Method for production of synthesis gas or enriched hydrogen gas mixture of water-alcohol mixtures

 

The invention relates to a catalytic method implementing the reaction of steam reforming of ethanol in order to obtain a synthesis gas or enriched hydrogen gas mixture, which can be used in various industries, including hydrogen energy, for example, as fuel for fuel cells. The inventive method is carried out in a reactor with two fixed layers of the catalyst. As the catalyst of the first layer using a catalyst containing as the active metal component IB group of the Periodic system (copper, silver, gold) and/or a noble metal selected from the group consisting of platinum, palladium, ruthenium, rhodium, iridium deposited on a graphite-like carbon carrier, the catalyst of the first layer contains an active ingredient in an amount of not less than 0.05 wt. %. As the catalyst of the second layer using a catalyst containing a metal of group VIII of the Periodic system, selected from the group consisting of Nickel, platinum, palladium, ruthenium, rhodium, iridium. In the reaction mixture is supplied to the second catalyst bed, pre introducing oxygen or carbon dioxide with a concentration of not higher than 50 vol.%. Isopera due to the use of water-ethanol mixtures, containing methanol, and prevent deactivation of the catalyst and formation of side products. 9 C.p. f-crystals, 8 PL.

The invention relates to a catalytic method implementing the reaction of steam reforming of ethanol in order to obtain a synthesis gas or enriched hydrogen gas mixture, which can be used in various industries, including hydrogen energy, for example, as fuel for fuel cells.

It is known that ethanol is widely available renewable raw materials, industrial production technology of which is well developed, for example, the biochemical processing of sugar cane, crops, or timber. The bioethanol is an aqueous solution containing about 12 wt.% of ethanol. Especially attractive were the processes that allow processing of bioethanol without distillation. This process is steam reforming of ethanol to produce synthesis gas or enriched hydrogen gas mixtures.

It is known that hydrogen steam reforming ethanol confirmed thermodynamically (K. Vasudeva, N. Mitra, P. Umasankar, D. Dhiugra, Int. J. Hydrogen Energy, Steam reforming of ethanolhanol response via reactions 25 (2000) 31), thus the main hydrogen-containing product of steam reforming of ethanol at moderate temperatures is methane, whereas at high temperatures and large molar relationship of water/ethanol is produced mainly hydrogen-containing mixture.

There is a method of steam reforming of ethanol on the cobalt-containing catalysts with the use of oxide and carbon carriers (F. Haga, T. Nakajama, H. Miya, S. Mishima, Catal. Lett. Catalytic properties of supported cobalt catalysts for steam reforming of ethanol, 48 (1997) 223). The disadvantage of this method is the formation of by-products such as methane, methanol, ethylene, acetaldehyde, diethyl ether. It is well known that in the presence of ethylene formation of carbon on the catalyst is greatly enhanced (J. R. Rosrup-Nielsen, Catalytic steam reforming, Catalysis Science and Technology, Eds. J. R. Anderson and M. Boudart, v.5, Ch.l, Springer-Verlag, Berlin, 1984).

A method of obtaining an enriched hydrogen gas mixture of steam conversion of ethanol promoted potassium Ni - and si-containing catalysts deposited on Al2About3(F. J. Marino, E. G. Cerrela, S. Dunalde et al., J. Hydrogen Energy, Hydrogen from steam reforming of ethanol. Characterization and performance of copper-nickel supported catalysts, 23 (1998) 1095). The main disadvantages of this method of carrying out steam reforming of ethanol enriched is digid, diethyl ether). The disadvantage is the need for more complex catalytic system (the introduction of the potassium promoter) to reduce the formation of side products.

In addition, the known method according to which the process of obtaining hydrogen is carried out in a reactor with two fixed layers of the catalyst using the catalyst Cu/SiO2in the first stage (S. Freni, N. Mondello, S. Cavallaro, G. Cacciola, V. N. Parmon, V. A. Sobyanin, React. Kinet. Catal. Lett. , Hydrogen production by steam reforming of ethanol two step process, 71 (2000) 143). At this stage of ethanol produces acetaldehyde, a steam conversion of which the second stage catalyst Ni/MgO leads to the formation of hydrogen-rich gas mixture. The disadvantage of this method is the rapid deactivation of the catalyst Cu/SiO2.

