CN1754825A - A kind of hydrogen through reforming oxidized methyl alcohol catalyzer and method for making and application - Google Patents
A kind of hydrogen through reforming oxidized methyl alcohol catalyzer and method for making and application Download PDFInfo
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- CN1754825A CN1754825A CNA2004100810062A CN200410081006A CN1754825A CN 1754825 A CN1754825 A CN 1754825A CN A2004100810062 A CNA2004100810062 A CN A2004100810062A CN 200410081006 A CN200410081006 A CN 200410081006A CN 1754825 A CN1754825 A CN 1754825A
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Abstract
A kind of hydrogen through reforming oxidized methyl alcohol catalyzer is an active ingredient with the sosoloid of cupric oxide and zinc oxide, chromic oxide, and the weight content of cupric oxide is 0.1-10% in the catalyzer, and the weight content of zinc oxide is 5-60%, and the weight content of chromic oxide is 3-40%; Catalyzer can be supported on the carriers such as aluminum oxide, zirconium white, cerium oxide, titanium oxide, trichroite, and vehicle weight content is 100-(Cu+ZnO+Cr
2O
3) %.The present invention adopts coprecipitation method or fast decomposition method to prepare the crystallite powder of high degree of dispersion, prepares low copper catalyst after the moulding.Utilize catalyzer to carry out the reaction of methyl alcohol partial oxidation reformation hydrogen production, temperature of reaction 280-400 ℃, normal pressure-2.0MPa, air speed is 1000-5000hr
-1, count water/methyl alcohol=1-3.0, O in molar ratio
2/ methyl alcohol=0.1-1.
Description
Technical Field
The invention relates to a technology for preparing hydrogen by partial oxidation of methanol, in particular to a low-copper catalyst with high stability and high selectivity.
The invention also relates to a preparation method of the catalyst.
The invention also relates to the application of the catalyst in the preparation of hydrogen by partial oxidation of methanol.
Background
The hydrogen production from methanol is an attractive research project in the fields of energy and chemical industry for nearly two-thirty years. In particular, in recent years, with the development of proton exchange membrane fuel cells, the technical problem of hydrogen supply is becoming more and more prominent, and methanol is considered to be a good hydrogen carrier. The methanol hydrogen production technology becomes a hot spot for research and development at home and abroad. The technical core is the preparation of the reforming catalyst for preparing hydrogen from methanol. Reformed hydrogen suitable for proton exchange membrane fuel cell hydrogen sources requires CO to be less than 10-100 ppm. Therefore, the methanol hydrogen production catalyst not only requires high activity and good stability, but also requires high selectivity to control the content of CO in the reformed hydrogen. When CO in the reformed hydrogen is lower than 1-2%, CO can be purified to be below 10-100ppm by utilizing a method for selectively removing CO in hydrogen through oxidation, and the CO can be supplied to a hydrogen source of the proton exchange membrane fuel cell for application.
The chemical reaction for preparing hydrogen from methanol is as follows:
side reaction:
both reactions are strongly endothermic and require external heat supply. The high temperature facilitates the hydrogen production reaction in view of the chemical reaction equilibrium limitations and methanol reforming catalytic kinetics. However, the high temperature on a typical catalyst is more favorable for the side reactions to proceed, resulting in more undesirable CO formation.
Adding oxygen (or air) into the hydrogen production reaction system to ensure that part of methanol and oxygen are subjected to oxidation reaction:
therefore, the endothermic reforming reaction and the exothermic partial oxidation reaction are coupled on the same catalyst, external heat supply is not needed, the hydrogen production efficiency is improved, the hydrogen production process is enhanced, the instant response time for meeting the hydrogen demand of the fuel cell is shortened, and the method is particularly suitable for application in mobile hydrogen sources of fuel cell electric automobiles, submarines, individual power supplies, dispersed power stations and the like.
