CN111185234A - Acetic acid catalytic oxidation supported catalyst, preparation method and catalytic oxidation process - Google Patents
Acetic acid catalytic oxidation supported catalyst, preparation method and catalytic oxidation process Download PDFInfo
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Abstract
The invention relates to an acetic acid catalytic oxidation supported catalyst, a preparation method and a catalytic oxidation process, belongs to the technical field of chemical catalytic oxidation, and solves the technical problem of low acetic acid removal rate in the prior art. The acetic acid catalytic oxidation supported catalyst is a metal-organic framework supported catalyst, and the metal-organic framework is a zirconium-based metal-organic framework or a copper-based metal-organic framework; the load component is metal nitrate. The preparation method of the supported catalyst for catalytic oxidation of acetic acid comprises the following steps: adding a metal salt precursor and an organic ligand into a solvent, performing ultrasonic dispersion, performing hydrothermal reaction, centrifuging, washing and drying to obtain a metal-organic framework; adding metal nitrate into the metal-organic framework, continuously stirring, drying and roasting to obtain the metal-organic framework supported catalyst. The catalyst can be used for catalytically oxidizing acetic acid into carbon dioxide and water, and the removal rate of the acetic acid reaches over 93 percent.
Description
Technical Field
The invention relates to the technical field of chemical catalytic oxidation, in particular to an acetic acid catalytic oxidation supported catalyst, a preparation method and a catalytic oxidation process.
Background
Water is an indispensable material resource for human life and production. With the rapid development of industrial production level, water is difficult to avoid being polluted by various substances and losing the use value of the water in the use process, and the problem of resource shortage caused by water body pollution is increasingly serious. According to the investigation of relevant departments, the industrial water in China accounts for about 11 percent of the total water consumption in China, a large amount of industrial wastewater is discharged when the industry uses water resources, and most of the industrial wastewater has the characteristics of high organic matter concentration, poor biodegradability, even a little toxicity to microorganisms and the like. The comprehensive treatment of the high-concentration organic wastewater difficult to degrade is highly valued at home and abroad and establishes strict standards. At present, partial waste water with simple components, good biodegradability and low concentration can be treated by the traditional process, and the waste water with high concentration and difficult biodegradation is still difficult to realize thorough treatment and has high economic cost, so that the development of a novel and practical water treatment technology has important social significance and economic value.
In recent years, advanced oxidation techniques mainly involving generation of radicals have been rapidly developed, such as wet air oxidation, hydrogen peroxide oxidation, ozone oxidation, supercritical water oxidation, and the like. The technology mainly utilizes the generated high-activity free radicals to attack the macromolecular refractory organic matters, react with the macromolecular refractory organic matters and destroy the molecular structure of the macromolecular refractory organic matters, so that the macromolecular refractory organic matters are converted into the biochemical degradable micromolecular organic matters and inorganic matters such as carbon dioxide, water and the like, thereby achieving the aim of removing pollutants. The catalytic wet oxidation can realize the high-efficiency oxidative degradation of organic pollutants by means of the action of a catalyst, obviously reduce the temperature and pressure of reaction, greatly reduce the process energy consumption, enable industrial application to become possible, and provide an effective novel treatment technology for high-concentration organic wastewater difficult to biodegrade.
Organic acid is difficult to remove by wet oxidation in organic compounds causing water pollution, and the oxidation difficulty of acetic acid is the greatest. Acetic acid is a major intermediate in the wet oxidation of numerous macromolecular organic species, and its further oxidation becomes a limiting step in many wet oxidation processes. Most studies currently select acetic acid as a model reactant for wet oxidation for use as a probe for catalyst preparation, screening, and optimization. In addition, theoretically, the catalyst screened by the acetic acid catalytic wet oxidation has certain universality on the catalytic wet oxidation of other organic matters, and also provides a certain research basis for the actual organic wastewater treatment. The catalyst is the core of catalytic wet oxidation technology, and common wet oxidation catalysts include noble metal catalysts and transition metal oxide catalysts. However, the former has high development cost, and the latter has a problem of dissolution of active components, which seriously results in the reduction of catalyst activity and secondary pollution to effluent, and these factors limit the large-scale practical application of the existing catalyst in the field of wastewater treatment. Therefore, the development of a novel efficient, stable and cheap wet oxidation catalyst for acetic acid pollutants in a water body is of great significance.
