KR20040110816A - Catalytic oxidation and adsorption agent for removing the odor and VOCs and its use - Google Patents

Abstract

PURPOSE: To provide a catalytic oxidation and adsorption agent capable of obtaining clean air by implanting ions of manganese, calcium and sodium into a synthetic zeolite with superior adsorptive and catalytic power, thereby forming a complex and improving strong oxidizing power, thereby completely removing malodor and volatile organic compounds, and a method for using the catalytic oxidation and adsorption agent. CONSTITUTION: The catalytic oxidation and adsorption agent for removing malodor and volatile organic compounds is characterized in that the catalytic oxidation and adsorption agent is prepared by supporting an inorganic oxidizer comprising 10,000 to 80,000 mg of potassium permanganate, 100 to 5,000 mg of sodium carbonate and 1,000 to 50,000 mg of sodium hypochlorite per 1 liter of water onto a synthetic zeolite, and the catalytic oxidation and adsorption agent is consisted of 96 to 99 wt.% of synthetic zeolite, 0.3 to 2.0 wt.% of potassium permanganate, 0.1 to 1.0 wt.% of sodium carbonate and 0.3 to 2.0 wt.% of sodium hypochlorite. The method for using the catalytic oxidation and adsorption agent for removing malodor and volatile organic compounds is characterized in that 0.368 to 1.102 kg of target gas is treated in 1 kg of the catalytic oxidation and adsorption agent for removing malodor and volatile organic compounds.

Description

Catalytic oxidation and adsorption agent for removing odors and volatile organic compounds and its use {Catalytic oxidation and adsorption agent for removing the odor and VOCs and its use}

The present invention relates to a catalytic oxidation and adsorption agent and a method of using the same to remove odors and volatile organic compounds (VOCs). Highly safe and easy to use for oxidative decomposition and decomposition of chemical gases, volatile organic compounds and odors generated from the storage and loading of products and volatile liquid substances, and the process emissions from synthetic organic compound manufacturing facilities. It is simple and relates to a catalytic oxidation and adsorbent that does not emit secondary pollutants and methods of use thereof.

Volatile organic compounds, ie VOCs, are petrochemical products with a vapor vapor pressure of more than 10.3 kilo Pascals (or 1.5 psia) in hydrocarbons. These are organic solvents and other substances that the Minister of Environment, in consultation with the head of the relevant central administrative agency. Substance (Article 39 (1) of the Enforcement Decree of the Atmospheric Environment Conservation Act) is defined as US EPA. "VOCs cause photochemical oxidation reactions with NOx by sunlight in the air, increasing the ozone concentration on the surface and causing smog. Organic compounds that cause this.

When looking at the characteristics of VOCs, there are a number of examples, but the representative substance itself is harmful to the human body (aromatic hydrocarbons: benzene, toluene, xylene, etc., halogen hydrocarbons: hydrocarbons containing Cl, F), and ozone generation near the surface Is contributing indirectly to global warming.

Exposure to high concentrations of VOCs causes acute disorders such as anesthesia (inhibition of the central nervous system), dizziness, paralysis and death. Specific toxicity of each substance is shown in Table 1 below, and ozone production is shown in Table 2 below.

matter Health disorder benzene Hematopoietic dysfunction (cytopenia, aplastic anemia), arrhythmia, carcinogenicity (leukemia) Halogenated hydrocarbons Hepatotoxicity, renal toxicity, cardiotoxicity (arrhythmia, sudden death), carcinogenicity in animals Methanol Blindness, metabolic acidosis Formaldehyde Allergic dermatitis, reduced lung function, carcinogenicity in animals Normal hexane Peripheral Nerve Disorder

Atmospheric Chemical Reactions of VOCs Remarks The most important role of VOCs in the atmosphere is the presence of NOx, which reacts with OH radicals and generates ozone, causing photochemical oxidants.VOC + 2NO + 2O ₂ → H ₂ O + 2NO ₂ + R 'C (O) R "NO ₂ + hv → NO + OO + O ₂ + M → O ₃ + M Thus, VOC + 3O ₂ → H ₂ O + O ₃ + R'C (O) R" VOCs present with NOx cause ozone

The modern society of Korea has been trying to improve national welfare and increase income since the rapid development of industry since 1980, but has emitted pollutants such as odors and VOCs from various raw materials and waste which are by-products of the industrial economy. In 1996, VOCs were released during the process of petroleum refining and petrochemical production at Yeocheon Petrochemical Complex, causing large complaints such as complaints of odor pollution from residents.In 1997, a large part of the causes of odor complaints in Sihwa area It is estimated to be due to emissions.