The methanol partial oxidation reforming catalyst in the prior literature is mainly based on a copper-based catalyst, and the catalyst is mostly modified from a copper-based methanol synthesis catalyst. The main active component of the catalyst is CuO, and the copper content in the catalyst is generally 20-60 wt%. The reaction temperature for preparing hydrogenfrom methanol is lower, generally 220-280 ℃, the low-temperature activity is good, the CO generation amount is less, and is 1% (dry basis) or even less. However, these catalysts have two drawbacks: 1) CuO in the copper-based catalyst is reduced to Cu and sintered due to the low melting point of copper. At high temperatures, deactivation of the catalyst active sites is exacerbated. Although there are reports in recent years that the addition of an auxiliary agent such as Mn, Cr, Zn or the like to a catalyst can maintain Cu on the surface of the catalyst0And Cu+Species to increase catalytic activity, or Al2O3、ZrO2、CeO2、TiO2The stability of the copper-based catalyst which is used as a carrier to improve the stability, but CuO is used as an active component, and the stability problem is not solved, and the catalyst is easy to deactivate particularly under the partial oxidation reforming atmosphere in the presence of oxygen. 2) The low temperature use is beneficial to maintaining the stability of the copper-based catalyst, but the low temperature is not beneficial to the endothermic hydrogen production reaction. The conversion rate of the methanol hydrogen production is difficult to reach 100% at the temperature lower than 300 ℃, which is not beneficial to ensuring the hydrogen production efficiency of the whole hydrogen production system.
There are reports in the literature on the development of copper-free catalysts for partial oxidation reforming of methanol, such as ZnO-Cr with ZnO as the active component2O3The catalyst is characterized by being used at a temperature of more than 400 ℃, having no activity at low temperature, having good stability, being used at a temperature of 600 ℃ and being beneficial to the endothermic hydrogen production reaction. However, these catalysts have poor selectivity and have a CO content in the reformed hydrogen of 4% (dry basis) or more. In order to be used in a proton exchange membrane fuel cell, the reformed hydrogen must first undergo a water-gas shift reaction:
converting CO to hydrogen. The CO after the shift reaction is generally 1-2% (dry basis) due to chemical equilibrium limitations. Then purified to 10-100ppm by CO selective oxidation reaction for use in fuel cells. The increase of the shift reaction process makes the whole methanol hydrogen production process more complicated, and is not beneficial to moving the hydrogen production source.
Disclosure of Invention
The invention aims to provide a low-copper catalyst for hydrogen production by methanol oxidation reforming at medium temperature (280-400 ℃).
Another object of the present invention is to provide a process for preparing the above catalyst.
The invention provides a low-copper methanol partial oxidation reforming hydrogen production catalyst, which takes a solid solution of copper oxide, zinc oxide and chromium oxide as an active component, wherein the weight content of copper (calculated by copper oxide) in the catalyst is 0.1-10%, the weight content of zinc oxide is 5-60%, and the weight content of chromium oxide is 3-40%; the catalyst can also be supported on a carrier, and the carrier can be one of alumina, zirconia, ceria, titania and cordierite, and the weight content of the carrier is 100- (Cu + ZnO + Cr)2O3)％。
The invention also provides a method for preparing the catalyst, which can be at least any one of the following methods:
(1) dissolving soluble salt with distilled water to obtain acidic salt solution, and mixing the acidic salt solution with 0.5-1M Na solution as precipitation alkali under high speed stirring2CO3Dripping the solution or ammonia water into a precipitation tank in a concurrent flow manner, controlling the temperature to be 40-50 ℃ and the pH value to be 7-7.5 to prepare microcrystals with high dispersion degree, and then tabletting, rolling balls or extruding strips to form the finished catalyst.
(2) Quantitatively weighing the salt of each component, mixing and grinding, instantly decomposing at high temperature, quenching to prepare powder with high dispersity, and tabletting, extruding or rolling to obtain the finished catalyst.
(3) The soluble salt of each component according to the proportion is dissolved and dipped on the carrier of alumina, zirconia, ceria, titania and cordierite, and is roasted for 2 to 4 hours at 500 ℃.
The catalyst provided by the invention is used for partial oxidation reforming of methanol to prepare hydrogen, the reaction temperature range is 280-400 ℃, the pressure range is normal pressure-2.0 MPa, and the space velocity range is 1000-5000hr-1(space velocity of methanol amount to volume of catalyst), and (by mol ratio) water/methanol is 1-3.0, O2Methanol is 0.1-1.
