CN1270540A - Catalytic conversion of gases via cation-exchangeable alumino-silicate materials - Google Patents

Abstract

A process for catalytic conversion and/or adsorption of gases inclusive of NOx, SOx, CO2, CO, dioxins and PAHs and combinations thereof wherein said gases may contain particulates which include contacting one or more of such gases with an alumino-silicate material having: (i) a primarily tetrahedrally co-ordinated aluminium as established by the fact that the <27>Al Magic Angle Spinning (MAS) provides a single peak at 55-58 ppm (FWHM = SIMILAR 23 ppm) relative to Al(H2O)6<3+>; and (ii) a cation exchange capacity of at least 1 meq 100 g<-1> in aqueous solution at room temperature.

Description

Catalytic conversion of gases through cation-exchangeable aluminosilicate materials

Technical Field

The present invention relates to the catalytic conversion and/or adsorption of gas mixtures comprising nitrous oxide, nitric oxide, nitrogen dioxide (collectively "NO") using aluminosilicate materials_X"), and/or other contaminant gases, including but not limited to SO_X、CO₂CO, dioxins and polycyclic aromatic hydrocarbons (collectively "PAHs"), as well as mixtures thereof. The invention also relates to the above-mentioned gas mixture or gas also containing particles.

These toxic or polluting gases are frequently encountered in many industrial processes (e.g. combustion of coal, production of chemicals) and in combustion processes of internal combustion engines, the proportions of which are variable. In NO_XIn the case of (a), these aluminosilicate materials convert environmentally harmful chemicals into harmless gases, such as gas and/or water and/or oxygen.

It has now been found that certain aluminosilicate materials, as described herein, can function as catalysts, catalytically convert these gases or gas mixtures, or adsorb these gases or gas mixtures. These chemistries can generally be run at elevated temperatures ranging from 200 ℃ to 850 ℃ and over a wide range of flow rates and gas compositions.

Background

Currently, there are two types of removal of NO from industrial flue gases_XIndustrial process of (1). The first is based on titanium oxide catalysts, which are usually promoted by oxides of vanadium, tungsten, iron, molybdenum, cobalt, manganese, uranium, copper, chromium or niobium to facilitate the selective catalytic reduction of NO by ammonia_XAn overview of this issue has been provided (g.c. bond and s.f. tahir, 1991, appl.catal.711; h.bosch and f.jassen, 1988, cata.today 2369). The reaction of this industrial process can be expressed as follows:

the latter catalyst systems are typically operated at temperatures of 300 ℃ and 400 ℃ when SO is present in the exhaust gas_XWhen used, exhibit good poisoning resistance. Industrially, catalysts are fabricated as plate or honeycomb monoliths and operated in parallel flow mode to minimize the possibility of catalyst bed plugging by particulates (f. nakajima and i.hamada, 1996, cat. today 29109). Although this catalyst has good selectivity to the desired product, it has several disadvantages in its practical application. These disadvantages include low abrasion resistance, limited to relatively low reaction temperatures (< 425 ℃), and high cost. Further, the ammonia reagent contaminates the fly ash produced in the system, creating other difficulties for long term effective use in industrial environments. Ammonia is itself difficult to store due to its flammability and toxicity, and thus, it is undesirable to use ammonia in residential areas.

Recent research has been directed towards improving the properties of the latter materials, including the preparation of clay mineral interlayer compounds containing titanium oxide and vanadium or copper species (n.yoshida and j.kato, 1996, Jpn, Kokai Yokkyo Kobo JP08, 117, 597). Similarly, Yang and Li (r.t. Yang and w.li, 1995, j.catal.155414) studied Fe³⁺Ion exchanged TiO₂The properties of pillared clays. However, when SO is present₂And H₂O (a component usually present in industrial flue gas), WO₃/V₂O₅/TiO₂The catalyst is slightly poisoned, and the activity of the pillared clay material is due to the presence of SO₂And H₂O is enhanced. Suppose SO₂And H₂O increases the concentration of Bronsted acid sites (sites) on the catalyst surface-believed to be the center of the catalytic reaction.

The second method is to use a zeolite material to catalyze the reaction between the aforementioned ammonia and nitric oxide, although the optimum operating temperature in this example is rather high (about 500 ℃). For example, Famos et al (US 5451387) reported the use of iron ion-exchanged zeolites (e.g., ZSM5), Vanden Bleek et al disclosed the use of cerium ion-exchanged mordenite (Netherlands patent application NL 9302288). Sullivan et al, 1996, disclosed a Cu-ZSM5 catalyst (App. catalysis B: Environmental 7415-417) with comparable activity to conventional vanadium/titanium oxide SCR catalysts, Komatsu et al, 1995(J.Phys. chem.9913053) concluded that nitrate species formed on the surface of the zeolite subsequently reacted with ammonia to produce product nitrogen using infrared spectroscopy.

The direct decomposition of nitric oxide into elements has been a serious challenge for scientists for decades. (M.Shelef, 1995, chem.Rev.95209-224). This reaction is a particularly attractive solution to the current contamination problem because no reducing agent is added. This reaction is:

Δ G ═ 20.7Kcal/mol (298K), although thermodynamically favourable, was not developed in any material until recently demonstrated by Iwamoto et al (1986, j. The major breakthrough included the discovery that the Cu-ZSM5 zeolite can donate NO at a sufficient rate at 500 deg.C_XDecomposed into elements. To date, Cu-ZSM5 has been considered unique among aluminosilicate materials. However, in practice, the Cu-ZSM5 catalyst was considered to be less active (Komatsu et al, 1995, J.Phys. chem.9913053). Furthermore, there does not appear to be any method that can increase the activity of Cu-ZSM5 by the required 1-2 orders of magnitude for industrial applications (Bogner et al, 1995, Applied Catalysis B: Environmental 7153-171). Common methods of increasing activity include increasing the operating temperature, but this results in a decrease in Cu-ZSM5 activity (Bogner et al, 1995, supra). According to Shelef (1995, supra), the root cause of the relatively low activity of Cu-ZSM5 is related to the crystal structure and the presence of Cu-impregnated pores for the catalyst reaction. Another reported direct decomposition of NO_XActive systems include yttrium barium copper oxide superconductors (YBCO) (Shimada et al, 1988, chem. letters, 1997) and layered aluminosilicate structures, particularly mica, in siliconCerium or lanthanum ions are incorporated into the acid salt backbone (e.hums, PCT international patent WO 96/00016). Nitrous oxide (N) may be converted by using anionic clay materials₂O) into nitrogen and oxygen, examples of anionic clay materials are hydrotalcite (hydrotalcites), schjogrenites and pyroaurites (Farris et al, US 5472677) containing e.g. alkali or alkaline earth metal activator species.

Due to difficulty in forming a catalyst suitable for industrial application directly used for decomposing NO_XCatalysts for the reaction, and the use of NO in various hydrocarbons_XSelective Catalytic Reduction (SCR). Hydrocarbons usually with NO_XContaminants are present in the exhaust stream together. In particular, the development of more combustion efficient lean burn engines for automobiles means that exhaust gases will be highly oxidized, and therefore, the challenge is to invent a catalyst that can selectively reduce NO in the presence of excess oxygen_X. The current commercial three-way catalyst involves supported on oxidationMixtures of platinum, rhodium and cerium oxide on aluminum coatings (washcoat) do not reduce NO satisfactorily under net oxidation conditions_X(k.c. taylor, 1993, catal.rev.sci.eng.35457). The use of methane (j.n.amor, 1995, catal.today 26147) has attracted attention because of its abundant source, relative cheapness, and general availability. Exhibit selective oxidation of NO by hydrocarbons_XThe active material is mainly a metal-exchanged zeolite (Komatsu et al 1995, Supra; K.C. Taylor, 1993, Supra; Bogner et al 1995, Supra). However, SO₂And H₂O is a typical two component in industrial exhaust gas and is generally detrimental to catalytic activity, and it is currently estimated that zeolite systems are one of four factors that are too low in activity for industrial practice (k.c. taylor, 1995 supra). Thus, even for the most promising applications-selective catalytic reduction of NO_XThe use of zeolite substrates or metal-exchanged zeolites has not been used in industry.

In International patent WO95/00441, the specification describes a kaolin derivative having a high specific surface area, 45m, compared to the starting kaolin material²G to 400m²(ii)/g, high cation exchange capacity for ammonium ion exchange, 50-450meq/100 g. It is also speculated that this property may make kaolin derivatives useful in replacing conventional catalysts, such as catalysts used in reforming (rearrangement) and conversion of hydrocarbons. Another application is the loading of lanthanide and/or transition metals on kaolin derivatives for catalytic redox reactions such as the dehydrogenation of methanol to produce methyl formate. Specific examples are also included in this specification, using kaolin derivatives with copper exchanged for alkali metal cations, and dehydrogenation of methanol to methyl formate at elevated temperatures and ethanol to acetaldehyde at elevated temperatures. However, in WO95/00441, the catalysis of methanol and ethanol vapors is the only example using a metal-exchanged kaolin derivative as catalyst.

However, it has now been found that the aluminosilicate materials described herein, including the amorphous derivatives of kaolin as disclosed in WO95/00441, can be used to selectively catalytically reduce and/or directly decompose NO_XGases and gases such as CO, CO₂、SO_XAnd dioxin, PAHs and other toxic gases are converted into products harmless to the environment. E.g. in the catalytic conversion of NO_XThe catalytic mechanism on gases appears to include the electronic configuration when the exchangeable metal ions are supported by aluminosilicate derivatives, and appears to have an unexpected effect on the overall catalytic activity of the catalyst.

Summary of The Invention

The aluminosilicate materials useful in the present invention have aluminum with a predominantly tetrahedral coordination and a cation exchange capacity in aqueous solution of at least 1meq/100g at room temperature. The CEC of such materials is preferably higher than 100meq/100g, more preferably 160-900meq/100g, and particularly preferably 350-450meq/100g, as determined by the methods defined in the prior art (e.g.WO 96/18576 and WO 96/18577).

The fact that aluminosilicate materials have aluminum with a predominantly tetrahedral coordination is evidenced by the fact that:²⁷AL magic angle rotation (Ma)gic Angle Spinning, MAS) gave a single peak at 55-58ppm (FWHM ═ 23ppm), corresponding to Al (H)₂O)₆ ⁺³。

The aluminosilicate materials useful in the present invention may also include exchangeable cations, either ammonium or alkali metal ions, which may be partially or fully coated with a second selected from the alkaline earth metals Mg²⁺、Ca²⁺、Sr²⁺And Ba²⁺(ii) a Transition metal Cr²⁺、Mn²⁺、Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Ag⁺(ii) a Heavy metal Pb²⁺、Cd²⁺、Hg²⁺(ii) a Lanthanide La³⁺And Nd³⁺Or actinide UO₂ ²⁺Secondary metal (secondary metal) exchange of one.