By referring to relevant data, the problems and the disadvantages of the existing catalytic wet oxidation water treatment technology are mainly reflected in the following aspects:
(1) the method is difficult to realize complete catalytic oxidation treatment on industrial wastewater with high organic matter concentration and poor biodegradability, wherein further oxidation of acetic acid is usually a limiting step, and the conversion rate is low (generally lower than 60%);
(2) the method depends heavily on high temperature, high pressure and necessary liquid phase conditions, correspondingly requires high temperature resistance, high pressure resistance and corrosion resistance of reaction equipment materials, and has high technical cost due to complex process flow;
(3) in the homogeneous catalysis wet oxidation process, because the catalyst and the wastewater are completely mixed, the dissolution phenomenon of the catalyst is serious, and the lost catalyst needs to be recovered by subsequent treatment in order to prevent secondary pollution;
(4) in the heterogeneous catalysis wet oxidation process, the cost is increased due to the higher loading of the noble metal catalyst, and the activity and stability of the non-noble metal catalyst are still far away from the practical application;
(5) the catalytic oxidation process using acetic acid as a probe molecule has few reports, and most of the catalysts and process conditions provided by the research have low-temperature activity on the acetic acid oxidation reaction.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide an acetic acid oxidation catalyst, a preparation method and a catalytic oxidation process. At least one of the following technical problems can be solved: (1) the high-efficiency catalytic conversion of acetic acid in a liquid phase, namely, under the conditions of proper reaction temperature, reaction pressure, reactant proportion and the like, the acetic acid is converted into nontoxic carbon dioxide and water by using a catalyst, and the conversion rate of the acetic acid can reach more than 93 percent; (2) the heterogeneous catalysis of the acetic acid catalyst reduces the loss of active components, namely, the active components of the catalyst are embedded or loaded on a carrier with a proper pore structure and physicochemical properties, so that the stability of the catalyst is enhanced, and the loss of the active components is reduced; (3) the non-noble metal catalyst reduces the cost, and the temperature and pressure conditions of the reaction are economical and feasible, namely the non-noble metal is used for replacing noble metal to reduce the preparation cost of the catalytic material, and the economical and feasible reaction temperature and pressure conditions are selected to reduce the operation cost of the process on the premise of ensuring the ideal reaction conversion rate.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides an acetic acid catalytic oxidation supported catalyst which is a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, wherein the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is a metal-organic framework supported catalyst, and the metal-organic framework is a zirconium-based metal-organic framework or a copper-based metal-organic framework; the load component is metal nitrate; the products of the catalytic oxidation of acetic acid are carbon dioxide and water.
In one possible design, the zirconium-based metal-organic framework has a UIO-66 topology; the copper-based-metal organic framework has a MOF-74 topology.
In one possible design, the metal loading of the metal-organic framework supported catalyst is 0.5 to 20.0 wt%.
The invention also provides a method for catalytically oxidizing the supported catalyst by the acetic acid, which is characterized by comprising the following steps of:
s1: weighing a metal salt precursor and an organic ligand according to a ratio, adding the metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion and dissolution at room temperature to obtain a mixed liquid;
s2: adding the mixed liquid into a reaction device for hydrothermal reaction to obtain a reaction product;
s3: centrifuging, washing and drying the reaction product to obtain a metal-organic framework;
s4: dissolving metal nitrate in deionized water, adding a metal-organic framework, and continuously stirring to obtain a stirred mixture;
s5: and drying and roasting the stirred mixture to obtain the metal-organic framework supported catalyst.
In one possible design, in S1, the ultrasonic dispersion time is 10-45 min; the organic ligand is one of terephthalic acid, amino group and sulfonic group modified terephthalic acid.
In one possible design, in S2, the hydrothermal reaction temperature is 150-350 ℃.
In one possible design, in S3, the drying time is 12-24 hours, and the drying temperature is 80-120 ℃.
