CN105457647B - Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof - Google Patents

Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof Download PDF

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CN105457647B
CN105457647B CN201510910721.0A CN201510910721A CN105457647B CN 105457647 B CN105457647 B CN 105457647B CN 201510910721 A CN201510910721 A CN 201510910721A CN 105457647 B CN105457647 B CN 105457647B
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coo
citric acid
circulating gas
nitrate
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CN105457647A (en
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徐华龙
沈伟
秦枫
孙文杰
尹国平
邓支华
汪林涛
付义发
周拥军
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Hubei Hongyuan Pharmaceutical Technology Co ltd
Fudan University
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    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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    • 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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Abstract

The invention belongs to the technical field of chemical catalysts, and particularly relates to ABO3La type nano perovskite catalyst1‑XBiXCoO3And a preparation method and application thereof. Mixing lanthanum nitrate, cobalt nitrate and bismuth nitrate with sucrose and citric acid, adjusting the solution to be neutral to form gel, and then carrying out heat treatment under nitrogen atmosphere to obtain the nano La1‑ XBiXCoO3A perovskite type catalyst. The catalyst prepared by the invention has good activity and stability, can be used for circulating gas purification in a process for producing glyoxal by oxidizing ethylene glycol air, and particularly can efficiently oxidize organic matters in the circulating gas under the working condition that the glyoxal is produced by oxidizing ethylene glycol air so as to achieve the purpose of purifying the circulating gas.

