞
周国治
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北京科技大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/14—Monocyclic dicarboxylic acids
    • C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/307—Monocyclic tricarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage

Definitions

  • the invention belongs to the field of comprehensive utilization of resources, and relates to a method for preparing metal-organic framework materials from solid wastes of metallurgical mines.
  • Metal-organic framework (MOF, metal-organic framework) materials are mainly composed of aromatic acid or base nitrogen and oxygen polydentate organic ligands, and a three-dimensional network structure crystal material formed by the hybridization of inorganic metal centers.
  • MOF material has high specific surface area, large porosity and functional pore structure, which can effectively store energy gas; due to its structural characteristics, it shows excellent performance in gas-liquid separation; it also has good Catalytic, optical, magnetic properties and many other performances.
  • the proposed preparation method not only realizes the recycling and utilization of resource solid waste, but also provides a new idea for the preparation of MOF materials, which can prepare high value-added materials and has extremely high application value.
  • the embodiments of the present disclosure disclose a method for preparing metal-organic framework materials using solid waste from metallurgical mines to solve any of the aforementioned and other potential problems in the prior art.
  • the embodiments of the present disclosure disclose a method for preparing metal-organic framework materials using solid waste from metallurgical mines.
  • the method specifically includes the following steps:
  • the specific process of S1) is: the ratio of the volume of the iron-containing waste to the concentrated strong acid or alkali is 3-5:4-6, the centrifugal separation factor Fr is controlled at 7000-10000, and the drying temperature is 70 ⁇ 150°C, drying time is 12 ⁇ 36h.
  • the particle size of the solid waste from the metallurgical mine in S1) is 50-250 microns;
  • the concentrated strong acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid;
  • the strong alkali is sodium hydroxide or potassium hydroxide.
  • the process of S2) is: the feeding ratio of the mixed metal salt is 13-133 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  • the process of S2) is: the feeding ratio of the organic matter is 5-50 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  • the organic solvent in S2) and S3) is dimethylformamide, dimethylacetamide, diethylformamide or ethanol.
  • the organic matter in S3) is C 8 H 6 O 4 , C 14 H 10 O 4 , C 4 H 6 N 2 or C 9 H 6 O 6 .
  • the process in S5) is: the temperature is 70-150°C, and the constant temperature time is 18-30h.
  • the process of S6) is: the drying temperature is 40-90° C., and the drying time is 8-20 h.
  • a metal-organic framework material which is prepared by the above-mentioned method.
  • the present invention finds a method for utilizing metallurgical slag, minerals, dust and waste metal alloys in iron and steel plants.
  • This method is synthesized at a relatively low temperature, without high temperature, high oxygen and high pressure of foreign aid.
  • Figure 1 is a flow chart of a method for preparing metal-organic framework materials using solid waste from metallurgical mines of the present invention.
  • the embodiment of the present disclosure discloses a method for preparing metal-organic framework materials using solid waste from metallurgical mines, and the method specifically includes the following steps:
  • the specific process of S1) is: the ratio of the volume of the iron-containing waste to the concentrated strong acid or alkali is 3-5:4-6, the centrifugal separation factor Fr is controlled at 7000-10000, and the drying temperature is 70 ⁇ 150°C, drying time is 12 ⁇ 36h.
  • the particle size of the solid waste from the metallurgical mine in S1) is 50-250 microns;
  • the concentrated strong acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid;
  • the strong base is sodium hydroxide or potassium hydroxide.
  • the process of S2) is as follows: the feeding ratio of the mixed metal salt is 13-133 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  • the process of S2) is: the feeding ratio of the organic matter is 5-50 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  • the organic solvent in S2) and S3) is dimethylformamide, dimethylacetamide, diethylformamide or ethanol.
  • the organic ligand in S3) is C 8 H 6 O 4 , C 14 H 10 O 4 , C 4 H 6 N 2 or C 9 H 6 O 6 .
  • the process in S5) is: the temperature is 70-150°C, and the constant temperature time is 18-30h.
  • the process of S6) is: the drying temperature is 40-90° C., and the drying time is 8-20 h.
