TWI357355B - Vermiculite supported catalyst for co preferential - Google Patents

Description

1357355 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a cc> oxidizing catalyst prepared by using a brittle stone as a carrier, in particular, a selective oxidation reaction for hydrogen in a hydrogen-rich gas. Catalyst, this catalyst can selectively oxidize C0 and reduce the CO concentration in hydrogen-rich gas under the condition of reducing hydrogen consumption to provide proton exchange membrane fuel cell (PEMFC). A hydrogen-rich gas containing a low CO concentration.

[Prior Art] A fuel cell uses hydrogen as an anode fuel and oxygen as a cathode fuel. Hydrogen can be produced by a recombinant hydrogen production reaction of an organic substance such as methanol, ethanol or liquefied petroleum gas. For example, in a sterol recombination reaction, methanol and water can react to form helium and double emulsified carbon. Unfortunately, the general recombination hydrogen production reaction is accompanied by a cesium concentration of C0 gas' and C0 easily poisons the anode material of the proton exchange membrane fuel cell. Therefore, the C0 gas in the argon-rich gas generated by the recombination reaction must be removed to a very low concentration. . Since the gas-generating end of the recombination reaction is a hydrogen-rich gas having a high concentration of C0, the concentration of C0 in the hydrogen-rich gas is generally reduced by the water-gas shimming reaction. In the stage of water-gas transfer reaction, an appropriate amount of water can be introduced to reduce the temperature of the hydrogen-rich gas after the recombination reaction to a temperature suitable for the catalyst for the water-gas transfer reaction. In addition, adding an appropriate amount of water can also increase the water medium. The water/carbon ratio of the feed to the gas shift reaction stage, the higher water/carbon ratio will facilitate the transfer of the water gas transfer reaction. However, the concentration of co-rich hydrogen gas after the water-gas transfer reaction still cannot meet the requirements of PEMFC. With regard to current technological developments, the hydrogen-rich gas required for PEMFC needs to have a c〇 concentration of less than 30 ppm. Therefore, after the water-gas shift reaction stage, the CO in the hydrogen-rich gas needs to be further removed. 5 1357355 *c〇 Selective oxidation reactions are often utilized to further remove co in the hydrogen-rich gas after the water-gas transfer reaction. The so-called co-selective oxidation reaction uses a co-selective oxidation catalyst to describe the reaction of helium with co, but reduces the reaction of oxygen with hydrogen. According to the literature, c〇 selective oxidation catalysts are mostly noble metal catalysts using alumina, titania, cerium oxide or zeolite as carriers, and the precious metal surface contains #, shouting. Miscellaneous County (4) #面龄 is the main factor determining the effectiveness of the catalyst, but the heterogeneity of the catalyst can also be touched by Wei, including the surface area of the carrier, the surface acid content, thermal stability, pore size and pore size distribution. . $国专利4, i34, 86() reveals a way of producing a catalyst, the catalyst composition of which is precious metal,