In one possible design, in S3, the roasting temperature is 450-750 ℃, and the roasting time is 3-6 h.
The invention also provides an acetic acid catalytic oxidation process, which comprises the following steps:
s1: carrying out tabletting or granulation treatment on the metal-organic framework supported catalyst, and placing the metal-organic framework supported catalyst into a reaction container;
s2: introducing gas and an acetic acid solution into the reaction vessel;
s3: heating the reaction vessel, pressurizing and starting catalytic oxidation reaction;
s4: after the reaction is completed, the content of acetic acid after the reaction is measured, and the acetic acid conversion removal rate is calculated.
In one possible design, in S2, the flow rate of the introduced gas is 50-300 mL/h, and the flow rate of the acetic acid solution is 1-100 mL/h;
s3, heating the reaction container to 150-250 ℃ and the reaction pressure is 0.5-8 MPa.
The invention has the following beneficial effects:
(1) according to the method, acetic acid with the greatest degradation difficulty is used as a probe molecule, a high-efficiency heterogeneous copper-zirconium-cerium (Cu-Zr-Ce) ternary non-noble metal catalyst is developed, and the acetic acid is catalytically oxidized into carbon dioxide and water, so that the catalyst not only can realize the high-efficiency catalytic oxidation of the acetic acid, but also can play a good catalytic effect in the liquid-phase oxidation process of other oxygen-containing organic compounds (propionic acid, lactic acid, acrylic acid and the like) with similar molecular structures, and therefore, the catalyst has a good application prospect in the field of organic wastewater purification;
(2) according to the method, the molecular structure and the kinetic diameter characteristic of acetic acid molecules are comprehensively considered according to the acidic characteristic of an acetic acid aqueous solution, two catalyst pore channel structures are provided in a targeted manner, the mass transfer rate in the reaction process can be ensured, and the acidic sites are provided to help the acetic acid to be completely oxidized, so that the reaction selectivity is improved;
(3) the catalyst developed by the application can realize the high-efficiency catalytic conversion of acetic acid in a liquid phase, meets the use requirements of pressure resistance, corrosion resistance, two-way air inlet, one-way liquid inlet and the like by reactor structure design and process condition parameter optimization according to the activity of the catalyst, takes air or oxygen as an oxygen source, converts the acetic acid into nontoxic carbon dioxide and water by using the catalyst under the conditions of reaction temperature (150-;
(4) the acetic acid catalyst developed by the application is heterogeneous, so that the loss of active components is reduced, namely the active components of the catalyst are embedded or loaded on a carrier with a micropore-mesopore or micropore structure and physicochemical properties, the stability of the catalyst is enhanced, and the loss of the active components is reduced;
(5) the non-noble metal catalyst developed by the application has the advantages that the cost is reduced, the reaction temperature and pressure conditions are economical and feasible, namely, the non-noble metal is used for replacing noble metal to reduce the preparation cost of the catalytic material, and the economical and feasible reaction temperature and pressure conditions are selected to reduce the operation cost of the process on the premise of ensuring the ideal reaction conversion rate.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic view of an apparatus for catalytic oxidation of acetic acid according to the present invention.
Reference numerals:
1-a first mass flow meter; 2-a second mass flow meter; 3-a gas mixing valve; a 4-acetic acid feed storage tank; 5-a pump; 6-a reaction tube; 7-catalyst bed layer; 8-heating furnace; 9-product analyzer; 10-back pressure valve.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The invention provides an acetic acid catalytic oxidation supported catalyst, namely a heterogeneous ternary non-noble metal catalyst, in particular to a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst which can catalyze and oxidize acetic acid, and the product is carbon dioxide and water. Compared with the existing acetic acid catalytic oxidation supported catalyst which is prepared by adopting noble metal, the Cu-Zr-Ce non-noble metal is adopted, so that the cost can be obviously reduced.
The heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is a metal-organic framework supported catalyst, and comprises a metal-organic framework and a metal nitrate, wherein the metal-organic framework comprises a metal precursor and an organic ligand.
