CN111185181A - Acetic acid catalytic oxidation amorphous catalyst, preparation method and catalytic oxidation process - Google Patents
Acetic acid catalytic oxidation amorphous catalyst, preparation method and catalytic oxidation process Download PDFInfo
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- CN111185181A CN111185181A CN202010018500.3A CN202010018500A CN111185181A CN 111185181 A CN111185181 A CN 111185181A CN 202010018500 A CN202010018500 A CN 202010018500A CN 111185181 A CN111185181 A CN 111185181A
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 322
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 56
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000012716 precipitator Substances 0.000 claims abstract description 16
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- 239000000047 product Substances 0.000 claims abstract description 14
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- 238000001035 drying Methods 0.000 claims description 13
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
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- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
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- 238000009279 wet oxidation reaction Methods 0.000 description 13
- 238000013461 design Methods 0.000 description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
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- RFHOKFXRZASHTN-UHFFFAOYSA-N [Ce].[Cu].[Zr] Chemical compound [Ce].[Cu].[Zr] RFHOKFXRZASHTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/60—
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- B01J35/613—
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- B01J35/615—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Abstract
The invention relates to an acetic acid catalytic oxidation amorphous 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 amorphous catalyst is a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst which is an amorphous ternary metal mixed oxide catalyst, and the structural formula of the catalyst is as follows: xCuO-yZrO2‑zCeO2Wherein, in the step (A),x: y: z ═ 1 to 2: (1-5): (1-5); the products of the catalytic oxidation of acetic acid are carbon dioxide and water. The preparation method comprises the following steps: dissolving a metal salt precursor in a solvent to obtain a precursor mixed solution; dripping a precipitator into the precursor mixed solution, aging the generated precipitate for 24-48 h at room temperature, and performing centrifugal separation; and roasting the solid obtained by centrifugal separation in air to obtain the amorphous catalyst for catalytic oxidation of acetic acid. The catalyst can be used for catalytically oxidizing acetic acid into nontoxic and pollution-free carbon dioxide and water, and the removal rate of the acetic acid reaches more than 93%.
Description
Technical Field
The invention relates to the technical field of chemical catalytic oxidation, in particular to an acetic acid catalytic oxidation amorphous 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 amorphous catalyst which is a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, and products of the acetic acid catalytic oxidation are carbon dioxide and water.
In one possibilityIn the design of (2), the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is an amorphous ternary metal mixed oxide catalyst, and the structural formula of the amorphous ternary metal mixed oxide is as follows: xCuO-yZrO2-zCeO2Wherein, x: y: z ═ 1 to 2: (1-5): (1-5).
In one possible design, the amorphous ternary metal mixed oxide catalyst is obtained by a metal salt precursor salt co-precipitation method.
In one possible design, the metal salt precursor salt is one or more of a nitrate or chloride salt of copper, zirconium, cerium.
In one possible design, in the metal salt precursor salt coprecipitation, the precipitator is ammonia water, and the solvent is one or more of water, methanol and ethanol.
In one possible design, the specific surface area of the amorphous ternary metal mixed oxide catalyst is 80-300 m2And/g, the pore structure is a microporous structure.
The invention also provides a method for catalyzing and oxidizing the amorphous catalyst by the acetic acid, which comprises the following steps:
s1 preparation of CuO and ZrO2、CeO2Dissolving the metal salt precursor in a solvent according to a certain proportion to obtain a precursor mixed solution;
s2, dripping a precipitator into the precursor mixed solution according to the volume ratio of the metal salt precursor to the precipitator of 1: 5-1: 10 to generate a precipitate;
s3: aging the precipitate at room temperature for 24-48 h, and performing centrifugal separation;
s4: and roasting the solid obtained by centrifugal separation in air to obtain the amorphous ternary metal mixed oxide catalyst.
In one possible design, in S3, the drying temperature is 80-120 ℃; the drying time is 12-24 h.
In one possible design, in S4, the roasting temperature is 450-750 ℃; the roasting time is 3-6 h.
The invention also provides an acetic acid catalytic oxidation process, which adopts the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst and comprises the following steps:
s1: carrying out tabletting or granulation treatment on the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, and placing the catalyst in a reaction vessel;
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.
