TW200904513A - Gas cleaning method for organic compound with low concentration - Google Patents

Abstract

A gas cleaning method to treat the low concentration organic compounds, specially for odor compounds such as dimethyl-sulfur (DMS), dimethyl-di-sulfur(DMDS), hydrogen sulfide (H2S), formaldehyde, acetic acid, isopropyl alcohol and acetone. It comprises: at least a catalyst adsorption unit deposited in parallel or in series; and/or an ozone generator, which supplies ozone to the catalyst adsorption unit and enhances the adsorption effect of the catalyst, oxidoreduction reaction at a low temperature or decomposition reaction to covert to something harmless or processable. By the method, the catalyst adsorption part is with better effect and longer service life.

Description

200904513 IX. Description of the invention: [Technical field to which the invention pertains] The present invention discloses a method for purifying ___, especially for a material pair comprising _ = for example, dimercaptosulfur (DMS), dimercapto And. Materials. Methods for the purification of sulphur (DMDs), hydrogen sulfide (H2S) sulphide and W, acetic acid, (tetra) alcohol, (iv) and other malodorous compounds. The invention is mainly used for increasing, media efficiency, and prolonging the touch.

Medium life and suitable for purification and treatment of high air volume and low concentration (4) (4) H panel manufacturing and other clean room air purification or purification of exhaust gas: At the same time, the same as the appropriate waste water plant, paint Qing and (4) chemical industry and other air purification . [Prior Art] Recently, the international community has paid more and more attention to environmental issues, industrial safety and hygiene, and purification of molecular pollutants in clean rooms of high-tech factories, considering the harmful effects of industrial waste gas on the environment and the workers and the general public. Emission standards are becoming more stringent, and domestic and foreign regulations have established relevant emission and odor emission standards. On the other hand, high-end processes of high-tech factories have recently dealt with difficult-to-treat molecular pollutants such as sulfur compounds and low-boiling organic compounds. The degree of purification required before the introduction of external air into the clean room is more stringent. For example, in the semiconductor wafer fabrication plant and the TFT-LCD panel photovoltaic manufacturing panel process, the stripper used in the stripping process is mainly composed of a high-boiling and almost completely water-soluble stripper. Organic compounds, including monoethanolamine (MEA), dimercaptoarrene (DMS0) 200904513, and bismuth zero (10) Bo 1 in the ^ ^ ^ ^, to the photoresist - methyl (tetra) is a kind of high-cut Sexual and low volatility liquid, but it is very easy to form and treat dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) gaseous pollutants during the treatment. However, conventional adsorption, condensing, and absorption methods cannot completely remove low-boiling and low-soluble dimethyl sulphur and dimethyl disulfide, and they produce malodor at low concentrations.