Specifically, the metal-organic framework may be a zirconium-based metal-organic framework or a copper-based metal-organic framework; the metal nitrate can be one or more of copper nitrate, zirconium nitrate and cerium nitrate; the metal precursor is a zirconium metal salt precursor or a copper metal salt precursor. In particular, the zirconium-based metal-organic framework has a UIO-66 topology; the copper-based-metal organic framework has a MOF-74 topology.
The specific surface area of the metal-organic framework supported catalyst is 300-3000 m2A specific surface area of 800 to 1500m2(ii)/g; the pore channel structure of the metal-organic framework supported catalyst is a micropore-mesopore secondary structure.
The metal-organic framework supported catalyst is a supported catalyst, the metal-organic framework is a carrier, the metal nitrate is a load, and the metal load is 0.5-20.0 wt%.
The metal-organic framework supported catalyst can have a UIO-66 topological structure and comprises a zirconium-based metal-organic framework, copper nitrate and cerium nitrate, wherein the loading amounts of copper and cerium on a zirconium-based carrier are 0.5-20.0 wt%, and the exemplary loading amount is 5.0-15.0 wt%; the carrier can also have an MOF-74 topological structure, and comprises a copper-based metal organic framework, zirconium nitrate and cerium nitrate, wherein the loading amounts of zirconium and cerium on a copper-based carrier are 10.0-20.0 wt%, and are 15.0-18.0 wt% for example.
The invention provides a method for preparing an acetic acid catalytic oxidation supported catalyst, in particular to a method for preparing a metal-organic framework by a hydrothermal method and preparing a metal-organic framework supported catalyst by using the metal-organic framework and a metal salt, which comprises the following steps:
s1: weighing a metal salt precursor and an organic ligand according to a ratio, adding the metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion and dissolution at room temperature to obtain a mixed liquid;
s2: adding the mixed liquid into a reaction device for hydrothermal reaction to obtain a reaction product;
s3: centrifuging, washing and drying the reaction product to obtain a metal-organic framework;
s4: dissolving metal salt in deionized water, adding a metal-organic framework, and continuously stirring to obtain a stirred mixture;
s5: and drying and roasting the stirred mixture to obtain the metal-organic framework supported catalyst.
Exemplarily, in the step S1, the ultrasonic dispersion time is 10 to 45 min; the organic ligand is one of terephthalic acid, amino and sulfonic group modified terephthalic acid; in S2, the hydrothermal heating temperature is 150-350 ℃, namely the hydrothermal reaction temperature is 150-350 ℃; in S3, drying for 12-24 hours at 80-120 ℃;
in S4, the metal salt (active component) is one or more of copper nitrate, zirconium nitrate and cerium nitrate, and the active component is loaded by an impregnation method; in S5, the roasting temperature is 450-750 ℃, and the roasting time is 3-6 h.
The invention provides an acetic acid catalytic oxidation process, which adopts the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst to carry out catalytic oxidation on acetic acid and comprises the following specific steps:
s1: carrying out tabletting or granulation treatment on the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, and placing the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst in a reaction container;
s2: introducing gas (oxygen or air) and acetic acid solution into the reaction container;
s3: heating the reaction vessel, pressurizing and starting catalytic oxidation reaction;
s4: after the reaction is completed, the content of acetic acid after the reaction is measured, and the acetic acid conversion removal rate is calculated.
Specifically, in S1, the heterogeneous ternary non-noble metal catalyst is a metal-organic framework supported catalyst or a amorphous ternary metal mixed oxide catalyst;
in S2, the gas flow rate is 50-300 mL/h, preferably 80-200 mL/h; the flow rate of the acetic acid solution is 1-100 mL/h, preferably 5-50 mL/h;
s3, heating the reaction container to a temperature of 150-250 ℃, namely a catalytic oxidation reaction temperature of 150-250 ℃, preferably 200-250 ℃, and more preferably 200-230 ℃; the applied pressure is 0.5-8MPa, preferably 2.5-6 MPa;
calculation of acetic acid conversion removal rate in S4: the reaction product of acetic acid and a heterogeneous ternary non-noble metal catalyst is CO2And water, and quantitatively measuring the mass of the acetic acid through liquid chromatography to obtain the mass of the acetic acid removed by the reaction, and further calculating the removal rate of the acetic acid.
