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    • 专利摘要:
    A catalytic device used for eliminating nitrogen oxides, carbon monoxide and residual hydrocarbons contained in exhaust gases comprises metal phthalocyanines and a carrier. The phthalocyanines are deposited on the carrier or introduced therein, and the system comprised of the carrier and the phthalocyanines is treated at temperatures higher than 120<o>C with nitrogen oxides and/or mixtures of nitrogen oxide and carbon monoxide and/or oxygen and/or mixtures of oxygen and carbon monoxide or with nitrating or oxidizing solutions. Instead of being activated by nitrating or oxidizing gases or solutions, the system may also be activated by intimately mixing metal oxides and metal phthalocyanines on and in a carrier.
    公开号:SU1657048A3
    申请号:SU874202069
    申请日:1987-02-24
    公开日:1991-06-15
    发明作者:Штайнбах Фридрих；Трамс Норберт；Йессе Дитер
    申请人:Штайнбах Фридрих；
    IPC主号:
    专利说明:

    This invention relates to the preparation of a catalyst for the removal of oxides of nitrogen, carbon monoxide and / or residual hydrocarbons from exhaust gases.
    The purpose of the invention is to obtain a catalyst with increased activity by depositing metal phthalocyanine on a carrier or impregnating the carrier with metal phthalocyanine and treating with an activating agent, which uses nitrogen oxides or a mixture containing oxides of nitrogen and carbon monoxide and / or oxygen, or nitrating or oxidizing. gases or vapors, at a temperature of 190-580 ° C, or nitrating or oxidizing solutions
    According to the proposed method, metal phthalocyanines are simultaneously or sequentially applied to the carrier or
    impregnate the carrier, or first treat the metal with an activating agent metal phthalocyanines, and then apply to the carrier or impregnate the carrier with them
    Metal phthalocyanines are dissolved in a solvent, powder or molded products are impregnated with a solution, and the solvent is removed or metal phthalocyanines are prepared as a suspension, or oxides, sulfides, carbonates, aluminosilicates or zeolite are precipitated from solutions with metal phthalocyanine powder suspended in them. metal phthalocyanine suspension or paste and precipitated and dried sludge or, respectively, the resulting suspension or paste is granulated or molded, dried or calcined at temperatures about 600 ° C
    ABOUT
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    The method also provides for the pncino-rhenia of metal phthalocyanines by converting into soluble derivatives, impregnating the carrier and removing the solvent or synthesizing the metal phthalocyanine in the carrier or in it.
    Example 1.60 g of purified copper phthalocyanine (Cu-FC) is dissolved in 1.6 l of formic acid at 80 ° C. A cordierite basket heated to 90 ° C (4 x 6 inches, 100–150 mm) is immersed in this solution for 15 min, and then cyiiiai at 90 ° for 7–10 hours. When the cell is impregnated, approximately 11 g of phtotocyanin is impregnated copper (2% Cu-FC of total weight). Medium treatment with a gas mixture of nitrogen from 1000 hours per million of nitric oxide and 3000 parts of i.a million of carbon monoxide at
    bulk rg-tod
    and temperature.
    increasing at 12 o'clock from room temperature to 580 ° C, and cooling the gas mixture n i oh, e get a catagizagor occupying the whole volume (full contact),
    On the catalyst thus made on the wear; e serves a non-nutritional mixture with a volume of 250 h with a starting temperature of 180 ° C, degree of conversion at 440 ° C 5 ° C- /, at 520 ° C 9)% Measurement time 450 hours
    The manufactured killer is tested in a test mixture, the CO has been completely replaced by a x-stake, (naturally l-ii The degree of NSC conversion with the same accuracy, M 1 oglt / idCb is almost unchanged.
    In addition to this, it is possible to use a gas stream (r, pop, vergeyut gas flow (and 500,000 h filter is not included after 50 h, there is no painting of the metal, it means that there is no metallocyanin (MFC).
    The weight of the supported catalyst (550 t i-j, 11 g of Cu-FC them) remains constant with a ± ± 0.1 mg, i.e. not also unnumbered catalyst material. The rd rate for testing (500000 h) is ten t - times higher than the upper boundaries - technically recommended volumetric speeds
    Made from Cu-FC on cordyritic cellular catalysis carrier, oro is subjected to life test. At 30 ° C, the conversion is 55%, and the efficiency has decreased noticeably for more than 1100 hours.
    The FC impregnated copper acidic carrier is heated in pure N0 at a flow of 0.6 n / h for 12 hours to 500 ° C and maintained at this temperature for 3 hours. After cooling in nitrogen, the catalysis obtained
    five
    0
    five
    0
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    The torus basically has the same activity; the initial temperature is 200 ° C, 90% conversion at 520 ° C. Measurement time 220h
    The proposed catalyst was exposed to a test gas, to which 100 ppm of nitrogen dioxide was added. The purification of nitrogen dioxide was complete, the conversion of nitrous oxide remained unchanged,
    The corresponding catalysts were manufactured with FC pedi in acetic acid. The transformation is similar.
