WO2016041380A1

WO2016041380A1 - Supported catalyst suitable for purifying air at normal temperature

Info

Publication number: WO2016041380A1
Application number: PCT/CN2015/080483
Authority: WO
Inventors: 许钧强; 康伦国; 姚东生
Original assignee: 合众（佛山）化工有限公司
Priority date: 2014-09-19
Filing date: 2015-06-01
Publication date: 2016-03-24
Also published as: CN105478134A; CN105478134B

Abstract

The present invention relates to a supported catalyst suitable for purifying air at normal temperature, comprising copper, cerium and manganese as active ingredients with nano-attapulgite or a nano-sepiolite powder as a carrier wherein the content of copper, cerium and manganese accounts for 15%-40% of the total mass and the molar ratio thereof is 1 : 1 : 1 - 1 : 2 : 4; the raw materials are ultrasonically dispersed for 1 h, stirred for 2 h-4 h under the conditions of 30°C-50°C, dried at 110°C-120°C for 5 h-10 h for activation, calcined in a muffle furnace at 500°C-800°C for 3 h-6 h and then ground to a fineness of not more than 20 μ; the supported catalyst prepared in the present invention has strong adsorption capacity, can remove benzene, toluene, xylene, formaldehyde, CO, NO, SO₂ and other harmful gases in air continuously and efficiently, has a high processing efficiency, low costs, wide economic applicability and does not produce secondary pollution, and is suitable for removing pollutants in houses, offices, hotels, meeting rooms, furniture stores, building material markets and other spaces.

Description

Applicable supported catalyst for purifying air at normal temperature

Technical field

The invention relates to a preparation method of a supported catalyst for purifying air, in particular to a suitable supported catalyst for purifying air at a normal temperature, and belongs to the technical field of catalysts.

Background technique

Most of the life of a person lives and works indoors. The environmental pollution caused by indoor decoration has caused people's illness, disability, and death. It has become a social problem. Indoor environmental pollution has been listed as one of the "Top Ten Killers". Gas has a great impact on the human body, and it is easy to cause respiratory diseases, cancer, leukemia, and neurological diseases, especially for pregnant women, children, and the elderly.

Usually, people are used to ventilating for two months after renovation and then staying. However, indoor decoration pollution is mainly chemical pollutants such as formaldehyde, benzene, ammonia, etc. The release period of such pollutants is up to 15 years, and it is not a problem of two months to solve the problem. In the enclosed room of summer air conditioning and cold winter heating, Due to the lack of outdoor fresh air, the damage is even more serious! When you are in a newly renovated new home or new office, hotel, conference room, furniture mall, building materials market, etc., do you have headaches, dazzling, cough, chest tightness, nausea, vomiting, etc. Indoor invisible killer caused by air pollutants. The main pollution of indoor air comes from materials such as construction, decoration and furniture, including formaldehyde, benzene and ammonia. Among them, formaldehyde pollution is the most harmful to human health.

At present, the methods for purifying air on the market are as follows: 1. Bamboo charcoal and activated carbon adsorption method, but the adsorption capacity of bamboo charcoal and activated carbon is very limited, only has some effects on benzene, the adsorption effect on formaldehyde is not good, and there is a problem of absorption saturation. When the temperature is low, the absorption amount is relatively large, and the temperature rise is released again.

2, formaldehyde scavenger or formaldehyde lyase, these are chemical methods to "remove" formaldehyde, the essence of this method is to reduce the target substance to reduce toxicity or conversion to non-toxic substances, formaldehyde can be oxygen The formation of formic acid can also be reduced to methanol. The toxicity of these two substances still exists, which is easy to cause secondary pollution, and it is impossible to "spray forever".

3, photocatalyst method, but the photocatalyst should play a role, there must be ultraviolet light to stimulate, no effect at night and no visible light. In addition, the particles of the photocatalyst are very small and easily suspended in the air. It is like dust and cannot be seen with the naked eye. Even if it is inhaled, it is not noticeable, and it is easy to cause secondary pollution, which is likely to cause damage to the human lungs. There are also photocatalysts that have the property of decomposing organic substances, which can damage any organism such as leather products, hair grass and high-grade clothing and skin. However, photocatalyst manufacturers do not mention it, do not inform consumers, and even mislead consumers of photocatalysts as long as they have Light is good, and such behavior should be blamed. In fact, photocatalysts have a limited effect on removing polluting gases from the air, so they are rarely used in developed countries as civilian photocatalytic materials.

4. The plasma technology method is to generate a large amount of plasma to oxidize formaldehyde in the air to achieve the purpose of purifying air. This method is easy to generate ozone to cause secondary pollution to the air, and the device is complicated and consumes a large amount of energy; the conventional thermal catalytic oxidation method It is the use of a catalyst to catalyze the oxidation of formaldehyde under the action of thermal energy. However, this method generally requires a higher temperature.