The closest is the way (C. D. Belyaev, V. Century Galvita. C. N. Parmon, G. L. Semin, V. A. Sobyanin, P., Tsyrulnikov. Catalyst and method for producing synthesis gas or enriched hydrogen gas mixture of water-alcohol mixtures, RF Patent 2177366, 7 01 J 23/40, 01 3/00, 27.12.2001) obtaining enriched hydrogen gas mixture in the reactor with two fixed layers of the catalyst, where the catalyst of the first layer using the catalyst containing the first metal, selected from the group consisting of platinum, palladium, ruthenium, rhodium, iridium deposited on a graphite-like carbon media, and as the catalyst of the second layer using a catalyst containing a metal of group VIII of the Periodic system, selected from the group consisting of Nickel, platinum, palladium, ruthenium, rhodium, iridium, for example, using known industrial Nickel-containing catalysts for methane conversion GIAP-16 (Handbook of apothica // ed Melnikova E. J. M.: Chemistry, 1986. 512 C.). The disadvantages of this method are the availability of by-product (methane), and relatively high contents in the products of carbon monoxide, which is poisonous for low-temperature fuel cells. It is not possible to use the resulting gas mixture to supply low-temperature fuel cells without significant cost reduction of the concentration of carbon monoxide.

Task to be solved by the present invention is directed, is to increase the efficiency of the process of steam reforming of ethanol with the purpose of obtaining a hydrogen-rich gas mixture by preventing deactivation of the catalyst and reduce the formation of side products.

The task resettle with two fixed layers of the catalyst, moreover, in the reaction mixture is supplied to the second catalyst bed, pre introducing oxygen or carbon dioxide in a concentration of not higher than 50 vol.%.

As alcohol use ethanol or methanol-ethanol mixture in a water-alcohol mixture having a concentration of alcohol of 1 to 50 vol.%. The process in the first layer is carried out at a temperature not lower than 200oSince, in the second layer is not less than 500oC. the Reaction is carried out at a pressure of not lower than 0.1 ATM.

Depending on the applied first layer of catalyst in the steam reforming process can be done in two ways.

(1) Ethanol or ethanol-water mixture on the first layer of catalyst (catalysts: platinum, palladium, ruthenium, rhodium, iridium) is transformed into a gaseous mixture of CO, CH4and H2by the reaction With2H5HE=CH4+WITH+H2, (1) which is then on the second layer of the catalyst is converted into synthesis gas enriched with hydrogen gas mixture according to the reaction: CH4+ 2H2O=CO2+4H2; (2) H2+CO2=CO+H2O (3) introduction after the first layer in the reaction mixture of oxygen along with reactions (2) and (3) reaction takes place (4): CH4+ 0.5 O2=CO+2H2. (4) (2) Ethanol or ethanol-water mixture at lane2H5OH=CH3CHO+H2(5) and then a second layer of the catalyst mixture of acetaldehyde and hydrogen is converted into synthesis gas or enriched hydrogen gas mixture for reaction
CH3CHO+3H2O=2CO2+5H2(6)
H2+CO2=CO+H2O. (7)
With the introduction of after the first layer in the reaction mixture of oxygen along with the reactions (6) and (7) reaction takes place (8)
CH3CHO+0.5 O2=2CO+2H2. (8)
The steam reforming reaction of ethanol is carried out in a flow reactor with two fixed layers of the catalyst. The reactor was a quartz tube with an inner diameter of 8 mm Layers consisted of 0.5-1 g of catalyst was mixed with 5 g of inert material SiC. The volumetric rate varies in the range of 1000-100000 h-1the temperature of the first layer is 200-450oWith the temperature of the second layer 650-800oC. the Reaction proceeds in the range of pressures of 1-10 ATM. The reaction gas mixture has a composition from 1 to 50 vol.% With2H5HE H2O. All presents data obtained after the catalysts for 25 hours.

The invention is illustrated by the following examples.

Example 1.

Steam reforming of ethanol-enriched hydrogen mixture is carried out at atmospheric on the catalyst 1 wt.% Pd/C at a temperature of 330oC, flow rate of 2200 h-1and atmospheric pressure. The reaction mixture consists of about 11.2.% With2H5HE+88,8% vol. H2O. After the first layer in the gas mixture is introduced 3% vol. About2. The second layer includes an industrial catalyst GIAP-16 in number 1, the results are shown in table 1. Data from the prototype are given in table 1A.