Affecting the living environment around the factory and causing public protests, it also affects the yield of high-end processes in other high-tech factories around the house. In the air, the purification technology of organic compound gas can use physical methods, chemical methods and mixing methods. The physical method is a mechanical separation method, a filtration method, an adsorption method, a washing method, and an electrostatic method in which the air is passed through a purification apparatus using physical steps of absorption, adsorption, separation, and the like to remove low-concentration organic compounds in the air. The chemical methods for hanging are thermal oxidation and catalytic combustion. The purification equipment currently used in China is treated by suction and simple filter or general adsorption or washing and washing. This traditional equipment and method cannot effectively purify sulfur compounds such as dimethyl sulfide and dimethyl disulfide. Gas is the main cause of air pollution odor; at the same time, it also causes the contaminated gas to lead into the high-order process clean room such as semiconductor wafer manufacturer and TFT-LCD panel photoelectric manufacturing factory, which affects the product yield. One of the main sources of things. In addition, catalytic catalysts are used to purify sulfur-containing compounds in the air. The catalytic catalyst has the advantages of high removal efficiency of sulfur-containing compounds, low reaction temperature, low energy consumption, and avoidance of secondary pollutants. , 200904513 is an environmentally friendly catalytic purification technology. However, the most important breakthrough of this technology is the development of low-temperature oxidation catalyst. Due to the poor processing efficiency of low-concentration organic compounds, the catalyst developed must have the following characteristics: 1. Nano-catalyst load with low-temperature oxidation activity. The technology utilizes the unique catalytic properties of the nanocatalyst, the small-grain catalyst carrier has small particle size, the channel 16, the intra-crystal diffusion resistance is small, the exposed atoms are many (30% higher), and there are numerous crystal gaps (secondary holes). It has a strong adsorption capacity and is advantageous for macromolecular or liquid phase reactions. The reactants and products can diffuse rapidly in the pores of the porous catalyst carrier, reducing clogging or carbon deposition, and reducing the rate of catalyst deactivation to extend the life of the catalyst. • 2. Adsorption/catalytic substrate synthesis technology with mesoporous characteristics. Using high surface area and pore characteristics of mesopores to improve the adsorption removal efficiency of sulfur-containing compounds, it is estimated that 30% increase due to pore volume and porosity. The amount of adsorption, and the increase of intergranular voids can adsorb larger molecules, the overall catalyst efficiency can be increased by 30 ° /. the above. 3, k liter oxidation activity auxiliary technology, regardless of the adsorbent or catalyst, will be partially covered with the use of time 'designed with low voltage excitation system oxygen or water gas to produce a higher oxidation activity Oxidation aids, such as: 〇2, 〇H〇·, 〇3, etc., accelerate the redox cycle on the surface of the catalyst, and increase the degradation of the surface pollutants of the catalyst to achieve the purpose of reducing carbon deposition, which is expected to be greatly improved. The life of the catalyst. 200904513 SUMMARY OF THE INVENTION In order to improve the problems faced by the above-mentioned prior art, an object of the present invention is to provide a gas purification method for a low concentration organic compound, comprising: at least one catalyst adsorption unit arranged in parallel and/or in series And an ozone generating unit for providing ozone to the catalyst adsorption unit for enhancing the adsorption function of the catalyst or the low-temperature redox or decomposition reaction. The gas purification filter device of the low concentration organic compound in the air of the present invention may comprise a plurality of catalyst adsorption units, wherein the catalyst adsorption unit type may be a fixed bed type, a rotary wheel type, a turret type or a fluidized bed. Each of the catalyst adsorption units may simultaneously perform an adsorption reaction or a catalyst redox or decomposition reaction; or, the adsorption catalyst unit may partially perform an adsorption reaction while partially performing a catalyst redox or decomposition reaction. In addition, the present invention provides a gas purification method for a low concentration organic compound, which comprises the following steps: (1) providing a gas purification filter material of a low concentration organic compound in air, wherein the catalyst adsorption unit is filled with a catalyst adsorption material (2) The air containing the low concentration organic compound to be treated is introduced into the device, and the catalyst adsorption unit filled with the catalyst adsorption material is further subjected to a chemical adsorption reaction, and at the same time, the cleaned air flow after adsorption is discharged; (3) Selection Turn on and/or close the relevant valve group, select whether to introduce the ozone generated by the ozone generating unit, and make the catalyst adsorption unit filled with the catalyst adsorbing material, further carry out chemical adsorption reaction and low temperature oxidation or reduction reaction of 200904513, and discharge at the same time (3) opening and/or closing the relevant valve group, introducing the adsorbed saturated adsorbent material into the water vapor or vapor generated by the water vapor or steam generating unit to further carry out the catalyst adsorbing material. Activated regeneration or replacement. The chemical reaction formula in the steps (2) and (3) is exemplified by the organic waste gas of the low-concentration organic malodorous compound DMS: a. Chemical adsorption alone

Ma++ DMS + Ma+--S(CH3)2 ; or: b, on-line ozone enhanced oxidation reaction Ma++ DMS Ma+ -S(CH3)2 ;

