Catalyst and method for producing synthesis gas steam reforming hydrocarbons

 

(57) Abstract:

The invention relates to catalysts and method of steam reforming of hydrocarbons, in particular methane to produce synthesis gas. Describes a catalyst for the generation of synthesis gas steam reforming hydrocarbons comprising oxides of Nickel, lanthanum deposited on alumomagnesium oxide carrier, and optionally containing zirconium dioxide in a ratio of components, wt. %: Nickel oxide 3,7-16,0; lanthanum oxide is 0.1-4,1; zirconium dioxide 0,1-2,2; alumomagnesium media else. Alumomagnesium carrier has the form of a 3-lestnica with three cylindrical holes with equal wall thickness in cross section. Also described is a method of obtaining synthesis gas steam reforming of hydrocarbons at 750-950oWith the presence of the catalyst according to the invention. The technical result is an increase in the duration of operation of the catalyst with high activity and increased usage of the active ingredient. 2 S. and 1 C.p. f-crystals, 1 Il., table 1.

The invention relates to catalysts for steam reforming of hydrocarbons, in particular methane to produce synthesis gas.

The process of catalytic conversion of hydrocarbons with water vapor traditionally use the and, as well as in hydrogen energy.

The chemical composition of the catalyst has been the subject of analysis in a large number of works. It Is Known [Century. Century. Veselov, N. P. Galenko. Catalytic conversion of hydrocarbons. Kiev: Naukova Dumka, 1979, S. 56-190], which is the first in a series of reactivity in the reaction of steam reforming of hydrocarbons Ru and Rh, namely:

Ru, Rh>Ni, Pt, Pd>Re>Co

However, the most popular in the industry have been catalysts containing as an active ingredient Nickel metal due to its availability and relatively low cost. In addition, the active component on the basis of Nickel metal has the lowest propensity for oxidation, acarnania and superusuario. Therefore, most of the catalysts for steam reforming of hydrocarbons are Nickel metal supported on a carrier, which is used or metal oxides: MgO, Al2ABOUT3, ZrO2[A. C. the USSR, N 383347, 25.02.1979; H Satterfield. Practical course of heterogeneous catalysis, M.: Mir, 1984, S. 361-371; A. C. the USSR, N 1734820, 23.05.1992;], or a binary oxide composition: Al-Ca-O, Al-Mg-O, Y-Zr-O and others [Century. Century. Veselov, N. P. Galenko. Catalytic conversion of hydrocarbons. Kiev: Technology Is Bobrov, E. M. Moroz, V. A. Sobyanin, V. Y. Gavrilov. Preparation and activity of Ni/Y-Zr-O - catalysts for steam reforming of methane.//Kinetics and catalysis, 38 (1997) 114-118], or composite materials such as Alo/Al2ABOUT3[L. L. Kuznetsova, V. N. Ananin, A. V. Pashis, V. V. Belyaev. Studies of composite catalysts of nickel on metal-ceramic substrates. //React.Rinet.and Catal.Lett., 43 (1991) 545-558].

However, due to the relatively high temperatures of the process of conversion of hydrocarbons, the presence of water vapor, the nature of the hydrocarbons, the search continues catalytic compositions, distinguished primarily by the presence of promoters in the active component. In industrial processes, steam reforming of natural gas and methane proven catalysts of the type GIAP-16, 17, 18, which represents a promoted Nickel oxide deposited on a pre-formed high-temperature aluminum oxide having the form of a ring [A. S. the USSR. N 383347, B 01 J 11/32, 25.02.1979] .

Analysis of existing catalysts for conversion of hydrocarbons shows that in addition to the Nickel-containing active component consists of various structure-forming additives (kaolin, cement, clay, graphite, and others). The catalysts prepared by different methods: by coprecipitation suitable for the project; by impregnation of the support with solutions of the corresponding salts. The content of Nickel in the catalyst varies between 10-60 wt.%.