    Similar catalysts are made with FCs of cobalt and FCs of nickel instead of FCs of copper. Activation is carried out with a test gas. Initial EPR tours pjl OTbi catalyst from FC cobalt on a carrier 280 ° С, from FC Niql, 190 ° С
    11 p and m; 2 500 g pieces of tubes made of baked glass otkrto cellular structure of length 2; ri, outer diameter 7 mm and internal - mm) are treated known riviHO example 1 Impregnated pieces, tubes of gpecheng stsl klac are placed in a test reactor, so that .ch uncontrollable m, in a volume of 1 liter, and by means of a hegogka test jrn is transferred to an active catalyst (after heating for three hours for 12 hours and then for two hours at 10 cm1) jaiop on a carrier with 2 wt.% Cu-FC of the total weight has an initial temperature of paboibi 180 ° C Growth 70% at 400 ° С
    Corresponding catalysts were irradiated with Cu OAC in acetic acid (160 i Gi-FC t; 2 l acetic acid at G, Cj. The degree of conversion is similar.
    In the same way, catalysts containing cobalt FCs instead of FCs of copper, and Cobalt FCs of Chalcion Activation, produced by test gas, were heated from the same way. The temperature of the start of operation of the catalyst F of cobalt on the carrier is 280 ° C. catalyst FG mi; e: but with a ssitele - 190 ° C,
    PRI me R 3 According to examples 1 and 2, manufactured with FC, nickel kalalizatch) 2 carried with / Ni-FC per 50 g cordierite or 500 g of sintered flowed tube pieces) used at /1.OunC to test gas at different volumetric speeds: at 200, the conversion is 100 / at 400–86% and at 1400–5%. The total measurement time is from 700 h.
    EXAMPLE 4 Cyolite granulate (type Vi is impregnated according to the method of example i of FC m – ° di, 100 ml impregnated with grains (application of 0.8 wt.% Ci-FC Acquiote test - JSOM (post heating Beats - for 12 hours and then 4 hours at 540 ° C).
    The catalyst thus obtained is tested with a test mixture at a space velocity of 1000 at 400 ° C., a conversion of 60%.
    EXAMPLE 5 Kieselguhr (powder) is impregnated using the method of Example 1 of FC of copper (strong mixing is necessary) and transferred into grains by wiping through a sieve. After activation with test gas (12 hours heating, then 4 hours at 540 ° C), 100 ml of these grains (application of 7.7 wt.% Cu-FC with test mixture at a space velocity of 1000) at 300 ° C show a conversion of 50%.
    Use 500 g of zeolite powder (type ZSM), the application of 4.6 wt.% Cu-FC. The loading of grains into 100 ml after activation gives a conversion of 80% at 300 ° C.
    Use 500 g of zinc oxide powder (deposition of 6.2 wt.%), And titanium oxide (deposition of 10.4 wt.%). On a load of impregnated grains, a conversion of 35% is obtained at 300 ° C.
    500 g of talcum powder (application 7.5% by weight) or another magnesium silicate (application 7.8% by weight) are impregnated and molded into grains. After activation with test gas at 540 ° С, 1 l of grain loading at 250 h has a starting temperature of 60 ° С. At 250 ° C, the conversion is 80%.
    If this catalyst at 240 ° C is exposed to a test mixture consisting of 100 ppm N0, 1000 ppm CO and N2. (the rest), the conversion is 78%.
    Example B. For the preparation of Example 1 on a supported catalyst, fragments of flower pots are used together with cellular cordierite. The temperature of the start of work is 200 ° C, the transformation due to the worst geometry is below 40% at 520 ° C.
    Take 500 g of fragments of flower pots with an average size of 0.5 cm. Drawing 0.6 wt.% Cu-FC. The debris of flower pots on the outside compacted, they have fine pores.
    Example. Analogously to example 2 impregnated balls of alumina from non-calcined alumina, Impregnation reaches the extreme layers. The supported catalysts at 1000 h-i and 450 ° C activated in the test gas at 500 ° C give a conversion of 40%.
    The catalyst thus produced is tested with test gas without CO, but from 1000 ppm to N0 and MN3. The conversion at 450 ° C is 35%.
    Try on Zinc oxide, or titanium oxide, or alumina is mixed with water into a pasty mass and about 10% by weight of FC powder of copper is mixed in. The blue pastes thus prepared are molded in example 5 through a sieve into grains. After conversion to the active catalyst in the test gas at 540 ° C for 4 hours, catalysts are obtained with a conversion of 30-40% at 400 ° C.
    500 g of oxide powder are mixed with 200 ml of water at room temperature, grains
    0 after the sieve is dried at 120 ° C for 48 h in air in an oven.
    The activation is carried out by heating for 12 hours and then 4 hours at 540 ° C, then cooled in the test gas for 10 hours.
    5 Other pastes thus prepared were smeared on metal sheets or applied by immersing sheet metal (for example, aluminum). Pre-folded or rolled into rollers
    0 sheets were installed in a test reactor. After activation by the test gas at 500 ° C, the starting temperature is 220 ° C; at 500 ° C, the conversion is 70%.
    5 The drying of the molded metal sheets is carried out in an oven in air at 60 ° C for 24 hours and then at 120 ° C for 24 hours. When the drying is accelerated, the applied layer is destroyed.
    0 If cobalt FCs are used in catalysts instead of FCs of copper, the temperature of the start of work generally rises by about 20–30 ° C.
    PRI me R 9. From A (OH) h. silicate on three, triethanolamine at 90 ° C in the usual way produces a synthesis of zeolite (NaY), which is modified in the presence of. of the highly stirred suspension of FC of copper. The precipitated zeolite is mixed with a suspended powder of FC copper. After drying according to Example 5, grains are obtained. The catalyst thus prepared shows activity as in Example 4.