Description

Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to a nano perovskite type catalyst La1-XBiXCoO3And a preparation method and application thereof.
Background
The main stream production method is to adopt an adiabatic bed reactor, the ethylene glycol and air carry out the partial oxidation reaction of the ethylene glycol at the temperature of 400-. The reaction of partial oxidation of glycol to glyoxal is a strong exothermic reaction, and in order to maintain a stable reaction temperature, part of nitrogen in the product gas after the reaction is circulated in the system as heat transfer gas, so that circulating gas is always circulated in the reaction system during the reaction. When glycol is subjected to air oxidation reaction, besides glyoxal, byproducts such as formaldehyde, acetaldehyde, glycolaldehyde, formic acid, acetic acid and the like can be generated, and volatile organic compounds in circulating gas seriously affect the quality of glyoxal products on one hand and cause the discharge of waste water and waste gas on the other hand, thereby bringing great pressure to environmental protection. The existing reaction system washes the circulating gas by a water washing tower, but the effect is very limited, and if organic matters in the circulating gas can be removed, the improvement of the product quality and the environmental friendliness of production can be facilitated.
The circulating gas for producing glyoxal by air oxidation of ethylene glycol contains about 6% of oxygen, the content of volatile organic compounds is hundreds of ppm, and the best method is to directly remove the volatile organic compounds such as formaldehyde in the circulating gas by catalytic combustion reaction. However, since the recycle gas is circulated in the reactor, the purification of the recycle gas cannot affect the main reaction, i.e. the temperature of the recycle gas cannot be changed and the oxygen content cannot be increased, which puts extremely high requirements on the catalyst. The circulating gas for producing the glyoxal by the air oxidation of the glycol contains a large amount of saturated water vapor, the oxygen content in the circulating gas is low, and a common catalyst for the catalytic combustion of volatile organic compounds has almost no activity under the working condition.
Chinese patent ZL201010564984.8 reports that La prepared by citric acid combustion method1-XBiXCoO3Perovskite structure catalystAnd high activity is shown in catalyzing the complete oxidation reaction of the methanol. In the catalyst, a certain amount of lanthanum nitrate, cobalt nitrate and bismuth nitrate are dissolved by a dilute nitric acid solution, and then the ratio of metal ions to citric acid is 1: 1.1 addition of citric acid, after complete dissolution at 700C, ventilation drying, then 600-700 in a muffle furnace0And C, roasting to obtain the catalyst. The catalyst crystal grain obtained by high-temperature roasting is micron-sized, has high activity only under higher oxygen concentration, and is suitable for removing volatile organic compounds in the air. In the case of the recycle gas of the glyoxal production process, which has an oxygen content of only about 6%, the catalyst disclosed in this patent is difficult to remove volatile organic compounds therefrom, and it is required to develop a catalyst having high activity at a low oxygen content.
Disclosure of Invention
The invention aims to provide a nano perovskite type catalyst La capable of efficiently removing volatile organic compounds under low oxygen content1-XBiXCoO3And the preparation method thereof are applied to the catalytic purification of the circulating gas in the process of producing the glyoxal by oxidizing the ethylene glycol air.
The invention provides a nano perovskite type catalyst La1-XBiXCoO3The preparation method comprises the following specific steps:
(1) according to La1-XBiXCoO3Value of X in (1), 0.05<X<0.3, weighing lanthanum nitrate, cobalt nitrate, bismuth nitrate and concentrated nitric acid according to the proportion, dissolving the mixture in deionized water to prepare a nitrate solution, wherein the molar ratio of the nitric acid to the metal ions to the water is (1-2) to (2-4) to 70; weighing citric acid and sucrose, dissolving in deionized water to prepare a citric acid solution, wherein the molar ratio of the sucrose to the citric acid to the water is (1-2): (4-8): 40;
(2) heating a nitrate solution to 70-80 ℃, dropwise adding a citric acid solution under stirring at the temperature, wherein the molar ratio of the added citric acid to the metal ions is 1: 1-1: 2; fully and uniformly mixing the nitrate solution and the citric acid solution, and adjusting the pH of the solution to 7 by using concentrated ammonia water; keeping the mixture at the temperature of 75-80 ℃ for 2-3 hours to obtain gel;
(3) coagulating the obtained productDrying the gel at 90-100 ℃ to form dry gel, and then treating for 0.5-1 hour at 350-400 ℃ in nitrogen atmosphere to obtain the nano perovskite catalyst La1-XBiXCoO3。
In the preparation method, lanthanum element and bismuth element form perovskite ABO3The A site in the structure and the cobalt element form the B site: wherein 0.05<X<0.3. The sum of lanthanum and bismuth and the molar weight ratio of cobalt to oxygen in the catalyst are 1:1: 3.
in the preparation method, the cane sugar is carbonized firstly and then is further oxidized into carbon dioxide in the citric acid combustion process, and the process can stabilize La1-XBiXCoO3The nanostructure of (1).
In the sol-gel method used in the invention, citric acid is a fuel in the process of calcining xerogel and serves as a reducing agent, nitrate serves as an oxidizing agent, when the content of nitrate is lower, citric acid is not completely combusted, the emitted heat is less, the heat required by crystal growth cannot be reached, the product is in an amorphous state, and meanwhile, the insufficient amount of nitrate causes sucrose to become carbon residue, which affects the purity and performance of the product. Too large a nitrate amount causes too rapid combustion and produces too large grains. The metal ions, the citric acid, the nitric acid and the cane sugar have proper burning rate when the proportion is proper, so that the nano-crystal is obtained.
In the preparation method, the dried xerogel is treated for 0.5 to 1 hour at 350 to 400 ℃ in nitrogen atmosphere, and under the condition, the citric acid and the cane sugar can be burnt out to obtain the nano-grade perovskite catalyst La1-XBiXCoO3。
The catalyst prepared by the method can be used for circulating gas purification in a process of producing glyoxal by oxidizing ethylene glycol air, and specifically, volatile organic compounds such as formaldehyde in the circulating gas are subjected to catalytic combustion reaction on the catalyst by directly utilizing oxygen in the circulating gas, so that the purpose of circulating gas purification is achieved, a catalytic bed is not required to be additionally heated or air is not required to be added, and the method is very economical and environment-friendly.
Detailed Description
The invention is further illustrated by the following examples:
the catalytic combustion reactor for purifying the circulating gas is arranged in a circulating gas circuit for producing the glyoxal, and the installation position of the reactor is before the circulating gas and the glycol raw material are mixed. The circulating gas purification catalyst is filled in the reactor, the temperature of the circulating gas is 300-350 ℃, and the air speed of the circulating gas is 1000h-1. The performance of the catalyst is expressed by the conversion rate of complete oxidation of organic matters in the circulating gas, and when the conversion rate reaches 100%, all the organic matters in the circulating gas are oxidized into carbon dioxide.
Nano perovskite type catalyst La1-XBiXCoO3The preparation method comprises the following specific steps:
(1) according to La1-XBiXCoO3Wherein the X value (X is 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30) is proportionally determined by dissolving a certain amount of lanthanum nitrate, cobalt nitrate and bismuth nitrate and a certain amount of concentrated nitric acid in a certain amount of deionized water to prepare a nitrate solution, wherein the molar ratio of the nitric acid to the metal ions to the water is 1:2: 70. Dissolving a certain amount of citric acid and sucrose in deionized water to prepare a citric acid solution, wherein the molar ratio of the citric acid to the sucrose is 1:4: 40;
(2) the nitrate solution was heated to 80 ℃ and the citric acid solution was added dropwise with stirring at this temperature, the molar ratio of the amount of citric acid added to the metal ions being 1: 2. The nitrate solution and the citric acid solution are fully and evenly mixed, and then the pH value of the solution is adjusted to 7 by using concentrated ammonia water. Maintaining at 80 deg.C for about 2 hours to obtain gel;
(3) drying the obtained gel at 100 ℃ to obtain dry gel, and then treating the gel for 0.5 hour at 350 ℃ in nitrogen atmosphere to respectively obtain the nano perovskite catalyst La0.95Bi0.05CoO3(catalyst A), La0.9Bi0.1CoO3(catalyst B)，La0.85Bi0.15CoO3(catalyst C), La0.8Bi0.2CoO3(catalyst D), La0.75Bi0.25CoO3(catalyst E) and La0.7Bi0.3CoO3(catalyst)F）。
The catalytic performance of catalysts A-F for the purification of recycle gas in the process of ethylene glycol air oxidation to glyoxal is shown in Table 1.
TABLE 1 reactivity of the catalysts
Figure DEST_PATH_IMAGE002
。