The catalyst provided by the invention has the following advantages:
1. the low-copper catalyst has high activity and good selectivity when used for hydrogen production by partial oxidation reforming of methanol, and has the temperature of 280-400 ℃, the pressure of normal pressure of-2.0 MPa and the space velocity of 1000-5000hr-1(space velocity of methanol amount to volume of catalyst), and (by mol ratio) water/methanol is 1-3.0, O2When methanol is 0.1-1, the conversion rate of methanol is 90-100%, and CO in reformed hydrogen is less than 1% (dry basis volume%). The reformed hydrogen gas is directly subjected to CO selective oxidation removal without CO shift reaction, and CO can be purified to be below 10-100ppm to supply hydrogen to a fuel cell.
2. The catalyst of the invention has good stability, and the activity is not reduced after the reaction lasts for 100 hours.
3. The catalyst of the invention is used in the reaction of hydrogen production by methanol oxidation reforming, and does not need pre-reduction.
4. Compared with the existing copper-based catalyst, the catalyst of the invention has good temperature resistance and wide application temperature range: 280-400 ℃, and the temperature range is in the middle temperature region.
5. The catalyst and the hydrogen production technology of the invention simplify the hydrogen production process. The methanol is completely converted to prepare the hydrogen at the effective medium temperature use temperature, and the methanol utilization rate is high. And meanwhile, the generation of CO can be effectively controlled, so that a subsequent CO removal process does not need a CO conversion reaction process, the flow is simplified, the hydrogen production process is enhanced, the compactness, the miniaturization and the microminiaturization of a hydrogen production system are facilitated, and the control of the hydrogen production system is facilitated.
In a word, the invention adopts coprecipitation method or quick decomposition method to prepare high-dispersion degree microcrystal powder, low-copper catalyst is prepared after molding, copper enters into zinc-chromium oxide crystal structure to form solid solution, and the catalyst has high activity and high hydrogen production selectivity for methanol partial oxidation reforming hydrogen production reaction and good stability due to the mutual synergistic effect of the promoter and the main catalyst. The hydrogen production reaction is carried out in the medium temperature range of 280-400 ℃, which is beneficial to the complete conversion of methanol and the control of the generation amount of CO, and the catalyst is different from the common copper-based catalyst and is easy to oxidize and sinter.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the effects of the present invention can be achieved as long as the operation conditions of the present invention are met, so that the following examples are only for helping understanding the essence of the present invention, and are not intended to limit the scope of the present invention.
Example 1
0.0607 g of copper nitrate, 44 g of zinc nitrate and 13.2 g of ammonium dichromate are weighed, and all the three components are dissolved in 500ml of distilled water to be used as a solution A; a 0.5M sodium carbonate solution was prepared as solution B. 100ml of distilled water was added to the precipitation tank, heated to 40 ℃ and then the solution A and the solution B were added to the tank through two dropping funnels, respectively, under rapid stirring (stirring speed 400 rpm) and in constant parallel flow. In the precipitation process, the pH is kept at about 7.5, the temperature is 40-45 ℃, the dropped sodium carbonate solution is 1.1 times of the theoretical calculation value, after the precipitation is completed, the solution is aged for 1 hour, washed to be neutral, filtered, a product is baked in an oven overnight at 500 ℃ for 3 hours, powder is ground into 100 meshes, sieved and tabletted to form the product. The weight composition of the obtained catalyst is as follows: 0.1% of CuO-60% of ZnO-39.9% of Cr2O3。
Example 2
6.0734 g of copper nitrate, 43.8 g of zinc nitrate, 9.9 g of ammonium dichromate and 3 g of urea are weighed, mixed and ground uniformly in a mortar, put into a muffle furnace at 500 ℃ for rapid decomposition, then cooled to 20 ℃, and the powder is sieved by a 100-mesh sieve and then is rolled and molded. The weight composition of the obtained catalyst is 10 percent of CuO-60％ZnO-30％Cr2O3。
Example 3
After dissolving 1.5 g of copper nitrate, 21.2 g of zinc nitrate and 6.1 g of ammonium dichromate in 40ml of an aqueous solution, 100 g of Al was immersed in the solution2O3Drying on the ball at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr to obtain the final catalyst (0.45% CuO-5% ZnO-3.6% Cr)2O3)/90.95％Al2O3(wt％)。
Example 4
1ml (1.2 g) of the catalyst of example 1 was mixed with 1ml of quartz sand calcined at 1000 ℃ and 20 to 30 mesh, and the mixture was charged into a reactor thermostatic section having an inner diameter of 10 mm. Preheating the mixed solution of methanol and water at 200 ℃ and then introducing the preheated mixed solution into a reactor. H2O/CH3OH (molar ratio) 1-3/1, O2/CH3OH (molar ratio) 0.16 at 400 deg.C, P at normal pressure-2.0 MPa, S.V at 1000 deg.C for 5000hr-1The conversion rate of methanol is 90-99%, the CO content in the tail gas product is less than 1% (volume%), the reaction lasts for 50 hours, the activity is not obviously reduced, and the stability is good.