  • a metal-organic framework material which is prepared by the above-mentioned method.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for preparing a metal-organic framework (MOF) using solid waste from a metallurgical mine, relating to the field of comprehensive utilization of resources. The method dissolves solid waste from a metallurgical mine using a concentrated strong acid or a strong alkali to obtain a mixed metal salt. An organic substance is used as an organic ligand, the mixed metal salt and the organic ligand are dissolved in an organic solvent, and the mixture is kept at 70-150°C for 18-30 h to synthesize an MOF. The new method for preparing an MOF containing a valuable metal element using solid waste from a metallurgical mine has wide range of raw material resources, can effectively use metallurgical slag, minerals, dust, and other waste metal alloys containing valuable metal elements, and features a simple synthesis method and moderate synthesis conditions. The method is suitable for the comprehensive utilization of metallurgical slag, minerals, dust, and waste metal alloys.

Description

一种利用冶金矿山固废制备金属—有机骨架材料的方法Method for preparing metal-organic framework material by using solid waste of metallurgical mine 技术领域Technical field
本发明属于资源化综合利用领域，涉及一种利用冶金矿山固废制备金属—有机骨架材料的方法。The invention belongs to the field of comprehensive utilization of resources, and relates to a method for preparing metal-organic framework materials from solid wastes of metallurgical mines.
背景技术Background technique
我国有大量的含金属元素的冶金渣、矿物、粉尘以及大量的含铁废弃金属合金，仅高炉渣的年产量就高达20000万吨以上，而现有大大小小的尾矿库400多个，全部的金属矿山堆存的尾矿达到了50亿吨以上，而且以5亿吨每年尾矿的速度增长；近年来，我国每年有接近28万吨的不锈钢粉尘产出，粉尘中含有Fe、Cr、Ti等有价金属，同时废钢等一系列含铁金属合金大量产出，综合利用价值极高。传统的有价金属回收中，面临着高能耗高污染的问题，新方法的提出具有极高的意义。my country has a large amount of metallurgical slag, minerals, dust and iron-containing waste metal alloys containing metal elements. The annual output of blast furnace slag alone is as high as more than 200 million tons, and there are more than 400 large and small tailings ponds. The tailings stockpiled in all metal mines has reached more than 5 billion tons, and it is increasing at a rate of 500 million tons of tailings per year. In recent years, my country has produced nearly 280,000 tons of stainless steel dust each year, and the dust contains Fe and Cr. Valuable metals such as, Ti, and a series of ferrous metal alloys, such as scrap steel, are produced in large quantities, with extremely high comprehensive utilization value. In the traditional recycling of valuable metals, it is faced with the problems of high energy consumption and high pollution. The new method is of great significance.
金属—有机骨架(MOF,metal-organic framework)材料主要由芳香酸或碱的氮、氧多齿有机配体，通过无机金属中心杂化形成的立体网络结构晶体材料。同时，MOF材料具有高的比表面积、大孔隙率和和功能型孔道结构，能够有效的存储能源气体；由于其结构的特性，在气液相分离方面均表现出优异的性能；还具有良好的催化、光学、磁性性质等诸多方面的性能。该制备方法的提出，不仅仅实现资源固废的回收利用，还为MOF材料的制备提供了一种新的思路，可制备高 附加值材料，具有极高的应用价值。Metal-organic framework (MOF, metal-organic framework) materials are mainly composed of aromatic acid or base nitrogen and oxygen polydentate organic ligands, and a three-dimensional network structure crystal material formed by the hybridization of inorganic metal centers. At the same time, MOF material has high specific surface area, large porosity and functional pore structure, which can effectively store energy gas; due to its structural characteristics, it shows excellent performance in gas-liquid separation; it also has good Catalytic, optical, magnetic properties and many other performances. The proposed preparation method not only realizes the recycling and utilization of resource solid waste, but also provides a new idea for the preparation of MOF materials, which can prepare high value-added materials and has extremely high application value.
发明内容Summary of the invention
本公开实施例公开了一种利用冶金矿山固废制备金属—有机骨架材料的方法，以解决现有技术的上述以及其他潜在问题中任一问题。The embodiments of the present disclosure disclose a method for preparing metal-organic framework materials using solid waste from metallurgical mines to solve any of the aforementioned and other potential problems in the prior art.