Specifically, the kind of the catalyst is selected according to the pH of the prepared acetic acid solution. When the pH value of the acetic acid solution is less than 5, a metal-organic framework supported catalyst is selected; when the pH value of the acetic acid solution is 5-7, an amorphous ternary metal mixed oxide catalyst is selected.
The invention provides a device for catalytic oxidation reaction of acetic acid, which can be a fixed bed reaction device and comprises a gas circuit unit, a liquid circuit unit, a pressure control unit, a constant temperature reaction unit and a product analysis unit, and is shown in figure 1.
The gas path unit is used for introducing gas into the constant-temperature reaction unit;
the liquid path unit is used for introducing an acetic acid solution into the constant-temperature reaction unit;
the pressure control unit is used for controlling and adjusting the pressure of the constant temperature reaction unit.
The gas circuit unit and the product analysis unit are respectively connected with the lower end of the constant-temperature reaction unit; the liquid path unit and the pressure control unit are respectively connected with the upper end of the constant temperature reaction unit.
Specifically, the gas path unit comprises a first gas path pipeline and a second gas path pipeline, which are respectively used for introducing oxygen and protective gas, the first gas path pipeline is provided with a first mass flow meter 1 for controlling the flow rate of air or oxygen, the second gas path pipeline is provided with a second mass flow meter 2 for controlling the flow rate of inert gas, and the gas path unit is provided with a gas mixing pump 3 for mixing the air or oxygen in the first gas path pipeline and the inert gas in the second gas path pipeline; the liquid path unit comprises an acetic acid feeding storage tank 4 and a pump 5, and is used for storing an acetic acid solution and conveying the acetic acid solution to the constant-temperature reaction unit; the pressure control unit comprises a backpressure valve 10 which is used for adjusting and controlling the pressure of the constant temperature reaction unit; the constant-temperature reaction unit comprises a reaction tube 6 and a heating furnace 8, the reaction tube is positioned in the heating furnace, a catalyst is arranged in the reaction tube to form a catalyst bed layer 7, the reaction tube provides gas conveyed by the gas path unit and acetic acid solution conveyed by the liquid path unit to perform oxidation reaction under the action of the catalyst, and the heating furnace is used for heating the reaction tube; the product analysis unit is provided with a product analyzer 9 for analyzing and testing the acetic acid content and calculating the conversion rate of acetic acid.
Example 1
The metal-organic framework supported catalyst of the embodiment comprises a zirconium-based metal-organic framework and a metal nitrate (metal precursor) with UIO-66 topological structures, wherein the zirconium-based metal-organic framework is a carrier, and the metal nitrate is copper nitrate and cerium nitrate, and the metal-organic framework carrier is prepared by reacting the metal precursor with an organic ligand. The organic ligand is terephthalic acid.
Weighing a zirconium metal salt precursor and an organic ligand according to a ratio, adding a solvent, and performing ultrasonic dispersion at room temperature for 10 minutes to obtain a mixed liquid after completely dissolving the zirconium metal salt precursor and the organic ligand; and transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, setting the temperature to be 150 ℃, carrying out hydrothermal reaction, centrifuging and washing the obtained reactant, and drying at 80 ℃ for 24 hours to obtain the zirconium-based metal-organic framework carrier, namely the Zr-UiO-66 carrier.
The specific surface area of the metal-organic framework supported catalyst of the present example was 800m2(ii)/g; the pore channel structure of the metal-organic framework supported catalyst is a micropore-mesopore secondary structure.
In this example, the metal-organic framework supported catalyst was a supported catalyst, and the loading amounts of copper and cerium on the zirconium-based carrier were both 5.0 wt%.
Example 2
The metal-organic framework supported catalyst of the embodiment comprises a zirconium-based metal-organic framework and a metal nitrate (metal precursor) with UIO-66 topological structures, wherein the zirconium-based metal-organic framework is a carrier, and the metal nitrate is copper nitrate and cerium nitrate, and the metal-organic framework carrier is prepared by reacting the metal precursor with an organic ligand. The organic ligand is an amine group.