The treatment methods of these VOCs can be divided into the methods of recovering / reusing VOC materials and decomposing them. If the released VOCs are discharged at a relatively high concentration from a single outlet and are economical (ie, the cost of recovery is less than the cost of purchase), it is advisable to set up a recovery facility. Carbon adsorption, scrubbing and cryogenic condensation are recoverable technologies. If the recovery value of the VOCs is sufficient, the installation and operation of the recovery facility is efficient. However, if the VOCs are mixtures or hazardous substances rather than a single substance, or if there is no recovery value, it is preferable to install a decomposition facility rather than a recovery facility. , Thermal Oxidation, Catalytic Oxidation, Bio-Filtration, etc. are available techniques for the decomposition of VOCs and their characteristics can be summarized as shown in Table 3 below.

Control technology Capital cost Operating costs Use in the actual field Process flexibility Mass processing capacity Applicability to Low Contaminants Heat Incineration Absorption Absorption Livestock Filtration Catalyst Oxidation Photocatalytic Oxidation High and low High, medium, low, low 0000 × (0) ×× 00 ×× 000 000 ×××× 00000 ××

In addition, looking at the domestic prior patents related to the deodorant, Korean Registered Patent No. 332511 discloses a malodor treatment agent by mixing rice bran with yeast, adding zeolite, kneading and fermenting, and then mixing and drying iron sulfate. Patent No. 139559 discloses activated carbon fibers and nonwoven fabrics and a method of manufacturing the same. In addition, in Korean Patent Application No. 88-017920, the mordenite-based natural zeolite is heat treated at 200 to 350 ° C., followed by acid treatment with an aqueous hydrochloric acid solution of 0.8 N or less, followed by calcium ion exchange with an aqueous calcium chloride solution of 0.7 N or less. Disclosed is a method for producing a carbon dioxide adsorbent using a natural zeolite.

However, when looking at the disadvantages of the conventional odor and VOCs treatment method, since the odor removal efficiency is significantly lower, the initial construction cost is high, the secondary waste is generated, and the operating cost is also uneconomical, it is practically used in the field The value was significantly lower. In particular, in the case of a thermal incinerator, the operating cost is high due to the cost of auxiliary fuel, the gas flow rate is increased, so the residence time is shortened and incomplete combustion is not performed when the combustion gas is not well mixed, which is not suitable in the case of severe fluctuations in the flow rate. In addition, the increased gas flow rate lowers the combustion chamber temperature, lowering the treatment efficiency and is generally not cost effective for treating low concentration VOCs.

Catalytic incinerators also require less fuel and can be operated at lower temperatures. However, waste catalysts that require high initial costs, catalyst poisons and sometimes dust removal and non-recyclable waste must be treated as designated wastes. have.

If these incompletely installed or unprocessed odors and harmful gases spread around, they will return to us as environmental disasters that not only destroy the natural environment but also threaten humanity.