Metal, rare earth metals and active scales. Although its towel is a refractory material, it has better thermal stability, so it is often a side thorn. However, the shortcomings of the poisoning of the sulphide by the active materials are that the active sulphur reacts with the sulphur compounds such as sulphur dioxide to form a stable sulphuric acid. When the sulphuric acid is formed, it will be reproducible! This reduces the contact area and reduces the effectiveness of the catalyst. In order to overcome the problem that the carrier is poisoned by sulfides, U.S. Patent No. 5,922,294 discloses a catalyst containing a titanium oxide component, which is prepared by containing a titanium oxide composition, and can be used in a steam and locomotive exhaust gas treatment system. Another way to improve the effectiveness of the activity is to introduce a portion of the oxygen-containing component. Although U.S. Patent 4,134,856 discloses a process for preparing active aluminum containing cerium oxide by co-precipitation. U.S. Patent No. 6,235,255 discloses a platinum catalyst dispersed on a zeolite support which treats exhaust gases from a leanbum engine. US Patent 6,78_ discloses a high surface area carrier of 3/Furstone and active ingredients, and uses this carrier to make a metal containing ruthenium and money. This kind of precious gold medium can be used in the treatment of (7) ingredients. Steam and locomotive exhaust. 1357355 Chen et al (Inchati〇nal J〇umal 〇f) 〇 如 如 如 如 , , , , , , , , , , • • • • • • • • • • • • • 已 已 已 已 已 已 已 已 已 已 已 已 已 已 已 选择性 选择性 选择性In the reaction, it has the same C〇 removal rate and selectivity. The redox mechanism of the 钸-wrong oxide mainly uses the 钸-wrong oxide to provide oxygen and the c〇 reaction adsorbed on the catalyst, and then The oxygen in the air complements the characteristics of the oxygen defect of the 钸Zirconium emulsion. However, there is still a pressure difference between the powdery catalyst and the practical application. There are many catalysts prepared by using various carriers. It is used to treat the internal combustion engine exhaust gas containing components, or to suppress the concentration of c〇 gas in the hydrogen-rich gas generated by the recombination hydrogen production reaction. However, in terms of commercial applications, in addition to considering the micro-energy, Factors such as cost, durability, ease of preparation, or versatility must be considered. The present invention is a carrier stone for the preparation of a low-cost, high-resistant and record-reading CQ selective oxidation. The invention has not been disclosed yet. The stone is used as a carrier to prepare a C0 selective oxidation catalyst with high efficiency and high heat resistance. The _stone is fine, which can be used to make the contact area of the high contact side and the reaction gas. Minerals such as magnesium, aluminum and strontium have high water absorption, high pressure resistance, high water absorption, inertness and low cost. Therefore, the preparation of C〇 selective oxidation catalyst by using vermiculite as a carrier can satisfy the above commercial applications. [Embodiment] The preparation process of the catalyst is as follows: (1) first depositing the support on the stone, and calcining to form a support carrier-containing vermiculite carrier; (2) reusing the wet impregnation method to include The vermiculite carrier of the support is immersed in the raw material solution containing the catalyst 1357355 and the accelerator, and after drying and calcination, the co selective oxidation catalyst with vermiculite as the carrier is prepared. The co of the present invention The selective oxidation catalyst contains at least a catalyst agent, a support and a worm-to-stone carrier. A small amount of a promoter may also be added to enhance the catalyst performance. The catalyst in the present invention is mainly composed of copper oxide, and the promotion is added. Agent is a nucleus or a strong oxide, the carrier For the recording-error oxide, the catalyst is improved by the ability to enhance the oxygen exchange by the erbium-defect oxide. In the present invention, the weight ratio of the promoter to the catalyst is between 1:10 and 1:60. The optimum range is between 1:30 and 1:50. The weight ratio of the carrier to the catalyst is between 1:4 and 4: the best range is 1.5:1 to 4··1 The bribe stone disclosed in the present invention is a healthy (7) selective oxidation catalyst, and the first precipitation method will be used to precipitate the body salt on the Wei stone, and the new test will contain the dragon _ stone dump. The wet impregnation method will be used. The ruthenium ray is impregnated with a C 〇 selective oxidation catalyst which contains a surface 継 促 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Preparation The present invention uses a water-soluble copper salt hydrate as a catalyst raw material, a sieve salt hydrate and a (tetra) hydrate as a secret, and the money is made into a water-hydrate or a ••••• Things. The hydrazine hydrate can be an acid hydrate, zinc sulphate hydrate or chlorinated water. The hetero-hydrates (4) make the (iv) domain hydrates the best; the wrong-concrete compound and the sieve-salt compound are similar to the water (10), such as the yoghurt compound, the stagnation of the chlorophyll, and the like. The article 'is still optimal to use nitrate nitrate. The promoter raw material salt is similar to the support raw material salt, and the water-soluble difficult-to-hydrate can be hydrated by the acid hydrate, the sulfate hydrate or the gas. The salt is the same as the salt hydrate, but it is best to use the acid hydrate. The hydrated salt hydrate such as sulfuric acid, sulphate hydrate or gas sulphate is still preferred to use the weiwei hydrate. (4) Water miscellaneous _ hydrates engaged in _ Lin, water-soluble copper salt hydrate phase handle coffee transfer, Wei Cai and Tong Fu Cai silk and other steel salt hydrate, but the use of copper nitrate hydrate is the best. In order to explain the present invention, the application of the invention is merely a matter of fact that the conditions used in the present invention are some, but not all, of the scope of the present invention, and therefore cannot be scaled. It is decided to impose restrictions on the condition of silk circumference. Example 1: This example discloses a co-selective oxidation catalyst preparation step using a worm-to-stone carrier. Step i: Take 0.611 g of nitrate, add appropriate amount of deionized water, disperse the nitrate in water, and then insert the ultrasonic wave. The ship is about 1G minutes to completely dissolve the oxonium; Step 2 ··Add 5 The fine bismuth nitrate is dissolved in the foregoing, and an appropriate amount of deionized water is added to make the total weight of the solution be 8 g. ^ The solution containing the sulphuric acid sieve and the Gu oxygen solution is placed in the ultrasonic shock absorber. Make the acid sieve and Gu oxygen wrong completely dissolved to make the wrong solution (at this time, the decoration is wrong, the molar ratio is tender). Step 3: Take the gram stone, the pro-form is returned, and the positive value of the money is difficult. Between m and 'stay for about 4 hours to carry out the shoal; Step 4: Separate the solid containing the precipitate from the liquid in step 3 by means of the method, and the obtained solid is the slate carrier of the money, and then go Ion water washing Su; Step 5: The washed solid is placed in the air to be burned (heating rate: 4 hours to obtain the inclusion of _ stone surface; surface 6: the step $ made) The insect-to-stone carrier is immersed in a 5〇wt% copper silicate solution to impregnate the copper nitrate solution; the step is to leach the nitrate-dissolved (four) vermiculite «, first After drying for 2 hours to remove water, it was fired in air for 6 耽 (heating rate: 5 t/min) for 4 hours to complete the preparation of co-selective oxidation catalyst of insect-to-stone carrier 1357355. The contacted Wei Wei is as follows: it is made in a quartz tube with a diameter of 4_0 mm. The ends of the tube are made of quartz cotton, and the quartz reactor is placed in a high temperature furnace. The reaction temperature is adjusted by using a high-temperature furnace, and the flow rate of the reaction gas is measured by mass flow rate H (maSsfW. coffee mfc), and the gas flow rate after the reaction is measured by a bubble-type flow meter, and a micro gas chromatograph is used. Curry, she suppressed the 'A touch company', measured the group reduction of gas production. Table - for the catalyst performance test • • results 'C0 conversion rate, C0 selection rate and F / W value are defined as follows: C0辍彳h rate (3⁄4)-special material end C0 molar number - gas producing end C0 molar number feeding end C0 molar number χίυυ/° CO selectivity _ consumption of oxygen molars with C0 reaction and C0 reaction consumption Oxygen molar + +1! 2 reaction consumption xl 〇〇% gh) = feed flow rate ^ Catalyst species, accelerators and supports Weight _ In the catalyst performance test, the operating conditions are: take the catalyst weight · 27 grams; the feed gas composition is 1.99% CO, 1.74% 02, 15% C02 and 48% Η 2, the rest & The feed gas flow rate is 75.85 cc / min, at this time F / W is 29.16 L / gh. Table 1, catalyst performance test results (50 wt.% copper nitrate solution) reaction temperature (°c) feed end CO concentration (ppm) CO concentration at the gas producing end (ppm) CO conversion rate (%) c〇 selectivity (%) ----- ^7182___ __100 180 19900 7.3 99.96 160 19900 241 98.78 140 19900 6932 64.91 1357355 Example 2 The catalyst preparation process was the same as in Example 1, except that in the preparation step 6, the vermiculite support prepared in the step 5 was immersed in a 60 wt.% copper nitrate solution. The evaluation method of catalyst efficiency is also slightly different from that of Example i. The feed gas) and the feed gas flow rate are not easy to control due to the control. The feed gas compositions were 2.02% C〇, 1.74% 〇2, 15% C〇2 and 48, respectively. /.其余2 ‘the rest is ν2; and the feed gas flow rate is 72.55 ee/min, and the shoulder of this day is 27.89 L/g.h, and the Wei test results are shown in Table 2. Table 2, Catalyst effect $ test result (60 wt.% copper nitrate solution) Reaction temperature (°c) CO concentration at the feed end (ppm) CO concentration at the gas end (ppm) CO conversion rate (%) CO selectivity ( %) 180 20200 108 99.47 92 160 20200 1369 93.26 100 140 20200 7848 61.15 100

