TW200842106A - Hydrogen production via partial oxidation of methanol over Au-Cu/TiO2 catalysts - Google Patents

Abstract

Selective production of hydrogen by partial oxidation of methanol (CH3OH +1/2O2→2H2 + CO2) over Au-Cu/TiO2 catalysts was studied. This application improves purity of hydrogen and reduces CO content. The Au-Cu/TiO2 catalysts exhibit spherical gold and copper particles. They are distributed homogeneously over the support and exhibited a narrow size (about 1.8 nm) distribution over Au-Cu/TiO2 catalysts prepared by deposition-precipitation (DP) method. The Au-Cu/TiO2 catalysts were prepared from HAuCl4 solution, Cu(NO3) 2. 2.5H2O solution and TiO2 by DP method. The solutions and TiO2 were separately added drop wise to a stirred solution of NaOH at 70 DEG C. The pH value of the aged solution keeps at 7. The final solid was filtered, dried at 100 DEG C. The Au-Cu/TiO2 catalysts were tested by the partial oxidation of methanol reaction (POM) at 200 to 300 DEG C. The catalysts precipitated at pH 7 and uncalcined show highest activity for hydrogen generation. There is a small quantity of carbon monoxide detected, when the O2/CH3OH molar ratio in the feed is 0.3.

Description

200842106 IX. Description of the invention: [Technical field to which the invention pertains] The present invention utilizes a precipitation fixation method to prepare a titanium oxide supported nano-gold-copper bimetallic catalyst for the purpose of developing a partial oxidation reaction of methanol (CH3〇h + 1/2) 〇2 — 2H2 + c〇2) A procedure for preparing hydrogen to increase the purity of chlorine by reducing the carbon monoxide content. The preparation of the titanium oxide support nano gold_copper bimetallic catalyst is characterized by a diameter of about 18 nm and a spherical shape of gold crystal grains and copper crystal grains. The catalyst is prepared by a precipitation solidification method. First, a gold chlorate aqueous solution and an aqueous copper nitrate solution are mixed, and the pH of the aqueous solution is controlled to be 7 by using sodium hydroxide of 莫J molar concentration, and then one is added. The oxidized chin is gradually precipitated at 7 ° C for 2 hours. After washing, it is washed with water, filtered, and dried at f 100 C to prepare a titanium oxide-supported nano-copper bimetallic catalyst. Dish, 20 (M〇〇〇C. Partial oxidation of methanol at the reaction temperature of ~3〇〇〇c, can exert the most U and Wei selectivity. The ratio of gold to copper in the non-fine procedure is [(10) titanium oxide alone The support to copper bimetallic catalyst, when the feed ratio 〇 2 / CH3 〇 h is G 3, the reaction temperature is 25, with the second, 7n strip, the lower sterol conversion can reach 91%, and The hydrogen selectivity is 90% ': the production of the Erli-Oxide counter. Obviously, the gold-copper catalyst catalyzes the partial oxidation of methanol = alcohol conversion and selectively oxidizes carbon monoxide, so that there is only a small amount of hydrogen in the product. Emulsified carbon pollution. 0 [Prior Art] Yes, Meishang's catalyst is also recorded. Catalyst and low-pollution energy is a crisis facing Wantong. Therefore, the technology for developing high-efficiency power generation has been continuously changed. "(hyd which n energy) pollution of the exhaust gas, also avoids the W scene of the industrialization of the city It's just around the corner. Not only can it be reduced, but it's so good. Because of the transportation and storage of hydrogen, the main two suitable hydrogen source fuel cells used today are alcohol, natural gas, and light oil. Hydrocarbons are used as a source of hydrogen for the 200842106. Among them, methanol has high fuel quality, low price, easy access, easy storage and convenient transportation (Joensen and Rostmp-Nuelsen, in /· Power 5b muscle milk, vol. 105, pl95, published in 2002); and can generate hydrogen at a low reaction temperature of 200~400 ° C. Compared with traditional gasoline fuel, the generated carbon dioxide (C02) is reduced by about 50%, and There will be no air pollution sources such as NOx, SOx, and hydrocarbons, which is a big advantage for research and application of fuel cells on electric vehicles. Kim has long been difficult due to its chemical inertness and high dispersion. It is a less active catalyst. Until Hamta et al. found in J. Cata/·, vol.155, p301, 1989, the gold catalyst of the support has low temperature oxidation of carbon monoxide. After ability, it is widely studied ^ Yue from the production of hydrogen via reaction of alcohols of the following four ways to obtain catalyst:. ⑴ (2) ⑶ (4) Yue alcoholysis (methanol decomposition, MD) reaction