为了达到上述目的，本公开实施例公开了一种利用冶金矿山固废制备金属—有机骨架材料的方法，该方法具体包括以下步骤：In order to achieve the above objectives, the embodiments of the present disclosure disclose a method for preparing metal-organic framework materials using solid waste from metallurgical mines. The method specifically includes the following steps:
S1)将冶金矿山固体废物与浓强酸或强碱混合，充分溶解后，离心过滤分离，在烘箱中恒温干燥，得到混合金属盐；S1) Mix the solid waste of metallurgical mines with concentrated strong acid or strong alkali, and after fully dissolving, centrifuge and filter for separation, and dry in an oven at a constant temperature to obtain mixed metal salt;
S2)将混合金属盐溶解到有机溶剂中，得到第一溶液；S2) dissolving the mixed metal salt in an organic solvent to obtain a first solution;
S3)将有机配体溶解到有机溶剂中，得到第二溶液；S3) dissolving the organic ligand in the organic solvent to obtain a second solution;
S4)将S2)得到第一溶液和S3)得到第二溶液混合均匀，得到混合溶液，将所述混合溶液装入水热反应釜中，在烘箱中恒温一定时间，得到固液混合物；S4) Mixing the first solution obtained by S2) and the second solution obtained by S3) uniformly to obtain a mixed solution. The mixed solution is put into a hydrothermal reactor and kept at a constant temperature in an oven for a certain period of time to obtain a solid-liquid mixture;
S5)将S4)所得固液混合物进行加热恒温分离，得到固体粉末；S5) heating and isolating the solid-liquid mixture obtained in S4) to obtain a solid powder;
S6)将S5)所得固体粉末在无氧环境下恒温干燥。S6) Dry the solid powder obtained in S5) at a constant temperature in an oxygen-free environment.
根据本公开实施例，所述S1)的具体工艺为：含铁废弃物与浓强酸或强碱体积的比为3-5:4-6，离心分离因数Fr控制在7000～10000，干燥温度为70～150℃，干燥时间为12～36h。According to the embodiment of the present disclosure, the specific process of S1) is: the ratio of the volume of the iron-containing waste to the concentrated strong acid or alkali is 3-5:4-6, the centrifugal separation factor Fr is controlled at 7000-10000, and the drying temperature is 70～150℃, drying time is 12～36h.
根据本公开实施例，所述S1)所述冶金矿山固体废物粒度在50～250微米；所述浓强酸为浓硫酸、浓盐酸或浓硝酸；所述强碱为氢氧化钠或氢氧化钾。According to an embodiment of the present disclosure, the particle size of the solid waste from the metallurgical mine in S1) is 50-250 microns; the concentrated strong acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid; and the strong alkali is sodium hydroxide or potassium hydroxide.
根据本公开实施例，所述S2)的工艺为：混合金属盐的投料比 例为13～133mg/ml，超声波处理2-5分钟。According to the embodiment of the present disclosure, the process of S2) is: the feeding ratio of the mixed metal salt is 13-133 mg/ml, and the ultrasonic treatment is 2-5 minutes.
根据本公开实施例，所述S2)的工艺为：所述有机物的投料比例为5～50mg/ml，超声波处理2-5分钟。According to an embodiment of the present disclosure, the process of S2) is: the feeding ratio of the organic matter is 5-50 mg/ml, and the ultrasonic treatment is 2-5 minutes.
根据本公开实施例，所述S2)和S3)中的有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二乙基甲酰胺或乙醇。According to an embodiment of the present disclosure, the organic solvent in S2) and S3) is dimethylformamide, dimethylacetamide, diethylformamide or ethanol.
根据本公开实施例，所述S3)中的有机物为C 8H 6O 4、C 14H 10O 4、C 4H 6N 2或C 9H 6O 6。 According to an embodiment of the present disclosure, the organic matter in S3) is C 8 H 6 O 4 , C 14 H 10 O 4 , C 4 H 6 N 2 or C 9 H 6 O 6 .
根据本公开实施例，所述S5)中的工艺为：温度为70～150℃，恒温时间为18～30h。According to an embodiment of the present disclosure, the process in S5) is: the temperature is 70-150°C, and the constant temperature time is 18-30h.
根据本公开实施例，所述S6)的工艺为：干燥温度为40～90℃，干燥时间为8～20h。According to the embodiment of the present disclosure, the process of S6) is: the drying temperature is 40-90° C., and the drying time is 8-20 h.
一种金属—有机骨架材料，所述金属—有机骨架材料采用上述方法制备得到。A metal-organic framework material, which is prepared by the above-mentioned method.