In general, when odor or VOCs are treated by adsorption, a carrier such as activated carbon or zeolite is used as an adsorbent. However, side effects such as waste generation due to secondary pollution are very low. Existing activated carbon has almost no resources in Korea, such as coconut shell charcoal, palm shell charcoal, lignite charcoal, charcoal and ash, anthracite charcoal and petroleum coke, and imports 100% raw materials to process or import finished products to activate activated carbon. Was prepared and produced (Smisek and cerny, 1970). Imports of such raw materials waste foreign currency and are not considered to be desirable to enhance national competitiveness. In addition, gas (water vapor, carbon dioxide, etc.) and pickling generated by oxidation of carbon in the temperature range of 800-1000 ° C during the manufacturing process Chemicals in the process (inorganic chemicals such as zinc chloride, phosphoric acid and sulfuric acid) cause device corrosion and secondary environmental pollution, and have disadvantages such as complexity of the manufacturing process. In addition, the ability to remove VOCs from activated carbon shows that the demand for high-performance non-flammable absorbents is rapidly increasing due to the tightening of regulations on refinery oil reformers and gasoline, and the regulation of formaldehyde and organic solvents in the paint and carpet manufacturing sectors. However, although there are some differences depending on the properties of the gas, as well as a low adsorption rate of 10 to 36%, the service life (use time) is very short, it was found to be economical.

Synthetic zeolites are receiving great attention. Japanese engineering firms in this area are developing VOCs capture devices using hydrophilic synthetic zeolites that are high in silica.

Belgian chemists have developed a method for removing nitrogen oxide (NOx) from tailpipe emissions of internal combustion engines that inject excess air using zeolite to reduce fuel consumption and reduce carbon dioxide emissions [Angew. Chem. Int. Ed., 39, 2934 (2000).

Prof. Ahn Seong-yu of the University of Osaka's Department of Engineering highly disperses the titanium oxide photocatalyst with molecular structure control in zeolites with many micropores to decompose nitrogen oxides (NOx) into harmless nitrogen and oxygen. Succeeded in doing. In addition, the photocatalytic reaction of titanium oxide proceeded only in ultraviolet light, but Professor Lee succeeded in developing the second generation titanium oxide photocatalyst in which photocatalytic reaction proceeds efficiently in visible light by ion implantation of chromium and vanadium into titanium oxide. It has achieved the result of linking zeolite to full-fledged application of photocatalysts, such as expression and high activation of new functions using zeolite as a catalyst carrier, and extending the range of use of light to visible light by ion implantation (Japan Chemical Industries, 12.12. 1998).

Therefore, the present invention is a catalytic oxidation and adsorbent that can remove the eight odors and volatile organic compounds (VOCs) at the same time, the technology of the composition consisting of the adsorption method by the media (media) currently used and inorganic oxidizing agent having a strong oxidizing power As a new material incorporating, the composition of adsorbent with high surface area and inorganic oxidizer with good oxidizing ability is reversibly bonded to the adsorbent to form a composite, and research on catalytic oxidation and adsorbent with strong oxidizing power and excellent adsorption power, It was able to develop catalytic oxidation and adsorbent with excellent ability to remove odors and VOCs, and can be directly applied to existing treatment systems, oxidatively decomposes odors and VOCs to harmless substances at high efficiency and low cost, and supports carriers (catalytic oxidation and adsorbents). Self-regeneration in the adsorption tower of the Excellent catalytic oxidation and adsorbents have been developed and the present invention has been completed based on this.

Accordingly, an object of the present invention is to reversibly combine manganese, calcium, and sodium with synthetic zeolites having excellent adsorption and catalytic ability to form a complex, and to enhance strong oxidizing power, thereby completely treating odors and VOCs. The present invention provides a catalytic oxidation and adsorbent for removing odors and VOCs to obtain clean air.

Another object of the present invention is to provide a method of using the catalytic oxidation and the adsorbent.

The catalytic oxidation and adsorbent of the present invention for achieving the above object is prepared by supporting an inorganic oxidizing agent containing 10,000 to 80,000 mg of potassium permanganate, 100 to 5,000 mg of sodium carbonate and 1,000 to 50,000 mg of sodium hypochlorite per liter of water on a synthetic zeolite. And 96 to 99% by weight of synthetic zeolite, 0.3 to 2.0% by weight of potassium permanganate, 0.1 to 1.0% by weight of sodium carbonate and 0.3 to 2.0% by weight of sodium hypochlorite.

In addition, the method of using the above-described catalytic oxidation and the adsorbent according to the present invention for achieving the above another object is characterized in that 0.368 to 1.102 kg of the target gas is treated with respect to 1 kg of the adsorbent.