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 amorphous 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 products are carbon dioxide and water. Compared with the existing acetic acid catalytic oxidation amorphous catalyst prepared by noble metal, the Cu-Zr-Ce non-noble metal is adopted in the method, so that the cost can be obviously reduced.
The heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is a Cu-Zr-Ce amorphous ternary metal mixed oxide catalyst, and can be expressed as follows: xCuO-yZrO2-zCeO2Catalyst, wherein x is the fraction of CuO and y is ZrO2Z is CeO2X, y and z are CuO and ZrO2、CeO2Wherein x, y, z is (1-2): (1-5): (1-5).
xCuO-yZrO2-zCeO2The catalyst is prepared from metal salt precursor salt, a precipitator and a solvent according to a certain proportion. Specifically, the metal salt precursor salt is one or more of nitrates or chlorides of copper, zirconium and cerium, and the molar ratio of copper, zirconium and cerium is 1:1:1 to 1:5: 4; the precipitator is ammonia water; the solvent is one or more of water, methanol and ethanol.
According to xCuO-yZrO2-zCeO2The proportional relation of x, y and z in the catalyst designs the molar proportional relation of metal salt precursor salt, precipitant and solvent and the molar proportion of copper-zirconium-cerium. Specifically, the molar ratio of the copper, the zirconium and the cerium is 1:2:2 or 1:3:2, and the specific surface area is 150-300 m2/g。
The specific surface area of the amorphous ternary metal mixed oxide catalyst is 80-300 m2And/g, the pore structure is a microporous structure.
The invention also provides a method for preparing the amorphous catalyst for catalytic oxidation of acetic acid, in particular to a method for preparing the amorphous ternary metal mixed oxide catalyst by adopting a coprecipitation method, which comprises the following steps:
s1 preparation of CuO and ZrO2、CeO2Dissolving the metal salt precursor in a solvent according to a certain proportion to obtain a precursor mixed solution;
s2, dripping a precipitator into the precursor mixed solution according to the volume ratio of the metal salt precursor to the precipitator of 1: 5-1: 10 (specifically 1:10) to generate a precipitate;
s3: aging the precipitate at room temperature for 24-48 h, centrifuging, and drying;
s4: and roasting the dried solid in the air to obtain the amorphous ternary metal mixed oxide catalyst.
Specifically, in S1, the metal salt precursor salt is one or more of copper nitrate, zirconium nitrate and cerium nitrate; the solvent is one or more of water, methanol and ethanol; in S2, the precipitant is ammonia water; in S3, the drying temperature is 80-120 ℃; the drying time is 12-24 h; in S4, the roasting temperature is 450-750 ℃; 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 an 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: ternary complexes of acetic acid and heterogeneous phaseThe reaction product of the 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
A Cu-Zr-Ce amorphous ternary metal mixed oxide catalyst, namely xCuO-yZrO2-zCeO2Catalyst, x is the part of CuO, y is ZrO2Z is CeO2The number of parts of (A).
xCuO-yZrO2-zCeO2The catalyst is prepared from a metal precursor, a precipitator and a solvent according to a certain proportion. And designing the proportional relation among the metal precursor, the precipitator and the solvent according to the proportional relation among x, y and z. x: y: and z is 1:1: 1.
the metal precursor is nitrate of copper, zirconium and cerium, and the molar ratio of copper to zirconium to cerium is 1:1: 1; the precipitator is ammonia water; the solvent is water or methanol.
The specific surface area of the amorphous ternary metal mixed oxide catalyst is 150m2And/g, the pore structure is a microporous structure.
Example 2
A Cu-Zr-Ce amorphous ternary metal mixed oxide catalyst, namely xCuO-yZrO2-zCeO2Catalyst, x is the part of CuO, y is ZrO2Z is CeO2The number of parts of (A).
xCuO-yZrO2-zCeO2The catalyst is prepared from a metal precursor, a precipitator and a solvent according to a certain proportion. And designing the proportional relation among the metal precursor, the precipitator and the solvent according to the proportional relation among x, y and z. x: y: and z is 2: 5: 5.
the metal precursor is chloride of copper, zirconium and cerium; the precipitator is ammonia water; the solvent is water or ethanol.
The specific surface area of the amorphous ternary metal mixed oxide catalyst is 300m2And/g, the pore structure is a microporous structure.