Ma+--S(CH3)2+03 +Ma++DMSO (adsorption)+ 02 ; Ma+--S(CH3)2+203 +Ma++DMSOO (adsorption)+ 202 ; Ma+--S(CH3 ) 2+303 + Ma++S02 + 2C02 +3 H20. In the method for purifying a low concentration organic compound in the air of the present invention, the apparatus may comprise a plurality of catalyst adsorption units, which may perform steps (2) or (3) simultaneously; or, the plurality of contacts The medium adsorption unit may partially perform the step (2) and simultaneously perform the step (3). In the method for purifying a low concentration organic compound in the air of the present invention, the catalyst adsorbing material is composed of a catalyst carrier and a catalyst, wherein the catalyst carrier is selected from the group consisting of activated carbon, zeolite, alumina, and other porous materials. Or a mixture thereof of 200904513; an active portion of the catalyst, ~Ni, Cu, a grade N, a blt metal, which is selected from the shape of the Μη adsorbent material and is == 细 圭 is selected from & The straight spherical shape and the bee may preferably be in the form of a scorpion, a granule, or a plurality of layers: an under-stacked or a foamed form. " The purpose is to provide a gas purifying device and method for the low concentration of right-handed substances in the above air=Touch::r wherein the catalyst carrier is selected from activated carbon = other porous materials or complexes of aluminum telluride , Japanese people 舲. The boat is divided into N-orbit all belong to Gan Zongxi "...the 'active' of the active part of the catalyst, which is selected from the group consisting of MnFe, c〇Ni, Cu, % The best is selected from the group consisting of Cu; and the special limitation of the catalyst is that it is preferably in the form of a column, a granule, a true sphere, a honeycomb, an tier stack or a foam.触 According to the catalyst adsorbent of the present invention, it can be chemically adsorbed and can be reductively reduced. For example, the low-concentration organic malodorous compound coffee machine exhaust gas, in the case of chemical adsorption alone:

Ma + DMS M £ S (CH3) line strengthens the oxidation mechanism with ozone (which can extend the life of the adsorbent)