CH3OH 2H2 +CO steam reforming of methanol (SRM) reaction CH3OH + H20 ^ 3H2 + C02 sterol partial oxidation of methanol (POM) reaction CH3OH +1/2 02 2//2 + C02 Oxidation steam reforming of methanol (OSRM) reaction 2CH3OH +1/202 + H20 -> 5H2 + 2C02 Industrial hydrogen production is often carried out using steam recombination. Generally, the catalytic effect can be achieved with a copper catalyst at 200. (: There is good reactivity. Unfortunately, a large amount of carbon monoxide (>p/.) appears in the methanol steam recombination product, causing the poisoning of the platinum electrode of the proton exchange membrane fuel cell to cause the battery power to drop (Sekizawa et al. ; 7 /. Paradox / "People 〇 1.69, 0291, 1998). Therefore, a selective hydrogen permeable membrane is required (Emonts et al. J. Power νο1·71, p288, 1998), selective CO oxidation, water Additional equipment such as gas shift reaction to reduce the amount of carbon monoxide. The common method for preparing gold catalysts in the literature is the method of co-precipitation (c〇_precipitati〇n) (Haruta, 7 200842106)

Cato/. νο1·36, pi53, 1997), impregnation (Lin et al., Cato/. vol. 17, p245, 1993), deposition-precipitation (Hamta et al. vol .144, pl75, 1993), gas-phase grafting (Okumura C7z·· Leii·, p315, 1998), liquid phase grafting (iiqUi (j-phase grafting), colloidal mixing Colloid-mixing. The following is a brief description of various common processes for preparing gold-supported catalysts. (1) Commonly-prepared method: first mixing gold chlorate solution with nitrate metal and titrating with sodium carbonate solution a hydroxide or carbonate coprecipitate. The catalyst precursor is washed with water, filtered, dried, and finally calcined in air. (2) Precipitation fixation method: adding a gold chlorate aqueous solution to an oxide support, using an aqueous sodium carbonate solution Adjust the pH between 6 and 10. After curing for one hour, hydrogenation gold is generated on the surface of the catalyst. The catalyst precursor is washed with water, filtered, dried, and finally calcined under air. (3) Impregnation method: first chlorine The acid gold is dissolved in water, and the prepared solution and the desired load are The support is thoroughly mixed. After drying, a fresh sample is obtained. (4) Co-sputtering method: Under a large pressure, oxygen, gold and metal oxide are simultaneously sputter deposited on a substrate to form a film, and finally under air. The anneaj. Various preparation methods have their advantages and disadvantages. The gold catalyst prepared by the impregnation method has low dispersion and low catalytic activity. The gold particle size is about 8_3 nanometers (Haruta is in the ^) ^如人, νο1·144, pl75, published in 1993). The reason for the low activity may be that the precursor of gold is usually chloride. The low-temperature satin burns a lot of chloride ions on the support. Poisoning catalyst, high temperature but causing sintering phenomenon. Usually, the small particle gold carrier catalyst (<5^^) is really needed. The preparation method used by Cheyi is the common method and the sedimentation method. Batch 111^ mentioned in 2〇〇3 years that the preparation method has different effects on various catalyst carriers. The above method can produce gold crystal grains of semi-spherical ball with good thermal stability on the surface of metal oxide. People in vol.186, P458-p469, 1999 Under the calcination of the oxidized fault-loaded gold catalyst 4〇〇〇c, the crystal grains will grow to 4-6 nm or change the shape to become a symmetrical hexagon. The reactivity is often determined by the active site of the catalyst. Mavrikakis