In one aspect, the aluminosilicates used in the present invention are amorphous in nature and, therefore, include amorphous derivatives of kaolin as disclosed in WO95/00441 or KADs or aluminosilicate derivatives (ASDs) as disclosed in WO96/18576 or WO 96/18577. These amorphous states do not exhibit any extensive structural order, with broad peaks between 14 ° and 40 ° 2 θ (or in some cases between 22 ° and 32 ° 2 θ) when irradiated with CuK α X-. No sharp diffraction peaks were observed except for impurities. These KADs or ASDs can be prepared by reacting the starting aluminosilicate with MOH and/or MX, where M is an alkali metal and X is a halogen. These compounds may have a chemical composition of the general formula:

M_pAl_qSi₂O_r(OH)_sX_t·uH₂o wherein p is 0.2. ltoreq. p.ltoreq.2.0, q is 0.5. ltoreq.2.5, r is 4.0. ltoreq.12, s is 0.5. ltoreq.4.0, t is 0.0. ltoreq. t.ltoreq.1.0 and u is 0.0. ltoreq.6.0, M is an ammonium ion or an alkali metal ion, X is a halogen in which NH is as₄ ⁺、Na⁺、K⁺、Li⁺、Rb⁺The M of Cs can be exchanged for the secondary metal discussed above.

On the other hand, the alkali metal aluminosilicate used in the present invention may include amorphous or low or partially crystalline aluminosilicate having a packing (filled) silica polymorphic structure, which is prepared by reacting a starting aluminosilicate material or a mixture containing alumina and a compound containing silicon oxide with a reactant containing an alkali metal oxide or an alkali metal hydroxide. These silicon oxide-filled polymorphs include prokaliophilite, triclopyr, eucryptite, nepheline. These polymorphic forms are packed with a phospho-quartz, cristobalite, a derivative of the quartz structure. These materials are disclosed in WO96/12678, which is incorporated herein by reference.

The aluminosilicate materials useful in the present invention include modified kaolins, which may be prepared from kaolins (group) minerals, including the expansion and contraction of layers in kaolins (group) minerals, which layers comprise one Si-tetrahedral platelet (sheet) and one Al-octahedral platelet. Modified kaolin and its cation-exchangeable derivatives of aluminosilicate materials are disclosed in WO97/15427, which is incorporated herein by reference.

According to one form of the invention, the aluminosilicate material described above may be used in the presence of a hydrocarbon for NO_XStable conversion to N₂And H₂O, effecting Selective Catalytic Reduction (SCR). These materials can be produced in a variety of pore sizes and surface structures and can contain a large amount of surface-bound metals, such as copper, iron, cerium or cobalt, to NO_XIs active. In addition, the cation-exchangeable materials described in WO95/00441, WO96/18576, WO 96/18577 and WO96/12678 can also affect this catalytic conversion, although at lower conversion levels. Further, if the gas stream contains a certain amount of para-NO_XConversion of the active metal ion, any form of the above aluminosilicate material will affect the conversion. In this form, metal ions from the gas stream are adsorbed onto the aluminosilicate substrate and similar NO occurs in the presence of hydrocarbons_XAnd (4) selective catalytic conversion.

Exchangeable properties of the metal ions for subsequent catalytic properties, and high surface area for the metal-loaded substrate (BET value > 40m²/g) is a desirable attribute of aluminosilicate materials. For example, Table 1 lists conventional aluminosilicate materials such as ZSM5, kaolin clay and pillared clays withComparative values of Cation Exchange Capacity (CEC) and surface area of aluminosilicate materials described in WO95/00441, WO96/18576, WO 96/18577.

As shown in Table 1, the range of values obtained for the aluminosilicates described herein is significantly greater thanOther practitioners used as NO on trial_XThe value obtained by reducing the catalyst. The combination of these properties, and thermal stability above 800 ℃, with NO_XThe catalytic reaction of (3) provides advantageous conditions. In a preferred form of the invention, these materials are stable up to 600 ℃ and hot and humid conditions in the presence of water, which conditions might otherwise cause degradation of competing products.

It has been surprisingly found that the ionic form, i.e. electronic or valence state, of metal exchange caused by the cation exchange process of aluminosilicate materials affects the conversion of such materials to, for example, NO_XDioxins and/or PAHs or mixtures thereof. The properties of the electronic states of a typical sample are described herein and are determined using spectroscopic and adsorption/desorption methods, as shown in table 2, which are known to those skilled in the art. For specific data, the electronic states of comparable metal-exchanged zeolite species were compared.

In another aspect of the invention, in_XIn the presence of toxic gases, these materials can also react with NO_XReaction, not due to SO_XThe presence of (a) significantly reduces the catalytic performance.

In a further aspect of the invention, these energetic materials are reacted with organic gaseous compounds such as dioxins and Polycyclic Aromatic Hydrocarbons (PAHs).

Processes for preparing these novel aluminosilicate materials have been described in WO95/00441, WO96/18576, WO 96/18577 and WO96/12678 and may also be obtained by other routes as described in WO 97/15427. It will be apparent to those skilled in the art that a wide selection of key physical and chemical properties can be obtained from this group of new materials by selecting the appropriate method of preparation, or a combination of these methods, such as those disclosed in the aforementioned documents. These major physical and chemical properties include surface area, cation exchange capacity, availability of catalytic sites (availability of sites), relative percentages of mesoporous and microporous sites, and Si/Al ratio. In this specification, the summary in table 2 indicates various general methods of producing new materials for the specific sample numbers exemplified.

Subtle changes in bulk properties within and between the various samples listed in table 2 can be achieved by controlling the products or intermediates using techniques conventionally known in the art. For example, the degree of cation exchange achieved by the second exchange with copper nitrate solution in Table 2 can be significantly increased or decreased by altering the molar concentration of the copper nitrate solution and/or the kinetics of the exchange reaction. In addition, solutions containing other metals, such as cobalt acetate and copper acetate (or mixtures thereof) may be used to obtain the appropriate degree of copper and/or cobalt exchanged aluminosilicate material. These metal exchanged aluminosilicate materials are suitable materials for catalytic conversion of gases.

The properties of the metal ions on the surface of the aluminosilicate are best revealed by X-ray photoelectric spectroscopy (XPS). For example, XPS studies on copper exchanged KAD materials show that there are two common copper species present on the catalyst surface: typical copper oxide species are represented by the sub-band at 933.5 eV, and Cu incorporated into the aluminosilicate framework is represented by the sub-band at 935.5 eV⁺Ions. As is evident from the XPS data shown in table 3 for a small group of all samples, the relative concentrations of the different types of copper species are controlled by the characteristics of the KAD substrate and, therefore, the KAD manufacturing process.

A common property determined by those skilled in the art of catalytic materials is related to the chemical composition of the substrate, which determines the active site of the catalytic or decomposition reaction. The compositions of these materials are described in terms of either bulk or surface chemistry. The overall chemical composition of these new materials has been described in the previously referenced documents. These bulk chemical compositions are determined using known techniques, such as electron microprobe analysis and wet chemical analysis, using atomic absorption spectroscopy and/or inductively coupled plasma spectroscopy.

The surface chemistry of these new materials can be readily obtained by one of ordinary skill in the art of X-ray photoelectron spectroscopy (XPS). Generally, the method detects the upper surface layer of the catalyst material by comparing the spectral peak heights to a calibrated standard composition and provides quantitative data. Table 4 provides the surface chemical compositions of the various catalyst materials tested for the gas applications listed below. These data are average scans of millimeter scale areas of powdered material that was crushed prior to testing as a catalyst.

Other important characteristics, such as element ratios, can be determined from these data. Thus, the Si/Al, K/Al and Cu/Al ratios for the samples listed in this specification can be obtained from XPS measurements and are listed in Table 5.

As can be seen from the data set forth in Table 5, the Si/Al ratios for all samples ranged from 1.0 to 1.5This is important to prove that at the appropriate temperature, NO is present_XOr direct decomposition of NO_XHas proper catalytic activity. In contrast, NO is generally recommended for exhaust gases_XThe Si/Al ratio of the catalyzed zeolite > 15(Yoshimura et Al, Jpn, Kokai Tokkyo Koho JP08,108,043(96, 108.043). the ratio of Cu-ZSM5 is also listed in Table 5 as an example the new materials disclosed in this specification have very low Si/Al ratios, as shown in Table 5, and are not easily obtainable by conventional zeolite preparation methods.

Without being bound by theory, the above-described characteristics of metal-exchanged aluminosilicate materials represent an effective chemical transformation (catalyzed), decomposition or adsorption of toxic inorganic gases such as NO_XToxic organic gases such as dioxins and polycyclic aromatic hydrocarbons.

These aluminosilicate materials can be formed into specific shapes or monolithic blocks by conventional ceramic forming techniques. However, to date, most of these materials have been used in powder or pellet form and preheated by high temperature sintering in a stream of air at 500 ℃ for two hours.

The process of the invention is suitable for the reduction of NO in the presence of an organic reducing agent at temperatures of 200-650 DEG C_XIn which NO_XIs alumino silicateAnd (4) adsorbing the salt material. Organic reductants include hydrocarbons, including alkanes, alkenes, aromatic hydrocarbons including benzene, polycyclic hydrocarbons, and oxygenated organic compounds, including alcohols and aldehydes.

The temperature of 200 ℃ and 650 ℃ depends on the choice of organic reducing agent. The method can be used for treating waste gas from a smelting furnace, an incinerator or automobile waste gas.

The process may also use nitrogenous reductants to reduce NO_XNitrogenous reductants include ammonia and urea. Temperatures of 200 ℃ and 650 ℃ may be used for ammonia applications and temperatures of 350 ℃ and 500 ℃ may be used for urea applications.

The method of the present invention can also be used to directly react NO at temperatures of 200-_XDecomposed into nitrogen. Aluminosilicate materials for this particular use contain Fe, Cu or Ag or other metals listed in table 8.

With respect to CO₂Using basic oxides (including CaO and MgO) or other alkaline earth oxides and transition metal oxides (including CuO, ZnO orIron oxides). This can be achieved by reacting an aluminosilicate material (hereinafter referred to as an aluminosilicate derivative or ASD) with a soluble salt of the relevant oxide (e.g. a nitrate or halide), followed by drying and heating.

Containing CO₂Of gas or CO₂Can itself pass through ASD, allowing CO₂Adsorbed by the ASD. Suitable temperatures are from room temperature to 300 ℃.

For treating CO analogously to that described above₂Can be used for treating a substrate comprising SO₂SO of (A)_XIn which SO_XBy ASD, it is adsorbed by ASD or reduced to sulfur. Adsorption of SO₂The temperature of (A) is usually between 0 and 500 ℃ and more preferably between room temperature and 150 ℃. The ASD may be doped with a basic metal oxide or a transition metal oxide as described above.

The process of the invention may also be used for the separation of SO₂By oxidation to SO₃Wherein an ASD containing Pt, Pd, Ag, Cu, Co, Mn or Cr is used at a temperature of 150-650 ℃. Similar processes can be used to oxidize CO to CO₂。

In treating dioxins or PAHs, ASD containing Pt, Pd, Ag, Cu, Co, Mn or Cr may be used at a temperature of 250-650 ℃. Dioxin is converted into H₂O, HCl and CO₂. Examples of treatment of dioxins are shown in table 9.

As regards the treatment of PAHs, gases which are suitably treated by the process of the invention include anthracene, fluorene, pyrene, perylene, chrysene, naphtalene.

In the examples mentioned above, it will be appreciated that the conversion or percentage removal of the gas stream treated by the catalyst of the present invention is dependent upon the temperature used, with higher temperatures being more effective in removing gaseous contaminants from the gas stream.

As for stationary flue gases from power plants, chemical treatment plants, furnaces, etc., the conversion or removal is about 30-40% at a temperature of about 200-250 ℃. This conversion can be increased to 60% when the temperature reaches 350 ℃.

For automobiles, the conversion may be greater than 80% at a temperature of 450-.

The following examples illustrate various properties of these aluminosilicate materials when used to catalytically convert gas streams from high temperature combustion.