本发明特点如下：The features of the present invention are as follows:
(1)本发明找到了一种钢铁厂冶金渣、矿物、粉尘以及废弃金属合金的利用方法。(1) The present invention finds a method for utilizing metallurgical slag, minerals, dust and waste metal alloys in iron and steel plants.
(2)本方法在较低温度下合成，无需高温、高氧以及外援高压。(2) This method is synthesized at a relatively low temperature, without high temperature, high oxygen and high pressure of foreign aid.
(3)该方法与传统固废利用比较，有效的降低了能源消耗，钢铁厂冶金渣、矿物、粉尘以及废弃金属合金的回收以及利用提供了一个全新的思路，具有很大的指导意义。(3) Compared with traditional solid waste utilization, this method effectively reduces energy consumption. The recovery and utilization of metallurgical slag, minerals, dust and discarded metal alloys in iron and steel plants provides a new idea and has great guiding significance.
附图说明Description of the drawings
图1为本发明一种利用冶金矿山固废制备金属—有机骨架材料的方法的流程框图。Figure 1 is a flow chart of a method for preparing metal-organic framework materials using solid waste from metallurgical mines of the present invention.
具体实施方式detailed description
此处所描述的具体实例仅仅用于解释本发明，并不用于限定本发明，本领域技术人员应当理解，本发明的方法并不仅限于利用冶金矿山固废制备含有价金属元素的MOF材料。现将本发明的具体实例叙述于后。The specific examples described here are only used to explain the present invention, not to limit the present invention. Those skilled in the art should understand that the method of the present invention is not limited to the use of metallurgical mine solid waste to prepare MOF materials containing valence metal elements. Specific examples of the present invention will now be described below.
如图1所示，本公开实施例公开了一种利用冶金矿山固废制备金属—有机骨架材料的方法，该方法具体包括以下步骤：As shown in FIG. 1, the embodiment of the present disclosure discloses a method for preparing metal-organic framework materials using solid waste from metallurgical mines, and the method specifically includes the following steps:
S1)将冶金矿山固体废物与浓强酸或强碱混合，充分溶解后，离心过滤分离，在烘箱中恒温干燥，得到混合金属盐；S1) Mix the solid waste of metallurgical mines with concentrated strong acid or strong alkali, and after fully dissolving, centrifuge and filter for separation, and dry in an oven at a constant temperature to obtain mixed metal salt;
S2)将混合金属盐溶解到有机溶剂中，得到第一溶液；S2) dissolving the mixed metal salt in an organic solvent to obtain a first solution;
S3)将有机配体溶解到有机溶剂中，得到第二溶液；S3) dissolving the organic ligand in the organic solvent to obtain a second solution;
S4)将S2)得到第一溶液和S3)得到第二溶液混合均匀，得到混合溶液，将所述混合溶液装入水热反应釜中，在烘箱中恒温一定时间，得到固液混合物；S4) Mixing the first solution obtained by S2) and the second solution obtained by S3) uniformly to obtain a mixed solution. The mixed solution is put into a hydrothermal reactor and kept at a constant temperature in an oven for a certain period of time to obtain a solid-liquid mixture;
S5)将S4)所得固液混合物进行加热恒温分离，得到固体粉末；S5) heating and isolating the solid-liquid mixture obtained in S4) to obtain a solid powder;
S6)将S5)所得固体粉末在无氧环境下恒温干燥。S6) Dry the solid powder obtained in S5) at a constant temperature in an oxygen-free environment.
根据本公开实施例，所述S1)的具体工艺为：含铁废弃物与浓强酸或强碱体积的比为3-5:4-6，离心分离因数Fr控制在7000～10000，干燥温度为70～150℃，干燥时间为12～36h。According to the embodiment of the present disclosure, the specific process of S1) is: the ratio of the volume of the iron-containing waste to the concentrated strong acid or alkali is 3-5:4-6, the centrifugal separation factor Fr is controlled at 7000-10000, and the drying temperature is 70～150℃, drying time is 12～36h.
根据本公开实施例，所述S1)所述冶金矿山固体废物粒度在 50～250微米；所述浓强酸为浓硫酸、浓盐酸或浓硝酸；所述强碱为氢氧化钠或氢氧化钾。According to an embodiment of the present disclosure, the particle size of the solid waste from the metallurgical mine in S1) is 50-250 microns; the concentrated strong acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid; and the strong base is sodium hydroxide or potassium hydroxide.