et al., such as human 1 machine, ν〇1·64, ρ104-Ρ1〇6, found that the reactivity of gold is closely related to its oxide support. The smaller the gold crystal, the sharper the age of the gold atoms at the edge. Edge gold atom and carrier 8 200842106 Strong mutual _. On the other side, because of the deformation side, there will be a souther oxygen atom concentration near the edge gold atom and a higher oxidation activity. QB_zzi et al. ^u·44, H20!1 (4) The surface of the gold surface will not rhyme-oxidize Broken, it will only adsorb on the gold atoms of the IV, the edge and the ^ corner. Park and Lee studied the metal of the catalyst gas surface at different calcining temperatures in 1999. (4) Gold coffee y ton and oxidized gold (Au (〇H)" fine (8) ^ f now the higher the calcination temperature will make _ The gold of the silk surface increases, but there is no significant increase in the activity of carbon monoxide, so the oxidation of gold reacts with carbon monoxide. It is more active than the gold of the genus. However, H resistance & Seeing, by % heart 3, 1997 and Gnsel et al. c_/· Γο, ν〇ΐ·72, 1-2, pl23-pl32, in 2002, they held the opposite. They believed that the gold ship’s gold-oxidation The carbon oxidation reaction is the position of the ruthenium. ^Transmitted, and filled with stone 彳 & & amp 关 关 加热 加热 加热 加热 加热 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 关 蒸汽 蒸汽 蒸汽 蒸汽 蒸汽 蒸汽% (inhibition), usually by water-gas transfer reaction (Water'Gas Shift, WGS) to reduce carbon monoxide to 〇 5~2 %. Traditional petrochemical industry usually uses • Fe3〇4_Cr〇3/A12〇3 and Cu -Zn〇/Al2〇3 catalyst for catalytic reaction. So (4) et al. j ν〇1·1=, p354, I9% year tried to use iron oxide to carry gold catalyst and oxidized inlaid gold The catalytic reaction of the gas-catalyzed hydrothermal gas indicates that the iron oxide-supported gold catalyst is active at low temperatures, but the oxidation-supporting gold-loaded catalyst is not, and the activity of the ferric oxide-supporting gold catalyst is also great at high temperatures. The gold catalyst and other commercial catalysts were supported. The nickel hydroxide-supported gold catalyst was also found to be active in the recombination reaction of the hydrothermal gas. After comparing the ferric oxide-supported gold catalyst, the oxidized three After carrying the catalytic effect of the gold catalyst and the titanium dioxide-supported gold catalyst, it was found that the titanium dioxide-supported gold catalyst is a more efficient catalyst for the steam recombination reaction. Considering the partial oxidation of methanol. This is another major hydrogen production route. Huang and Wang are in ^^ Μ % ρ28λ. In 1986, oxygen was added to the reaction strip of methanol strip, and it was found that hydrogen can be produced. Rate. From the kinetics of the sterol partial oxidation reaction, Huang and Chren determined in your κ νο1·40, Ρ43, 1988 that the methanol conversion rate will increase due to the addition of oxygen. The rate of dissociative adsorption is the rate. Decision In recent years, Cubeir〇_在义处/· AV〇L, 168, P307-p322, published in 1998, conducted a partial oxidation reaction of methanol with a palladium catalyst. It was observed that even if there is a considerable difference in the surface area of the catalyst. Zirconium oxide has good catalytic activity, whether it is oxidation or oxygen 9 200842106. However, the partial oxidation of methanol by i plus % zirconium dioxide supported palladium catalyst generates a large amount of carbon monoxide. Direct decomposition of methanol. In the application of electric vehicle fuel cells, methanol reforming reaction (steam reforming 〇f me^anol, SRM) and methanol partial gasification reaction 011 〇 瓜 瓜 瓜 她 她 肪 肪 肪 肪 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她The partial oxidation reaction of sterol is an exothermic reaction, and not only oxygen (〇2) can be used instead of steam as an oxidant, and an additional heating source is not required to continuously supply heat, so that a large amount of research has been conducted in recent years. Huang and Wang were p/. Cate/., νο1·24, ρ287. In 1986, oxygen was first added to the methanol hydrothermal recombination reaction, and a copper-catalyst was used to catalyze the partial oxidation of methanol. Kumar et al. (1992) published a catalyst for catalyzing methanol with zinc oxide supported copper catalyst at the Argon National Laboratory. Accompanying the oxidation reaction. Later, Alej〇 et al., Cato/, A, v〇i162, p28i_p297, 1997, found that there is a direct relationship between the activity of zinc oxide and the area of copper metal shouting. In addition, they also added bismuth oxide in the zinc oxide-supported copper touch. Although the oxidized bismuth has the effect of increasing the stability of the contact and prolonging the system, the reduction of the land will also reduce the conversion rate of methanol. Wa^ig et al. J· Mo/. Cte” A, v〇U9i, 叩冲34, 2〇〇3 years attempted to add rhetoric in copper/bismuth and monoxide-supported copper catalyst. Not only can the activity of the catalyst be improved: but the stability of the contact is also helpful. However, adding excessive riding will cause the formation of large particles of copper oxide, which will reduce the activity. Some scholars _ non-copper catalyst for sterol Oxidation-catalyzed reaction. Cubeirc and Fi(10) • In C-·, A, V〇1·168, P307, the year published a choice to use catalytic catalysts for catalysis research. Research S Sodium sulphur scale or chromium dioxide as support Du Lin is miscellaneous. However, a partial oxidation reaction is carried out with a 1 wt% dioxane-bearing heterocatalyst, and a large amount of carbon monoxide is formed by direct decomposition of the reaction. Professor Ye Junxi et al. S2002 Reaction Engineering Seminar In the paper, the methanol partial oxidation reaction was tested by the method of stagnation of the stagnation of the gold, and it was found that the conversion rate of methanol increased with the increase of the molar ratio of the methanol feed. The oxygen/methanol feed was not increased. The ear ratio is approximately equal to 〇·5^ and its hydrogen production will be highest. The partial oxidation activity of the system, and the selectivity of the emulsified carbon is also much lower than that of the copper catalyst. Among them, the oxidized gold-loaded catalyst has good catalytic activity and t gas selectivity, and the production of carbon monoxide Less than 1000 Peng. But the oxidation of 200842106 Ming loaded with Jinxian County's turning miscellaneous, will produce red amount of acid fs|. This laboratory c et d. in ¥ (10) / · A, vol. 290, p. 138, 2 〇〇5 years and (4) 3〇2, p i57, a fine 6-year paper, found that a titanium oxide and secret titanium · the age of the shop can be shouted low - oxidation ^ 篁 风 ' ' because of the opportunity to test the protons _ Saki Battery Essence C). Most of the patents related to the Golden Caterpillar patent are in the oxidation of carbon oxide. = Jun Yiren, the use of zinc oxide as a support for the preparation of supporting gold catalyst, at low temperatures The methanol part is 12263G8'_year), but there is no patent for the partial oxidation of methanol to produce hydrogen in the case of the titanium oxide used in this case.