Examples example 1 decomposition of NO_X

Laboratory scale experiments were conducted in fixed bed microreactor systems modified to accommodate NO_XPreliminary study of reduction. The microreactor components including the fixed bed reactor, the in-situ transfer FTIR chamber and the DRIFTS chamber in combination as an in-line mass spectrometer, gas chromatography and gas chromatography-FTIR measurement cell are shown in fig. 1.

For decomposition of NO_XThe performance of five types of copper exchange materials was investigated. An appropriate amount of K-KAD was added to an aqueous solution of copper nitrate at pH 6.5 and stirred for 2 hours at room temperature. In this experiment, the following reaction parameters were used:

catalyst temperature: 550 deg.C

Starting NO_XConcentration: 2000ppm of

Flow rate (hourly space velocity of Gas (GHSV)): 15,000hr^-1

The conversion data for these experiments is shown in FIG. 2, which shows that the copper exchanged catalyst Cu-KAD3-1 is directly decomposing NO_XThe aspect does have good potential because NO at 550 ℃_XThe conversion of (a) is 100% and the flow rate is close to the industrial conditions. The conditions used in these preliminary experiments for copper exchange catalyst materials were much more stringent than those used when Cu-ZSM5 was studied previously (N.Yoshida and Y.Kato, 1996, Supra). Comparing the data provided by Iwamoto et al (1986, Supra) with the calculations from these preliminary experiments revealed that the copper exchange catalyst material was at least an order of magnitude more active than Cu-ZSM5 under the same conditions.

The enhanced catalytic activity and good deactivation resistance of Cu-KAD (or Cu-ASD) is related to the nature of the copper species present on the catalyst surface. As shown in FIG. 3, in situ FTIR studies showed that NO was adsorbed and then adsorbed compared to Cu-KAD or Cu-ASD_X/O₂The structure of the material exposed on Cu-ZSM5 was significantly different. Importantly, the Cu-KAD or Cu-ASD catalyst promotes the formation of adsorbed nitrate, nitro and nitrite-based species. Adelman et al(1996, appl. Cat. B.11L 1) recently summarized NO on Cu-ZSM5 zeolite_XThe mechanism of selective reduction with alkanes particularly emphasizes the importance of adsorbing nitrate and nitro species in the reaction. Similarly, Centi et al (1996, J.chem.Soc.Faraday Trans.925129) used in combination¹³C MAS NMR, FTIR, reactivity tests, and UV-VIS-NIR reflectance spectroscopy confirm that the reaction between the adsorbed nitrate species and the hydrocarbon first results in an organic nitro species, which forms an integral with the catalytic reaction. Thus, adsorption of NO on Cu-KAD or Cu-ASD catalysts_XAn increase in the concentration of the substance is advantageous for the catalytic process. Example 2 spectra of copper and potassium exchanged aluminosilicate

For NO on copper and potassium exchanged KAD materials_XAnd O₂The interaction between them was investigated by FTIR, and the spectral data are shown in tables 6 and 7. This data provides information about the nature of surface sites on the new material and the catalytic and/or reductive NO reduction of the active species at these sites_XBasic information of the effect in the gas. For comparison, similar data on Cu-ZSM5 are also shown in the table.

The infrared data show that a mixture of potassium and copper species is present on these catalysts, since the concentration of potassium and copper species is about 1390-^-1And 1360cm^-1There is an energy band in which the copper exchange catalyst is prepared from the potassium form. XPS studies support this reasoning because potassium is present in all copper exchanged samples. However, copper exchanged samples containing little or no exchanged potassium may also be similarly considered suitable for materials that catalyze or direct decomposition reactions. Example 3 in the reaction with NO_XSpectrum of cobalt exchanged aluminosilicate material during reaction

Cobalt exchanged aluminosilicates are similar to Cu-KAD or Cu-ASD in that they are characterized by their inherently high surface area, possess an aluminosilicate matrix, and exhibit the potential for "over-exchange" reactions. As shown in Table 7, Co-KAD was prepared by contacting K-KAD with a cobalt nitrate solution. One example of the superior adsorption properties of cobalt exchanged KAD materials relative to conventional cobalt exchanged zeolites (e.g., Co-ZSM5) is provided by FTIR spectral analysis of NO at room temperature_X/O₂As recorded by exposure to the catalyst surface. Fig. 4 shows the case of these spectral data.

It is clear that the intensity of the Co-ZSM5 band suitable for the mode of adsorption of nitro and nitrite based species (Adelman et al, 1996, J.Catal.158327) is very low relative to all Co-KAD materials. In addition, there is evidence of the presence of Co and potassium species, as measured by the concentration at approximately 1390 and 1360cm^-1As the band indicates. Example 4 Selective catalytic reduction and direct decomposition of NO from incinerator_X

Tests were conducted using potassium, cobalt and copper based catalyst materials with the exhaust stream from an industrial municipal incinerator in brisban australia. Testing of exhaust gases from the main chamber, the combustion zone (ignition zone) and the secondary chamber of an incineratorStream, waste with high oxygen content to ensure combustion conditions produced with high NO_XAnd (4) concentration. The flow diagram and the gas flow sampling points of this incineration system are shown in figure 5. It should be noted that the sample is not taken from the top of the flue gas stack, but is taken at a high concentration of the target gas (e.g., NO)_XWater vapor, SO_XEtc.) are sampled.

On the day of testing, Lurgi Pitch (waste from an alumina refinery) was incinerated. Incineration of these materials produces large quantities of hydrocarbons and oxygen (as well as NO) in the chamber_X). Within these gas streams, there are large amounts of water vapor, hydrocarbons (mainly light hydrocarbons) and SO_XIt is normal, although its amount is not accurately monitored in the test. Data on the hydrocarbon concentration can be obtained from the secondary chamber (about 3ppm), but the hydrocarbon concentration fluctuates rapidly in the primary chamber and is difficult to determine. However, as will be appreciated by those skilled in the art, the hydrocarbon concentration in the primary incineration chamber may exceed 500 ppm.

To perform all the tests, the setup shown in fig. 6 was used. In this arrangement, a plunger of catalyst material (. phi. -5.0-5.5 mm, 60-70mm long) was inserted into the center of a 900mm long quartz tube and held in place with quartz wool (quartz wool). For baseline measurements, the gas stream was directed into a parallel quartz tube containing only quartz wool.

In all cases except for sample K-KAD5-15, the reactor tube was placed in an 860mm Lindberg furnace at a temperature of 500 ℃ (± 50 ℃). In the case of sample K-KAD5-15, the reaction was carried out at a temperature of 400 ℃ (± 50 ℃). The air flow was then conditioned using a PermaPure dryer to remove particulates and moisture. NO_XThe concentration of (C) is determined using 0-2000ppm of Infrared NO from Analytical Development Company (Analytical Development Company)_XAnd (5) monitoring by a detector.

The gas passes through the catalyst material at a rate of 1.0-1.2 liters/minute { Gas Hourly Space Velocity (GHSV) to 60,000h^-1The velocity of the jet is discharged. The sampling time for all gases was 20-30 minutes.

In situ testing of the catalyst material demonstrated that NO was present at the flow rates and moderate temperatures used_XIs reduced toIs obvious and can be realized. In the set of catalyst materials tested, the conversion efficiency of sample K-KAD3-8 was less than 90%, while the conversion efficiency of the other catalysts was greater than 90%. Operation of these catalysts with different hydrocarbon and/or steam mixtures at different temperatures will result in different conversion efficiencies. For example, for sample K-KAD3-8, NO in the gas stream treated with this catalyst material was due to the relative lack of hydrocarbons in the secondary chamber_XThe reduction rate was low (-11.5% conversion). However, in this case, the relative absence of hydrocarbons demonstrates that NO can occur even at 500 ℃ (± 50 ℃) using this catalytic material_XDirect decomposition of (2). In the examples listed for the gases from the main chamber and the combustion zone, NO occurs by a selective catalytic reduction process in the presence of new material, assuming the concentration of hydrocarbons is rather high_XReduction of (2). Because the materials are stable at temperatures up to about 750 c and operate significantly at lower temperatures (e.g., 400 c), there is an opportunity to optimize these materials for higher conversion over a wider range of operating conditions. Example 5 Selective catalytic reduction of NO in Diesel exhaust_X

The exhaust gases from diesel engines were tested using cobalt and copper based catalyst materials. In all experiments, the setup shown in fig. 6 was used. In this arrangement, a plunger of catalyst material (. phi. -5.0-5.5 mm, 60-70mm long) was inserted into the center of a 900mm long quartz tube and held in place with quartz wool (quartz wool). For baseline measurements, the gas stream was directed into a parallel quartz tube containing only quartz wool. In all cases, the reactor tubes were placed in an 860mm Lindberg furnace at a temperature of 500 ℃ (± 50 ℃), and then the gas flow was adjusted using a Perma Pure dryer to remove particles and moisture. NO_XConcentration of (D) is determined by using infrared NO of 0-2000ppm analytical development company_XAnd (5) monitoring by a detector. The gas passes through the catalyst material at a rate of 1.0-1.2 liters/minute { Gas Hourly Space Velocity (GHSV) to 60,000h^-1The velocity of the jet is discharged. The sampling time for all gases was 20 minutes.

Table 9 lists the field tests conducted with five copper and cobalt based catalyst materialsTo get from firewoodConversion of NO in oil engine exhaust_XThe raw and derived data.

In-situ tests with these catalyst materials demonstrated that NO is present at the flow rates and moderate temperature conditions used_XIs obvious and is achievable. Of the catalyst materials tested, the conversion efficiency of the sample Co-KAD3-5 was a minimum of 91%, while the conversion of the other catalysts was greater than 91%. These catalysts will yield different conversion efficiencies operating at different temperatures with different hydrocarbon and/or steam mixtures. Additional tests were performed with these materials after a period of cooling and deactivation for 24 hours or more. Subsequent tests were carried out under similar conditions as given in Table 9, showing that these new materials also maintain the reduction of NO from diesel engine exhaust after a period of time at room temperature and ambient humidity_XThe ability of the cell to perform. Example 6 Selective catalytic reduction of NO in Diesel exhaust Using propane or Diesel Fuel_X

The test was performed on a KUBOTA GV1120 diesel engine, where the exhaust from the running engine was connected to a gas injection system. Additional hydrocarbons are then added to the exhaust stream as a mixture of propane and nitrogen or diesel fuel. This mixture is then contacted with the appropriate amount of catalyst placed in the reaction tube, which is located in a furnace using an arrangement similar to that shown in figure 6. The treated gas was analyzed by FTIR gas cell, passed through a dehumidifier and then treated with specific infrared NO_XAnd (5) analyzing by an analyzer.

For the calibration test at the start, no propane flow was used, so the off-gas passed through an empty pipe. The Cu-KAD3-7 and Co-KAD3-7 samples were tested at temperatures ranging from 380 ℃ to 550 ℃. In these tests, the engine load was kept constant at around 75%. The oxygen content in the gas stream was 14.9% when the engine was started, but not loaded, and 13.0% when the engine load was 75%. Under these application conditions, NO due to direct decomposition_XThe conversion remained below 10%. However, when these catalysts are used, the exhaust gas is analyzedAddition of propane to NO in the stream_XThe conversion is very favourable. FIG. 7 shows a series of test results demonstrating NO for Cu-KAD3-7_XConversion is related to the amount of different propane in the gas stream. Under these conditions, propane to NO for maximum conversion_XIs about 4: 1.