These catalysts are characterized by high values of mechanical strength and stability. However, studies associated with increased stability, thermal stability of the catalysts, continue. In recent years in several countries, the most widely used catalysts for synthesis using the native complex geometric shapes. This is because when carrying out highly endothermic reactions, which include the steam reforming reaction of hydrocarbons in tubular reactors can cause non-uniformity of the temperature over the cross section of the pipe reactor. The parameters of the stationary heat transfer layer from flowing in the gas phase can significantly increase due to the shape and structure of the grain, because it determines the flow regime of the stream of the gas phase. Thus, in particular, catalysts for steam reforming of hydrocarbons company Topsoe represent a cylinder with seven holes [H Satterfield. Practical course of heterogeneous catalysis, M.: Mir, 1984, S. 361-371]; catalysts obtained according to [US Pat. RE 32,044, B 01 J 021/04; B 01 J 023/74; 03.12.1985], pre the segment, circle, square, hexapole, oval or sine wave.

Closest to the proposed catalyst is a Nickel catalyst for conversion of hydrocarbons [US Pat. N 3993459, C 01 B 2/16; B 01 J 23/10; 23.11.1976]. The catalyst was prepared by impregnation of the oxide alumomagnesium media, which is a plate with approximately parallel channels, a solution of the nitrate salts of lanthanum, cobalt, Nickel, uranium, cerium and/or thorium from subsequent stages of drying at 80-180oC and calcination at 500-900oC. the Catalyst has a composition, wt.%: (2,0-13,0) active component (98-87) media. In this case, the composition of the active component comprises, by weight. %: - (54-90)La2ABOUT3, (2-29)Soo (1-10)NiO, (0,1-8)UO2, (0,1-9)CeO2(ThO2); the composition of the medium: (0-50)MgO, (100-50)Al2ABOUT3.

The disadvantages of this catalyst include:

1. Complex oxide, the combination of the active component including a relatively expensive and rare raw materials containing cobalt, uranium, thorium.

2. The relatively high content of oxides of cobalt and lanthanum.

The invention solves the problem of increasing the duration of stable operation of the catalyst with high activity and increased utilization Akti the hydrocarbons, comprising oxides of Nickel, lanthanum deposited on alumomagnesium oxide carrier, and optionally containing zirconium dioxide in a ratio of components, wt.%:

Nickel oxide - 3,7-16,0

The lanthanum oxide is 0.1 to 4.1

The Zirconia - 0,1-2,2

Alumomagnesium media - Rest

Alumomagnesium carrier has the form of a 3-lestnica with three cylindrical holes with equal wall thickness in cross section.

The task is also solved by a method for production of synthesis gas steam reforming hydrocarbons at a temperature of 750-950oWith the presence of the above catalyst.

The method of producing catalyst includes obtaining alumomagnesium carrier having the form of trilistnika with three cylindrical holes (drawing), and impregnating it with a solution of nitrate salts of Nickel, zirconium and lanthanum with subsequent stages of drying at 110-130oC and calcination at 500-900oC for 4 hours. The resulting catalysts are characterized by high activity in the reaction of steam reforming of methane at 750oC. using the proposed catalysts speed the conversion of methane or greater than, or comparable to the rate of methane conversion on the known catalysts. So, the natural grain and 26-30 cm3/GS ATM at a fraction of 0.25-0.5 mm; at the same time on the catalysts GIAP-8, 16 (ring) she is 2.0-2.3 cm3/GS ATM on natural grains and 14-27 cm3/GS ATM at a fraction of 0.25-0.5 mm; catalyst company TOPSOE (cylinder with seven holes: one in the center and six on the periphery), it is 8.0 cm3/GS ATM on natural grains and 20.0 cm3/GS ATM at a fraction of 0.25-0.5 mm

Distinctive features of the proposed catalyst are:

1. The composition of the active component of the catalyst, comprising, by wt.%: (3,7-16,0)NiO, (0,1-2,2)ZrO2, (0,1-4,1)La2ABOUT3.

2. The form of granules, which are trehlistnyj with three cylindrical holes (drawing), allowing to increase the utilization of the active component. In addition, the proposed form of pellets allows to achieve a high turbulence in the flow of the reaction gas in the industrial tubular reactor, providing a minimal pressure drop across the layer height in the implementation of the turbulent regime, and this in turn contributes to a significant increase of heat transfer from the walls of the reactor to the catalyst layer and Vice versa.

