The method of purification of hydrogen-containing gas mixture of carbon monoxide

 

The invention relates to a process for the catalytic purification of hydrogen-containing gas mixtures of carbon monoxide and can be used in various fields of chemical industry, for example in the production of ammonia, and hydrogen energy, in particular, as a fuel for fuel cells. Purification of hydrogen-containing gas mixture of carbon monoxide is carried out by oxidation of carbon monoxide by oxygen or air, which consists in conducting the process in the reactor at a temperature not lower than the 20oC and a pressure not lower than 0.1 ATM in two stages, each of which contains at least one layer of catalyst. In the first stage as an active component of the catalyst take CuO-CEO2or MnO2-SEO, and the second catalyst containing an active component based on noble metals or their compounds with other metals. The invention improves the efficiency of the oxidation of CO in hydrogen-rich gas mixtures to less than 10 ppm. 7 C. p. F.-ly, 1 table.

The invention relates to a process for the catalytic purification of hydrogen-containing gas mixtures of carbon monoxide. Hydrogen is one of the most important industrial ha as well as in hydrogen energy, in particular, as a fuel for fuel cells.

It is known that fuel cells are seen as a real alternative to internal combustion engines, because they have much higher efficiency, they are quiet, can operate at sufficiently low temperature (80-110oC).

There are two main method of supplying hydrogen to the fuel cell (J. V. Ogden, M. M. Steinbugler, T. G. Kreutz. A Comparison of Hydrogen, Methanol and Gasoline as Fuels for Fuel Cell Vehicles: Implications for Vehicle Design and Infrastructure Development, Journal of Power Sources, vol.79 (1999) pp. 143-168).

By the first method, the hydrogen serves in pure form from the storage tanks, where it is compressed. The disadvantage of this method is the necessity of using equipment operating at high pressures, which adds cost and complexity to the process and increases the consumption of plants.

On the second way hydrogen is produced in a catalytic chemical process of substances-sources of hydrogen to the vehicle. As sources of hydrogen are hydrocarbons, alcohols, dimethyl ether and other It material using steam and/or oxygen in the conversion process in the hydrogen-containing gas is carbon at a concentration of more than about 0.001.% (10 ppm) is poison to the fuel electrode of the low-temperature polymer fuel cell. Therefore, such a hydrogen-containing gas mixture to be cleaned of carbon monoxide before it is supplied to the fuel cell. From all existing methods such cleaning is the most advanced purification by oxidation of carbon monoxide.

Known reactions occurring during the implementation of such cleaning: 2CO+O2-->2CO2, 2H2+O2-->2H2O(gas).

Indicators of treatment efficiency of the hydrogen-containing gas mixtures from SB are the concentration of CO at the outlet of the reactor and selectivity for oxygen, which is defined as the ratio of the number of oxygen spent on the oxidation of CO, the amount of oxygen consumed by both reactions:There is a method of carrying out oxidation reactions of carbon monoxide in the presence of hydrogen, which catalyst is used SIO deposited on SEO2(G. Avgouropoulos, T. Ioannides, N. To. Matralis, J. Batista, S. Hocevar, Catal. Letters 73, 1, 2001). The copper content in this catalyst ranges from 2.8 to 8.7 wt.%. The disadvantages of this method are the low selectivity of the process, a significant drop in catalyst activity when added to the reaction mixture of carbon dioxide and water vapor, in this case, the temperature of the process is the ITA (US Patent 6168772, C 01 B 31/20, 2001), in which a multistage reactor for selective oxidation with the optimization of the amount of oxygen at each stage. The content of platinum in that the catalyst is 6.4 wt.%. The disadvantage of this method is a significant hardware complexity of the system, as well as a very high content of platinum. Work in the field of CO oxidation in hydrogen-rich gas mixtures (Igarashi N., Uchida N., Suzuki, M., Sasaki Y., Watanabe M. Removal of carbon monoxide from hydrogen-rich fuels by selective oxidation over platinum catalyst supported on zeolite. // Applied Catal. A:General, 159, (1997), 159-169; M. Watanabe, H. Uchida, H. Igarashi, M. Suzuki Pt Catalyst Supported on Zeolite for Selective Oxidation of CO in Reformed Gases. // Chem. Lett. , (1995) 25) showed that this catalyst operates at temperatures exceeding 200o(I.e., approximately 100oWith higher than the operating temperature of the fuel cell). In addition, in the presence of N2About significant reduction in catalyst activity.