    5 For the synthesis, the following solutions are used.
    Sodium liquid glass with a density of 1.37: 100 g of the solution contains 27.35 g of SI02 (0.46 mol) and 8.3 g of Na20 (1.134 mol).
    0
    A solution of sodium aluminate is obtained from aluminum hydroxide (crushed to fine powder, purified): 1000 g of solution contain 2.5 mol A (OH) 3 and 5 mol NaOH.
    5 Gels of aluminosilicates are prepared by combining diluted solutions. With vigorous stirring, Cu-FC powder is added, the amount of which corresponds to the calculated 2% deposition. Cu-FC particles act like a germ
    crystallization. Drying at 80 ° C for 12 hours, at 120 ° C for 12 hours and at 150 ° C for 12 hours.
    In a similar way, particles of aluminum hydroxide impregnated with C-FC are precipitated from a solution of the aluminum salt with ammonia after drying, heating and activation in the test gas to obtain an active catalyst with a starting temperature of 200 ° C,
    50 ml of a mixed suspension of 1 g Cu-FC in 10 ml of formic acid is added to 500 ml of a half-concentrated aqueous solution of aluminum chloride (35 g A Oz / OO ml). With constant stirring, add NaOH particles until then. until A (OH) drops out h. The amorphous precipitate is filtered off with suction with a water vacuum pump, washed with water and the blue cake on the filter is dried in a drying cabinet at 120 ° C for 72 hours. The product is a solid colored by the presence of Cu-FC. it is crushed into crumbs, which form a bulk layer.
    An example. 4 g of dihydrooxide-cyclotetraisoindolenin are obtained from 15 g of FC of copper by oxidizing 10 ml of 95% nitric acid in ice vinegar (5 parts of nitric acid per 100 parts of glacial acetic acid) and treatment with 20% ammonia . The purified hydroxide is dissolved in a 7% ethanol solution of ascorbic acid, and cordyritic cellular carrier is impregnated with the resulting solution. Recovery to FC of copper is performed by heating and drying at 90 ° C. The process is repeated three to four times. Approximately 2 g of FC of copper (complete contact) is fixed on the blue carrier (full contact), which is converted into active catalyst by treatment with test gas. Initial operation temperature 180 ° С.
    Example 11.15 gCFM is introduced by slow kneading into 120 g of 26% sulfuric acid (oleum), while cooling the mixture is brought to almost 45 ° C and then heated to 60 ° C. The solution is kneaded into a mixture of 0.5 l of saturated sodium chloride solution, 400 g of ice, the suspension is diluted with cold water until Zl Cu-FC sulfonic acid is filtered off. The sulfonic acid solution in water is used to impregnate the cordy carrier. After drying and activation, a catalyst is prepared, analogous to Example 1, on a carrier with the same activity and adhesion strength.
    Accordingly, the use of FC cobalt, get a catalyst with similar properties.
    Example12. With stirring, 20 g of chloromethyl-Cu-FC in a solution of 50 g of tetramethylthiourea in 250 ml of water at 50 ° C gives a water-soluble isothiuronyl salt. After impregnation at 50 ° C, 20 g of cordieritic cellular structure, or of Kieseleur or NaY grains, by cleavage of the hydrophilic group in a weakly alkaline solution (50 ml of 2N are added.
    NaOH at 50 ° C) receive insoluble FCs. After drying the carrier at 120 ° C for 24 hours, activation by heating for 12 hours to 520 ° C and keeping at this temperature for 4 hours, get the corresponding
    full contacts, which are converted to active catalysts by treatment with a test gas. Application of 4-5 wt.% Cu-FC, the conversion of 70% at 400 ° C. Example 13. Solution 10 g phthaloic
    brilliant blue 1FGM in 200 ml of formamide is used to impregnate the carrier heated to 100 ° C. After 12 hours of drying at 130 ° C, the carrier is completely stained with copper FC. Procedure when
    Repeat once or twice. 2.1 g of copper, introduced in this way and applied in the amount of copper, are transferred into the active catalyst with the help of test gas.
    PRI me R 14. 100 g of NaY zeolite granulate are treated twice for 24 hours with a 0.025 molar solution of copper acetate and dried for 24 hours at 250 ° C (introduction of copper by ion exchange). The fuzhazites saturated with copper ions under nitrogen are mixed with 125 g of phthalodinitrile and heated under vacuum in an autoclave for 16 hours at 250 ° C. In this case, direct synthesis of FC media occurs on the surface and inside zeolites.
    The dark blue granulate is washed in acetone; it contains approximately 2.8 g of FC of copper. The catalyst thus obtained is transferred to the active form with a test gas at 250 ° C. Initial temperature
    work in the boot 180 ° C.
    Using cordierite cellular carrier, the catalyst described in Example 1 is prepared.
    Similarly, a catalyst is prepared using nickel acetate and cobalt.
    In Example 15. 18 g of tetracyanobenzene 50 g of kieselgur, which was previously soaked with a 1 molar solution of copper acetate for 24 hours, is dried at
     in a drying oven for 24 hours, followed by heating in an autoclave under vacuum at ZOOiS. Receives polymer FC copper (10 g Cu-FC 50 g of diatomaceous earth), which in example 5 is converted into active
    catalyst. Activity: 50% conversion at 400 ° C and 250.