Looking at the present invention in more detail as follows.

Zeolite is a silicate mineral of aluminum containing alkali metals such as sodium and potassium and alkaline earth metals such as calcium and containing crystal water. There are many kinds, but two types of clonotilolite and mordenite are widely distributed. There is. The study of zeolite synthesis, which was initiated by mineral scientists to interpret the conditions and environment of natural zeolites, was successfully conducted in the 1940s by a series of synthesis experiments focused on Union Carbide for industrial applications. It started in earnest from the beginning. The synthesis of zeolites is generally accomplished by hydrothermal synthesis in the temperature range below 200 ° C.

Depending on the nature of the starting materials, the zeolite synthesis method can be divided into (1) aluminosilicate gel (Aluminosilicate gel) as a raw material, and (2) natural silicate minerals. In general, the synthesis of the zeolite does not require a special pressure condition, the reaction proceeds at a low temperature to become a zeolite relatively easily.

Since zeolite's crystal water exists as a water molecule unlike ordinary structure water, it is called "non-water" and dehydration by heating does not destroy the structure, and the water molecule remains as a spongy structure or void. Adsorption of moisture or gas has a characteristic of returning to the original form, and its use has been broadened by using adsorption, moisture absorption, and cation exchangeability. In other words, the physical adsorption properties and chemical cation substitution are used to remove harmful constituents from exhaust gases such as automobiles, to purify wastewater in factories, to remove heavy metal ions from waste mines, to plating, to remove heavy metals from wastewater, and to decolorize wastewater in dyeing factories. It is being used gradually. It is also used as a desiccant for air or gas, desulfurizer for liquid propane or natural gas, adsorbent for fragrances, deodorant, hard water softener, etc., and is also used as a filler for making paper.

The chemical composition of the zeolite, which is an essential component of the present invention, is shown in Table 4, and the properties are shown in Table 5, and any product having such conditions and properties may be used as a product or a carrier, and the present invention In the zeolite of Gangseo Chemical was used.

division Chemical Composition by Composition SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO Na ₃ O LG Loss Surface area (m ² / g) compo (%) 65-70 10-14 1.5-3.0 0.6-1.5 1.0-1.5 - 5-8 220-300

Rule Ministry of Environment Notice No. 1998-124 ('99 .11.12) Standard, specification and labeling period of water treatment agent division standard result pH 5.0-12.0 10.3 Sieve residue over 90 fitness Hardness 80% or more fitness Base displacement capacity 130ml / 100g 153 arsenic Less than 2ppm 0 lead Less than 10ppm 0 Cadmium Less than 1ppm 0 Mercury 0.2ppm or less 0.0904

The catalytic oxidation and adsorbent according to the present invention is highly resistant to the above-described synthetic zeolite, and can support the removal of odors and VOCs by supporting inorganic oxides including potassium permanganate, sodium carbonate and sodium hypochlorite, which are excellent in deodorizing components. .

The inorganic oxide includes 10,000 to 80,000 mg of potassium permanganate, 100 to 5,000 mg of sodium carbonate and 1,000 to 50,000 mg of sodium hypochlorite per liter of water.

The catalytic oxidation and adsorbent according to the present invention obtained by supporting the inorganic oxide at room temperature in a synthetic zeolite, dehydrating and drying it, 96 to 99% by weight of synthetic zeolite, 0.3 to 2.0% by weight potassium permanganate, 0.1 to 1.0% by weight sodium carbonate and It consists of 0.3-2.0 weight% of sodium hypochlorite.

When the content of potassium permanganate having strong oxidizing power is less than 0.3% by weight in the inorganic oxidant supported on the synthetic zeolite, the oxidizing power is lowered, and when it is supported in excess of 2.0% by weight, further improvement in oxidizing power is inefficient. In addition, if the supporting content of the deodorizing function of sodium carbonate is less than 0.1% by weight, the deodorizing ability is lowered. If the supporting content of the sodium carbonate is more than 1.0% by weight, the surface area of the zeolite is lowered to lower the adsorption power of each inorganic oxidant, and the sodium hypochlorite having the decolorizing ability When the supported content of is less than 0.3% by weight, the decolorization ability is lowered. When the supported content of is lower than 2.0% by weight, the surface area of the zeolite is lowered, thereby lowering the adsorption power of each inorganic oxidant and failing to achieve adsorption balance.