Task to be solved by the present invention is directed, is to increase the efficiency of oxidation of CO in hydrogen-rich gas mixtures to less than 10 ppm, i.e., lower operating temperatures, increasing the selectivity of the process, as well as a reduction in the content of noble metals in the catalyst D. the OIC mixture of carbon monoxide by oxidation with oxygen or air in two stages, both the first and second stage can be used at least one catalyst bed.

At the first stage, the use of highly selective catalysts based on copper or manganese, which as an active ingredient use CIO-CEO2or Mno2-SEO2content SIO or MnO21-10 wt.% as in massive form and deposited on oxides of aluminum, zirconium, silicon, and/or compounds based on them, or graphite-like carbon material.

In the second stage using catalysts based on noble metals as the active component contains platinum, palladium, ruthenium, rhodium, iridium, mainly, ruthenium and platinum, deposited on the oxides of aluminum, zirconium, cerium, silicon and/or compounds based on them, or graphite-like carbon carrier in an amount not less than 0.01 wt.%, mostly 0.05-5 wt.%, as well as catalysts, the active ingredient of which consists of mixtures, compounds or alloys of the metals (platinum, palladium, ruthenium, rhodium, rhenium, iridium, cobalt, gold, copper, manganese, iron, and other ), containing two or more metals deposited on oxides of aluminum, zirconium, cerium, silicon and/or compounds based on them, and tlou catalyst as at first, and the second stage operates at different temperatures.

Oxygen or air into the reaction zone is served only on the first stage. The process is carried out at a molar ratio of oxygen to carbon monoxide, present in the enriched hydrogen gas mixture from 0.5 to 3, at a temperature not lower than the 20oWith the pressure of not lower than 0.1 ATM. The purified hydrogen-containing gas mixture may contain its composition is not less than 0.1 vol.% carbon dioxide is not less than 0.1 vol.% water vapor, not less than 0.1 vol.% of nitrogen.

The process of purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in a flow reactor in two stages, each stage contains at least one layer of catalyst. The reactor is a quartz tube with an inner diameter of 8 mm Each layer of the catalyst contains from 0.3 to 1 g of catalyst was mixed with 1 g of inert material SiC. As catalysts for the first stage take CuO-CEO2or Mno2-SEO2massive or deposited on the oxides of aluminum, zirconium, silicon, and/or compounds based on them, or graphite-like carbon media. As the catalyst of the second stage take the catalysts with the active component based on noble metals supported on oxides of aluminum, C is rerout in the range of 0.1-100 cm3.g-1.with-1the temperature of the layers of the catalysts is in the range of 20-250oC, the Reaction is carried out in the pressure range of 0.1-10 ATM. The reaction gas mixture has a composition 10-100 vol.% H2, 0-30% vol. CO2, 0.01-2% vol. CO, 0.01-5% vol. About2, 0-10% vol. H2Oh, 0-90% vol. N2.

The essence of the invention is illustrated by the following examples.

Example 1. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer at a temperature of 130oWith is a catalyst containing 5 wt.% CiO-CEO2. In the second layer at a temperature of 110oWith is a catalyst containing 1.0 wt.% Ru/C. the Reaction gas mixture consists of 1 vol.% CO, 1.2% vol. O2, 74.8% vol. H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer of 5 cm3g-1-with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 1).

Example 2. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer at a temperature of 160oWith notarization, containing 1.0 wt. % Pt/C. the Reaction gas mixture consists of 1 vol.% WITH, about 1.2. % O2, 74.8% vol. H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer 3.3 cm3g-1-with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 2).