The long term stability of these catalysts was also tested under typical exhaust gas conditions, samplesThe results of the Co-KAD3-7 test are shown in FIG. 8. NO within a few hours (up to 13 hours)_XIs stable and above 80%, it is clear that the catalyst reaches a similar activity (or NO) after a period of time (e.g. about 1.5 hours) has ceased due to cooling to below 350 c_XConversion rate). Reactivation after a period of time corresponds to the normal operating mode of a car or a stationary diesel engine.

For some applications utilizing diesel engines, the use of propane is not suitable because of the need to store propane. Thus, these catalysts were similarly tested to determine NO by injecting diesel fuel into the exhaust stream_XThe conversion of (a). As shown in FIG. 9, addition of diesel fuel at these standard operating conditions results in NO_XThe conversion rate reaches about 70%. Example 7 use of NH₃Selective catalytic reduction of NO_X

The catalyst was prepared as follows. First converting K-KAD to NH₄ ⁺KAD, with TiCl₄Mixing, then TiCl is brought about by adding an aqueous ammonia solution₄And (4) hydrolyzing. Finally, the Ti-KAD is dried at 120 ℃ and sintered at 500 ℃ and impregnated with a suitable amount of a solution of ferric nitrate, niobium chloride, tin chloride, ammonium metavanadate or ammonium metatungstate. This material was then sintered at 500 ℃ before use in the microreactor shown in FIG. 10. The preparation of the above Fe-Ti-KAD, Fe-Sn-Ti-KAD, Fe-W-Ti-KAD, Fe-Nb-Ti-KAD, V-Sn-Ti-KAD and V-W-Ti-KAD catalysts are shown in Table 10, NO removal_x(DeNO_x) The activity was measured as shown in Table 11. The dependence of the activity of the iron-based catalyst on temperature is shown in fig. 11 and that of the vanadium-based catalyst is shown in fig. 12. Example 8 direct NO_X

By using iron nitrate and/or iron nitrate and ceriumExchanging the K-KAD with water solution to prepare Fe-KAD catalyst. To increase the concentration of iron and/or cerium after the exchange, the solution was purged with nitrogen to remove dissolved oxygen. Varying between pH2-4 as described in figure 13 to prepare different ion-KAD catalysts. Direct decomposition of NO using these catalysts_XThe results are shown in FIG. 13. Example 9 reduction of dioxins in waste gas streams

Introduction to the word

Polychlorinated dibenzo-ortho-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), generally collectively referred to as "dioxins", are formed downstream of the combustion chamber, typically via a known De Novo synthesis process, as the gases are cooled. This occurs in the temperature range of 250-400 c, formed by the reaction between incomplete combustion products in the presence of chlorine feed. Certain materials may act as catalysts for these reforming reactions. However, current research indicates that some substances may be converted into dioxins and other organic micropollutants (micro-polutants) into non-toxic by-products.

Of particular interest is NO_XReduction catalysts, which have been reported in the literature to have the potential to reduce the concentration of dioxins and related micropollutants.

To investigate the possibility of using KADs to reduce dioxins in the air stream, a series of tests were conducted on a pilot scale pathological waste (pathologist waste) incinerator equipped with a shell and tube heat exchanger and a bag collector.

Test apparatus

The incinerator is of a two-chamber design comprising a primary chamber where solid waste is burned and a secondary/post-combustion chamber to oxidize combustible gases and particulate matter discharged from the primary chamber.

The main chamber is a static fireplace (hearth) design, using a series of pushers (ram) to slowly push the waste into the burners to burn completely ash. The sub-chamber enables all the effluents generated in the main chamber to be maintained at a temperature of 800-.

The main chamber is operated under reducing (air-lean) conditions. Due to the lack of air, the volatile components of the waste are gasified. The combustible gas produced is mixed with air as fuel and completely oxidized in the secondary chamber. Natural gas is used as a supplemental fuel in both chambers.

The exhaust gas from the secondary chamber enters an air cooled heat exchanger and the gas temperature drops to 200 ℃. This maximizes the formation of dioxins by the De Novo process. The gas then passes through a bag collector and is filtered before being discharged through a stack.

There are two main reasons for introducing bag collectors in the experimental design:

(1) simulating industrial conditions (the most readily available technology used by most modern incineration equipment is bag collectors); and

(2) the gas stream is filtered prior to KAD so that there is a minimal chance of misleading the results due to KAD filtering.

The incineration system is shown in figure 14.

During the test, the incinerator was fed in batches every 10 minutes, the waste being carefully prepared, at a feed rate of 10 kg/hr. The waste contained 30% PVC, 60% shredded newspaper and 10% water (by weight).

For the catalytic tests, the experiment was run at a gas exit space velocity (gas flow (mls/hr)/catalyst volume (mls)) of 60,000hr^-1Under the conditions of (1). A plunger of KAD material is inserted into the center of the quartz tube and held in place with quartz wool. For baseline testing, the gas flow was directed through a parallel quartz tube containing only quartz wool. Catalytic and baseline studies were performed simultaneously.

The parallel quartz tube reactor tubes were all placed in a Lindberg furnace of 860mm length at 450 ℃ (± 20 ℃). The temperature was adjusted with a Eurotherm controller. In each test, the system was pre-conditioned (preconditioned) for 60 minutes prior to sampling. Samples were then collected over a period of 60-90 minutes.

Test method

Dioxin (DIOXIN)

PCDDs and PCDFs were sampled using a paired USEPA modified method 5 sampling system according to USEPA method 23, "determination of polychlorinated dibenzo-ortho-dioxins and polychlorinated dibenzofurans from stationary sources. Each sampling system sequentially comprises the following components: a nozzle, a quartz probe, a heated particle filter, a condenser, an XDA-2 adsorbent module (XDA-2 adsorbent module), an impinging sampler bank (Impinger bank), a diaphragm pump, and a gas meter.

By passing the quartz probe through the Lindberg furnace before the particle filter, it is possible to make the catalytic test apparatus a sampling system.

Before use, all parts used in contact with the sample were washed with pure solvent. Prior to sampling, XAD-2 resin was standard doped with isotopically labeled PCDD and PCDF substitutes. The filter, resin and collided sample solution are extracted with organic solvents and the extract is purified by chemical treatment and solid phase chromatography techniques.

The extraction and purification method is based on USEPA method 3540 (solid phase Soxhlet extractor extraction), 3545 (solid phase pressurized fluid extraction), 3510 (aqueous phase liquid/liquid extraction), 3520 (Florisil:) 3640 (gas chromatography).

The determination of PCDDs and PCDFs was performed using high resolution gas chromatography and low resolution mass spectrometer according to USEPA method 8280. For each class (four to eight), this method provides data on toxic 2, 3, 7, 8-chlorinated PCDDs and PCDFs and all non-2, 3, 7, 8-chlorinated PCDDs and PCDFs. The total toxic equivalent (I-YEQ) for each class was calculated using NATO (International) toxicity equivalent factors (I-TEFs).

The sampling/testing apparatus is shown in fig. 15.

Nitrogen oxides

Using Testo 350 series NO/NO₂/NO_XThe analyzer, following Victorian EPA standard analytical procedure B12- "total nitrogen oxides", monitors nitrogen oxides. Calibrated with NATA-signed Nitric Oxide (NO) full scale gas (span gas) and zeroed with instrument grade nitrogen.

Oxygen gas

Oxygen concentration was monitored using a Testo 350 series analyzer according to Victorian EPA standard analytical procedure B12- "oxygen (instrumental method)". Calibrated with ambient air and zeroed with instrument grade oxygen.

The estimation accuracy is +/-5%,

dioxins and NO_XThe results are shown in tables 12 and 13. The combined dioxin results are listed in tables 14 to 17.

The above embodiments are directed to NO_XAnd dioxins use aluminosilicate materials as catalysts, it being noted that aluminosilicate materials and their pairing for NO_XAnd dioxins are examples of heterogeneous catalysis (e.g., in Raymond Chang, ed "chemistry" 5 th edition (McGraw-Hill Inc. published 1994)). This catalysis suggests the use of a solid catalyst in a gas phase reaction system to effect oxidation with dioxin and NO_XA reduction reaction takes place. Similarly, as previously mentioned, the aluminosilicate materials of the present invention are capable of catalyzing SO_XCO or CO₂、PAHs。

With respect to PAHs, example 9 can also be used to apply the aluminosilicate material of the present invention to PAHs under similar conditions.

Table 1 comparison of desirable properties of catalyst materials

	ZSM5	Kaolin clay	Pillared clay	M-KAD or M-ASD
					ECE(meq/100g)	～50	＜10	～100	～100-900
Surface area (m)2g-1)	400	＜10	～100-250	～5-450

Table 2 summary of general preparation method of cation exchange KAD material

Preparation method	Without second exchange	Second exchange w Cu(NO3)2	Second exchange w Co(NO3)2
				KF + Kaolin	K-KAD3-1	Cu-KAD3-1	CoKAD3-1
KCl+KOH+ Kaolin clay	K-KAD3-5 and K-KAD3-7	Cu-KAD3-5， Cu-KAD3-7 and Cu-KAD0.5-13	Co-KAD3-5， Co-KAD3-7 and Co-KAD0.5-13
				KOH + Kaolin Soil for soil	K-KAD3-8， K-KAD5-15 and K-KAD-5-16	Cu-KAD5-15 and Cu-KAD5-16	Co-KAD5-15 and Co-KAD-5-16

TABLE 3 XPS data for copper-exchanged aluminosilicate derivatives

Bonding energy (eV)	Area of the band (arbitrary unit)
							CuKAD3- 1	CuKAD3- 5	CuKAD3- 7	CuKAD3- 13	CuKAD5- 16	Cu-ZSM5
	933.5	302	670	529	763	280							700
935.5							181	819	847	619	939	480

Table 4 summary of XPS analysis of catalyst materials

		Element (atomic%)
											Sample number	C	K	O	Si	Al	F	Cl	Cu	Co	Fe
K-KAD3-1	3.40	18.00	46.10	12.60	8.10	11.80	0.00	0.00	0.00	0.00
											K-KAD3-5	2.60	10.30	58.00	15.60	11.50	0.60	1.10	0.00	0.00	0.40
K-KAD3-7	3.00	9.20	59.70	15.00	11.40	1.20	0.60	0.00	0.00	0.00
											K-KAD5-16	4.80	11.50	59.10	14.10	10.50	0.00	0.00	0.00	0.00	0.00
CuKAD3-1	8.80	7.00	51.80	15.70	na	8.10	0.00	2.70	0.00	0.00
											CuKAD3-5	5.80	3.30	60.30	14.50	10.70	1.40	0.00	3.50	0.00	0.00
CuKAD3-7	4.00	1.10	63.80	14.70	11.30	1.70	0.00	3.60	0.00	0.00
											CuKAD½-13	7.20	3.00	60.50	13.80	10.90	1.60	0.00	3.10	0.00	0.00
CuKAD5-16	3.50	3.40	62.40	13.90	11.90	1.30	0.00	3.60	0.00	0.00
											CoKAD3-1	5.10	7.60	47.70	13.20	9.80	10.80	0.00	0.00	5.90	0.00
CoKAD3-5	14.70	6.00	53.30	13.10	10.10	0.00	0.30	0.00	2.50	0.00
											CoKAD3-7	4.50	4.40	62.50	15.40	10.20	0.00	0.00	0.00	3.10	0.00
CoKAD½-13	5.20	5.60	58.90	13.40	12.30	0.00	0.00	0.00	4.70	0.00
											CoKAD5-16	6.90	5.30	58.60	12.30	12.30	0.00	0.00	0.00	4.50	0.00