根据本公开实施例，所述S2)的工艺为：混合金属盐的投料比例为13～133mg/ml，超声波处理2-5分钟。According to the embodiment of the present disclosure, the process of S2) is as follows: the feeding ratio of the mixed metal salt is 13-133 mg/ml, and the ultrasonic treatment is 2-5 minutes.
根据本公开实施例，所述S2)的工艺为：所述有机物的投料比例为5～50mg/ml，超声波处理2-5分钟。According to an embodiment of the present disclosure, the process of S2) is: the feeding ratio of the organic matter is 5-50 mg/ml, and the ultrasonic treatment is 2-5 minutes.
根据本公开实施例，所述S2)和S3)中的有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二乙基甲酰胺或乙醇。According to an embodiment of the present disclosure, the organic solvent in S2) and S3) is dimethylformamide, dimethylacetamide, diethylformamide or ethanol.
根据本公开实施例，所述S3)中的有机配体为C 8H 6O 4、C 14H 10O 4、C 4H 6N 2或C 9H 6O 6。 According to an embodiment of the present disclosure, the organic ligand in S3) is C 8 H 6 O 4 , C 14 H 10 O 4 , C 4 H 6 N 2 or C 9 H 6 O 6 .
根据本公开实施例，所述S5)中的工艺为：温度为70～150℃，恒温时间为18～30h。According to an embodiment of the present disclosure, the process in S5) is: the temperature is 70-150°C, and the constant temperature time is 18-30h.
根据本公开实施例，所述S6)的工艺为：干燥温度为40～90℃，干燥时间为8～20h。According to the embodiment of the present disclosure, the process of S6) is: the drying temperature is 40-90° C., and the drying time is 8-20 h.
一种金属—有机骨架材料，所述金属—有机骨架材料采用上述方法制备得到。A metal-organic framework material, which is prepared by the above-mentioned method.
实施例1：Example 1:
S1)将80克国内某钢铁厂的粉尘(粒度200微米)与100ml的浓强酸混合，溶解后离心过滤分离(离心分离因数Fr控制在7000)，将得到的液体在烘箱中120℃恒温24h，得到混合盐。S1) Mix 80 grams of dust from a domestic steel plant (with a particle size of 200 microns) with 100 ml of strong acid, dissolve and separate by centrifugal filtration (the centrifugal separation factor Fr is controlled at 7000), and place the resulting liquid in an oven at 120°C for 24 hours. Get mixed salt.
S2)将1.2g混合盐加入15ml二甲基乙酰胺中，超声波处理5分钟，得到第一溶液。S2) Adding 1.2 g of mixed salt to 15 ml of dimethylacetamide, and ultrasonic treatment for 5 minutes to obtain the first solution.
S3)将0.2g C 8H 6O 4加入15ml二甲基乙酰胺中，超声波处理5分钟，得到第二溶液。 S3) Add 0.2g of C 8 H 6 O 4 to 15 ml of dimethylacetamide, and ultrasonically treat for 5 minutes to obtain a second solution.
S4)将第一溶液和第二溶液混合，超声波处理3分钟，得到混合液，S4) Mix the first solution and the second solution, and ultrasonically treat them for 3 minutes to obtain a mixed solution,
S5)将混合液移入40mL的不锈钢水热反应釜中，在110℃恒温20h。反应结束后，将反应所得固液混合物抽滤分离，用醇清洗4次；S5) Transfer the mixed solution into a 40mL stainless steel hydrothermal reaction kettle and keep it at 110°C for 20h. After the reaction, the solid-liquid mixture obtained from the reaction is separated by suction filtration, and washed with alcohol 4 times;
S6)将分离所得粉末在氩气氛围中，60℃干燥12h，得到金属—有机骨架材料。S6) drying the separated powder in an argon atmosphere at 60° C. for 12 hours to obtain a metal-organic framework material.
实施例2：Example 2:
S1)将80克国内某钢铁厂的粉尘(粒度200微米)与100ml的浓强酸混合，溶解后离心过滤分离，(离心分离因数Fr控制在8500)将得到的液体在烘箱中120℃恒温24h，得到混合盐。S1) Mix 80 grams of dust from a domestic steel plant (with a particle size of 200 microns) with 100 ml of strong acid, dissolve and separate by centrifugal filtration, (the centrifugal separation factor Fr is controlled at 8500), and place the resulting liquid in an oven at 120°C for 24 hours. Get mixed salt.