Example 3: The preparation process of the catalyst was the same as in Example 1 except that in the preparation step 6, the cerium ore obtained by the step 5 was changed to *25 Wt.%; G Xiaoyi solution towel. The method of tracing is also the same as in the example i, except that the feed gas concentration and the feed gas flow rate are slightly different due to the difficulty of control. The feed gas composition was 2.01% c〇, 1.73% 〇2, 15% C02 and 48% H2, and the rest was n2; and the feed gas flow rate was 72.55 cc/min 'At this time, F/W was 27_89 L/gh, The performance test results are shown in Table 3. 1357355 Check-II, Catalytic effect (25 wt·% copper nitrate solution) Reaction temperature (°c) CO concentration at the feed end - Xppm) '1.-/0* Moon suction net bath gas end CO concentration (ppm) CO conversion rate (%) CO selectivity (%) 180 --20100 _ 17 99.91 79.24 160 ·____20100 615 96.95 100 140 __20100 8792 56.35 100 From the results of Table 1 to Table 2, in the same reaction temperature range, 50% copper nitrate solution can obtain the best catalyst efficiency, and when the reaction temperature is 18〇〇c, the conversion rate of c〇 can reach 99 96%, and the CO selectivity is 74.82%. - Example 4: The preparation process of the catalyst is the same as in Example 1, except that in the preparation steps 1 and 2, 1 - 146 g of nitrate and 5 g of 7 g of lanthanum nitrate are respectively taken, and an appropriate amount of deionized water is added to prepare The total weight is 1168 grams of sputum-wrong solution (the molar ratio of garnish to wrong is 〇8/〇2). The evaluation method of the catalyst Wei was also the same as that of the example 1, except that the feed gas concentration was slightly different due to the difficulty of control. The feed gas compositions were 2.01% CO, 1.75% 〇2, 15%%, and 48% & respectively, and the rest were Ν2. The performance test results are shown in Table 4. Table 4: Results of the test (钸C reaction temperature (°C) CO concentration at the feed end 1 u, 〇/u CO concentration at the gas end CO selectivity (%) (ppm) (PPm) CO conversion (%) 180 20100 175 QO 1 ς —---- Q1.19 160 20100 ____2743 yy, iD 9Λ ΛΠ 100 140 20100 — 9739 51.43 100 12 1357355 Example 5: The preparation process of the catalyst is the same as in Example 1, except in preparation step 1 In step 2, 1.744 g of zirconyl nitrate and 4709 g of lanthanum nitrate were respectively taken, and an appropriate amount of deionized water was added to prepare a ruthenium-iridium solution having a total weight of 11.68 g (at this time, the molar ratio of yttrium-zirconium was 0.7/ 0.3) The evaluation method of catalyst performance is also the same as the actual & example_1. The performance test results are shown in Table 5. Table 5. Catalyst performance test results (钸-zirconium molar ratio is 0.7/03 Reaction temperature (°c) CO concentration at the feed end (ppm) CO concentration at the gas end (ppm) CO conversion (%) CO selectivity (%) 180 19900 155 99.25 95.25 160 19900 2305 88.65 100 140 19900 14205 29.16 100