Table 5 summary of XPS data for catalyst samples

Sample number	Si/Al ratio	Ratio of K/Al	Cu/Al ratio	Ratio of Co to Al	Surface area (m2g-1)
						K-KAD3-1	1.55	2.22	-	-	40
K-KAD3-5	1.36	0.89	-	-	21
						K-KAD3-7	1.32	0.81	-	-	40
K-KAD5-16	1.34	1.10	-	-	121
						Cu-KAD3-1	-	-	-	-	5
CuKAD3-5	1.36	0.31	0.33	-	45
						CuKAD3-7	1.30	0 10	0.32	-	168
CuKAD½-13	1.27	0 28	0.28	-	28
						CuKAD5-16	1.17	0.29	0.30	-	92
Cu-ZSM5	25.23	-	1.11	-	-
						Co-KAD3-1	1.35	0.77	-	0.60	-
Co-KAD3-5	1.30	0 59	-	0.25	-
						Co-KAD3-7	1.49	0 43	-	0.30	-
Co-KAD½-13	1.09	0.46	-	0.38	-
						Co-KAD5-16	1.00	0.43	-	0.37	-

TABLE 6 FITR data for copper exchanged KAD material and Cu-ZSM5

Band position Device for placing (cm-1)	Area of sub-band
							Cu- KAD3-1	Cu- KAD3-5	Cu- KAD3-7	Cu- KAD0.5- 13	Cu- KAD5-16	Cu- ZSM5
	1575	0.010	0.011	0.010	0.029	0.022							0.004
1495							0.018	0.045	0.039	0.054	0.054	0.041
	1400	0.056	0.111	0.014	0.028	0.038							-
1360							0.016	0.057	0.007	0.017	0.020	0.009
	1310	0.042	0.083	0.066	0.106	0.092							0.028
1260							0.009	0.014	0.007	0.025	0.033	-

Table 7 summary of FITR data for adsorption of nitro, nitrite and nitrate species on select catalyst materials

Band position (cm-1)	Area of sub-band
					K-KAD3-1	K-KAD3-5	K-KAD3-7	K-KAD5-16
	1390	0.087	0.404	0.303					0.457
1360					0.122	0.566	0.248	0.428
	1317	0.000	0.065	0.076					0.153
1270					0.020	0.031	0.018	0.050

Table 8 field testing of catalyst materials: reduction of NO from incinerator effluent gas_X

Sample (I)	Discharge of water and gas Yuan (original) -Yuan (original) Incinerator	Estimated hydrocarbons (ppm)	NOXw/o Catalyst and process for preparing same (ppm)	NOXAnd catalyst Agent for chemical treatment (ppm)	Conversion rate%
						K-KAD5-15	Main chamber	＞500	217～269	16-29	90.3
K-KAD3-8	Auxiliary chamber	～3	302～331	266-294	11.5
						K-KAD3-8	Main chamber	＞500	122～160	13-24	87.5
K-KAD3-8	Main chamber	＞500	105～142	11-20	86.7
						Cu-KAD3-7	Main chamber	＞500	134～179	3-7	96.8
Cu-KAD5- 15	Main chamber	＞500	89～126	5-11	92.3
						Co-KAD3-7	Combustion zone	＞500	92～123	6-9	93.0
Co-KAD5- 15	Combustion zone	＞500	66～92	2-6	94.9
						Co-KAD3-5	Combustion zone	＞500	92～123	＜2-10	93.8

Table 9 field testing of catalyst materials: reduction of NO from diesel exhaust_X

Sample (I)	Estimated hydrocarbons (ppm)	NOXw/o catalyst Reagent (ppm)	NOXAnd catalysis Agent (ppm)	Conversion rate%
					Cu-KAD3-7	＞500	845-1023	21-69	95.2
Cu-KAD5-15	＞500	710-862	35-51	94.5
					Co-KAD3-7	＞500	682-794	28-60	94.0
Co-KAD5-15	＞500	910-1187	55-86	93.3
					Cu-KAD3-5	＞500	653-698	49-73	91.0

TABLE 10 preparation of the catalysts

Catalyst and process for preparing same	Si/Al molar ratio	Sintering temperature (. degree. C.)
			Fe-Ti-KAD	1.5	500
Fe-Sn-Ti-KAD	1.5	500
			Fe-W-Ti-KAD	1.5	500
Fe-Nb-KAD	1.5	500
			V-Sn-Ti-KAD	1.5	500
V-W-Ti-KAD	1.5	500

TABLE 11 DenO_XDetermination of Activity

Catalyst particle size; 10-20 mesh (0.84-1.68mm)

The amount of catalyst used; (0.3ml)

Gas flow rate; (0.5/min)

Space Velocity (GHSV); 100,000h^-1

Gas composition; NO 200ppm, NH₃＝240ppm，O₂＝3％；CO₂＝12％，H₂O＝12％TABLE 12 Dioxin results

Experiment of	KAD	I-TEQ does not KAD(ng/Sm3)	I-TEQ has KAD(ng/Sm3)	Percent removal
					1	Cu-KAD	7.75	1.83	76.5
2	Mn-KAD	7.20	2.85	60.4
					3	Co-KAD	7.83	3.75	52.1
4	Cr-KAD	8.44	1.94	77.0
					5	Ni-KAD	7.72	3.66	52.6
6	Fe-KAD	7.18	2.39	66.7
					7	K-KAD	7.45	4.04	45.8

Watch 13

Experiment of	KAD number	Flat with KAD Homo NOXConcentration of (mg/Nm3)	Flat without KAD Homo NOXConcentration of (mg/Nm3)	Percent removal
					1	Cu-KAD	32(29-34)	327(314-340)	90
2	Mn-KAD	41(40-42)	215(205-224)	81
					3	Co-KAD	30(27-32)	237(228-246)	87
4	Cr-KAD	50(61-65)	300(293-307)	83
					5	Ni-KAD	32(30-34)	243(237-249)	87
6	Fe-KAD	51(47-54)	230(227-233)	78
					7	K-KAD	54(52-55)	195(188-202)	72

Table 14 dioxin profile for experiment 1-dry gas volume sampled for baseline study 0.952m³@20 ℃, 101.3kPa and 14.9% O₂Dry gas volume sampled 0.538Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	2.97	5.52	0.1	0.552
Non-2378 tetrachlorodibenzofurans	52.1	96.8	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.883	1.64	1	1.64
Non-2378 tetrachlorodibenzo-o-dioxin	7.53	14.0	0	0
12378 pentachlorodibenzofurans	3.55	6.60	0.05	0.33
					23478 pentachlorodibenzofurans	2.17	4.03	0.5	2.02
Non-2378 pentachlorodibenzofurans	44.9	83.5	0	0
					12378 pentachlorodibenzo-o-dioxin	0.715	1.33	0.5	0.664
Non-2378 pentachlorodibenzo-o-dioxins	4.47	8.31	0	0
123478 Hexachlorodibenzofuran	3.01	5.59	0.1	0.559
					123678 Hexachlorodibenzofuran	4.90	9.11	0.1	0.911
234678 Hexachlorodibenzofuran	2.62	4.87	0.1	0.487

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.312	0.580	0.1	0.0580
Non-2378 hexachlorodibenzofuran	14.9	27.7	0	0
					123478 hexachlorodibenzo-o-dioxin	0.442	0.822	0.1	0.822
123678 hexachlorodibenzo-o-dioxin	0.718	1.33	0.1	0.133
					123789 hexachlorodibenzo-o-dioxin	0.610	1.13	0.1	0.113
Non-2378 hexachlorodibenzo-o-dioxin	4.59	8.53	0	0
1234678 Heptachlorodibenzofuran	6.52	12.1	0.01	0.121
					1234789 Heptachlorodibenzofuran	0.946	1.76	0.01	0.0176
Non-2378 Heptachlorodibenzofurans	3.16	5.87	0	0
					1234678 Heptachloro dibenzo-o-dioxin	2.63	4.89	0.01	0.0489
Non-2378 heptachloro dibenzo-o-dioxin	2.51	4.67	0	0
Octachlorodibenzofuran	4.99	9.28	0.001	0.00928
					Ochlorodibenzo-o-dioxin	4.40	8.18	0.001	0.000818
Total toxicity equivalent: 7.75ng/Sm3(based on NATO)

Table 15 dioxin profile from experiment 1-dry gas volume sampled by KAD3 test 0.928m³@19 ℃, 101.3kPa and 14.9% O₂Dry gas volume sampled 0.526Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.344	0.654	0.1	0.0654
Non-2378 tetrachlorodibenzofurans	19.2	36.5	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.169	0.321	1	0.321
Non-2378 tetrachlorodibenzo-o-dioxin	3.77	7.17	0	0
12378 pentachlorodibenzofurans	0.790	1.50	0.05	0.0751
					23478 pentachlorodibenzofurans	0.426	0.810	0.5	0.405
Non-2378 pentachlorodibenzofurans	9.24	17.6	0	0
					12378 pentachlorodibenzo-o-dioxin	0.228	0.433	0.5	0.217
Non-2378 pentachlorodibenzo-o-dioxins	0.752	1.43	0	0
123478 Hexachlorodibenzofuran	0.922	1.75	0.1	0.175
					123678 Hexachlorodibenzofuran	0.702	1.33	0.1	0.133
234678 Hexachlorodibenzofuran	0.782	1.49	0.1	0.149

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I- TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.0998	0.190	0.1	0.0190
Non-2378 hexachlorodibenzofuran	9.56	18.2	0	0
					123478 hexachlorodibenzo-o-dioxin	0.0995	0.189	0.1	0.0189
123678 hexachlorodibenzo-o-dioxin	0.106	0.202	0.1	0.0202
					123789 hexachlorodibenzo-o-dioxin	0.309	0.587	0.1	0.0587
Non-2378 hexachlorodibenzo-o-dioxin	1.07	2.03	0	0
1234678 Heptachlorodibenzofuran	4.63	8.80	0.01	0.0880
					1234789 Heptachlorodibenzofuran	0.0829	0.158	0.01	0.00158
Non-2378 Heptachlorodibenzofurans	2.33	4.43	0	0
					1234678 Heptachloro dibenzo-o-dioxin	3.71	7.05	0.01	0.0705
Non-2378 heptachloro dibenzo-o-dioxin	1.76	3.35	0	0
Octachlorodibenzofuran	2.23	4.24	0.001	0.00424
					Ochlorodibenzo-o-dioxin	1.43	2.72	0.001	0.00272
Total toxicity equivalent: 1.83ng/Sm3(based on NATO)

TABLE 16 Dioxin Profile of experiment 2-sampled from baseline studyDry gas volume 0.935m³@23 ℃, 101.3kPa and 15.1% O₂Dry gas volume sampled 0.505Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	3.19	6.31	0.1	0.631
Non-2378 tetrachlorodibenzofurans	49.8	98.6	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.431	0.854	1	0.854
Non-2378 tetrachlorodibenzo-o-dioxin	7.29	14.4	0	0
12378 pentachlorodibenzofurans	3.72	7.37	0.05	0.369
					23478 pentachlorodibenzofurans	2.40	4.76	0.5	2.38
Non-2378 pentachlorodibenzofurans	24.9	49.3	0	0
					12378 pentachlorodibenzo-o-dioxin	0.697	1.38	0.5	0.690
Non-2378 pentachlorodibenzo-o-dioxins	4.73	9.37	0	0
123478 Hexachlorodibenzofuran	2.35	4.66	0.1	0.466
					123678 Hexachlorodibenzofuran	3.63	7.19	0.1	0.719
234678 Hexachlorodibenzofuran	2.79	5.53	0.1	0.553