S2)将0.6g混合盐加入15ml二甲基甲酰胺中，超声波处理3分钟，得到第一溶液。S2) Adding 0.6 g of mixed salt to 15 ml of dimethylformamide and ultrasonic treatment for 3 minutes to obtain the first solution.
S3)将0.1g C 4H 6N 24加入15ml二甲基甲酰胺中，超声波处理3分钟，得到第二溶液。 S3) Add 0.1g of C 4 H 6 N 24 to 15 ml of dimethylformamide, and perform ultrasonic treatment for 3 minutes to obtain a second solution.
S4)将第一溶液和第二溶液混合，超声波处理3分钟，得到混合液，S4) Mix the first solution and the second solution, and ultrasonically treat them for 3 minutes to obtain a mixed solution,
S5)将混合液移入40mL的不锈钢水热反应釜中，在110℃恒温20h。反应结束后，将反应所得固液混合物抽滤分离，用醇清洗4次。S5) Transfer the mixed solution into a 40mL stainless steel hydrothermal reaction kettle and keep it at 110°C for 20h. After the reaction, the solid-liquid mixture obtained from the reaction was separated by suction filtration, and washed with alcohol 4 times.
S6)将分离所得粉末在氩气氛围中，60℃干燥12h，得到金属—有机骨架材料。S6) drying the separated powder in an argon atmosphere at 60° C. for 12 hours to obtain a metal-organic framework material.
实施例3Example 3
S1)将80克国内某钢铁厂的粉尘(粒度200微米)与100ml的浓强酸混合，溶解后离心过滤分离(离心分离因数Fr控制在10000)，将得到的液体在烘箱中120℃恒温24h，得到混合盐。S1) Mix 80 grams of dust from a domestic steel plant (with a particle size of 200 microns) with 100ml of strong acid, dissolve it and separate by centrifugal filtration (the centrifugal separation factor Fr is controlled at 10000), and place the resulting liquid in an oven at 120°C for 24h. Get mixed salt.
S2)将0.2g混合盐加入15ml二乙基甲酰胺中，超声波处理3分钟，得到第一溶液。S2) Add 0.2g of mixed salt to 15ml of diethylformamide, and ultrasonic treatment for 3 minutes to obtain the first solution.
S3)将0.4g C 8H 6O 4加入45ml二乙基甲酰胺中，超声波处理3分钟，得到第二溶液。 S3) Add 0.4g of C 8 H 6 O 4 to 45 ml of diethylformamide, and ultrasonically treat for 3 minutes to obtain a second solution.
S4)将第一溶液和第二溶液混合，超声波处理3分钟，得到混合液，S4) Mix the first solution and the second solution, and ultrasonically treat them for 3 minutes to obtain a mixed solution,
S5)将混合液移入70mL的不锈钢水热反应釜中，在110℃恒温20h。反应结束后，将反应所得固液混合物抽滤分离，用醇清洗4次。S5) Transfer the mixed solution into a 70mL stainless steel hydrothermal reactor, and keep it at 110°C for 20h. After the reaction, the solid-liquid mixture obtained from the reaction was separated by suction filtration, and washed with alcohol 4 times.
S6)将分离所得粉末在氩气氛围中，60℃干燥12h，得到金属—有机骨架材料。S6) drying the separated powder in an argon atmosphere at 60° C. for 12 hours to obtain a metal-organic framework material.
以上仅为本发明的优选实施例，并非因此即限制本发明的专利保护范围，凡是运用本发明说明书及附图内容所作的等效结构变换，直接或间接运用在其他相关的技术领域，均同理包括在本发明的保护范围内。The above are only the preferred embodiments of the present invention, which do not limit the scope of patent protection of the present invention. Any equivalent structural transformations made using the contents of the description and drawings of the present invention are directly or indirectly applied to other related technical fields. Management is included in the protection scope of the present invention.