Example 6: The preparation process of the catalyst was the same as in Example 1, except that in the preparation step 步骤 and the step 2, 2.991 g of cerium nitrate and 3.462 gram of cerium nitrate were respectively taken, and an appropriate amount of deionized water was added to prepare a total weight.钸·68 βί克's 钸-wrong solution (in this case, the molar ratio of 钸-error is 〇5/〇5). The evaluation method of the catalyst performance is also the same as that of the first embodiment, and the performance test results are shown in Table 6. . Mohr ratio is 0.5/0.5) Reaction temperature (°C) CO concentration at the feed end _(PPm) CO concentration at the gas producing end (ppm) CO conversion rate (%) CO selectivity (%) 180 _ 19900 10260 48 79 100 160 __19900 15698 20.03 100 140 19900 18455 6.35 100 13 74.82% Comparison table... The results of Table 4, Table 5 and Table 6 show that, besides the catalyst salt solution, the irradiance and the carrier salt aqueous solution are called the wrong molar ratio. It is also a factor affecting the performance of the catalyst. Among them, the performance of the c〇 selective oxidation catalyst prepared by the errby is the best. When the reaction temperature is the boot, the conversion rate of c〇 can reach the load, at this time (7) The selection rate is poor. Example 7: Preparation of the catalyst _Wei _ method _ that is, only in the evaluation _ performance test • the experiment takes the case of the catalyst, the weight of the catalyst is a5GG7g, the feed gas flow rate is nee-(at this time) _ is Feng (four), the composition of the feed gas is 2鸠CO, U3%〇2, Lan^2/, and the remainder is N2′, the reaction II volume is ny, and the performance test results are shown in Table 7. Table VII. -----ZZ ^-- Reaction temperature (°c) CO concentration at the feed end Cppm) CO concentration at the gas producing end (ppm) CO conversion rate (%) CO selectivity (%) 180 20400 9 3 99.56 93 66 160 20400 1152 94.47 100 140 20400 6547 68.54 100 Comparative Example 1: In the catalyst preparation step, except in step 3, 14.6 g of 7*-active aluminum was immersed in the cerium-zirconium solution. Example 1. In the catalyst performance test, in addition to the catalyst weight of 804 g 'feed gas flow rate of 99.83 cc / min (F / W is 17_51 L / gh), the feed gas composition was 2.11% C 分别, 1.86% 〇2, 15% C02 and 48% H2, the rest is N2, and the reaction volume of I357355 is 2.85 cm3. The other catalyst performance evaluation methods are the same as those in the example i. The performance test results are shown in Table 8. . . Table 8. Catalyst performance test results with γ-activated aluminum as carrier. Reaction temperature (°c) CO concentration at the feed end (ppm) CO concentration at the gas producing end (ppm) CO conversion rate (%) —--- CO selection Rate (%) 180 21100 7721 64.64 42 76 160 21100 4772 ---- 77.97 51.09 145 21100 486 97.72 69.26 140 21100 1339 93.37 61.46 Comparative Example 2:

In the catalyst preparation step, the preparation process was the same as in Example 1 except that 14.6 g of 5 Α zeolite was immersed in the 钸-error solution in the step 3. In the catalyst performance test, in addition to the catalyst weight of 21485 grams, the feed gas flow rate is 100.5 cc / rnin (when F / w is 2 〇 8 L / g_h), the feed gas composition is 2.08% CO, 1.81〇/〇〇2, 15% c〇2 and 48% H2, the rest is N2, and the reactor volume is 2.72cm. The other catalyst effectiveness evaluation methods are the same as those in the example. The performance test results are shown in Table 9. Show...

Table IX, to 5A

Reaction temperature rc) CO concentration at the feed end (ppm) CO concentration at the gas producing end (ppm)

Tables 7 to 9 are negative CO conversion rates (%) C◦ selectivity (%) 9.34 11.00 5.67 When loading the same amount of catalyst and support (total weight 0.29 g),

15 1357355 The results of the test results of the singularity of the sapphire ', 7_ 姊 5A private, from "'. The fruit can be known as 纟 纟; 5 is the carrier Cq selective oxidation catalyst, with the best vector In the catalyst performance test conditions of Table 7, the c〇 selective oxidation catalyst with vermiculite as the carrier has the best catalyst performance at a reaction temperature of 18 ° C. At this time, c〇 conversion The rate was 99 56%, and the c〇 selectivity was 93'66%. The optimum reaction temperature was 145 in the performance test of c〇 selective oxidation catalyst with r_active aluminum or 5A zeolite as carrier. (: and 21 (TC, and the corresponding c〇 conversion rates are 97.72% and 2.96% respectively. --- Cu wt.% Ce wt.% ------Ί Zr wt.%策德25.64 30.86 2.38 Catalyst supported by r-activated aluminum 9.93 6.84 '''-^ 0.5 Catalyst supported by 5A zeolite 7.06 6.71 0.73 Note: Inductively coupled plasma atomic emission spectrometry (ICP-AES) The result of the analysis