    Similarly, a catalyst is prepared using zeolite granulate as a carrier. Application: 6 g of polymer Cu-FC per 50 g of type V zeolite.
    Example 16. A copper (cobalt, nickel or iron) plate with a size of 10–50 cm (laminated) is heated with tetracyanobenzene at 400 ° C in an autoclave under vacuum for 24 hours. A coating of a polymer FC of copper (cobalt, nickel, iron) is obtained, which by treatment with a test gas is transferred to the active state. The start temperature is 250 ° C.
    The thickness of the metal plates 0.2 mm. Each time, 2 gtetracyano-benzene was used in an autoclave. Polymer phthalocyanine coating is 1.1-1.3 wt.%.
    The activation is carried out by heating to 500 ° C for 4 hours and then keeping at this temperature for 12 hours.
    Similarly, a catalyst is prepared using metal powder, turning chips and metal wool.
    PRI me R 17. Impregnated according to example 1 of FC copper, cordierite cell carrier, after drying at room temperature, is immersed for a few minutes in concentrated nitric acid. After rinsing and drying, a catalyst is obtained, the starting temperature of which is 350 ° C, conversion of 40% at 440 ° C.
    The content of the applied substance before treatment with nitric acid is 2 wt.% Cu-FC (cf. example 1). After modification, the content of the active component is 0.6 wt.% Cu-FC, the rest is destroyed in the oxidizing solution.
    The cordierite cell carrier impregnated according to Example 1 FC of copper was dried for 30 minutes at room temperature and a mixture of 5 parts of 95% nitric acid and 100 parts of glacial acetic acid was lowered. After washing and drying, a catalyst is obtained, the initial operating temperature of which is 250 ° C, the conversion of 40% at 400 ° C.
    The content of the applied substance after treatment is 1/9 weight. Cu-FC.
    With an appropriate treatment of FC-impregnated cobalt with cordierite cellular carrier, a catalyst is obtained, the initial temperature of which is 290 ° C.
    PRI me R 18. FCs of copper are treated with stirring at room temperature for half an hour with a mixture of 5 parts of 95% nitric acid and 100 parts of glacial acetic acid. After filtering, rinsing and drying, a catalyst without support is obtained.
    From 15 g of Cu-FC get 11-12 g of activated catalyst. In accordance with Example 8, it is mixed with carriers. Get ready catalysts with the conversion at 350 ° 30-40%. Get 500 g of powdered oxide catalysts with the content of the applied substance 2-2.5 wt.% Cu-FC.
    PRI me R 19. 50 g exchanged for copper
    pajazite (see example 14) is stirred in a solution of 10 g of dicyanobenzene in 200 ml of nitrobenzene for 5 hours at 180 ° C. Through the deep blue product for 20 h, extracted with pyridine. Get 1.2 g FC of copper
    50 g of faujasite, which are converted into active catalyst by treatment with test gas. Starting temperature 180 ° С.
    Example 20. 200 g of sintered glass with
    open pores are treated with a solution of 50 g of CuCl2 in 1 l of water and then dried at 200 ° C. A mixture of 25 g of phthalic anhydride, 130 g of urea and 5 g of ammonium molybdate is melted and heated for 3 hours to 180 ° C with sintered glass soaked in copper salt. The product is poured with diluted hydrochloric acid and boiled. Then remove the media from this solution and wash them with cold diluted soda alkali and then with water. The product is dried. 11 g of FC of copper are obtained per 200 g of sintered glass carrier, which are converted into active catalyst by means of treatment with test gas. Starting temperature 180 ° С. Example21. An aluminosilicate monolith or a bundle of sintered glass tubes with open pores, or a monolith of cordierite (weighing 24 g each) at 90 ° C is impregnated with a suspension of FC of copper in formic acid and dried after draining the liquid. Catalysts are obtained on supports with the content of 1–4 wt.% FC of copper.
    After activation of example 1, receive
    in synthetic exhaust gas from Na from 1000 hours per million N0, 1000 hours, per million MNZ and 1% 02 at bulk speeds of 800-1000 hours, initial operating temperatures: 180 ° С
    (aluminosilicate carrier), 220 ° С (sintered glass carrier with open pores) and 210 ° С (cordierite carrier), and also turning 90% N0 at 320 ° С (aluminosilicate), 360 ° С (sintered open pores ) and 340 ° C (cordierite).
    PRI me R 22. The aluminosilicate monolith is treated at 90 ° C with a suspension of FC of copper in formic acid, and after draining the liquid and drying it is activated by heating in test gas for 20 hours at 530 ° C. The temperature of the start of work in the synthetic exhaust gas, corresponding to example 21, with a space velocity of 1500–120 ° C, conversion of 50% at 180 ° C90% at 230 ° C.
    The weight of the monolithic carrier is 12 g. The content of the applied substance is 4 wt.% S-FC.
    EXAMPLE 23: Cordyritic cellular carrier is impregnated with a single-molar aqueous solution of Cu (NO) g under vacuum. After drying at 120 ° C for two hours by heating in air at 500 ° C, CuO is obtained. The weight of cordierite cellular carrier is 24 g, the content of supported copper oxide is 6.2 wt.%.