Example 3. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer at a temperature of 160oWith is a catalyst containing 50 wt.% MnO2-SEO2. In the second layer at a temperature of 130oWith is a catalyst containing 0.5 wt.% Ru-Pt/C. the Reaction gas mixture consists of 1 vol.% WITH, 1.15% vol. O2, 74.85% H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer 3.3 cm3g-1with-1on the second layer 5 cm3Mr.-1; the process is carried out at atmospheric pressure. The results are shown in table (example 3).

Example 4. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer when temps layer at a temperature of 110oWith is a catalyst containing 1.0 wt.% Ru/C. the Reaction gas mixture consists of 1 vol.% WITH, about 1.2. % O2, 74.8% vol. H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer of 5 cm3g-1with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 4).

Example 5. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer at a temperature of 160oWith is a catalyst containing 5 wt.% CiO-CEO2/Al2About3. In the second layer at a temperature of 110oWith is a catalyst containing 1.0 wt.% t/A12About3. The reaction gas mixture consists of 1 vol.% WITH, 1.1% vol. About2, 74.9% vol. H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer 3.3 cm3g-1with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 5).

Example 6. Purification of hydrogen-containing gas mixtures of carbon monoxide is carried out in reacto aderrasi 5 wt.% CiO-CEO2. In the second layer at a temperature of 110oWith is a catalyst containing 1.0 wt. % Pt-Co/Al2O3. The reaction gas mixture consists of 1 vol.% WITH, about 1.0. %2, about 75. % H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer of 5 cm3g-1with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 6).

Example 7/ Clean hydrogen-containing gas mixtures of carbon monoxide is carried out in the reactor in two stages with two layers of catalyst. In the first layer at a temperature of 160oWith is a catalyst containing 5 wt.% CiO-CEO2/ZrO2. In the second layer at a temperature of 110oWith is a catalyst containing 1.0 wt.% PT-Co/SiO2. The reaction gas mixture consists of 1 vol.% CO, 1.2% vol. About2, 74.8% vol. H2, 3% vol. H2About 20 vol.% CO2. The volumetric feed rate of the reaction mixture on the first layer of 5 cm3g-1with-1on the second layer 5 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 7).

Example 8 (comparison). Cleaning the hydrogenous gseo2at a temperature of 190oC. the Reaction gas mixture consists of 1 vol.% WITH, 1.25 vol.% O2, 72.75% H2, 10% vol. H2Oh and 15 vol.% CO2. The volumetric feed rate of the reaction mixture 0.28 cm3g-1with-1; the process is carried out at atmospheric pressure. The results are shown in table (example 8).

These examples demonstrate high activity and selectivity of the proposed catalysts that can effectively reduce the CO content in the enriched hydrogen gas mixtures to levels below 10 ppm. The proposed catalysts offer the possibility of varying their chemical composition. The proposed method and the use of the proposed catalysts can significantly reduce the temperature of the process, to increase selectivity and reduce the content of noble metals in the catalyst.

Claims

1. The method of purification of hydrogen-containing gas mixture of carbon monoxide by oxidation of carbon monoxide by oxygen or air, which consists in carrying out the process in two stages with the catalysts at a temperature not lower than the 20oC and a pressure not lower than 0.1 ATM, the first of which is as active components the second active component based on noble metals or their compounds with other metals.

2. The method according to p. 1, in which as the carrier of the active components of the catalysts of the first and second stages use the oxides of aluminum, zirconium, silicon, and/or compounds on their basis and use a graphite-like carbon material.

3. The method according to PP. 1 and 2, in which catalysts contain active ingredients in an amount not less than 0.01 wt. %.

4. The method according to PP. 1-3, in which the process is carried out at a molar ratio of oxygen to carbon monoxide, present in the enriched hydrogen gas mixture from 0.5 to 3.

5. The method according to PP. 1-4, in which oxygen or air into the reaction zone is served only on the first stage catalyst.

6. The method according to PP. 1-5, in which the purified hydrogen-containing gas mixture contains not less than 0.1. % of carbon dioxide.

7. The method according to PP. 1-6, in which the purified hydrogen-containing gas mixture contains not less than 0.1. % water vapor.

8. The method according to PP. 1-7, in which the purified hydrogen-containing gas mixture contains not less than 0.1. % nitrogen.

 

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