Weighing a zirconium metal salt precursor and an organic ligand according to a ratio, adding the zirconium metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion at room temperature for 45 minutes to obtain a mixed liquid after the zirconium metal salt precursor and the organic ligand are completely dissolved; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, setting the temperature for hydrothermal heating at 350 ℃ for reaction, centrifuging and washing the obtained reactant, and drying at 120 ℃ for 12 hours to obtain the zirconium-based metal-organic framework carrier, namely the Zr-UiO-66 carrier.
The specific surface area of the metal-organic framework supported catalyst of the present example was 1500m2(ii)/g; the pore channel structure of the metal-organic framework supported catalyst is a micropore-mesopore secondary structure.
In this example, the metal-organic framework supported catalyst was a supported catalyst, and the loading amounts of copper and cerium on the zirconium-based carrier were both 15.0 wt%.
Example 3
A metal-organic framework supported catalyst comprises a metal-organic framework and metal nitrate (metal precursor), wherein the metal-organic framework is a carrier, and the metal-organic framework carrier is prepared by the reaction of the metal precursor and an organic ligand. The organic ligand is amino-modified terephthalic acid.
In this example, the metal-organic framework is a copper-based metal-organic framework; the metal nitrate is zirconium nitrate and cerium nitrate. The copper-based-metal organic framework has a MOF-74 topology.
Weighing a zirconium metal salt precursor and an organic ligand according to a ratio, adding the zirconium metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion at room temperature for 25 minutes to obtain a mixed liquid after the zirconium metal salt precursor and the organic ligand are completely dissolved; and transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, setting the temperature to 250 ℃ for hydrothermal reaction, centrifuging and washing the obtained reactant, and drying at 100 ℃ for 18 hours to obtain the copper-based metal-organic framework carrier.
The specific surface area of the metal-organic framework supported catalyst of this example was 1000m2(ii)/g; the pore channel structure of the metal-organic framework supported catalyst is a micropore-mesopore secondary junctionAnd (5) forming.
The metal-organic framework supported catalyst is a supported catalyst, and the loading amounts of zirconium and cerium on a copper-based carrier are both 10.0 wt%.
Example 4
A preparation method of a metal-organic framework supported catalyst adopts a hydrothermal method to prepare a metal-organic framework, and then carries out bimetal modification by a physical impregnation method, and comprises the following specific steps:
s1: weighing a metal salt precursor and an organic ligand according to a ratio, adding the metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion and dissolution at room temperature to obtain a mixed liquid;
s2: carrying out hydrothermal heating reaction on the mixed solution, centrifuging, washing and drying to obtain a metal-organic framework;
s3: dissolving metal nitrate in deionized water, adding a metal-organic framework, continuously stirring, drying and roasting to obtain the metal-organic framework supported catalyst prepared by a hydrothermal method.
Exemplarily, in the above S1, the ultrasonic dispersion time is 10 min; in S2, the hydrothermal heating temperature is 150 ℃, and the reaction vessel adopted by the hydrothermal heating reaction of the mixed solution is a stainless steel reaction kettle with a polytetrafluoroethylene lining; in S3, the metal nitrates (active components) are copper nitrate and zirconium nitrate, and the active components are loaded by an impregnation method; the drying time is 12h, and the drying temperature is 80 ℃; the roasting temperature is 450 ℃, and the roasting time is 3 h.
Example 5
A preparation method of a metal-organic framework supported catalyst adopts a hydrothermal method to prepare a metal-organic framework, and then carries out bimetal modification by a physical impregnation method, and comprises the following specific steps:
s1: weighing a metal salt precursor and an organic ligand according to a ratio, adding the metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion and dissolution at room temperature to obtain a mixed liquid;
s2: carrying out hydrothermal heating reaction on the mixed solution, centrifuging, washing and drying to obtain a metal-organic framework;
s3: dissolving metal nitrate in deionized water, adding a metal-organic framework, continuously stirring, drying and roasting to obtain the metal-organic framework supported catalyst prepared by a hydrothermal method.