Ma+ + DMS ^ Ma+-S(CH3)2 Ma+--S(CH3)2 + 〇3 + Ma+ + DMSO (adsorption) + 02 Ma+--S(CH3)2 + 2〇3 + Ma+ + DMSOO (Adsorption Sex) + 202 Ma+—S(CH3)2 + 303 + Ma+ + S02 + 2C02 +3H2〇 Therefore, the catalyst adsorbent of the present invention can be used in combination with the designed device, and the adsorbent adsorbent after adsorption can be taken out to other Device chemical regeneration reduction, 10 200904513 or direct chemical regeneration on the line. The following examples are merely illustrative of the invention and are not to be construed as limiting (10) of the invention. It should be noted that variations and substitutions equivalent to those of the material embodiments, such as those apparent to those skilled in the art, and which can be made without departing from the scope of the invention, are to be understood as Within the age of the invention. Therefore, the scope of the invention is defined by the scope of the following claims. [Example] Chemical adsorbent synthetic chemical adsorbent 1 50 g of copper nitrate containing crystal water was added to 500 ml of water, and then fully stirred until copper nitrate was completely dissolved, and 25 ml of copper nitrate solution was poured into 200 g of activated carbon. In a round bottle, remove the water by a rotary volatizer, then add the remaining 250 ml of copper nitrate solution, and then remove the water by a rotary volatizer. 'When the sample is dried at 12 〇t:, 248.5 g of the sample is obtained. Chemical adsorbent 2 50 g of copper nitrate containing crystal water was added to 5 ml of water, and then fully stirred until copper nitrate was completely dissolved, and 25 ml of a copper nitrate solution was poured into a round bottle containing 200 g of γ-type zeolite. After removing the water by a rotary volatizer, the remaining 250 ml of copper nitrate solution was added, and the water was removed by a rotary volatizer, and the sample was dried at 12 (rc, and 248 g of the sample was obtained. 200904513 Chemical adsorbent 3 After adding 79 g of potassium permanganate to 1000 ml of water, stir well until potassium permanganate is completely dissolved. Pour 1000 ml of the solution into 500 g of activated carbon and mix it thoroughly. After standing for 1 hour, the sample is taken. The sample was dried at 120 ° C, and 534 g of a sample was obtained. [Example 1] The first figure is a schematic diagram of a preferred embodiment of a gas purifying apparatus for a low concentration organic compound in the air of the present invention. The apparatus comprises a catalyst adsorption unit 11, The catalyst adsorbent material 111 is filled with a catalyst carrier and a catalyst, and the catalyst carrier is selected from the group consisting of activated carbon, zeolite, alumina, other porous materials or a mixture thereof; Active part The N-orbit metal is selected from the group consisting of Mn, Fe, Co, Ni, Cu, Pb or Zn; and a fan 30 is arranged in parallel, and the fan is disposed upstream or downstream of the catalyst adsorption unit 11 The air to be treated may be pumped through the catalyst adsorption material 111 to the catalyst adsorption unit 11; a control valve 41 for controlling whether ozone needs to enter the catalyst adsorption unit 11 and the catalyst adsorption material 111; and an ozone generation The unit 20 can provide ozone to the catalyst adsorption unit 11 and the catalyst adsorption material 111 for enhancing the adsorption function of the catalyst, low-temperature redox or decomposition reaction, and the adsorbent adsorbent material can be taken out and activated. The reduction treatment is further filled with a new product in the catalyst adsorption unit 11. [Embodiment 2] 12 200904513 Using the apparatus as described in Embodiment 1, the fan 3 is turned on, the crucible 41 is turned off, and the air inlet 31 can be opened via the blower 30. The treated gas of the low concentration organic compound is introduced into the catalyst adsorption unit 11 and the catalyst adsorption material 111 to perform a chemical adsorption reaction, and the adsorbed clean gas is discharged through a gas outlet 32. At the same time, the opening valve 41 can be selected. The ozone generated by the ozone generating unit 20 is introduced and the concentration of the ozone supply or the concentration is adjusted, so that the catalytic adsorbent ηι in the catalyst adsorption unit n which has been chemically adsorbed before can simultaneously perform low-temperature redox or decomposition reaction. The service life of the catalyst adsorbing material lu filled in the catalyst adsorbing unit 11 and the processing efficiency thereof are extended, and the generated clean gas is discharged from the gas outlet 32. The touch filled in the catalyst adsorption unit 11 The adsorbent material ln is adsorbed. After saturation, it can be subjected to regeneration and reduction reaction of the external catalyst adsorbing material. Examples 3-5 are difficult to treat the low-concentration organic malodorous compounds DMS, DMDS and Hj, respectively. The U gas of the treated low concentration organic compound was tested for the treatment efficiency of the catalyst adsorbing material filled in the apparatus of the present invention. The catalyst adsorbing materials used in Examples 3 and 4 were composed of adsorbent 丨, 2, and Example 5 The catalyst adsorbent material used was composed of adsorbent 3, and the results of the respective examples are shown in Tables 1, 2 and 3 below. At the same time, the adsorbent after the gas purification treatment of the low-concentration DMS and the DMDS organic sulfur compound of Example 3-4 is carried out, and the high-temperature desorption is immediately performed on the 'line exhaust gas analysis'. The result is shown in the second figure, in the second figure. The desorption tail gas analysis mass spectrum shows that a large amount of DMSO and DMSOO are present in the tail gas of the desorption process. 13 200904513 Table 1. Results of treatment efficiency of packed adsorbent by DMS. Catalytic linear velocity (m/s) DMS inlet Hanitude (ppb) DMS outlet concentration (ppb) removal efficiency (%) Catalyst lifetime (hrs) (efficiency) >95%) Ozone addition concentration (ppm) Ozone outlet concentration (ppm) 0.5 900 15 98.3% > 8,000 6.8 <0.1 0.5 3,600 20 99.4% > 4,000 6.8 <0.1 0.5 15,000 30 99.8% > 1,440 39.0 <0.1 1.0 1,800 18 —99.0% > 3,600 3.4 <0.1 1.0 150 1~3 >98.0% > 8,600 <0.4 <0.01 1.0 150 12 〜15 >90.0% >270 0 (no ozone Supply) 0 1.0 30 <1 >97.0% > 8,600 <0.1 <0.01 1.0 30 3~6 >80.0% -·-- >1,080 0 (no skunk supply) 0 As can be seen from the above table, When inputting high concentration DMS (900, 3, 600, 15,000, 1,800 ppb), the removal efficiency after adding ozone is over 98%' and has a long-acting catalyst life; and at low concentration DMS (150, 30 ppb) When the time is 'there is ozone, the removal efficiency is above 97%, and in the case of no ozone added, the removal efficiency is only greater than 90% and 80%, respectively. The effect of ozone addition on the removal efficiency, and at the bottom concentration, the addition of hexaoxide can effectively increase the catalyst life by more than eight times (8600: 1〇8〇). 2 ρ DMDS degree (ppb) removal efficiency (%) Catalyst lifetime (hrs) (efficiency > 95%) Ozone addition concentration (ppm) Ozone outlet concentration (ppm) 8 99.1% >3860 6.8ppm <0.1 12 99.7 % >1680 6.8ppm <0.1 15 99.2% > 1680 3.4ppm <0.1 Catalyst Adsorption Material Processing Results