Table 10, different loading Table 10 shows the catalyst prepared by different carriers, which consists of copper, bismuth and zirconium. It can be seen from the results of Table 10 that the catalyst containing insect-to-stone carrier has higher copper, bismuth and erroneous content than the catalyst with the active surface aluminum or 5A zeolite as carrier, which proves that the meteorite is indeed More catalyst and carrier can be loaded. Table XI, under the same amount of catalyst (total weight: 〇.29g) 'Different carrier catalyst space and required cost reactor volume (cm3) Cost (unit: US dollar) with stone-based carrier Medium 1.66 ------ 0.20 Catalyst with r-activated aluminum as carrier 2.85 ^----- 0.39 Catalyst with 5A zeolite as carrier 2.72 ' 1.53 1357355 - Table 11 shows the same amount of catalyst The required volume of the reactor is used in conjunction with the preparation of the different supports (4). It is shown that when the load is equal to __ and the support, the required amount of the bribe carrier is the smallest, and since the price of the worm to stone is lower than that of the plant or the zeolite, the cost is the lowest. Example 8: Catalyst Crane Process Same as Example In the preparation step 6, the insect-to-stone carrier prepared in the step 5 was modified to be immersed in the machine. Catalyst performance • The evaluation method is also the same as in Example i. Only the 气体·5g catalyst is used, because the feed gas concentration and feed. The gas flow rate control is not easy and slightly different. The feed gas composition is 2 〇 5% c 〇, ι 61% - 〇 2, IS% C 〇 2 and 48% H 2 , the balance is N 2 , and the feed gas flow is 1 〇 3 · 45 cc / min (this The F/W is 21.48 L/gh. 'The results of the performance test are shown in Table 12. Soil-catalyst performance test results (1.31wt·% cobalt nitrate) Reaction temperature (. 〇 feed end CO concentration (ppm) gas production end CO) agricultural degree (ppm) CO conversion rate (〇 / 〇) CO selectivity ( %) 180 20500 6 99.97 160 20500 101 99.51 / J .UU QA QQ 140 20500 1669 92.02 y*r, yy 100 Example 9: The catalyst preparation process is the same as in Example 1, except in the preparation step 6, the step 5 is The prepared vermiculite carrier was immersed in a mixture of 50 wt·% copper nitrate solution and 1.28 wt.% manganese nitrate. The evaluation method of catalyst efficiency was based on _ _ _ 'only take 〇 · 5 g touch, the secret The concentration of neon and the flow rate of feed gas are easy to control and there are some differences. The advanced age is 2.G3%C(), 161% 17 1357355 02, -150/〇C02 and 48% H2, and the rest is N2. a ^ Feeding emulsion /; il speed is ι〇3·63 cc/min (F/W is 21.51 L/gh at this time), and the performance test results are shown in Table 13. Table 13 Test results (1.28 by % nitrate) Reaction temperature (°c) CO concentration at the feed end _iPPm) CO at the gas producing end (ppm) CO conversion rate (〇/0) CO selectivity (%) 180 20300 17 99.92 76.63 160 20300 ------ 227 98.89 100 140 203 00 2854 87.32 100 —

Comparing the results of Tables VII, Twelfth and Table XIII, it is known that adding a small amount of _ to improve the catalyst performance is better when the reaction temperature is nautical time, and a small amount of nitrate is added. (7) Selective oxidation catalyst is preferred. Catalyst performance, at this time C0 conversion rate can reach 99.97%, C0 selectivity rate is 73.66%. [Simple diagram description] None [Main component symbol description] None

Claims (1)