    Then, analogously to example 22, is impregnated with a suspension of Cu-FC and dried for 12 hours. Drying at 120 ° С in air. Get the catalyst on the carrier with the content of the applied substance 6 wt.% CuO and 3.8 wt.% Cu-FC. It is treated at 320 ° C for 4 hours in the test gas with heating and cooling for 10 hours. The catalyst thus obtained is in synthetic abgas, described in Example 21, and at a space velocity of 1500 hours it has an initial operating temperature of 140 ° C and gives a conversion of 90 % at 240 ° C.
    PRI me R 24. Cordyritic cellular carrier (24 g) at 90 ° C is impregnated with a suspension of 160 g of FC of copper in 1.6 l of formic acid, which simultaneously contains 150 g of dissolved copper formate, and after draining the liquid is dried. In an oxidizing gas stream at 100-160 ° C, the copper form is converted to copper oxide.
    Subsequent treatment with the test gas at 320 ° C for 4 hours with heating and holding as described above.
    The catalyst thus obtained has, in a synthetic exhaust gas and at a space velocity according to Example 23, an initial operating temperature of 140 ° C and at 240 ° C shows a conversion of 90%.
    In a gas mixture of 3000 parts per million of CO (0.3%) and 1% of oxygen in nitrogen, this catalyst at 250 ° C causes complete conversion (residual CO content is less than 5 parts per million).
    In a gas mixture of 3000 parts per million of CO (0.3%), 1000 parts per million of propane (0.1%) and 2% of oxygen in nitrogen, this catalyst at 250 ° C shows complete conversion (residual CO and propane below 5 hours per million).
    In the gas mixture of 1000 parts per million N0 (0.1%). 1000 hours namGMNz (0.1%), 3000 h. on
    mln CO (0.3%), 1000 ppm (0.1%) and 2% oxygen in nitrogen, with a space velocity of 3000 and 240 ° C, this catalyst converts at N0 80%, for CO and propane - the total as a result, not more than 5 parts per million).
    Example 25: The cordycete body (12 g) is impregnated at room temperature with an aqueous solution of copper sulfate and cobalt nitrate (2 M solution relative to CuS04 and Co (MOh / 2). Three impregnations are carried out, then dried at 120 ° C for 12 hours in a drying oven. A load of 2.7 g of the sheath from wetting (1.8 wt.%) in a ratio of Cu504 / C0z04 1/1 occurs. Thus, the loaded carrier body is treated at 250 ° C in the test gas (1000 parts per million N0, 1000 hours per million NHj, 1% 02, the rest N2) for 12 hours, the heating sequence
    5 (8 h) and the termination of heating (8 h).
    The preloaded carrier body is impregnated with a suspension of Cu-FC in formic acid (160 g Cu-FC in 1.6 l of formic acid, see example 1) using Cu-FC. After drying at 120 ° C for 12 hours, a full catalyst loaded with 1 g of Cu-FC (0.6% by weight) is formed, which is activated during 90 hours in the test gas (periods
    5 heating and stopping heating 8 hours). The resulting catalyst at 230 ° C shows a 60% conversion.
    Example 26. The cordierite – cellular body (12 g) is first loaded with a mixture
    0 copper sulfate and cobalt oxide, and then using Cu-FC. Preparation is carried out as described in Example 25. The same loads are generated. Activation in the test gas is carried out at 190 ° C.
    5 in 192 h (8 days). A catalyst is formed with a 48% conversion at 170 ° C and a bulk velocity of 3000 hours.
    PRI me R 27. Cordyrtchaeous body (12 g) is impregnated with water 1 M
    0 manganese acetate solution at room temperature and dried in a drying cabinet for 12 h at 120 ° C. This procedure is carried out 4 times. Formed is loaded with 1 g Mp02 carrier body, which
    5 is treated in a test gas (see Example 25) at 220 ° C for 24 hours. The cordier body coated with wetting with Mp02 is then loaded with Mn-FC by impregnation with a suspension of 160 g Mp-FC in 1.6 l formic acid. Is formed
    loaded with 1 g of Mn-FC (8 wt.%) impregnated catalyst (complete), which is activated at 220 ° C for 24 hours in the test gas with heating and turning periods of 8 hours. The resulting catalyst gives a conversion of 93% at 150-160 ° C and at a space velocity of 3000.
    PRI me R 28. The cordycell body (12 g) is impregnated with ammonium vanadate in a hot saturated solution and ammonium vanadate is then dried in air at 120 ° C. This procedure is carried out 6-8 times (as many times as necessary to obtain a load of 15.7% by weight of ammonium vanadate, which corresponds to a load of 12.2% by weight of V20s). Pre-loaded body of the carrier in suspension WAFC (25 g WAFC in 250 ml of formic acid) is loaded with WEFC and again dried at 120 ° C in air. This impregnation should be repeated about 4 times (up to a load of 7.8 wt.% / OFC). The carrier loaded with both components is activated in the test gas (see Example 25) at 450 ° C for 12 hours. In this case, the active component is formed from WAFC and the V20s is wetted from vanadate. The catalyst treated in the test gas at 3000 gives a conversion of 89% at 325-355 ° C. For a conversion window of 80%, 290-400 ° C is sufficient.