Example 2.

Steam reforming of ethanol-enriched hydrogen mixture is carried out at atmospheric pressure in a flow reactor with two fixed layers of the catalyst. The first layer contains the catalyst 15 wt.% C/S, and the process it is carried out at a temperature of 340oC, flow rate 100000 h-1and atmospheric pressure. The reaction mixture consists of 15.3% vol. C2H5OH+84.7% vol. H2O. After the first layer in the gas mixture is injected 3.5% vol. About2. The second layer includes an industrial catalyst GIAP-16 in number 1, the results Obtained are shown in table 2. data from the prototype are given in table 2A.

Example 3.

Steam reforming ethanol-methanol mixture enriched in hydrogen mixture is carried out at atmospheric pressure in a flow reactor with two fixed layers of the catalyst. The reaction gas mixture from the and carry out the process of steam reforming at a temperature of 330oC and space velocity of the mixture 2200 h-1. After the first layer in the gas mixture is injected 3.5% vol. About2. The second layer includes an industrial catalyst GIAP-16 in number 1, the results are shown in table 3. Data from the prototype are given in table 3A.

Example 4.

Steam reforming of ethanol-enriched hydrogen mixture is carried out at atmospheric pressure in a flow reactor with two fixed layers of the catalyst. The process in the first layer is carried out on the catalyst 1 wt.% Pd/C at a temperature of 330oC, flow rate of 2200 h-1and atmospheric pressure. The reaction mixture consists of 10 vol.% C2H5OH+90 vol.% H2O. After the first layer in the reaction mixture is introduced 4.% About2. The second layer includes an industrial catalyst GIAP-16 in number 1, the results are shown in table 4.

Example 5.

Steam reforming of ethanol-enriched hydrogen mixture is carried out at atmospheric pressure in a flow reactor with two fixed layers of the catalyst. The process in the first layer is carried out on the catalyst 1 wt.% Pd/C at a temperature of 330oC, flow rate 2400 h-1and atmospheric pressure. The reaction mixture consists of about 11.2.% With2

These examples demonstrate the high activity, selectivity and stability of the catalysts in the process of conversion of water-alcohol mixtures enriched in hydrogen gas mixture.

The proposed method of processing ethanol, including ethanol, in the enriched hydrogen gas mixture allows the use of hydroalcoholic mixture without distillation, which has important technological value. The catalysts have a wide possibility of varying their chemical composition. The proposed method allows to reduce the formation of by-products, and products which are poisons for low-temperature fuel cells.


Claims

1. Method for production of synthesis gas or enriched hydrogen gas mixture of steam conversion of alcohols in the reactor with two fixed layers of the catalyst, as the catalyst of the first layer using a catalyst containing as the active metal component IB group of the Periodic system and/or a noble metal deposited on a graphite-like carbon media, and as the catalyst of the second layer using rolled the General on the second layer of the catalyst, pre introducing oxygen or carbon dioxide with a concentration of not higher than 50 vol.%.

2. The method according to p. 1, characterized in that the first catalyst layer contains a metal selected from the group consisting of copper, silver, gold.

3. The method according to p. 1, characterized in that the first catalyst layer contains a metal selected from the group consisting of platinum, palladium, ruthenium, rhodium, iridium.

4. The method according to PP.1-3, characterized in that the first catalyst layer contains an active ingredient in an amount of not less than 0.05 wt.%.

5. The method according to p. 1, characterized in that the catalyst of the second layer contains a metal selected from the group consisting of Nickel, platinum, palladium, ruthenium, rhodium, iridium.

6. The method according to PP.1-5, characterized in that as alcohol use ethanol or methanol-ethanol mixture.

7. The method according to any of paragraphs.1-6, characterized in that the process in the first layer is carried out at a temperature not lower than 200oC.

8. The method according to any of paragraphs.1-7, characterized in that the process in the second layer is carried out at a temperature not lower than 500oC.

9. The method according to any of paragraphs.1-8, characterized in that the reaction is carried out at a pressure of not lower than 0.1 ATM.

10. The method according to any of paragraphs.1-9, characterized in that Speer is

 

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