Supported catalysts for removing formaldehyde under normal temperature conditions have received extensive attention in recent years, but currently, room temperature-supported formaldehyde-removing catalysts contain precious metals such as gold, palladium, rhodium, iridium, and platinum. Due to the scarcity of precious metal resources, the price is expensive, which limits The promotion and application of formaldehyde removal by room temperature catalytic oxidation, such as patents CN100360224C, CN102284288B, CN103894194A contain precious metals. Patent CN103599793A, CN103433054A, CN101274281B although excluding precious metals, but only in the air VOC _S formaldehyde removal, and in addition to air VOC _S-trityl there formaldehyde, ammonia, carbon monoxide, nitric oxide, sulfur dioxide and other pollutants Therefore, it is very important to develop an economical catalyst that can effectively remove harmful substances in the air at normal temperature.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide an economical applicability and a supported composite catalyst capable of removing formaldehyde, triphenyl, CO, NO, and SO ₂ in air VOC _S under normal temperature conditions.

In view of the above technical problems, the composite catalyst carrier of the present invention is prepared by purifying nano attapulgite or nano-sorbitite powder and supporting manganese, copper and cerium oxide.

Nano attapulgite and nano-sorbitite powder are porous mineral crystal materials, and their microstructure has a unique crystal regular structure. There are a large number of nano-scale pores in the crystal, the pore size is 2.7-9.8 angstroms, and the surface of the micropores is polar. Due to its nanometer pore size, it can selectively adsorb toxic substances such as benzene, xylene, formaldehyde, carbon monoxide, sulfur dioxide and ammonia in the nanometer molecular diameter (formaldehyde, ammonia, benzene, toluene and xylene have molecular diameters of 0.4 to 0.62). Between nanometers, and these compounds are polar molecules, which are nano-scale polar compounds), so nano-attapulgite and nano-sepiolite powder pores have superior adsorption and sustainable functions.

Manganese-copper composite oxide can effectively treat harmful gases in the air such as formaldehyde, triphenyl, carbon monoxide, nitrogen monoxide and sulfur dioxide. Rare earth cerium oxide has redox characteristics, oxygen storage and synergistic catalysis, and can effectively increase manganese at normal temperature. The catalytic activity of the copper composite oxide can also improve the stability and anti-poisoning ability of the catalyst; the supported catalyst prepared by loading the manganese attapulgite composite oxide with nano attapulgite or nano sepiolite powder, and having a super-normal temperature at room temperature Strong adsorption capacity, can enrich a small amount of harmful gases in the air, and can effectively remove harmful gases in the air through synergistic catalytic oxidation of manganese-copper bismuth; and high treatment efficiency, low cost, wide economic applicability, no production Secondary pollution.

In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions: The present invention relates to a suitable load-type catalyst for purifying air at normal temperature, characterized in that copper, cerium and manganese are active components, and the carrier is a nano attapulgite rod. Soil or nano-porphyry powder, wherein the content of copper, barium and manganese is 15% to 40% of the total mass, and the molar ratio is 1:1:1 to 1:2:4.

The invention provides a preparation method of a suitable load-type catalyst for purifying air at normal temperature, and the preparation process is as follows: adding nano attapulgite or nano sepiolite powder to ethanol, deionized water, and adding nanometer cerium oxide by stirring under agitation. Ultrasonic dispersion for 1h, the nanosuspension was prepared, and then an aqueous solution of copper nitrate and manganese nitrate was added according to the formula molar ratio, and stirred at 30 to 50 ° C for 2 to 4 hours, the solution was removed, and dried at 110 to 120 ° C for 5 to 10 hours. After calcination at 500 to 800 ° C for 3 to 6 hours in a muffle furnace, the fineness is milled to 20 μ or less.

The applicable load-type catalyst for purifying air at normal temperature prepared by the invention has superior adsorption capacity, and can continuously and effectively remove triphenyl, formaldehyde, ketone, ammonia and carbon monoxide which are volatilized from the decoration materials used in the interior decoration process. Nitrogen oxide, sulfur dioxide and other harmful gases, high processing efficiency, low cost, wide economic applicability, no secondary pollution, suitable for home, office, hotel, conference room, furniture shopping mall, building materials market and other space pollutants Removal.

detailed description

Example 1:

70 g of nano attapulgite was weighed into 200 ml of ethanol-water solution, 7 g of nano-cerium oxide was added under stirring, and ultrasonic dispersion was carried out for 1 h to prepare a nano-attapulgite/cerium oxide suspension, and a 50% copper nitrate aqueous solution of 7.5 g and 50% nitric acid was added. 40 g of manganese aqueous solution was stirred at 40 to 50 ° C for 2 h, the solution was removed, dried at 110 ° C for 6 h, and calcined in a muffle furnace at 600 for 4 h, and then ground to a fineness of 20 μ to prepare a supported catalyst. The amount is 30%, and the molar ratio of copper, bismuth and manganese is 1:2:4.

Example 2:

Weigh 85g nano-boehmite powder into 200ml ethanol-water solution, add 6g nano-cerium oxide under stirring, and disperse ultrasonically for 1h to prepare nano-sepiolite powder/cerium oxide suspension, add 50% copper nitrate aqueous solution 6g and 50% manganese nitrate. 25 g of an aqueous solution was stirred at 40 to 50 ° C for 3 hours to remove the solution. After drying and activating at 120 ° C for 6 h, it was calcined in a muffle furnace at 700 for 4 h and then ground to a fineness of 20 μ to prepare a supported catalyst with a loading of 20% and a molar ratio of copper, ruthenium and manganese of 1:2: 3.