    Example 29. The cordy-cellular body (12 g) is loaded, as in Example 28, first with vanadium salt and then / OFC. Instead of ammonium vanadate, a solution of 30 g of V20s and 120 g of oxalic acid in 200 ml of water is used. 2-3 g of sodium tungsten are suspended in this solution. Impregnation and drying, as well as subsequent loading with the aid of HPLC, are similar to Example 28. A supported catalyst (complete) is formed, which is loaded with 15 wt.% Vanadium-oxalate complex and a small amount of tungstate as well. as using 8.9 wt.% UOFC. The carrier loaded with all components is activated, as in Example 28, for 12 hours at 450 ° C in the test gas. A catalyst is formed with 7.8 wt.% Of a sheath from wetting (washcoat) from V20s and sodium tungstate in a ratio of 10: 1, as well as from 8 to 9 wt.% Modified / OFC. The resulting catalyst at 255-290 ° C gives a conversion of 87%. 80% conversion window is reached at 210- 35 ° C.
    Example 30. A catalyst preform is obtained from 12 g of cordierite product by analogy with example 23. The product is impregnated with a mixture of solutions of Cu (MO3) 2 and Co (MOZ) 2,
    taken in equal parts, so that after drying and annealing, as described in example 23, a mixture of CuO and Co203 is formed (9.6% by weight of the oxide coating in equal parts). Immediately thereafter, at 90 ° C, a layer of FC of copper was deposited in formic acid, as described in example 22, and, as described in example 23, the catalyst was activated with test gas. The test gas consists of 1000 hours.
    per million N0, 1000 ppm per million MNZ, 1% 02 and N2 (the rest). 7.3% by weight of copper phthalocyanine is then applied to the carrier and washcoat and converted into a catalyst.
    A low-temperature, highly active catalyst with 85% conversion at 160 ° C is obtained, operating for 800 hours without a noticeable reduction in conversion. Neither the control of the weight of the catalyst and the fiber filter, nor the color of the latter showed ablation of the catalyst. The conversion test is carried out with the same test gas as the activation, but with different oxygen impurities (1-5%). The activity does not depend on the oxygen content.
    PRI me R 31. A series of 12 g cordyrite cell products are processed to apply a uniform coating by impregnation with a single molar solution of Cu (Moz) 2 and immediately after
    this by the decomposition of nitrate to CuO in a test gas mixture consisting of 1000 ppm N0, 1000 ppm in MPH, 1% 02 and N2 (the rest), at 340 ° C and a space velocity of 3000 and 10% CuO - Washcoat. Immediately after this, the samples are coated with a layer as a result of impregnation with a suspension of phthalocyanine in formic acid, respectively, with 7-8 wt.% Phthalocyanine. The activation of phthalocyanine is carried out in a gas
    consisting of 1000 parts per million N0. 1000 ppm million mnz, 0.05-5% 02 and N2 (the rest). The activity of the catalyst is similar to the activity in the case of using gas consisting of 1000 ppm N0, 1000 hours per
    million mnz, 1% 02 and N2 (the rest). This is true for finished compositions with 1-5% 02 in the activating gas. At 240 ° C and a space velocity of 3000, the conversion is 84%. With a lower oxygen content in the active gas, the activity is slightly lower, with a minimum oxygen content. It decreases to 76%.
    Example 32. Cellular product from cordierite is coated with a layer of CuO and copper phthalocyanine, activated with air at a space velocity of 1500-6000. The activity test is carried out with a gas consisting of 1000 ppm N0, 1000 ppm MNZ, 1% 02 and N2 (the rest). Optimum activity at a space velocity of 3000 hours 1 at 250 ° C corresponds to 88% conversion.
    EXAMPLE 33. A cordierite honeycomb product is coated as in Example 32, but the coating (Waschoat) consists of manganese oxide (manganese nitrate) and phthalocyanine manganese as a suspension in formic acid. The activation is carried out with test gas consisting of 1000 ppm N0, 1000 ppm MN3, 1% 02. N2 (the rest), as well as air activation, at 280 ° C, is brought to active catalysts . The transformation in the test gas consisting of 1000 ppm N0, 1000 ppm MNZ, 1% 02, N2 (the rest), at a flow rate of 3000 and 230-260 ° С 95-98%.
    EXAMPLE 34. Cellular product and a coating, as in Example 33, of manganese phthalocyanine, Activation of a gas burner with exhaust gases, consisting of 7% 02, 9% CO2, 9.5% H2O and N2 (rest). Test with test gas as in Example 33. Conversion and conversion maximum 95% as in Example 33.
    PRI me R 35. Cellular product from cordierite (12 g) is impregnated with an aqueous solution of ammonium vanadate with 7% V20s, and then dried. Then, a coating of UVPC is applied from the suspension in formic acid by repeated immersion until the layer is 6–8 wt.% UVPC. Then, it is activated with test gas consisting of 1000 ppm N0, 1000 ppm MN3, 1-5% 02 and No. (the rest) with a volume velocity of 3000 hours at 450 ° C. A catalyst is obtained which in the exhaust gas is combusted with NO additives (1000 ppm NO, 1000 ppm MNZ. 7% 02, 9% C02. 9.5% H20, N2 (the rest) gives a conversion of 92-99 %, calculated on N0, in the temperature range from 190 to 300 ° С with a space velocity of 3000 and 6000 h 1.
    - Example 36. The same type of catalyst compositions as in Example 35 (12 g of a carrier with a coating containing 7% V20s (Washcoat) and 6-8% by weight VOOLQ is activated in air at 450 ° C and 3000. The conversion is measured using a combustion gas as in Example 31, the same results are obtained as in the above example.