Treatment of inorganic oxides at room temperature may induce disintegration at high temperatures, resulting in spongy or pore structures, as well as generation of particles when cooled and returning to room temperature, thereby reducing the surface area of the zeolite. Because it can act as a cause.

That is, looking at the manufacturing process of the catalyst oxidizing and adsorbent for removing odors and VOCs according to the present invention, 1) wearing of the synthesized zeolite (product inspection, based on Table 5), 2) preparation of inorganic oxidant composition, 3) by supporting Ion exchange injection, 4) dehydration and drying, 5) quality inspection, 6) packaging and shipping.

Rotation speed, temperature and time of the dehydration and drying step is not particularly limited, and can be carried out under ordinary conditions, the rotation speed of dehydration is 1000 ~ 3000rpm, drying temperature is 110 ~ 160 ℃, drying time is 4 ~ 6 It may be about an hour.

On the other hand, the throughput of the catalytic oxidation and the adsorbent to the target gas according to the present invention treats 0.368 to 1.102 kg of the target gas with respect to 1 kg of the adsorbent, preferably 0.486 to 0.687 kg of contaminants per kg of the adsorbent. However, the present invention is not limited thereto, and in a batch reaction system, the catalytic oxidation and the capacity of the adsorbent depend on the amount of ions injected into the zeolite, the amount of zeolite and the contact time between the target gas, and the like.

In addition, the catalytic oxidation and adsorbent for the removal of odors and VOCs of the present invention, the catalytic oxidation of the adsorption prevention facility to the source of storage of petroleum products and volatile liquid substances, the process discharge material of the synthetic organic chemical manufacturing facilities and paint manufacturing facilities, It can be used as an adsorbent.

Although the present invention will be described in more detail with reference to the following examples, the scope of the present invention is not limited thereto.

Example 1

The inorganic oxide dissolved by adding 70,000 mg of potassium permanganate, 5,000 mg of sodium carbonate and 30,000 mg of sodium hypochlorite per liter of water was supported on synthetic zeolite at room temperature, dehydrated at 2000 rpm and dried at 150 ° C. for 5 hours to obtain a catalytic oxidation and adsorbent. Got it. As a result of analyzing the obtained catalyst oxidation and adsorbent, 98% by weight of synthetic zeolite, 1% by weight of potassium permanganate, 0.3% by weight of sodium carbonate and 0.7% by weight of sodium hypochlorite were formed, and the results of the other components are shown in Table 6 below.

division Analysis Remarks Exterior Purple particulate Ministry of Environment Notice 99-173 pH 10.5 " Volume specific gravity (g / cc) 0.47 " Average particle diameter 4 * 8 " Base substitution capacity (130ml / 100g) 153 " Specific surface area (m ² / g) 320 Pore Analyzer (Gemini 2375 v5.00) Arsenic (ppm) 0 Ministry of Environment Notice 99-173 Lead (ppm) 0.01 " Cadmium (ppm) 0 " Mercury (ppm) 0.009 "

Example 2

Table 7 shows the results obtained by treating the VOCs of 0.046 kg with respect to 1 kg of the catalytic oxidation and adsorbent prepared in Example 1 to obtain the pollutant concentration removal efficiency for each VOC.

division Measurement item Test Items unit Ben Jen toluene Acetone ammonia Mercaptan Deodorization test Initial concentration ppm 100 100 100 100 100 1 minute ppm 0 0 0 0 0 5 minutes ppm 0 0 0 0 0 24 hours ppm 0 0 0 0 0 Removal rate (%) 100 100 100 100 100

Example 3 and Comparative Example 1

As shown in Table 8 below, 0.046kg of VOCs was treated with respect to 1kg of the catalytic oxidation and adsorbent prepared in Example 1, and the pollutants were treated with existing activated carbon (Comparative Example 1) to obtain the pollutant concentration removal efficiency for each VOCs. The results are shown in Table 9 below.