Example 3:

Weigh 75g of nano attapulgite into 200ml ethanol-water solution, add 6.5g nano-cerium oxide under stirring, and disperse ultrasonically for 1h to prepare nano attapulgite/cerium oxide suspension, add 50% copper nitrate aqueous solution 14g and 50% nitric acid. 37.6 g of an aqueous manganese solution was stirred at 40 to 50 ° C for 2 h, the solution was removed, dried at 110 ° C for 6 h, and calcined in a muffle furnace at 700 for 4 h, and then ground to a fineness of 20 μ to prepare a supported catalyst. The loading was 30%, and the molar ratio of copper, bismuth and manganese was 1:1:1.

Example 4:

Catalyst performance test: The supported catalyst prepared in the example of the present invention was placed in a fixed bed reactor under the following conditions: gas composition: oxygen 20%, nitrogen 80%, formaldehyde gas, benzene gas respectively from formaldehyde gas generator, benzene The gas generator is generated and blown into the reaction system by nitrogen gas to control the concentration of formaldehyde gas to be 0.05% and the concentration of benzene gas to be 0.1%. After reacting at 25 ° C for 48 hours, according to the first method in GB/T18204.26-2000: The content of formaldehyde was measured by phenol reagent spectrophotometry, and the content of benzene was tested according to the provisions of Appendix B of GB/T18883-2002. The test results of catalytic performance, benzene removal rate, and removal effect durability of the three examples are shown in Table 1.

Table 1: Three Examples Catalytic Performance Test Results

项目project	实例1Example 1	实例2Example 2	实例3Example 3
项目project	实例1Example 1	实例2Example 2	实例3Example 3	甲醛去除率Formaldehyde removal rate	95.6％95.6%	92.5％92.5%	94.6％94.6%
甲醛去除效果持久性Formaldehyde removal effect persistence	76.4％76.4%	73.8％73.8%	75.2％75.2%	甲醛去除率Formaldehyde removal rate	95.6％95.6%	92.5％92.5%	94.6％94.6%
甲醛去除效果持久性Formaldehyde removal effect persistence	76.4％76.4%	73.8％73.8%	75.2％75.2%	苯去除率Benzene removal rate	97.5％97.5%	96.2％96.2%	95.6％95.6%
苯去除效果持久性Benzene removal effect persistence	77.5％77.5%	73.6％73.6%	74.8％74.8%	苯去除率Benzene removal rate	97.5％97.5%	96.2％96.2%	95.6％95.6%

Example 5:

Catalyst performance test: The supported catalyst prepared in the example of the present invention was placed in a fixed bed reactor under the following conditions: a gas sampler was used to take the automobile exhaust gas, a dryer was used to remove the moisture in the exhaust gas, and the CO in the exhaust gas was tested. The content of NO and SO ₂ was further injected into the reaction system by nitrogen gas, and after reacting at 25 ° C for 48 hours, the contents of CO, NO and SO ₂ were tested according to standard methods. The catalytic performance CO emission rate, NO removal rate, and SO ₂ removal rate test results of the three examples are shown in Table 2.

Table 2: Three examples to remove car exhaust performance test results

项目project	实例1Example 1	实例2Example 2	实例3Example 3
项目project	实例1Example 1	实例2Example 2	实例3Example 3	CO去除率CO removal rate	82.5％82.5%	80.6％80.6%	81.2％81.2%
NO去除率NO removal rate	78.4％78.4%	72.6％72.6%	75.3％75.3%	CO去除率CO removal rate	82.5％82.5%	80.6％80.6%	81.2％81.2%
NO去除率NO removal rate	78.4％78.4%	72.6％72.6%	75.3％75.3%	SO₂去除率SO ₂ removal rate	87.2％87.2%	86.5％86.5%	85.4％85.4%

While the invention has been described in detail and shown by the embodiments of the claims .

Claims

A suitable supported catalyst for purifying air at normal temperature, characterized in that copper, cerium and manganese are active components, and the carrier is nano attapulgite or nano-sorbitite powder, wherein the content of copper, strontium and manganese accounts for the total mass. 15% to 40%, the molar ratio is 1:1:1 to 1:2:4.
The method for preparing a suitable supported catalyst for purifying air at a normal temperature according to claim 1, wherein the preparation method comprises: adding nano attapulgite or nano-sorbitite powder to ethanol and deionized water. After stirring, the nanometer cerium oxide is added by stirring, and the nano-suspension is prepared by ultrasonic wave dispersion for 1 hour, and then an aqueous solution of copper nitrate and manganese nitrate is added according to the formula molar ratio, and stirred at 30 to 50 ° C for 2 to 4 hours to remove the solution. It is dried and activated at 110 to 120 ° C for 5 to 10 hours, and calcined at 500 to 800 ° C for 3 to 6 hours in a muffle furnace, and then the fineness is 20 μ or less.