    The same results are obtained if, instead of air, they are activated with waste gases of combustion with additives 1000 ppm MIO 1000 h. per million mnz.
    The same results are obtained if NO and MN3 are not added when activated.
    High activity is also maintained when activated with gas consisting of 1000 ppm N0, 1000 pg ng million
    NHs and N2 (the rest), with a volumetric rate of 3000.
    Activation can also be carried out with gas containing 1000 parts per million N0, 3000 hours.
    per million of CO and N2 (the rest).
    The activation is carried out with combustion exhaust gases, to which 0.2-0.5 non-combustible hydrocarbons are added for artificially controlled deterioration of combustion,
    0 activity is the same as in example 31.
    The activation is carried out with combustion exhaust gases, to which 500 ppm of CO2 are added. The activity is the same as in example 35.
    5 Activation is carried out with a mixture consisting of, in ppm: 2000 N0; 500 N02; 3000 WITH; 1000 mnz, the rest - N2. The activity is the same as in example 35.
    The activation is carried out by gas such
    The same composition as above, but 2% 02 is added. The activity remains unchanged, the conversion is 90-98% at 190-300 ° C and a space velocity of 3000 hours.
    Activation is carried out with air
    5 with the addition of 0.5% N0, the activity remains the same.
    The activation is carried out with combustion exhaust gases, which contain an additional 0.5% non-combustible hydrocarbon and
    0 enriched 2000 hours per million N0, the activity is the same as in example 36.
    The activation is carried out with a mixture consisting of C02, 1% 02, 1000 h, ppm N0, with the same result.
    5 All activations are carried out at a space velocity of 3,000 hours 1 and 450 ° C for 12 hours, when heated for 4 hours, 5 hours at 450 ° C and cooled for 3 to 4 hours.
    The following are examples illustrating the preparation of a catalyst in a known manner.
    PRI me R 37 (comparative). If the active catalyst is derived from pure copper phthalocyanine without any
    5 carrier, the degree of conversion of N0 is negligible due to the insufficient surface of the microcrystalline powder (degree of conversion of 3% at 425 ° C at a space velocity of 200 hours). If you raise
    0 space velocity, the powdered catalyst is partially blown out of the fluidized bed of the catalyst, the remaining catalyst is compacted and finally clogs the catalyst bed.
    5 In order to be able to apply a bulk rate (3000 hours and above) it is necessary to distribute the catalyst on the carrier. PRI me R 38 (comparative). The powdered copper phthalocyanine is distributed on the surface of the cell-like cordprite. Ri / nocrt are poured into the channels of the channel. P HLU nonet - (Osti, as a result, ground i decreases The procedure repeats: 3 times until the surface of your object is not iiv with yuli ftslotsyanin copper With the help of molded along the length of the VIMPCHI core premyos that they are An entire gtrmte dtzhe into the narrow channel of the gchkshch image is obtained by the golding of a carrier bearing 11 i phthalocyanine Öch orbashas gas gas mixture (ap mixture and processing in all stages of i and i, example i, volume velocity g) 0 h Catalyst they are also being described in approx I test with monolithic and 1000 h n) mln N0, 3000 h per m / n SS and N. (the rest of the volume is 250% at 10 times 40% at 10 ° rotation as a rule, if the activity remains the catalyst at 440 ° C, the decrease of r c for 80 h only to a value of 1e) 0 / pr1 at a higher reaction temperature reduces my shortness;
    When i e p 39 (. Comparative
    In order to avoid excess copper cobalt on rough ceramic surfaces, physical pricing is carried out according to Chrygier 38 4 g of phthalocyanine copper and a mixture are carried out to active, nor; 1 float on the bank of the main v i-rionci i driver as well as the n .ir-4 piv 3d test subject i az azo, osg (/ ii from 1000 ppm NO, S COO h not. / N CO and J ( g s gtlnoe) with a volume of up to 250 h but no rip higher than Pc, p “KRY rn-rnich activation (3700С)
    In the gas of Yu.orch Chtglli TciKO i, the composition of the ka- and opps IH-bit Hi g of g of c h when it comes i) n with t and,, ri and from pr PP.-n 1 O it about i | k in pin, with and not with i i t K10 u for mega gi, gs ii opt 40 1 | PR with g /
    PRI me R h j iC and h t / IL in.
    4 g of rd it; j ia m i i i ko are distributed on the surface of the cops t dr- - hr with the sooooooooo wear / fccc described in pg and 3G | both u and from ng, 1 o pol / h j from lat i; iiic dTOp as described by the retailer l i i r cases other catagistop: i / sp oi, -o as described in cp 11 .. / winners J3 and 39 not with oby .lnoi speed uoio h v ooih
    In cases of ear after 8 hours of trial, the catalyst activity is zero. EXAMPLE 4 (Comparative) The careful weighing of the catalyst before and after the catalytic test shows a loss of weight, which indicates the risk of the catalytically active substance. Rather, it occurs at large gas flows and higher temperatures. Nale, the case of carrier decolouration of the carrier Carrier is in example 38 after 80 hours with activity of about 15% of the initial activity of only 0.5 g more desirable than the uncovered number of esters; spruce (10.5 g of a surplus catalyst is carried away). In Example 39, after 400 hours, the initial content of the pure carrier recovers- - (4 (Copper phthalocyanine or the catalytic substance obtained by it completely disappears). In Example 39, the total weight loss is reached after 8 hours.