Example 3
The Cu-Zr-Ce amorphous ternary metal mixed oxide catalyst is prepared by adopting a coprecipitation method, namely:xCuO-yZrO2-zCeO2catalyst, wherein x is the fraction of CuO and y is ZrO2Z is CeO2X, y and z are CuO and ZrO2、CeO2X, y, z is 1:1: 1. the method comprises the following specific steps:
s1: dissolving a metal precursor in a solvent;
s2: adding a precipitant to obtain a precipitate;
s3: aging the precipitate at room temperature, separating, and drying;
s4: roasting in air to obtain CuO-ZrO2-CeO2A catalyst.
In this embodiment, in S1, the metal precursor is a solution prepared from copper nitrate, zirconium nitrate, and cerium nitrate in a certain ratio; the solvent is a mixture of deionized water and methanol; in S2, the precipitant is ammonia water, and ammonia water solution is dripped into the precursor mixed solution according to the volume ratio of the precursor to the precipitant of 1:5 to generate corresponding precipitate; in S3, the aging time is 24 h; the separation is centrifugal separation; the drying temperature is 80 ℃; the drying time is 12 h; in S4, the roasting temperature is 450 ℃; the roasting time is 3 h.
CuO-ZrO prepared in this example2-CeO2The specific surface area of the catalyst was 150m2And/g, the pore structure is a microporous structure.
Example 4
The Cu-Zr-Ce amorphous ternary metal mixed oxide catalyst, namely xCuO-yZrO is prepared by adopting a coprecipitation method2-zCeO2Catalyst, wherein x is the fraction of CuO and y is ZrO2Z is CeO2X, y and z are CuO and ZrO2、CeO2X, y, z is 2: 5: 5.
the method comprises the following specific steps:
s1: dissolving a metal precursor in a solvent;
s2: adding a precipitant to obtain a precipitate;
s3: aging the precipitate at room temperature, separating, and drying;
s4: roasting in air to obtain 2CuO-5ZrO2-5CeO2A catalyst.
In this embodiment, in S1, the metal precursor is a solution prepared from copper nitrate, zirconium nitrate, and cerium nitrate in a certain ratio; the solvent is a mixture of deionized water and methanol; in S2, the precipitant is ammonia water, and ammonia water solution is dripped into the precursor mixed solution according to the volume ratio of 1:10 of the precursor to the precipitant to generate corresponding precipitate; in S3, the aging time is 48 h; the separation is centrifugal separation; the drying temperature is 120 ℃; the drying time is 24 h; in S4, the roasting temperature is 750 ℃; the roasting time is 6 h.
2CuO-5ZrO prepared in this example2-5CeO2The specific surface area of the catalyst was 300m2And/g, the pore structure is a microporous structure.
Example 5
The catalytic oxidation reaction of acetic acid with amorphous ternary metal mixed oxide catalyst includes the following steps:
s1: 1.0g of xCuO-yZrO with the grain diameter of 60-80 meshes2-zCeO2Filling particles of the catalyst into a constant-temperature area of the fixed bed reactor;
s2: introducing oxygen, introducing acetic acid liquid, wherein the pH value of the acetic acid solution is 7, and the liquid flow rate is 50 mL/h; the flow rate of oxygen is 200 mL/h; the COD equivalent of the acetic acid is 5000 mg/L;
s3: heating and reacting after the gas and the liquid pass through the catalytic bed area in a countercurrent way, wherein the reaction temperature is 230 ℃; the reaction pressure is 6 MPa;
s4: and (5) carrying out catalytic reaction for 5h, and quantitatively analyzing the content of the acetic acid by using a high performance liquid chromatography to obtain the conversion removal rate of the acetic acid.
According to the scheme, after the reaction is stable, the conversion rate of acetic acid reaches 95%, and the products are carbon dioxide and water. The acetic acid can obtain ideal conversion rate under the reaction conditions and the action of the catalyst, meanwhile, the product has high selectivity, no secondary pollution is generated, and no catalyst loss phenomenon is found in the reaction process, which indicates that the catalyst has good stability in the reaction process.
Example 6
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.