Contaminant Types Initial concentration (ppm) Pain and speed Remarks Benzene (benzene) 200 ppm 1 L / min Inspection method: detector tube (GASTEC)-gas after passage is analyzed by detector tube Toluene (toluene) 300 ppm " Acetone) 450 ppm " NH ₃ (ammonia) 500 ppm " CH ₃ SH (mercaptan) 60 ppm "

division Comparative Example 1 Example 3 Remarks Concentration after treatment Processing efficiency Concentration after treatment Processing efficiency Benzene 140 ppm 30% 0 ppm 100% -After 30 seconds, the activated carbon treatment efficiency: 10-36%-Catalytic oxidation and adsorbent treatment efficiency: 100%-After 5 minutes of measurement, the performance of activated carbon deteriorated drastically, but the catalytic oxidation adsorbent did not change. None. Toluene 210 ppm 30% 0 ppm 100% Acetone 290 ppm 36% 0 ppm 100% NH ₃ 450 ppm 10% 0 ppm 100% CH ₃ SH 50 ppm 17% 0 ppm 100%

Example 4

As shown in Table 8, 0.046kg of VOCs were treated with respect to 1kg of the catalytic oxidation and adsorbent prepared in Example 1, and the pollutants were treated with the existing synthetic zeolite (Comparative Example 2) to obtain the pollutant concentration removal efficiency for each VOCs. The results are compared and shown in Table 10 below.

division Comparative Example 2 Example 4 Remarks Concentration after treatment Processing efficiency Concentration after treatment Processing efficiency Benzene 165 ppm 18% 0 ppm 100% -After 30 seconds after the passage of gas-Activated carbon treatment efficiency: 9-20%-Catalytic oxidation and adsorbent Treatment efficiency: 100%-After 5 minutes of measurement The performance of the zeolite dropped sharply, but the catalytic oxidation adsorbent of the present invention Was unchanged. Toluene 250 ppm 17% 0 ppm 100% Acetone 420 ppm 9% 0 ppm 100% NH ₃ 420 ppm 16% 0 ppm 100% CH ₃ SH 48 ppm 20% 0 ppm 100%

Example 5

The catalytic oxidation and adsorbent prepared in Example 1 was mounted on an existing activated carbon adsorption tower to measure the removal efficiency of each S-hour in the field of the petrochemical complex located in Ulsan Metropolitan City by time zone at the site. Indicated.

division Measuring time Before passing adsorption tower After passing through adsorption tower efficiency(%) toluene 2 hours after replacement 4 hours after 700ppm300ppm60ppm 0.6ppm00 99.9100100 Acetone 2 hours after replacement 4 hours after 190ppm250ppm420ppm 000 100100100

As can be seen through the above examples and comparative examples, the catalytic oxidation and adsorbent according to the present invention has a strong oxidizing power and adsorptive power to obtain clean air by almost completely treating odors as well as VOCs.

Claims (2)

Prepared by supporting an inorganic oxidizing agent containing 10,000 to 80,000 mg of potassium permanganate, 100 to 5,000 mg of sodium carbonate and 1,000 to 50,000 mg of sodium hypochlorite per liter of water in a synthetic zeolite, 96 to 99% by weight of synthetic zeolite and 0.3 to 2.0 of potassium permanganate A catalytic oxidation and adsorbent for removing odors and volatile organic compounds, characterized by consisting of weight percent, sodium carbonate 0.1 to 1.0 weight percent and sodium hypochlorite 0.3 to 2.0 weight percent. A method of using a catalytic oxidation and adsorbent for removing odors and volatile organic compounds by treating 0.368 to 1.102 kg of the target gas with respect to 1 kg of the catalytic oxidation and adsorbent for removing malodors and volatile organic compounds according to claim 1.