Exemplarily, in the above S1, the ultrasonic dispersion time is 45 min; in S2, the hydrothermal heating temperature is 350 ℃, and the reaction vessel adopted by the hydrothermal heating reaction of the mixed solution is a stainless steel reaction kettle with a polytetrafluoroethylene lining; in S3, the metal nitrates (active components) are zirconium nitrate and cerium nitrate, and the active components are loaded by an impregnation method; the drying time is 24h, and the drying temperature is 120 ℃; the roasting temperature is 750 ℃, and the roasting time is 6 h.
Example 6
A catalytic oxidation reaction of acetic acid with CuO-Ce2+The Zr-UiO-66 catalyst comprises the following steps:
s1: 1.0g of CuO-Ce with the grain diameter of 60-80 meshes2+Filling particles of the/Zr-UiO-66 catalyst into a constant temperature area of the fixed bed reactor;
s2: introducing air, introducing acetic acid liquid, wherein the pH of the acetic acid solution is 3, and the liquid flow rate is 20 mL/h; the gas flow rate is 50 mL/h; the COD equivalent of acetic acid is 1000 mg/L;
s3: gas and liquid are reacted in a countercurrent mode through the catalytic bed area, heating reaction is carried out, and the reaction temperature is 250 ℃; the reaction pressure is 2.5 MPa;
s4: and (5) carrying out catalytic reaction for 3h, and quantitatively analyzing outlet water by using a high performance liquid chromatography to obtain the acetic acid conversion removal rate.
According to the scheme, after the reaction is stable, the conversion rate of acetic acid reaches 93%, and the products are carbon dioxide and water. The acetic acid can obtain higher conversion rate under the reaction conditions and the action of the catalyst, and meanwhile, the reaction rate is higher, the product selectivity is very high, and no secondary pollution is generated.
Example 7
A catalytic oxidation reaction device for acetic acid can realize 2-path gas inlet and 1-path liquid-phase feeding, wherein the inner wall of a liquid-phase pipeline is coated with a polytetrafluoroethylene inner membrane to have corrosion resistance, and the reaction device can provide temperature and pressure condition control required by acetic acid oxidation, and is specifically shown in figure 1.
The reactor is of a fixed bed structure and is provided with 2 gas paths and 1 liquid path for feeding, wherein the gas paths are used for introducing air or a mixture of oxygen and inert gas, and the liquid paths are used for providing an aqueous solution of acetic acid, namely simulated polluted water; the catalyst is filled in a constant temperature area of the fixed bed reactor, the reaction temperature is measured by a thermocouple, and the reaction pressure is controlled by a back pressure valve.
The catalyst material is pressed into tablets and granulated before reaction evaluation and then is filled into the isothermal zone of the fixed bed reactor. Before the test starts, opening all valves in the system, enabling oxygen or air to fill the pipeline, closing all valves and closing gas; then, turning on a power supply of a heating furnace of the reaction system to preheat the reactor, and starting to test when the temperature in the reactor meets the test requirement; oxygen or air and acetic acid aqueous solution are respectively sent into a reactor through a gas path and a liquid path to start catalytic reaction, and the contact mode can be countercurrent or cocurrent; and quantitatively analyzing outlet water by using a high performance liquid chromatography after the catalytic reaction to obtain the acetic acid conversion removal rate.
Comparative example 1
D1: soaking 1.0g of commercial NiO/Al prepared by 60-80 meshes2O3Filling catalyst particles into a constant-temperature area of the fixed bed reactor;
d2: introducing oxygen or air, and introducing acetic acid liquid, wherein the flow rate of the liquid is 5-50 mL/h; the gas flow rate is 80-200 mL/h; the COD equivalent of the acetic acid is 1000-5000 mg/L;
d3: gas and liquid are reacted in a way of countercurrent flow through the catalytic bed area, the reaction temperature is 200-250 ℃, and the reaction pressure is 2.5-6 MPa;
d4: and (3) carrying out catalytic reaction for 3-20 h, and quantitatively analyzing outlet water by using a high performance liquid chromatography to obtain the acetic acid conversion removal rate.
After the reaction is stabilized, the conversion rate of acetic acid reaches 38%, and the products are formic acid, carbon dioxide and water.