Claims (10)

  1. 一种利用冶金矿山固废制备金属—有机骨架材料的方法，其特征在于，该方法具体包括以下步骤：A method for preparing metal-organic framework materials using solid waste from metallurgical mines, characterized in that the method specifically includes the following steps:
    S1)将冶金矿山固体废物与浓强酸或强碱混合，充分溶解后，离心过滤分离，在烘箱中恒温干燥，得到混合金属盐；S1) Mix the solid waste of metallurgical mines with concentrated strong acid or strong alkali, and after fully dissolving, centrifuge and filter for separation, and dry in an oven at a constant temperature to obtain mixed metal salt;
    S2)将混合金属盐溶解到有机溶剂中，得到第一溶液；S2) dissolving the mixed metal salt in an organic solvent to obtain a first solution;
    S3)将有机配体溶解到有机溶剂中，得到第二溶液；S3) dissolving the organic ligand in the organic solvent to obtain a second solution;
    S4)将S2)得到第一溶液和S3)得到第二溶液混合均匀，得到混合溶液，将所述混合溶液装入水热反应釜中，在烘箱中恒温一定时间，得到固液混合物；S4) Mixing the first solution obtained by S2) and the second solution obtained by S3) uniformly to obtain a mixed solution. The mixed solution is put into a hydrothermal reactor and kept at a constant temperature in an oven for a certain period of time to obtain a solid-liquid mixture;
    S5)将S4)所得固液混合物进行加热恒温分离，得到固体粉末；S5) heating and isolating the solid-liquid mixture obtained in S4) to obtain a solid powder;
    S6)将S5)所得固体粉末在无氧环境下恒温干燥。S6) Dry the solid powder obtained in S5) at a constant temperature in an oxygen-free environment.
  2. 根据权利要求1所述的方法，其特征在于，所述S1)的具体工艺为：含铁废弃物与浓强酸或强碱体积的比为3-5:4-6，离心分离因数Fr控制在7000～10000，干燥温度为70～150℃，干燥时间为12～36h。The method according to claim 1, wherein the specific process of S1) is: the ratio of the volume of the iron-containing waste to the concentrated strong acid or alkali is 3-5:4-6, and the centrifugal separation factor Fr is controlled at 7000～10000, drying temperature is 70～150℃, drying time is 12～36h.
  3. 根据权利要求1所述的方法，其特征在于，所述S1)所述冶金矿山固体废物粒度在50～250微米；所述浓强酸为浓硫酸、浓盐酸或浓硝酸；所述强碱为氢氧化钠或氢氧化钾。The method according to claim 1, wherein said S1) said metallurgical mine solid waste has a particle size of 50-250 microns; said concentrated strong acid is concentrated sulfuric acid, concentrated hydrochloric acid or concentrated nitric acid; said strong alkali is hydrogen Sodium oxide or potassium hydroxide.
  4. 根据权利要求1所述的方法，其特征在于，所述S2)的工艺为：混合金属盐的投料比例为13～133mg/ml，超声波处理2-5分钟。The method according to claim 1, characterized in that the process of S2) is: the mixing ratio of the metal salt is 13-133 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  5. 根据权利要求1所述的方法，其特征在于，所述S2)的工艺为：所述有机物的投料比例为5～50mg/ml，超声波处理2-5分钟。The method according to claim 1, wherein the process of S2) is: the feeding ratio of the organic matter is 5-50 mg/ml, and the ultrasonic treatment is 2-5 minutes.
  6. 根据权利要求1所述的方法，其特征在于，所述S2)和S3)中的有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二乙基甲酰胺或乙醇。The method according to claim 1, wherein the organic solvent in S2) and S3) is dimethylformamide, dimethylacetamide, diethylformamide or ethanol.
  7. 根据权利要求1所述的方法，其特征在于，所述S3)中的有机配体为C 8H 6O 4、C 14H 10O 4、C 4H 6N 2或C 9H 6O 6。 The method according to claim 1, wherein the organic ligand in S3) is C 8 H 6 O 4 , C 14 H 10 O 4 , C 4 H 6 N 2 or C 9 H 6 O 6 .
  8. 根据权利要求1所述的方法，其特征在于，所述S5)中的工艺为：分离温度为70～150℃，恒温时间为18～30h。The method according to claim 1, wherein the process in S5) is: the separation temperature is 70-150°C, and the constant temperature time is 18-30h.
  9. 根据权利要求1所述的方法，其特征在于，所述S6)的工艺为：干燥温度为40～90℃，恒温干燥时间为8～20h。The method according to claim 1, wherein the process of S6) is: the drying temperature is 40-90°C, and the constant-temperature drying time is 8-20h.
  10. 一种金属—有机骨架材料，其特征在于，所述金属—有机骨架材料采用如权利要求1-9任意一项的方法制备得到。A metal-organic framework material, characterized in that the metal-organic framework material is prepared by the method according to any one of claims 1-9.
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