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I- TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.237	0.469	0.1	0.0469
Non-2378 hexachlorodibenzofuran	20.7	41.0	0	0
					123478 hexachlorodibenzo-o-dioxin	0.328	0.649	0.1	0.0649
123678 hexachlorodibenzo-o-dioxin	0.472	0.934	0.1	0.0934
					123789 hexachlorodibenzo-o-dioxin	0.450	0.892	0.1	0.0892
Non-2378 hexachlorodibenzo-o-dioxin	4.22	8.36	0	0
1234678 Heptachlorodibenzofuran	8.48	16.8	0.01	0.168
					1234789 Heptachlorodibenzofuran	1.17	2.32	0.01	0.0232
Non-2378 Heptachlorodibenzofurans	3.60	7.12	0	0
					1234678 Heptachloro dibenzo-o-dioxin	1.90	3.76	0.01	0.0376
Non-2378 heptachloro dibenzo-o-dioxin	2.84	5.63	0	0
Octachlorodibenzofuran	4.82	9.54	0.001	0.00954
					Ochlorodibenzo-o-dioxin	4.44	8.80	0.001	0.00880
Total toxicity equivalent: 7.20ng/Sm3(based on NATO)

Table 17 dioxin profile from experiment 2-dry gas volume sampled by KAD9 test ═ 1.009m³@23 ℃, 101.3kPa and 15.1% O₂The volume of dry gas sampled was 0.545Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.319	0.586	0.1	0.0586
Non-2378 tetrachlorodibenzofurans	8.61	15.8	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.0353	0.0648	1	0.0648
Non-2378 tetrachlorodibenzo-o-dioxin	5.01	9.19	0	0
12378 pentachlorodibenzofurans	0.385	0.707	0.05	0.0354
					23478 pentachlorodibenzofurans	1.51	2.77	0.5	1.39
Non-2378 pentachlorodibenzofurans	18.9	34.6	0	0
					12378 pentachlorodibenzo-o-dioxin	0.472	0.866	0.5	0.433
Non-2378 pentachlorodibenzo-o-dioxins	1.68	3.08	0	0
123478 Hexachlorodibenzofuran	0.861	1.58	0.1	0.158
					123678 Hexachlorodibenzofuran	0.471	0.864	0.1	0.0864
234678 Hexachlorodibenzofuran	2.10	3.85	0.1	0.385

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.146	0.268	0.1	0.0268
Non-2378 hexachlorodibenzofuran	4.51	8.28	0	0
					123478 hexachlorodibenzo-o-dioxin	0.190	0.349	0.1	0.0349
123678 hexachlorodibenzo-o-dioxin	0.125	0.229	0.1	0.0229
					123789 hexachlorodibenzo-o-dioxin	0.156	0.287	0.1	0.0287
Non-2378 hexachlorodibenzo-o-dioxin	3.31	6.07	0	0
1234678 Heptachlorodibenzofuran	5.29	9.70	0.01	0.0970
					1234789 Heptachlorodibenzofuran	0.0823	0.151	0.01	0.00151
Non-2378 Heptachlorodibenzofurans	1.44	2.65	0	0
					1234678 HeptachlorodibenzoOrtho-dioxins	0.834	1.53	0.01	0.0153
Non-2378 heptachloro dibenzo-o-dioxin	1.99	3.66	0	0
Octachlorodibenzofuran	2.30	4.22	0.001	0.00422
					Ochlorodibenzo-o-dioxin	2.83	5.19	0.001	0.00519
Total toxicity equivalent: 2.85ng/Sm3(based on NATO)

Table 18 dioxin profile for experiment 3-dry gas volume sampled for baseline study 0.889m³@22 ℃, 101.3kPa and 14.0% O₂Dry gas volume sampled 0.573Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	4.55	7.94	0.1	0.794
Non-2378 tetrachlorodibenzofurans	84.6	148	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.479	0.836	1	0.836
Non-2378 IVChlorine dibenzo-o-dioxin	3.98	6.95	0	0
12378 pentachlorodibenzofurans	6.28	11.0	0.05	0.648
					23478 pentachlorodibenzofurans	3.71	6.47	0.5	3.24
Non-2378 pentachlorodibenzofurans	23.1	40.3	0	0
					12378 pentachlorodibenzo-o-dioxin	0.614	1.07	0.5	0.536
Non-2378 pentachlorodibenzo-o-dioxins	3.12	5.45	0	0
123478 Hexachlorodibenzofuran	3.88	6.77	0.1	0.677
					123678 Hexachlorodibenzofuran	2.91	5.08	0.1	0.508
234678 Hexachlorodibenzofuran	1.43	2.50	0.1	0.250

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.295	0.515	0.1	0.0515
Non-2378 hexachlorodibenzofuran	33.8	59.0	0	0
					123478 sixChlorine dibenzo-o-dioxin	0.466	0.813	0.1	0.0813
123678 hexachlorodibenzo-o-dioxin	0.306	0.534	0.1	0.0034
					123789 hexachlorodibenzo-o-dioxin	0.499	0.871	0.1	0.0871
Non-2378 hexachlorodibenzo-o-dioxin	2.88	5.03	0	0
1234678 Heptachlorodibenzofuran	6.12	10.7	0.01	0.107
					1234789 Heptachlorodibenzofuran	0.985	1.72	0.01	0.0172
Non-2378 Heptachlorodibenzofurans	2.67	4.66	0	0
					1234678 Heptachloro dibenzo-o-dioxin	1.51	2.64	0.01	0.0264
Non-2378 heptachloro dibenzo-o-dioxin	4.73	8.25	0	0
Octachlorodibenzofuran	5.35	9.34	0.001	0.00934
					Ochlorodibenzo-o-dioxin	3.14	5.48	0.001	0.00548
Total toxicity equivalent: 7.83ng/Sm3(based on NATO)

Table 19 dioxin profile from experiment 3-volume of dry gas sampled by KAD14 test of 1.109m³@24 ℃, 101.3kPa and 14.0% O₂Dry gas volume sampled 0.710Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.744	1.05	0.1	0.105
Non-2378 tetrachlorodibenzofurans	12.8	18.0	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.0960	0.135	1	0.135
Non-2378 tetrachlorodibenzo-o-dioxin	7.40	10.4	0	0
12378 pentachlorodibenzofurans	0.841	1.18	0.05	0.0592
					23478 pentachlorodibenzofurans	3.52	4.96	0.5	2.48
Non-2378 pentachlorodibenzofurans	10.3	14.5	0	0
					12378 pentachlorodibenzo-o-dioxin	0.388	0.546	0.5	0.273
Non-2378 pentachlorodibenzo-o-dioxins	3.03	4.27	0	0
123478 Hexachlorodibenzofuran	0.711	1.00	0.1	0.100
					123678 Hexachlorodibenzofuran	0.357	0.503	0.1	0.0503
234678 Hexachlorodibenzofuran	2.33	3.28	0.1	0.328

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.346	0.487	0.1	0.0487
Non-2378 hexachlorodibenzofuran	3.74	5.27	0	0
					123478 hexachlorodibenzo-o-dioxin	0.275	0.387	0.1	0.0387
123678 hexachlorodibenzo-o-dioxin	0.165	0.232	0.1	0.0232
					123789 hexachlorodibenzo-o-dioxin	0.0922	0.130	0.1	0.0130
Non-2378 hexachlorodibenzo-o-dioxin	2.16	3.04	0	0
1234678 Heptachlorodibenzofuran	5.94	8.37	0.01	0.0837
					1234789 Heptachlorodibenzofuran	0.0656	0.0924	0.01	0.000924
Non-2378 Heptachlorodibenzofurans	2.34	3.30	0	0
					1234678 Heptachloro dibenzo-o-dioxin	0.463	0.652	0.01	0.00652
Non-2378 heptachloro dibenzo-o-dioxin	2.56	3.61	0	0
Octachlorodibenzofuran	4.19	5.90	0.001	0.00590
					Ochlorodibenzo-o-dioxin	2.06	2.90	0.001	0.00290
Total toxicity equivalent: 3.75ng/Sm3(based on NATO)

Table 20 dioxin profile for experiment 4-dry gas volume sampled from baseline study 0.844m³@24 ℃, 101.3kPa and 13.8% O₂Dry gas volume sampled 0.556Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	4.27	7.68	0.1	0.768
Non-2378 tetrachlorodibenzofurans	82.1	148	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.897	1.61	1	1.61
Non-2378 tetrachlorodibenzo-o-dioxin	6.48	11.7	0	0
12378 pentachlorodibenzofurans	2.23	4.01	0.05	0.201
					23478 pentachlorodibenzofurans	2.75	4.95	0.5	2.47
Non-2378 pentachlorodibenzofurans	36.2	65.1	0	0
					12378 pentachlorodibenzo-o-dioxin	0.519	0.933	0.5	0.467
Non-2378 pentachlorodibenzo-o-dioxins	7.49	13.5	0	0
123478 Hexachlorodibenzofuran	2.98	5.36	0.1	0.536
					123678 Hexachlorodibenzofuran	4.70	8.45	0.1	0.845
234678 Hexachlorodibenzofuran	5.02	9.03	0.1	0.903

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.349	0.628	0.1	0.0628
Non-2378 hexachlorodibenzofuran	21.8	39.2	0	0
					123478 hexachlorodibenzo-o-dioxin	0.456	0.820	0.1	0.0820
123678 hexachlorodibenzo-o-dioxin	0.630	1.13	0.1	0.113
					123789 hexachlorodibenzo-o-dioxin	0.466	0.838	0.1	0.0838
Non-2378 hexachlorodibenzo-o-dioxin	3.07	5.52	0	0
1234678 Heptachlorodibenzofuran	7.91	14.2	0.01	0.142
					1234789 Heptachlorodibenzofuran	1.99	3.58	0.01	0.0350
Non-2378 Heptachlorodibenzofurans	5.39	9.69	0	0
					1234678 Heptachloro dibenzo-o-dioxin	5.78	10.4	0.01	0.104
Non-2378 heptachloro dibenzo-o-dioxin	3.13	5.63	0	0
Octachlorodibenzofuran	4.27	7.68	0.001	0.00768
					Ochlorodibenzo-o-dioxin	6.69	12.0	0.001	0.012
Total toxicity equivalent: 8.44ng/Sm3(based on NATO)

Table 21 dioxin profile from experiment 4-volume of dry gas sampled by KAD19 test 0.877m³@24 ℃, 101.3kPa and 13.8% O₂The volume of dry gas sampled was 0.578Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.432	0.747	0.1	0.0747
Non-2378 tetrachlorodibenzofurans	34.6	59.9	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.0952	0.165	1	0.165
Non-2378 tetrachlorodibenzo-o-dioxin	3.93	6.80	0	0
12378 pentachlorodibenzofurans	1.53	2.65	0.05	0.132
					23478 pentachlorodibenzofurans	0.757	1.31	0.5	0.655
Non-2378 pentachlorodibenzofurans	16.9	29.2	0	0
					12378 fiveChlorine dibenzo-o-dioxin	0.274	0.474	0.5	0.237
Non-2378 pentachlorodibenzo-o-dioxins	1.58	2.73	0	0
123478 Hexachlorodibenzofuran	0.648	1.12	0.1	0.112
					123678 Hexachlorodibenzofuran	0.907	1.57	0.1	0.157
234678 Hexachlorodibenzofuran	0.879	1.52	0.1	0.152