, 峨 峨 : : : : : : : ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° From the published patent, there is no method for producing hydrogen gas from the fine oxidized nano gold-copper bimetallic catalyst disclosed in the present invention. ^ 查二^fAbout the gold ¥ media announcement number announcement 曰 patent name 1 00534833 2003/06/01 palladium-gold catalyst used in the manufacture of vinyl acetate 2 00222233 1994/04/11 gold catalyst for carbon monoxide oxidation Preparation Method 3 00145039 1990/11/01 Discharge-driven gold catalyst for carbon dioxide laser Table II. Domestic Patent Publication No. Announcement on Production of Hydrogen 曰 Patent Name 1 1226308 2005/1/11 Hydrogen Low Temperature Process 2 00553898 2003/09/21 Promoting bio-sludge production by thermal pretreatment 11 200842106 Method of hydrogen Table 3 · US Bulletin on Bullion-related patents Announcement 曰 Patent name 1, 6,509, 293 January 21, 2003 Gold based heterogeneous carbonylation catalysts 2 6,506,933 January 14 2003 Vapor phase carbonylation process using gold catalysts 3 6,022,823 February 8, 2000 Process for the production of supported palladium-gold catalysts 4 5,550,093 August 27, 1996 Preparation of supported gold catalysts for carbon monoxide oxidation 5 5,336,802 August 9, 1994 Pretreatment of palladium- Gold catalysts us Eful in vinyl acetate synthesis 6 5,051,394 September 24, 1991 Method for production of ultra-fine gold particle-immobilized oxides