丄 30/:0 X. Patent application scope: Snow 疋 Public law preparation, the steps including the first fine field method will be carried on her carrier, then "The law will touch the Na (four) paste on the ground (four) _, the preparation of the material carrier on the vermiculite carrier, the stone is soaked in the aqueous solution containing the carrier, and then adjust the solution to the appropriate range with an alkaline solution. In order to carry out the spurt, after drying through the sputum and washing the dish, in the Xie 崎崎4 office, you will have the line stone health, including the steps: Step 1 · Take an appropriate amount of nitrate oxidized 'add deionized water to make _ oxygen dispersion In the water, put the ultrasonic wave in the earthquake for 1G minutes, so that the gas is completely dissolved; Step 2: Add the right amount of the two before the shot, and add from the fresh water, and then the stone containing sieve and the stone acid The wrong solution is placed in the ultrasonic oscillator to oscillate, so that the nitrate and the nitrate are completely dissolved to make the silk liquid, and the 钸 _ ear ratio is about _"; 衣! v Step 3 Take the appropriate stone to change the bubble in the prepared zirconium solution, and adjust the positive value of the solution with ammonia to make it between (1) and 11 and let it sit for about 4 hours. W over; consider the method to obtain the solids and liquids in the step 3 to separate the solids, the resulting solid is the short stone health containing the dry, washed with private f ion water; Step 5. Place the mixed solids in In the air, the calcination is carried out at a heating rate of about -4 hours to prepare a carrier-containing heterogeneous carrier; Step 6: The worm-to-stone carrier prepared in the step 5 is immersed in about copper silicate The solution is then impregnated with the Wei copper solution to the stone carrier, and the green is dried for about 2 hours to remove the water 19 2. After 'after the air, (4). (10) Burning, ascending sputum "The drought is 5C/min for about 4 hours, that is, the preparation of the CO selective oxidation catalyst for the carrier is completed. The preparation method of the oxidative catalyzed by the sulphide (7) is used in the table. The raw material of the preparation is a cerium salt and a zirconium salt. The preparation method of the C0 selective oxidation catalyst of the second aspect of the patent, which uses 4 cerium nitrate hydrate, barium sulfate hydrate or chlorinated hydrate. .^ Please use the preparation method of the C0 selective oxygen medium in the second item of the patent system, which is used as the two condensate and sulfur secret hydrate Wei Xu hydrate. S·If Shen Qingqing takes GG.__ The basic solution used for the preparation is sodium carbonate, sodium hydrogencarbonate, ammonia water, etc. The catalyst for the preparation method of the CO selective oxidation catalyst of the catalyst agent as in the first application of the patent scope is copper salt hydrate. 7. As claimed in the patent application, (7) A method for preparing a selective oxidation catalyst, wherein the copper salt hydrate used is copper nitrate hydrate, helium steel hydrate or copper chloride hydrate. The preparation method of the C0 selective oxidation catalyst of the fine enthalpy item, which is used for making The raw material of the accelerator is a lead salt hydrate or a salt hydrate. 9. The method for preparing a selective oxidation catalyst according to the seventh item (7) of the patent application, wherein the salt hydrate is a decomposed acid hydrate, A salt hydrate such as a sulphate hydrate or a chlorinated hydrate hydrate. 20 13:57355 The preparation method of the C0 selective oxidation m of the medicinal fine article 8 of the patent application, the clock salt hydrate used is a stone mystery Hydrate, thioheadate or chlorinated clock hydrate, etc. 一种 盐水 专利 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 制备 性 性 性 性 性 性(4) Dragon, as well as a promoter to enhance Na's performance, etc. 12. If the catalyst is applied for patent sub-item, the catalyst is selected from n-key, silver, iron-smelling, group, m-jin, copper, silver, One or more of a metal, a metal oxide or an alloy of gold. 13. The catalyst of the U of the patent application, wherein the promoter is selected from the group consisting of Ming, Meng, steel, Syria, and potassium. It is composed of one or several kinds of metals, metal oxides or alloys such as towns. The catalyst of the nth term, wherein the carrier species is selected from the group consisting of metal, metal oxide or alloy selected from the group consisting of: wrong, steel, sieve, town, copper, iron, titanium and tin. For example, the catalyst of claim 12, wherein the catalyst is an oxide of copper. 16. The catalyst of claim 13 of the patent scope, wherein the promoter is cobalt or a violent oxide. The catalyst of the range μ of the patent scope, wherein the carrier species is a decorative-junction oxide. 18. If the catalyst of the fifteenth item of the patent application scope, the copper oxide accounts for the weight percentage of the overall catalyst. Between 10% and 35%. 19. The catalyst of claim 16 of the patent scope, wherein the cobalt or manganese oxides account for the weight of the overall catalyst 21 13:57355 The percentage is between 0.1% and 1.0%. 20. The catalyst of claim 17, wherein the cerium-zirconium oxide comprises between 25% and 55% by weight of the total catalyst. twenty two