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.237	0.410	0.1	0.0410
Non-2378 hexachlorodibenzofuran	4.69	8.11	0	0
					123478 hexachlorodibenzo-o-dioxin	0.0794	0.137	0.1	0.0137
123678 hexachlorodibenzo-o-dioxin	0.262	0.453	0.1	0.0453
					123789 hexachlorodibenzo-o-dioxin	0.108	0.187	0.1	0.0187
Non-2378 hexachlorodibenzo-o-dioxin	1.56	2.70	0	0
1234678 Heptachlorodibenzofuran	5.97	10.3	0.01	0.103
					1234789 Heptachlorodibenzofuran	0.0748	0.129	0.01	0.00129
Non-2378 Heptachlorodibenzofurans	2.12	3.67	0	0
					1234678 Heptachloro dibenzo-o-dioxin	1.64	2.84	0.01	0.0284
Non-2378 heptachloro dibenzo-o-dioxin	1.38	2.39	0	0
Octachlorodibenzofuran	3.46	5.99	0.001	0.00599
					Ochlorodibenzo-o-dioxin	0.969	1.68	0.001	0.00168
Total toxicity equivalent: 1.94ng/Sm3(based on NATO)

Table 22 dioxin profile for experiment 5-dry gas volume sampled for baseline study 0.913m³@21 ℃, 101.3kPa and 14.9% O₂Dry gas volume sampled 0.514Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	3.23	6.28	0.1	0.628
Non-2378 tetrachlorodibenzofurans	45.1	87.7	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.424	0.825	1	0.825
Non-2378 tetrachlorodibenzo-o-dioxin	7.65	14.9	0	0
12378 pentachlorodibenzofurans	3.13	6.09	0.05	0.304
					23478 pentachlorodibenzofurans	2.49	4.84	0.5	2.42
Non-2378 pentachlorodibenzofurans	27.9	54.3	0	0
					12378 pentachlorodibenzo-o-dioxin	0.433	0.842	0.5	0.421
Non-2378 pentachlorodibenzo-o-dioxins	6.29	12.2	0	0
123478 Hexachlorodibenzofuran	4.97	9.67	0.1	0.967
					123678 Hexachlorodibenzofuran	4.49	8.74	0.1	0.874
234678 Hexachlorodibenzofuran	3.38	6.58	0.1	0.658

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.314	0.611	0.1	0.611
Non-2378 hexachlorodibenzofuran	29.8	58.0	0	0
					123478 hexachlorodibenzo-o-dioxin	0.459	0.893	0.1	0.0893
123678 hexachlorodibenzo-o-dioxin	0.647	1.26	0.1	0.126
					123789 hexachlorodibenzo-o-dioxin	0.566	1.10	0.1	0.110
Non-2378 hexachlorodibenzo-o-dioxin	3.01	5.86	0	0
1234678 Heptachlorodibenzofuran	7.36	14.3	0.01	0.143
					1234789 Heptachlorodibenzofuran	0.765	1.49	0.01	0.0149
Non-2378 Heptachlorodibenzofurans	3.47	6.75	0	0
					1234678 Heptachloro dibenzo-o-dioxin	2.90	5.64	0.01	0.0564
Non-2378 heptachloro dibenzo-o-dioxin	2.17	4.22	0	0
Octachlorodibenzofuran	7.59	14.8	0.001	0.0148
					Ochlorodibenzo-o-dioxin	4.76	9.26	0.001	0.00926
Total toxicity equivalent: 7.72ng/Sm3(based on NATO)

Table 23 dioxin profile from experiment 4-volume of dry gas sampled by KAD23 test of 0.968m³@21 ℃, 101.3kPa and 14.9% O₂The volume of dry gas sampled was 0.545Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.972	1.78	0.1	0.178
Non-2378 tetrachlorodibenzofurans	35.5	65.1	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.181	0.332	1	0.332
Non-2378 tetrachlorodibenzo-o-dioxin	2.58	4.73	0	0
12378 pentachlorodibenzofurans	1.60	2.94	0.05	0.147
					23478 pentachlorodibenzofurans	1.74	3.19	0.5	1.60
Non-2378 pentachlorodibenzofurans	22.4	41.1	0	0
					12378 pentachlorodibenzo-o-dioxin	0.628	1.15	0.5	0.576
Non-2378 pentachlorodibenzo-o-dioxins	2.56	4.70	0	0
123478 Hexachlorodibenzofuran	0.692	1.27	0.1	0.127
					123678 Hexachlorodibenzofuran	1.05	1.93	0.1	0.193
234678 Hexachlorodibenzofuran	1.15	2.11	0.1	0.211

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.166	0.305	0.1	0.0305
Non-2378 hexachlorodibenzofuran	8.34	15.3	0	0
					123478 hexachlorodibenzo-o-dioxin	0.196	0.360	0.1	0.0360
123678 hexachlorodibenzo-o-dioxin	0.148	0.272	0.1	0.0272
					123789 hexachlorodibenzo-o-dioxin	0.194	0.356	0.1	0.0356
Non-2378 hexachlorodibenzo-o-dioxin	2.14	3.93	0	0
1234678 Heptachlorodibenzofuran	4.65	8.53	0.01	0.0853
					1234789 Heptachlorodibenzofuran	0.213	0.391	0.01	0.00391
Non-2378 Heptachlorodibenzofurans	2.94	5.39	0	0
					1234678 Heptachloro dibenzo-o-dioxin	3.88	7.12	0.01	0.0712
Non-2378 heptachloro dibenzo-o-dioxin	2.73	5.01	0	0
Octachlorodibenzofuran	4.53	8.31	0.001	0.00831
					Ochlorodibenzo-o-dioxin	0.958	1.76	0.001	0.00176
Total toxicity equivalent: 3.66ng/Sm3(based on NATO)

Table 24 dioxin profile for experiment 6-dry gas volume sampled from baseline study 0.965m³@21 ℃, 101.3kPa and 14.7% O₂The volume of dry gas sampled was 0.561Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	2.65	4.73	0.1	0.473
Non-2378 tetrachlorodibenzofurans	51.8	92.4	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.539	0.961	1	0.961
Non-2378 tetrachlorodibenzo-o-dioxin	6.84	12.2	0	0
12378 pentachlorodibenzofurans	2.95	5.26	0.05	0.263
					23478 pentachlorodibenzofurans	2.85	5.08	0.5	2.54
Non-2378 pentachlorodibenzofurans	34.6	61.7	0	0
					12378 pentachlorodibenzo-o-dioxin	0.634	1.13	0.5	0.564
Non-2378 pentachlorodibenzo-o-dioxins	4.79	8.53	0	0
123478 Hexachlorodibenzofuran	3.23	5.75	0.1	0.575
					123678 Hexachlorodibenzofuran	3.56	6.34	0.1	0.634
234678 Hexachlorodibenzofuran	3.60	6.42	0.1	0.642

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.255	0.454	0.1	0.0454
Non-2378 hexachlorodibenzofuran	20.3	36.1	0	0
					123478 hexachlorodibenzo-o-dioxin	0.344	0.614	0.1	0.0614
123678 hexachlorodibenzo-o-dioxin	0.572	1.02	0.1	0.102
					123789 hexachlorodibenzo-o-dioxin	0.502	0.895	0.1	0.0895
Non-2378 hexachlorodibenzo-o-dioxin	4.14	7.38	0	0
1234678 Heptachlorodibenzofuran	8.19	14.6	0.01	0.146
					1234789 Heptachlorodibenzofuran	1.03	1.83	0.01	0.0183
Non-2378 Heptachlorodibenzofurans	3.16	5.63	0	0
					1234678 Heptachloro dibenzo-o-dioxin	2.63	4.68	0.01	0.0468
Non-2378 heptachloro dibenzo-o-dioxin	2.51	4.47	0	0
Octachlorodibenzofuran	4.99	8.90	0.001	0.00890
					Ochlorodibenzo-o-dioxin	4.40	7.85	0.001	0.00785
Total toxicity equivalent: 7.18ng/Sm3(based on NATO)

Table 25 dioxin profile from experiment 6-dry gas volume sampled by KAD25 test 0.875m³@21 ℃, 101.3kPa and 14.7% O₂Dry gas volume sampled 0.509Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	0.565	1.11	0.1	0.111
Non-2378 tetrachlorodibenzofurans	29.3	57.5	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.122	0.240	1	0.240
Non-2378 tetrachlorodibenzo-o-dioxin	2.6	5.22	0	0
12378 pentachlorodiphenylAnd furan	1.41	1.39	0.05	0.139
					23478 pentachlorodibenzofurans	0.799	1.57	0.5	0.785
Non-2378 pentachlorodibenzofurans	14.8	29.1	0	0
					12378 pentachlorodibenzo-o-dioxin	0.363	0.714	0.5	0.357
Non-2378 pentachlorodibenzo-o-dioxins	1.14	2.23	0	0
123478 Hexachlorodibenzofuran	0.708	1.39	0.1	0.139
					123678 Hexachlorodibenzofuran	0.886	1.74	0.1	0.174
234678 Hexachlorodibenzofuran	1.10	2.17	0.1	0.217

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.124	0.244	0.1	0.0244
Non-2378 hexachlorodibenzofuran	5.55	10.9	0	0
					123478 hexachlorodibenzo-o-dioxin	0.122	0.239	0.1	0.0239
123678 hexachlorodibenzo-o-dioxin	0.0952	0.187	0.1	0.0187
					123789 hexachlorodibenzo-o-dioxin	0.175	0.343	0.1	0.0343
Non-2378 hexachlorodibenzo-o-dioxin	1.30	2.56	0	0
1234678 Heptachlorodibenzofuran	3.66	7.19	0.01	0.0719
					1234789 Heptachlorodibenzofuran	0.102	0.201	0.01	0.00201
Non-2378 Heptachlorodibenzofurans	2.24	4.41	0	0
					1234678 Heptachloro dibenzo-o-dioxin	2.38	4.68	0.01	0.0468
Non-2378 heptachloro dibenzo-o-dioxin	1.47	2.89	0	0
Octachlorodibenzofuran	3.32	6.53	0.001	0.00653
					Ochlorodibenzo-o-dioxin	0.774	1.52	0.001	0.00152
Total toxicity equivalent: 2.39ng/Sm3(based on NATO)

Table 26 dioxin profile for experiment 7-dry gas volume sampled for baseline study 0.951m³@25 ℃, 101.3kPa and 13.8% O₂Dry gas volume sampled 0.625Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	3.54	5.66	0.1	0.566
Non-2378 tetrachlorodibenzofurans	46.9	75.0	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.571	0.914	1	0.914
Non-2378 tetrachlorodibenzo-o-dioxin	8.14	13.0	0	0
12378 pentachlorodibenzofurans	3.57	5.71	0.05	0.286
					23478 pentachlorodibenzofurans	3.74	5.98	0.5	2.99
Non-2378 pentachlorodibenzofurans	28.5	45.6	0	0
					12378 pentachlorodibenzo-o-dioxin	0.791	1.27	0.5	0.633
Non-2378 pentachlorodibenzo-o-dioxins	4.08	6.53	0	0
123478 Hexachlorodibenzofuran	3.91	6.26	0.1	0.626
					123678 Hexachlorodibenzofuran	2.55	4.08	0.1	0.408
234678 Hexachlorodibenzofuran	2.70	4.32	0.1	0.432