SUMMARY OF THE INVENTION The paste of the present invention is prepared by the method of smear-forming method to prepare oxidized simplified green-green copper double-gold fine medium for the purpose of partial oxidation reaction (CH3〇H + "2〇2~2+ c〇2) A procedure for preparing hydrogen for use in a method of reducing the purity of hydrogen in the south - the carbon oxide content. The residual titanium support of the invention is characterized by the fact that the nano-gold-copper and the genus of the genus of the genus are in the form of a spherical shape of the gold crystal and the copper medium, and the preparation method is adopted. _ copper aqueous solution two, two Xiao 〇 1 material sulphur sodium hydroxide to control the acidity of the aqueous solution pH value of 7, and then ΐΓ ΐΓ ΐΓ ΐΓ , , , 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐 逐渐Next, prepare a nano-silver of titanium carbide support nano-gold; change the different calcination 12 200842106 temperature 20 (K400 C. in 200~3 〇 (the partial oxidation of sterol at TC reaction temperature, can play the best The activity and hydrogen selectivity. The gold-copper ratio of the non-calcining procedure is the oxidized chelating gold-copper bimetallic catalyst. When the feed ratio 〇2/CH3〇h is 〇·3, the reaction temperature is 2, Under the condition of pH of 7曰, the methanol conversion rate can reach %%, and the chlorine gas selectivity is only a small amount: the oxidation of iron oxide. Obviously, gold and catalyst can catalyze the partial oxidation reaction of sterol. , the high cap is identifiable and can selectively oxidize carbon monoxide, so that only a few of the hydrogen products are - Anti-corrosion of oxidized stone. The gold precursor is gold chlorate solution. It is best to prepare _ molar concentration. After preparing the filtered filter cake, it needs to be washed twice or less to remove chloride ions. [Embodiment] Preparation of titanium oxide support nano gold-copper bimetallic catalyst by solid concealer 4-L The present invention uses a precipitation fixation method to prepare a titanium oxide support nano gold-copper bimetallic catalyst. O.lg gold chlorate and 0.18g copper nitrate, mixed with 4.9g titanium oxide in deionized water of 2〇〇mi, prepared by titration and immobilization method for titanium oxide copper nano copper catalyst The step is to adjust the pH value of the pH by using an aqueous solution of sodium hydrogen sulfide, and to produce a precursor containing gold and copper on the surface of the catalyst, which is subjected to pretreatment such as washing, filtering, drying and calcining. The titanium oxide support nano gold-copper ( 1:1%) The preparation steps of the bimetallic catalyst are described as follows: 〇jg gold chlorate and 〇J8g copper nitrate are prepared separately into a 10 ml solution, which is added dropwise to 200 ml of 70QC deionized water. Then add 4.9g of titanium oxide. In the suspension of the above step, 卩1|^灿011 is used to control the value of 卩11. Maintain at 7, _ maintain the temperature at C ' continue to stir for 2 hours, that is, a sinking liquid, after the sedimentation of the temple, the suspension is filtered by a suction device and a filter cake is obtained, using 5 times less than five times 〇 cc pure water h wash, the cleaned catalyst precursor 'distributed in 1 ° ° C for more than 24 hours to remove moisture. The implementation method according to the embodiment 1, only to change the preparation of titanium oxide nano gold - The {11] value of the copper bimetallic catalyst is controlled at 5. Embodiment 3. According to Embodiment 1, the pH of the prepared titanium oxide support nano gold-copper bimetallic catalyst is controlled at 9. 13 200842106 Preparation A comparison of the effect of the pH of the catalyst on the metal grain size is shown in Table 1. Table 1 - 制备% % Preparation of Metallic Grains a Small Effect Experimental Calcination Temperature (Qc) Prepared pH Metal Grain Size (nm) Embodiment 1 Uncalcined 7 1.8 Embodiment 2 Uncalcined 5 2.7 Embodiment 3 Not calcined 9 1.9 Embodiment 4. In the Beiga mode, the prepared catalyst precursor is placed in a high temperature furnace and calcined at 2 ° C to prepare a titanium oxide having a calcination temperature of 2 ° C. Support nano gold _ copper bimetallic catalyst. Embodiment 5. According to the first embodiment, the prepared catalyst precursor is placed in a high temperature furnace and calcined at 400 C to prepare a titanium oxide support nano gold-copper bimetallic contact at a calcination temperature of 4 〇 0 °c. Media. TEM results for the preparation of uncalcined and different calcination temperature catalysts are shown in Figure 1. Uncalcined and metal grain sizes at 200 ° C and 400 ° C satin temperature, as shown in Table 2 and Figure 1. Metallic grain size at 30 °C and 400 °C calcination temperature Experimental calcination temperature (°C) Metal grain size (nm) Embodiment 1 —---, / not calcined 1.8 Embodiment 4 200 2.0 Embodiment 5 400 2.1 Hydration method 6, partial oxidation of methanol to produce hydrogen This study used methanol partial oxidation reaction as the activity test of titanium oxide supported nano-copper bimetallic catalyst, the whole system under proper temperature control, The activity test of the catalyst is carried out in combination with the product analysis of the gas chromatography technique. The detailed steps are as follows: the catalyst prepared in Embodiment 1 is loaded in the reaction tube; the temperature of the reactor is controlled at 250 〇C; And oxygen is fed and the oxygen/sterol feed molar ratio is set to 〇·3, and partial oxidation of methanol is carried out to the reaction bed for 90 minutes. Embodiment 7.14 200842106 In the same manner as Embodiment 6, the catalyst prepared in Embodiment 2 is loaded in a reaction tube. Embodiment 8. In the same manner as Embodiment 6, the catalyst prepared in Embodiment 3 is loaded in a reaction tube. The effect of different preparation catalyst pH on methanol conversion rate and hydrogen selectivity rate is shown in Table 3 and Figure 2. The pH value of the experimentally prepared sterol conversion rate (%): the flat hydrogen selectivity rate (%). 91 90 Application mode 7 5 87 75 Mode 8 9 83 93 Complex formula 9· _ Same as Embodiment 6, except that the oxygen/sterol feed molar ratio is set to 〇”. The formula is the same as the method of the sixth method, but the oxygen/methanol complement molar ratio is set to 〇·5. The effect of different oxygen/sterol feed molar ratios on methanol conversion and hydrogen selectivity is shown in Figure 3. ^