Example 5
1ml (1.0 g) of the catalyst of example 2 was used for the evaluation, and the experimental procedure and the apparatus were the same as those of example 4. When the temperature is 350 ℃, the space velocity is 5000hr-1At normal pressure, H2O/CH3OH (molar ratio) 1.2/1, O2/CH3OH (molar ratio) 0.16, methanol conversion 98%, CO content 0.9% (dry basis volume%).
At a temperature of 400 ℃, the methanol conversion was 100% and the CO content was 1% (dry basis volume%).
At 400 ℃ after 3 hours the temperature was reduced to 350 ℃ with a methanol conversion of 97% and a CO content of 0.95% (dry basis vol%). The reaction was continued to the end of 100 hours. The reactivity differs very little from the initial activity at this point, the methanol conversion being 95.5% and the hydrogen-selective CO content being less than 1% (dry basis vol%).
Comparative example
Weighing 18 g of copper nitrate, 31 g of zinc nitrate and 9 g of ammonium dichromate, uniformly mixing and grinding in a mortar, quickly decomposing in a muffle furnace at 500 ℃, then quenching to 20 ℃, sieving powder by a 100-mesh sieve, and then rolling and molding. The obtained catalyst comprises 30% of CuO-43% of ZnO-27% of Cr2O3。
The activity of 1ml of this catalyst was evaluated in the same manner as in example 4. When the temperature is 350 ℃, the space velocity is 3000hr-1At normal pressure, H2O/CH3OH＝1.2/1，O2/CH3OH (molar ratio) 0.16, methanol conversion 100%, CO content 1.5% (dry basis volume%). Four days after evaluation, the activity was unstable, the methanol conversion rate decreased from 100% to 91% on the first day of the initial activity, decreased by 2-3% each day thereafter, and decreased at a slower rate, and the methanol conversion rate decreased to about 80% on the fifth day, and the CO content was 0.8% (dry basis volume%).
Claims (10)
1. The catalyst for hydrogen production by methanol oxidation reforming comprises solid solutions of copper oxide, zinc oxide and chromium oxide as active components; the weight content of copper in the catalyst is 0.1-10 percent calculated by copper oxide, the weight content of zinc oxide is 5-60 percent, and the weight content of chromium oxide is 3-40 percent.
2. The catalyst of claim 1, wherein the catalyst is supported on a carrier, and the carrier is one of alumina, zirconia, ceria, titania, and cordierite, and the weight content of the carrier is 100- (Cu + ZnO + Cr)2O3)％。
3. A method for preparing the catalyst of claim 1, which comprises the following main steps:
the active components are mixed and ground evenly, roasted for 1 to 3 hours at the temperature of 500-550 ℃, taken out and cooled to room temperature, and the prepared powder is pressed into tablets, extruded into strips or rolled balls to prepare the catalyst.