Claims (4)

1. Nano perovskite type catalyst La1-XBiXCoO3The preparation method is characterized by comprising the following specific steps:
(1) according to La1-XBiXCoO3Value of X in (1), 0.05<X<0.3, weighing lanthanum nitrate, cobalt nitrate, bismuth nitrate and concentrated nitric acid according to the proportion, dissolving the mixture in deionized water to prepare a nitrate solution, wherein the molar ratio of the nitric acid to the metal ions to the water is 1-2: 2-4: 70; weighing citric acid and sucrose, dissolving in deionized water to prepare a citric acid solution, wherein the molar ratio of the citric acid to the sucrose is 1-2: 4-8: 40;
(2) heating a nitrate solution to 70-80 ℃, dropwise adding a citric acid solution under stirring at the temperature, wherein the molar ratio of the added citric acid to the metal ions is 1: 1-1: 2; fully and uniformly mixing the nitrate solution and the citric acid solution, and adjusting the pH of the solution to 7 by using concentrated ammonia water; keeping the mixture at the temperature of 75-80 ℃ for 2-3 hours to obtain gel;
(3) drying the obtained gel at 90-100 ℃ to obtain dry gel, and then treating the dry gel for 0.5-1 hour at 350-400 ℃ in nitrogen atmosphere to obtain the nano perovskite catalyst La1-XBiXCoO3。
2. The method according to claim 1, wherein the molar ratio of the sum of lanthanum and bismuth to the molar amount of cobalt and oxygen in the catalyst is 1:1: 3.
3. La as a nano perovskite type catalyst obtained by the production method as set forth in any one of claims 1 to 21-XBiXCoO3。
4. The nano perovskite catalyst La of claim 31-XBiXCoO3The method is applied to the purification of the circulating gas in the process of producing the glyoxal by oxidizing the ethylene glycol air, and is characterized in that the oxygen in the circulating gas is used for carrying out catalytic combustion reaction on the formaldehyde in the circulating gas on a catalyst, so that the circulating gas is purified.
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CN105907033B (en) * 2016-06-22 2018-07-17 广西利升石业有限公司 A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide
CN111054352B (en) * 2018-10-16 2022-07-12 中国石油化工股份有限公司 Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof
CN111054355B (en) * 2018-10-16 2022-10-11 中国石油化工股份有限公司 Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas
CN111054368B (en) * 2018-10-16 2022-07-12 中国石油化工股份有限公司 Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application
CN114345124B (en) * 2022-01-14 2023-11-03 广东九田环保科技有限公司 Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof
CN116082130B (en) * 2023-02-03 2024-03-29 杭州富阳永星化工有限公司 Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver

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