    Example 42 (comparative) In the flow down flow in the i, test unit under test, a filter that is filled with 5–10 g glass fiber glass Fiberglass 0 can fisiTb be easily removed through the gas-permeable lid of the filter chamber.
    After switching on the filtering chamber, the same experiments were carried out as described in examples 38-40. Glass fiber after a lost activity catalyst dyes in gray-blue and a strong penetration i showed that a predominant part of the entrained copper phthalocyanine and substance g / and ator is deposited with fiberglass. The weight gain of fiberglass in the filter corresponds to the weight loss of the ceramic carrier by 10%.
    Comparative experiments (examples 38-42) indicated that the catalyst obtained in a known manner could not be kept by the PCT-PCN-M nose and cart. i technical Tpt lin rot in the relevant / and constant or- and pre-run and ch} ablation are carried out by e. It takes place only when using the proposed method: 1 p1-1 tprpr nori (jv with nyp on proposed i, oci-6j state level 1100 h (example 1) and 700 h primes 3) does not reduce the activity
    EXAMPLE 43 (Comparative41 Cordpriest Sooto-Spas product (12 g) is obtained as described in Example 38 (by physically covering the porous ceramic surface with phthalocyanine m °; and with the distribution and strengthening of the vibrator, Equipped with 7 May, the carrier is treated with a known way l get a RK catalyst
    Examples show that MFC fixation using the methods of impregnation and synthesis leads to the interaction of organic matter of MFC with inorganic carriers by infrared bands, this interaction after the transfer of the dye into the active catalyst is maintained, prevents entrainment and increases the catalytic activity compared to the catalyst obtained by the known in a way.
    权利要求:
    Claims (8)
    [1]
    1. A method for producing a catalyst for removing oxides of nitrogen, carbon monoxide and / or residual hydrocarbons from exhaust gases containing metal phthalocyanine, including treating the catalyst with an activating agent containing oxides of nitrogen and / or oxygen at elevated temperatures, characterized in that in order to obtain a catalyst with increased activity, metallophthalociaiin is applied on a carrier or carrier is impregnated with metal phthalocyanine and the treatment is carried out with an activating agent, which is used as nitrogen oxides and and a mixture comprising nitrogen oxides and carbon monoxide and / or oxygen, or nitro, or oxidizing gases or vapors at temperature 190-580 ° C, or nitro, or oxidizing solutions.
    [2]
    2. A method according to claim 1, characterized in that the metal phthalocyanines together with the oxides of transition metals are simultaneously or sequentially applied to the carrier or impregnated with the carrier.
    -
    [3]
    3. A method according to claim 1, characterized in that the metal cyanines are treated with oxides of nitrogen and / or mixtures of nitrogen with oxides of nitrogen and carbon monoxide, or with nitrating or oxidizing gases or vapors at 190-580 ° C or nitrating or oxidizing solutions and finally, it is applied to the carrier or impregnated with the carrier.
    [4]
    4. A method according to claim 1, characterized in that the metal phthalocyanine dissolves
    in a solvent, the solution is impregnated with a powder or molded products and the solvent is removed.
    [5]
    5. Method according to paragraphs. 1 and 2, distinguished by 15 u and with the fact that metal phthalocyanines
    is prepared as a suspension in a liquid, the powder is impregnated with a suspension or molded products and the liquid is removed.
    [6]
    6. Method according to paragraphs. 1 and 2, which differs from the fact that oxides, sulfides, carbonates, aluminosilicates or zeolites are precipitated from solutions with a metal phthalocyanine powder suspended in them, or that a suspension or paste is prepared from the carrier powder and metal phthalocyanine powder, and that the precipitated and dried precipitate or, accordingly, the resulting suspension or paste is granulated or molded, finally dried or calcined at temperatures up to 600 ° C.
    [7]
    7. Method according to paragraphs. 1 or 2, characterized in that the metal phthalocyanine is dissolved by transferring into soluble derivatives, the carrier is impregnated with a solution and the solvent is removed.
    [8]
    8. Method according to paragraphs. 1 or 2, characterized in that the metal phthalocyanine is synthesized in a carrier or ne.
    25
    thirty
    35
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    同族专利:
    公开号 | 公开日
    JPS63500575A|1988-03-03|
    US4970188A|1990-11-13|
    DK85787A|1987-02-19|
    DD247389A5|1987-07-08|
    EP0228398B1|1989-03-08|
    EP0228398A1|1987-07-15|
    DE3522637C1|1986-10-02|
    DE3662234D1|1989-04-13|
    DK85787D0|1987-02-19|
    WO1987000077A1|1987-01-15|
    AT41106T|1989-03-15|
    引用文献:
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    DE3917890A1|1989-06-01|1990-12-06|Steinbach Friedrich|SUPPORTED CATALYSTS FOR THE REMOVAL OF NITROGEN OXIDE, CARBON MONOXIDE AND ORGANIC COMPOUNDS FROM EXHAUST GAS|
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    US5954948A|1996-05-13|1999-09-21|Uop Llc|Hydrocarbon conversion process using a sulfur tolerant catalyst|
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    JPH09299811A|1996-05-17|1997-11-25|Ngk Insulators Ltd|Honeycomb structure body|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3522637A|DE3522637C1|1985-06-25|1985-06-25|Catalyst for removing nitrogen oxides, carbon monoxide and / or residual hydrocarbons from exhaust gases|
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