In summary, the disclosure background of the method for catalytic oxidation of acetic acid provided by the present invention is a novel treatment technology for industrial wastewater with high organic concentration and poor biodegradability, wherein acetic acid is selected as a probe molecule as an organic pollutant with the greatest degradation difficulty, and is used for catalyst development and screening, reactor structure design and process condition parameter optimization. Specifically, the process adopts copper-zirconium-cerium (Cu-Zr-Ce) ternary catalysts with different structures, uses clean, cheap and easily available air or oxygen as an oxygen source, and completely oxidizes acetic acid into carbon dioxide and water in a fixed bed reactor under the reaction conditions of 150-250 ℃ and 0.5-8MPa, wherein the removal rate of organic matters reaches more than 93%. The method has the advantages of high reaction efficiency, deep purification degree, low catalyst cost and the like, and has wide application prospect
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The supported catalyst for catalytic oxidation of acetic acid is a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is a metal-organic framework supported catalyst, and the metal-organic framework is a zirconium-based metal-organic framework or a copper-based metal-organic framework; the load component is metal nitrate; the products of the catalytic oxidation of acetic acid are carbon dioxide and water.
2. The supported catalyst for catalytic oxidation of acetic acid according to claim 1, wherein the zirconium-based metal-organic framework has a topology of UIO-66; the copper-based-metal organic framework has a MOF-74 topology.
3. The supported catalyst for catalytic oxidation of acetic acid according to claim 2, wherein the metal loading of the metal-organic framework supported catalyst is 0.5-20.0 wt%.
4. A process for preparing a supported catalyst for the catalytic oxidation of acetic acid according to any one of claims 1 to 3, comprising the steps of:
s1: weighing a metal salt precursor and an organic ligand according to a ratio, adding the metal salt precursor and the organic ligand into a solvent, and performing ultrasonic dispersion and dissolution at room temperature to obtain a mixed liquid;
s2: adding the mixed liquid into a reaction device for hydrothermal reaction to obtain a reaction product;
s3: centrifuging, washing and drying the reaction product to obtain a metal-organic framework;
s4: dissolving metal nitrate in deionized water, adding a metal-organic framework, and continuously stirring to obtain a stirred mixture;
s5: and drying and roasting the stirred mixture to obtain the metal-organic framework supported catalyst.
5. The supported catalyst for catalytic oxidation of acetic acid according to claim 4, wherein in S1, the ultrasonic dispersion time is 10-45 min; the organic ligand is one of terephthalic acid, amino group and sulfonic group modified terephthalic acid.
6. The method for preparing the supported catalyst for catalytic oxidation of acetic acid according to claim 4, wherein the hydrothermal reaction temperature in S2 is 150-350 ℃.
7. The method according to claim 4, wherein the drying time in S3 is 12-24 hours, and the drying temperature is 80-120 ℃.
8. The method according to claim 7, wherein in S3, the roasting temperature is 450-750 ℃, and the roasting time is 3-6 h.
9. A process for catalytic oxidation of acetic acid, wherein the supported catalyst for catalytic oxidation of acetic acid according to any one of claims 1 to 3 is used, comprising the steps of:
s1: carrying out tabletting or granulation treatment on the metal-organic framework supported catalyst, and placing the metal-organic framework supported catalyst into a reaction container;
s2: introducing gas and an acetic acid solution into the reaction vessel;
s3: heating the reaction vessel, pressurizing and starting catalytic oxidation reaction;
s4: after the reaction is completed, the content of acetic acid after the reaction is measured, and the acetic acid conversion removal rate is calculated.
10. The catalytic oxidation process of acetic acid according to claim 9, wherein: in the S2, the flow rate of the introduced gas is 50-300 mL/h, and the flow rate of the acetic acid solution is 1-100 mL/h;
and in the S3, heating the reaction container to 150-250 ℃, wherein the reaction pressure is 0.5-8 MPa.
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| CN1583256A (en) * | 2004-06-09 | 2005-02-23 | 中国科学院大连化学物理研究所 | Nobel metal catalyst for treating industrial waste water, preparing method and use thereof |
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| CN1583256A (en) * | 2004-06-09 | 2005-02-23 | 中国科学院大连化学物理研究所 | Nobel metal catalyst for treating industrial waste water, preparing method and use thereof |
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