The catalytic properties of the proposed catalysts in the reaction of steam reforming of methane ASCS.% H2O. the Composition of the initial reaction mixture and the products analyzed chromatographically. The catalysts before experiments restore the flow of hydrogen at 750oWith, 1-2 hours. The activity of the catalysts is characterized by the value of K= r/RCH4where r is the rate of steam reforming of methane, PCH4- pressure of methane in the reaction mixture. The catalyst used in the form of fractions of 0.25-0.5 mm, in the form of natural grain and testing is carried out at 750oC.

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

Example 1. 4.5 g of MgO is mixed with 72.5 g lOO, 40.6 g Al2ABOUT3, 8,3 ml of 66% aqueous solution NGO3and 80 ml of N2O for 40-60 minutes in a Z-shaped mixer, is then formed in the form of 3-lestnica with 3 cylindrical holes. Alumomagnesium carrier air-dried to 12-15 hours, then in an oven at 110-130oC, and then calcined at a temperature of 800-1400oC. the resulting carrier has a composition, wt.%: 4,2 MgO-95,8 Al2ABOUT3.

10 g of the granules of the carrier is impregnated with at capacity with an aqueous solution obtained by the mixture of 2.6 ml of a solution of Ni(NO3)2with a concentration of 154 g NiO/l, 1.0 ml of a solution of La(NO3)3with a concentration of 1 and a temperature of 110-130oC and then calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, wt.%: 3,7 NiO-0,1 ZrO2-1,8 La2ABOUT3-94,4 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 2. Similar to example 1. The difference is that the carrier is impregnated with the solution obtained by the mixture of 2.6 ml of a solution of Ni(NO3)2with a concentration of 154 g NiO/l, 1.0 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 0.06 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/L. the Sample is dried at a temperature of 110-130oC and then calcined in a furnace at a temperature of 500oC and then subjected to repeated impregnation with a solution of nitrate salts. After the second impregnation, the sample was also dried in a drying Cabinet at 110-130oC and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, wt.%: 7,4 NiO-0,2 ZrO2-3,6 La2ABOUT3-88,8 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 3. Similar to example 1. 2 with a concentration of 154 g NiO/l, 0.2 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 0.5 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/L. the resulting catalyst has a composition, by weight. %: 4,0 NiO-0,7 ZrO2-0,2 La2ABOUT3-95,1 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 4. Similar to example 1. The difference is that the carrier is impregnated with a solution prepared by mixing 3.0 ml of a solution of Ni(NO3)2with a concentration of 154 g NiO/l, 0.2 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 0.5 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g Zr2/L. the Sample is dried at a temperature of 110-130oC, then calcined in a furnace at a temperature of 500oWith and subjected to repeated impregnation with a solution of nitrate salts. After the second impregnation, the sample was also dried in a drying Cabinet at 110-130oC and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, by weight. %: 7,8 NiO-1,6 ZrO2-0,36 La2ABOUT3-90,24 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oS; Kato carrier impregnated with the solution, the obtained mixture of 2.3 ml of a solution of Ni(NO3)2with a concentration of 250 g NiO/l, 1.5 ml of a solution of La(NO3)3with a concentration of 173 g La2O3/l and 0.2 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/L. the Sample is dried at a temperature of 110-130oC, then calcined in a furnace at a temperature of 500oWith and subjected to repeated impregnation with a solution of nitrate salts. After the second impregnation, the sample was also dried in a drying Cabinet at 110-130oC and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, wt.%: 10,3 NiO-0,3 ZrO2-4,1 La2ABOUT3-85,3 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 6. Similar to example 1. The difference is that the carrier is impregnated with a solution obtained by mixing of 2.9 ml of a solution of Ni(NO3)2with a concentration of 250 g NiO/l, 0.1 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 1.0 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/L. the Sample is dried at a temperature of 110-130oC, then calcined in a furnace at a temperature of 500oWith and subjected to repeated profits and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, wt.%: 11,5 NiO-2,2 ZrO2-0,3 La2ABOUT3-86,0 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 7. Similar to example 6. The difference is that the catalyst is tested in the reaction of steam reforming of methane at 750oWith fractions of 0.25-0.50 mm; catalytic properties shown in the table.