(s ') 14 200904513 It can be seen from the above table that regardless of the input concentration of DKlSpGO, 3,600, 1,800 ppb), the removal efficiency after the ozone is more than 990 / 〇, and the long-acting catalyst life . Table 3. Results of H2S test filling catalyst adsorption material. Catalyst line speed h2s h2s Removal efficiency Catalyst life (hrs) — ~ Ozone addition: Agriculture-~~~~--- Ozone outlet thick (m/s Entrance concentration (ppb) outlet concentration (ppb) (%) (efficiency > 95%) degree (ppm) S Γηητπ'ΐ 0.5 900 10 98.9% >2880 6.8ppm <0.1 0.5 3,600 15 99.6% > 1440 6.8ppm <0.1 1 1,800 13 99.3% > 1440 3.4ppm ----~_ <0.1 '~-—— As can be seen from the above table, regardless of the input concentration, H2S (90〇, 3, 6() (), 1,800 ppb), the removal efficiency after adding ozone is more than 98%, and has a long-lasting catalyst life. INDUSTRIAL APPLICABILITY The gas purification method of the low-concentration organic compound of the present invention and the catalyst adsorbing material used therefor can treat a gas containing a malodorous compound such as dimethyl sulfide (DMS) or dimercapto disulfide (DMDS). Sulfide such as hydrogen sulfide (HA) and a hydrogen compound containing a malodorous compound such as a road, acetic acid, isopropanol or acetone, which can solve the problem that a conventional treatment device cannot or does not handle a gas of a certain low concentration of an organic compound, and It can increase catalyst efficiency and extend catalyst life. It is an excellent technology that meets environmental protection and energy requirements. It is worthy of high-tech wafer fabrication, photovoltaic panel manufacturing, coating and printing industry and related industries with high air volume and low concentration emission. At the same time, it can also be used in the high-tech wafer system 15 200904513 manufacturing, photovoltaic panel manufacturing clean room clean air purification sulfur compounds and carbon monoxide compounds air molecules micro-pollutants AMC purification. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a schematic view showing a preferred embodiment of a gas purifying apparatus for a low concentration organic compound in the air of the present invention. The second graph desorbs the exhaust gas analysis mass spectrum, which is the result of the Mass analysis on the desorption line. r [Description of main component symbols] II Catalyst adsorption unit 20 Ozone generation unit 30 Fan 31 Low concentration organic gas inlet 32 Gas outlet U 41 Valve III Catalyst adsorbent

16

Claims (1)