4. A method according to claim 3, characterized in that the powder produced is passed through a 100 mesh sieve.
5. A method for preparing the catalyst of claim 1, which comprises the following main steps:
a) dissolving soluble salt of each component of the active component by distilled water to prepare solution A;
b) fitting for mixingPreparing a precipitation alkali solution with the concentration of 0.5-1M as a solution B, wherein the precipitation alkali solution is Na2CO3A solution or ammonia;
c) under stirring, the solution A and the solution B are dripped into a precipitation tank in parallel, the temperature is controlled to be 40-50 ℃, and the pH value is controlled to be 7.3-7.7 until the precipitation is complete;
d) washing the precipitate to neutrality, drying at 100 ℃ and 110 ℃ for 10-12 hours, roasting at 500 ℃ and 550 ℃ for 2-3 hours, and tabletting, rolling balls or extruding the ground powder to form the catalyst.
6. The process as claimed in claim 5, characterized in that the stirring speed in step c is 400-600 rpm.
7. The process of claim 5, wherein the precipitate prepared in step c is aged for 1 to 2 hours before step d is carried out.
8. The method of claim 5, characterized in that the powder ground in step d is passed through a 100 mesh screen.
9. A method for preparing the catalyst of claim 1, which comprises the following main steps:
dissolving soluble salt of each component of the active component by distilled water, soaking the soluble salt on a carrier, and roasting the carrier at the temperature of 500-550 ℃ for 2-4 hours to prepare the catalyst.
10. Application of the catalyst of claim 1 in hydrogen production reaction by methanol oxidation reformingWith the following conditions: the temperature is 280--11-3.0 of water/methanol in molar ratio, O2Methanol is 0.1-1.
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| CNB2004100810062A CN1331599C (en) | 2004-09-30 | 2004-09-30 | Catalyst for methanol oxidation and reforming for hydrogen making, manufacture method and uses |
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Cited By (7)
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| CN101795765B (en) * | 2007-08-14 | 2013-08-07 | 犹德有限公司 | Catalyst, its preparation method and its use for decomposing N2O |
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN103566941A (en) * | 2013-02-04 | 2014-02-12 | 中国科学院大连化学物理研究所 | Methanol steam catalytic reforming hydrogen production catalyst and preparation method thereof |
| CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
| CN107128875A (en) * | 2016-05-31 | 2017-09-05 | 浙江理工大学 | A kind of producing hydrogen, catalyzing system, hydrogen manufacturing system comprising the catalyst system and catalyzing and application thereof |
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| KR100400591B1 (en) * | 2000-07-18 | 2003-10-08 | 미쯔이카가쿠 가부시기가이샤 | Catalyst for steam reforming of methanol and method for producing hydrogen therewith |
| CN1090998C (en) * | 2000-08-14 | 2002-09-18 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
| CN1397484A (en) * | 2002-08-13 | 2003-02-19 | 上海燃料电池汽车动力系统有限公司 | Catalyst for preparing hydrogen by reforming methanol vapour |
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| CN101795765B (en) * | 2007-08-14 | 2013-08-07 | 犹德有限公司 | Catalyst, its preparation method and its use for decomposing N2O |
| CN103566941A (en) * | 2013-02-04 | 2014-02-12 | 中国科学院大连化学物理研究所 | Methanol steam catalytic reforming hydrogen production catalyst and preparation method thereof |
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN104084211A (en) * | 2014-07-10 | 2014-10-08 | 中国科学院上海高等研究院 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
| CN104084211B (en) * | 2014-07-10 | 2017-01-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
| CN107128875A (en) * | 2016-05-31 | 2017-09-05 | 浙江理工大学 | A kind of producing hydrogen, catalyzing system, hydrogen manufacturing system comprising the catalyst system and catalyzing and application thereof |
| CN107128875B (en) * | 2016-05-31 | 2021-04-06 | 浙江理工大学 | Hydrogen production catalytic system, hydrogen production system comprising catalytic system and application of catalytic system |
| CN113000057A (en) * | 2021-02-02 | 2021-06-22 | 湖南大学 | Loaded with Cu/ZnO/CeO2Preparation method and application of porous material of catalyst |
| CN114570376A (en) * | 2022-03-07 | 2022-06-03 | 安徽海华科技集团有限公司 | Catalyst for synthesizing menthone and method for synthesizing menthone |
| CN114570376B (en) * | 2022-03-07 | 2024-01-26 | 安徽海华科技集团有限公司 | Catalyst for synthesizing menthone and method for synthesizing menthone |
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