• Experiment S^___ Oxygen/methanol feed Mohr than methanol conversion (%) Helium wandering----- ------^ Hydrogen selectivity (%) Mode ό 0.3 91 90 — Mode 9 0.1 85 ----------. 85 ^Mode 10 0.5 ------- 86 7Q Formula Π · Equation 6 'Only the catalyst prepared by the money method 4 is loaded into the reduction tube. The formula 12 is the same as the formula f, except that the preparation of the fifth embodiment is carried out in a reaction tube. The preparation of different paper temperatures __ in the case of A and the selection rate _ ring as shown in Table 5 15 200842106 and Figure 4. Table 5. Sterol conversion and hydrogen selectivity at different calcination temperatures Experimental calcination temperature (°c) Methanol conversion (%) Hydrogen selectivity Embodiment 6 Uncalcined 91 90 Embodiment 11 200 87 81 Embodiment 12 400 83 92 to - Embodiment 13. The same as Embodiment 6, except that the reaction temperature was changed to 200 °C.

Embodiment 14. In the same manner as Embodiment 6, except that the reaction temperature was changed to 225 °C. Embodiment 15. The same as Embodiment 6, except that the reaction temperature was changed to 2,750C. Embodiment 1 & Same as Embodiment 6, except that the reaction temperature was changed to 300 °C. Methanol conversion rate, hydrogen selectivity and _ oxidized carbon selection and reaction temperature are shown in Figure 5. ’,

ZHAO, JIAO Experimental Embodiment 13 Embodiment 14 Embodiment 6 Embodiment 15 Conventional *Mode 16 Reaction temperature (°C) 200 225 250 275 300 Methanol conversion rate (%) 71 80 91 89 90 Hydrogen selectivity (%) ) a 96 97 90 67 Carbon oxide selectivity (%) b 1.7 2.0 3.9 15.2 ^ Hydrogen selective drunk (% b (hidden generation - b · - gasification carbon selectivity (%) = (one negative media, bucket number) Xl00 fire generation mole number / methanol consumption mole number) χ1〇〇16 200842106 [Simple diagram of the diagram] Figure 1. Transmissive electron micrograph of Au-Cu/Ti02 (mwt%) catalyst at different calcination temperatures Figure 2. Relationship between sterol conversion and hydrogen selectivity for catalysts prepared at different pH values. Figure 3. Relationship between methanol conversion and hydrogen selectivity for different oxygen/sterol feed molar ratios. Figure 4. Relationship between sterol conversion and hydrogen selectivity at different calcination temperatures. Figure 5. Relationship between methanol conversion, hydrogen selectivity and carbon monoxide selectivity at different reaction temperatures. ^ [Main Component Symbol Description] No 17

Claims (1)

200842106 X. Patent application scope ·· 1. Catalyst method, and use methanol part 〇·3, reaction - kind to prepare titanium oxide nano gold, t oxidation reaction to produce high purity hydrogen. Its temperature is ~ miscellaneous. Titanium oxide Wei won the reaction of the current 2 gas / methanol molar ratio - preparation, the preparation method is as follows: "Gold-steel and metal catalyst using precipitation fixation method a. First weigh gold chlorate and copper nitrate dissolved separately (U wt% or more of titanium oxide nanokina ^ touch ^ added titanium oxide leak, formulated into b · in the suspension of step a, added dropwise and sputum, dangerous to maintain pH 7; • 旲 ear / chen Degree of sodium hydroxide aqueous solution, and c. After the sinking hall, filter the suspension and obtain a d_ will be washed after the catalyst precursors ^ just twisted ^ ^ Wei points; /, phase in the dry for more than 24 hours to remove water e · dry The catalyst precursor is placed high _, in the fine ~ gamma qc:: ir1 - 5. If you apply for the special fiber around the first _ method, the surface of the cap oxygen is pure oxygen or air. 6. If you apply for a patent scope! The method of the item wherein the oxygen/methanol feed ratio is 〇(4). 7·If you apply for special fiber circumference! The method is called the towel reaction, so that the temperature of Guanxian and the calcination temperature is between 200 and 400 °C. 8. The method of claim 1, wherein the reaction temperature is from room temperature to 〇c. 9. The method of claim 1, wherein the reaction time is more than 1 minute. 18