200904513 X. Patent application scope: 1. A gas purification method for a low concentration organic compound, comprising the following steps: (a) providing a gas purification filter device with a low concentration organic compound, comprising a catalyst adsorption unit, and The catalyst adsorption unit is filled with a catalyst adsorption material; (b) the air of the low concentration organic compound to be treated is introduced into the device, and the catalyst adsorption unit filled with the catalyst adsorption material is further subjected to a chemical adsorption reaction, and simultaneously Exhaust the cleaned air stream after adsorption; (c) Select to open and/or close the relevant valve group, select whether to introduce the ozone generated by the ozone generating unit, and further chemicalize the catalyst adsorption unit filled with the catalyst adsorbing material. The adsorption reaction and the low-temperature redox or decomposition reaction simultaneously discharge the cleaned gas stream after adsorption. 2. For the gas purification method of the low concentration organic compound in the first application of the patent scope, wherein the chemical reaction formula of the DMS in the steps (2) and (3) is: (a) chemical adsorption alone Ma+ + DMS Ma+-S(CH3)2 ; (b) Ozone enhanced oxidation on the line Ma+ + DMS + Ma+--S(CH3)2 ; Ma+--S(CH3)2 + 03 + Ma+ + DMSO (adsorption) + 〇2 Ma+--S(CH3)2 + 203 + Ma+ + DMSOO (adsorbing) + 202 ; 17 200904513 Ma'-S(CH3)2 + 3〇3 + Ma+ + S02 + 2c〇2 +3Η20. 3. The method for purifying a low concentration organic compound according to claim 1 or 2, further comprising the step (4) of: opening and/or closing the relevant valve group to introduce the adsorbed saturated adsorbent into the water. The water or vapor generated by the gas or steam generating unit is further activated or reactivated or replaced by the catalytic adsorbent. η 4. The gas purification method of the low concentration organic compound according to claim 3, further comprising the step (5) of: setting an air purification treatment device to finally process the new pollutant generated in the step (3). 5. The method for gasification of a low concentration organic compound of the invention of claim i or 2, wherein the at least one catalyst adsorption unit can simultaneously perform step (2) or step (3); wherein the catalyst adsorption unit is also Step (2) may be partially performed while step (3) is partially performed. 6'If the application of the low-concentration organic compound gas in the first or second patent range (the method of 'the + ozone generating unit can generate ozone on the line, can also produce ozone supply outside the line. The gas purification of the low-concentration organic compound of item 6==, wherein the ozone generating unit is an on-line generation method, which comprises a method of dividing the line, an external line, an electrolysis method, a silent discharge method, a tip discharge method, and a plasma method. A method for applying a gas of a low concentration organic compound according to claim 1 or 2, wherein the catalyst adsorbent is composed of a catalyst carrier and a catalyst. 9. A low concentration organic compound as in claim 8 A gas purification method, wherein the catalyst carrier is selected from the group consisting of activated carbon, zeolite, alumina, 18 200904513 other porous materials or mixtures thereof. • If the gas concentration of the low-concentration organic compound in the eighth paragraph of the patent scope is applied, the shape of the catalyst adsorbing material may be cylindrical, granular, true spherical, honeycomb or multi-layer stacked or foamed. shape. i. For example, the gas concentration method of the low concentration organic compound in the eighth item of the patent scope is that the active part of the 5 hai catalyst is N-orbit metal (transition metal ―member), which is selected from the group consisting of Mn, Fe, Co, and Ni. , Cu or Zn. 12. A gas purification method for a low concentration organic compound according to the U of claim U, wherein the active portion of the catalyst is Cu. 13. A catalyst-adsorbing material for a gas-based method of a low-concentration organic compound according to the first or second aspect of the patent application, which is composed of a catalyst carrier and a catalyst. ~ 14.= The catalyst adsorption material of claim 13 of the patent scope, wherein the tactile system is selected from the group consisting of activated carbon, buddha, oxidized, and other porous materials. AH invites the catalyst adsorption material of the 13th patent (4), wherein the shape of the catalyst anger material can be cylindrical, granular, true spherical, honeycomb-like multi-layer stacked or foamed. 16' = Please select the adsorption catalyst of the 13th item, wherein the activity W of the catalyst is N-〇rblt metal (transition metal first type), and is selected from _, Fe, Co, Ni, Cu, pb Or Zn. I. The adsorption catalyst of claim 16 wherein the active portion of the contact is Cu. * 19