Example 7
A fixed bed reaction device shown in figure 1 is adopted for carrying out catalytic oxidation reaction of acetic acid, and a homogeneous Cu-Zr-Ce ternary non-noble metal catalyst is adopted, and the method comprises the following steps:
s1: 1.0g of xCuO-yZrO with the grain diameter of 60-80 meshes2-zCeO2Filling the particles of the catalyst into a reaction tube 6 of the fixed bed reactor to prepare a catalyst bed layer 7;
s2: introducing oxygen into the first air path pipeline, adjusting the first mass flow meter 1, and controlling the flow rate of the oxygen to be 200 mL/h; introducing inert gas into the second gas path pipeline, adjusting the second mass flow meter 2 and controlling the flow rate of the inert gas; adjusting a gas mixing pump 3, and controlling the mixing ratio of the oxygen and the inert gas;
s3: adding an acetic acid solution with the pH value of 7 into an acetic acid feeding storage tank 4, and controlling the flow rate of the acetic acid solution to be 50mL/h through a pump 5;
s4: the mixed gas and the acetic acid solution enter a reaction tube 6, enter a catalyst bed layer 8, and open a heating furnace 6 for heating reaction at the reaction temperature of 230 ℃;
s5: adjusting a back pressure valve 10, and controlling the reaction pressure to be 6 MPa;
s6: and (5) carrying out catalytic reaction for 5h, and quantitatively analyzing the content of the acetic acid by using a high performance liquid chromatography to obtain the conversion removal rate of the acetic acid.
According to the scheme, after the reaction is stable, the conversion rate of acetic acid reaches 95%, and the products are carbon dioxide and water. The acetic acid can obtain ideal conversion rate under the reaction conditions and the action of the catalyst, meanwhile, the product has high selectivity, no secondary pollution is generated, and no catalyst loss phenomenon is found in the reaction process, which indicates that the catalyst has good stability in the reaction process.
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 amorphous catalyst for catalytic oxidation of acetic acid is characterized by being a heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, and products of catalytic oxidation of acetic acid are carbon dioxide and water.
2. The acetic acid catalytic oxidation amorphous catalyst according to claim 1, wherein the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst is an amorphous ternary mixed metal oxide catalyst, and the amorphous ternary mixed metal oxide has a structural formula: xCuO-yZrO2-zCeO2Wherein, x: y: z ═ 1 to 2: (1-5): (1-5).
3. The amorphous catalyst for catalytic oxidation of acetic acid according to claim 2, wherein the amorphous ternary mixed metal oxide catalyst is obtained by coprecipitation of metal salt precursor salts.
4. The acetic acid catalytic oxidation amorphous catalyst according to claim 3, wherein the metal salt precursor salt is one or more of nitrate or chloride salts of copper, zirconium, cerium.
5. The amorphous catalyst for catalytic oxidation of acetic acid as claimed in claim 3, wherein in the coprecipitation of the metal salt precursor salt, the precipitant is ammonia water, and the solvent is one or more of water, methanol and ethanol.
6. The amorphous catalyst for catalytic oxidation of acetic acid according to any one of claims 1 to 5, wherein the specific surface area of the amorphous ternary metal mixed oxide catalyst is 80 to 300m2And/g, the pore structure is a microporous structure.
7. A process for preparing an acetic acid catalyzed oxidation amorphous catalyst as claimed in any of claims 1 to 6, comprising the steps of:
s1 preparation of CuO and ZrO2、CeO2Dissolving the metal salt precursor in a solvent according to a certain proportion to obtain a precursor mixed solution;
s2, dripping a precipitator into the precursor mixed solution according to the volume ratio of the metal salt precursor to the precipitator of 1: 5-1: 10 to generate a precipitate;
s3: aging the precipitate at room temperature for 24-48 h, and performing centrifugal separation;
s4: and roasting the solid obtained by centrifugal separation in air to obtain the amorphous ternary metal mixed oxide catalyst.
8. The method according to claim 7, wherein in the S3, the drying temperature is 80-120 ℃; the drying time is 12-24 h.
9. The method according to claim 7, wherein in the S4, the roasting temperature is 450-750 ℃; the roasting time is 3-6 h.
10. A process for the catalytic oxidation of acetic acid, wherein the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst according to any one of claims 1 to 6 is used, comprising the following steps:
s1: carrying out tabletting or granulation treatment on the heterogeneous Cu-Zr-Ce ternary non-noble metal catalyst, and placing the catalyst in a reaction vessel;
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.
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