Example 8. 4.5 g of MgO is mixed with 62.5 g lOO, 48,4 g Al2ABOUT3, 11 ml 73%-aqueous solution NGO3and 70-75ml H2O for 40-60 minutes in a Z-shaped mixer, is then formed in the form of 3-lestnica with 3 cylindrical holes. Alumomagnesium carrier air-dried to 12-15 hours, then in an oven at 110-130oC, and then calcined at a temperature of 800-1400oC. the resulting carrier has a composition, wt.%: 4,1 MgO-95,9 Al2ABOUT3.

10 g of the granules of the carrier is impregnated with at capacity with an aqueous solution obtained by mixing of 2.7 ml of a solution of Ni(NO3)2with a concentration of 250 g NiO/l, 0.1 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 0.9 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/HP Way is Noah impregnation with a solution of nitrate salts. After the second impregnation, the sample was also dried in a drying Cabinet at 110-130oC and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, by weight. %: 10,3 NiO-1,9 ZrO2-0,1 La2ABOUT3-87,7 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 9. 9.5 g of MgO are mixed from 68.9 g lOO, and 38.6 g of Al2O3, 7 ml 73%-aqueous solution HN3and 76 ml of N2About for 40-60 minutes in a Z-shaped mixer, is then formed in the form of 3-lestnica with 3 cylindrical holes. Alumomagnesium carrier air-dried to 12-15 hours, then in an oven at 110-130oC, and then calcined at a temperature of 800-1400oC. the resulting carrier has a composition, wt.%: 8,9 MgO-To 91.1 Al2ABOUT3.

10 g of the granules of the carrier is impregnated with at capacity with an aqueous solution obtained by mixing of 2.9 ml of a solution of Ni(NO3)2with a concentration of 250 g NiO/l, 0.1 ml of a solution of La(NO3)3with a concentration of 173 g La2ABOUT3/l and 1.0 ml of a solution of ZrO(NO3)2with the concentration of 118.8 g of ZrO2/n. The sample is dried at a temperature of 110-130oC, then calcined in a furnace at a temperature of 500o is t in a drying Cabinet at 110-130oC and calcined in a furnace at a temperature of 500-900oC for 4-6 hours. The resulting catalyst has a composition, by weight. %: 10,0 NiO-2,0 ZrO2-0,2 La2ABOUT3-87,8 Mg-Al-o Catalyst in the form of pellets tested in the reaction of steam reforming of methane at 750oC; catalytic properties shown in the table.

Example 10. Similar to example 9. The difference is that the catalyst is tested in the reaction of steam reforming of methane at 750oWith fractions of 0.25-0.50 mm; catalytic properties shown in the table.

As seen from the above examples and data tables, the present invention enables the process of steam reforming of hydrocarbons to produce synthesis gas with high activity, ensuring stable operation of the catalyst in the effective use of the active component.

1. Catalyst for production of synthesis gas steam reforming hydrocarbons comprising oxides of Nickel, lanthanum deposited on alumomagnesium oxide carrier, characterized in that it further contains zirconium dioxide in a ratio of components, wt. %:

Nickel oxide - 3,7-16,0

The lanthanum oxide is 0.1 to 4.1

The Zirconia - 0,1-2,2

Alumomagnesium media - Rest

3. Method for production of synthesis gas steam reforming hydrocarbons at a temperature of 750-950oIn the presence of Nickel-containing catalyst, wherein the catalyst used is a catalyst composition, wt. %:

Nickel oxide - 3,7-16,0

The lanthanum oxide is 0.1 to 4.1

The Zirconia - 0,1-2,2

Alumomagnesium media - Rest

this alumomagnesium carrier has the form of a 3-lestnica with three cylindrical holes with equal wall thickness in cross section.

 

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