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.391	0.626	0.1	0.0626
Non-2378 hexachlorodibenzofuran	24.7	39.5	0	0
					123478 hexachlorodibenzo-o-dioxin	0.578	0.925	0.1	0.0925
123678 hexachlorodibenzo-o-dioxin	0.672	1.08	0.1	0.108
					123789 hexachlorodibenzo-o-dioxin	0.471	0.754	0.1	0.0754
Non-2378 hexachlorodibenzo-o-dioxin	5.85	9.36	0	0
1234678 Heptachlorodibenzofuran	9.67	15.5	0.01	0.155
					1234789 Heptachlorodibenzofuran	1.88	3.01	0.01	0.0301
Non-2378 Heptachlorodibenzofurans	3.49	5.58	0	0
					1234678 Heptachloro dibenzo-o-dioxin	3.52	5.63	0.01	0.0563
Non-2378 heptachloro dibenzo-o-dioxin	4.81	7.70	0	0
Octachlorodibenzofuran	6.37	10.2	0.001	0.0102
					Ochlorodibenzo-o-dioxin	6.11	9.78	0.001	0.00978
Total toxicity equivalent: 7.45ng/Sm3(based on NATO)

Table 27 dioxin profile from experiment 7-volume of dry gas sampled by KADK test 0.943m³@25 ℃, 101.3kPa and 13.8% O₂Dry gas volume sampled 0.620Nm³@0 ℃, 101.3kPa and 11% O₂

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					2378 Tetrachlorodibenzofuran	1.53	2.47	0.1	0.247
Non-2378 tetrachlorodibenzofurans	31.8	51.3	0	0
					2378 Tetrachlorodibenzo-o-dioxin	0.361	0.582	1	0.582
Non-2378 tetrachlorodibenzo-o-dioxin	3.79	6.11	0	0
12378 pentachlorodibenzofurans	1.74	2.81	0.05	0.140
					23478 pentachlorodibenzofurans	1.53	2.47	0.5	1.23
Non-2378 pentachlorodibenzofurans	19.2	31.0	0	0
					12378 pentachlorodibenzo-o-dioxin	0.581	0.937	0.5	0.469
Non-2378 pentachlorodibenzo-o-dioxins	2.72	4.39	0	0
123478 Hexachlorodibenzofuran	2.09	3.37	0.1	0.337
					123678 Hexachlorodibenzofuran	2.23	3.60	0.1	0.360
234678 Hexachlorodibenzofuran	1.81	2.92	0.1	0.292

PCDD and PCDF	Quality (ng)	Concentration (ng)5/Sm3)	I-TEF	I-TEQ(ng/Sm3)
					123789 Hexachlorodibenzofuran	0.237	0.382	0.1	0.0382
Non-2378 hexachlorodibenzofuran	8.48	13.7	0	0
					123478 hexachlorodibenzo-o-dioxin	0.497	0.802	0.1	0.0802
123678 hexachlorodibenzo-o-dioxin	0.168	0.271	0.1	0.0271
					123789 hexachlorodibenzo-o-dioxin	0.414	0.668	0.1	0.0668
Non-2378 hexachlorodibenzo-o-dioxin	1.83	2.95	0	0
1234678 Heptachlorodibenzofuran	5.72	9.23	0.01	0.0923
					1234789 Heptachlorodibenzofuran	0.880	1.42	0.01	0.0142
Non-2378 Heptachlorodibenzofurans	2.67	4.31	0	0
					1234678 Heptachloro dibenzo-o-dioxin	3.25	5.24	0.01	0.0524
Non-2378 heptachloro dibenzo-o-dioxin	3.17	5.11	0	0
Octachlorodibenzofuran	4.84	7.81	0.001	0.00781
					Ochlorodibenzo-o-dioxin	1.49	2.40	0.001	0.00240
Total toxicity equivalent: 4.04ng/Sm3(based on NATO)

TABLE AND FIGURE DESCRIPTION TABLE 12Sm³Dry gas volume, cubic meter, 0 ℃, 101.3kPa and 11% O₂. TABLE 13Nm³Dry gas (dry gas)Volume, cubic meter, 0 ℃, 101.3kPa and 7% O₂. Tables 14-27 ng-nanogram (10)^-9G) Sm³Dry gas volume, cubic meter, 0 ℃, 101.3kPa and 11% O₂. International toxicity equivalent factor I-TEQ is the international toxicity equivalent based on 2, 3, 7, 8-TCDD. FIG. 1 is a combined microanalysis/vibration spectroscopy apparatus. FIG. 2(a) Cu-ZSM5 (squares) and (b) Cu-KAD3-1 (circles) for NO decomposition_XComparison of (1). FIG. 3 is in NO_X(1300ppm)O₂(1.7%) FTIR spectra obtained after exposure to (a) Cu-ZSM5 and (b) Cu-KAD 3-5. FIG. 4 is in NO_X(1300ppm)/O₂(1.7%) FTIR spectra of adsorbates produced upon exposure to (a) CoKAD3-1, (b) CoKAD3-5, (c) CoKAD3-7, (d) CoKAD 041-13, (e) CoKAD5-16 and (f) Co-ZSM5(Si/Al ratio 40: 1). FIG. 5 is a schematic view of an incinerator configuration and gas sampling points. FIG. 6 is a schematic diagram of a field test setup. FIG. 7 NO of Diesel exhaust_XConversion as a function of propane combustion. FIG. 8 life study of catalytic efficiency during diesel engine operation.FIG. 9 relationship between catalyst performance and diesel injected into a line. NO of diesel engine exhaust with and without addition of diesel fuel_XAnd (4) conversion rate. FIG. 10 for NO removal_XA microreactor system was investigated. FIG. 11 uses NH₃And using iron-based catalysts, NO_XReduction of (2). FIG. 12 uses NH₃And using vanadium-based catalysts, NO_XReduction of (2). FIG. 13 direct decomposition of NO_X. Figure 14 pilot scale incineration system. Figure 15 sampling/testing apparatus incorporating the USEPA MM5 sampling system in conjunction with a catalyst reactor.

Claims (29)

1. A catalytic conversion and/or adsorption process for the production of a catalyst comprising NO_X、SO_X、CO₂CO, dioxins and PAHs and mixtures thereof, wherein the gas may contain particles, the process comprising contacting one or more of these gases with an aluminosilicate material having:

(i) the fact that aluminum is predominantly tetrahedrally coordinated is due to²⁷Al magic Angle rotation (MAS) gave Al (H) at 55-58ppm (FWHM ═ 23ppm)₂O)₆ ³⁺(ii) a single peak of (a); and

(ii) the cation exchange capacity in aqueous solution at room temperature is at least 1meq/100 g.

2. The process as claimed in claim 1, wherein the reduction of NO in the presence of an organic reducing agent is carried out at 200-650 ℃_XIn which NO_XAdsorbed by aluminosilicate materials.

3. The process of claim 2 wherein the organic reducing agent is selected from the group consisting of hydrocarbons including alkanes, alkenes, and aromatics.

4. The process of claim 2 wherein the organic reducing agent is selected from the group consisting of alcohols and aldehydes.

5. The process of claim 2 wherein the organic reducing agent is selected from the group consisting of olefins and alcohols.

6. The method of claim 1, wherein NO is reduced_XIs carried out at a temperature of 200-650 ℃ in the presence of a nitrogenous reductant comprising urea or ammonia.

7. The process of claim 6 wherein the nitrogenous reductant is urea at a temperature of 350-500 ℃.

8. The process of claim 6 wherein the nitrogenous reductant is ammonia at a temperature of 200-650 ℃.

9. The process of claim 1 wherein NO is added at a temperature of 200-850 ℃ in the presence of an aluminosilicate material comprising Fe, Cu or Ag_XDirectly decomposed into nitrogen.

10. The process of claim 1, wherein the CO is in the presence of an aluminosilicate material doped with an alkali metal oxide or a transition metal oxide₂Adsorbed by aluminosilicate materials.

11. The method of claim 10, wherein the basic metal oxide is CaO or MgO.

12. The method of claim 10, wherein the transition metal oxide is selected from CuO, ZnO, or iron oxide.

13. The process as claimed in claim 1, for the oxidation of CO to CO at temperatures of 150-650 ℃₂Wherein the aluminosilicate material contains Pt, Pd, Ag, Cu, Co, Mn or Cr.

14. The process of claim 1, for the reaction of SO at 0-500 ℃₂Reduction to sulfur, in which SO₂Adsorbed by an aluminosilicate material containing an alkali metal oxide including MgO or CaO or a transition metal oxide including CuO, ZnO or iron oxide.

15. The method of claim 14, wherein the temperature is from room temperature to 150 ℃.

16. The process as claimed in claim 1, for reacting SO at a temperature of 150-650 ℃₂By oxidation to SO₃Wherein the aluminosilicate material contains Pt, Pd, Ag, Cu, Co, Mn or Cr.

17. The process of claim 1 for converting dioxins to carbon dioxide, water and hydrogen chloride at temperatures of 150 ℃ and 650 ℃, wherein dioxins are adsorbed by aluminosilicate material.

18. The process of claim 17 for converting PAHs at temperatures of 150 ℃ > 650 ℃, wherein the PAHs are catalyzed by an aluminosilicate material.

19. The process of any preceding claim, wherein the gas is passed through a plug of aluminosilicate in the conduit.

20. The process of claim 19, wherein the aluminosilicate material has a CEC of greater than 100meq/100 g.

21. The method of claim 20, wherein the aluminosilicate material has a CEC of between 160-900meq/100 g.

22. The method of claim 21, wherein CEC is between 350-450meq/100 g.

23. The process of claim 19 wherein the aluminosilicate material has exchangeable cations which are ammonium ions or alkali metal ions, the cations being optionally substituted with the alkaline earth metal Mg²⁺、Ca²⁺、Sr²⁺And transition metal Ba²⁺，Cr³⁺、Mn²⁺、Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Ag⁺Heavy metal Pb²⁺、Cd²⁺、Hg²⁺La of lanthanide series³⁺、Nd³⁺Or actinide UO₂ ²⁺Partially or fully exchanged.

24. The process of claim 19, wherein the aluminosilicate material is amorphous and does not exhibit any extensive structural order, having a broad peak between 14 ° and 40 ° 2 Θ, when irradiated with CuK α.

25. The method of claim 24, wherein the amorphous materials are prepared by reacting a starting aluminosilicate with MOH and/or MX, wherein M is an alkali metal and X is a halogen.

26. The process of claim 19 wherein the aluminosilicate material is an amorphous or low or partially crystalline aluminosilicate of a packed silica polymorphic structure prepared by reacting a starting aluminosilicate material or mixture comprising alumina and a compound comprising silica with a reactant comprising an alkali metal oxide or hydroxide.

27. The method of claim 19, wherein the aluminosilicate material comprises modified kaolin, preparable from a kaolin-like mineral, comprising expansion and contraction of layers in the kaolin-like mineral, the layers comprising one Si-tetrahedral platelet and one Al-octahedral platelet.

28. The process of claim 19, wherein the aluminosilicate material has a Si/Al ratio of from 1.0 to 1.5.

29. The method of claim 19, wherein the conduit comprises two or more spaced apart plugs of aluminosilicate material.

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