Catalyst and method for producing carbon and hydrogen from methane

 

(57) Abstract:

The invention relates to the production of carbon, preferably filamentous, and hydrogen from hydrocarbons. The inventive catalyst contains, wt%: Nickel oxide - 69 - 74; copper oxide - 9,5 - 12; aluminum hydroxide - 9,5 - 12 and iron oxide - 2 - 12. The specified catalyst allows 651 - 800oC to process methane or metabodrene mixture with 70 - 80% utilization. 2 S. and 1 C.p. f-crystals, 1 table.

The invention relates to the production of carbon, preferably filamentous and hydrogen from hydrocarbons. Filamentous carbon is formed in the form of a bundle of filaments with a diameter of several hundred angstroms and a length up to several microns. Due to the presence of fine particles of Nickel and iron filamentous carbon has ferromagnetic properties and can be used to obtain a ferromagnetic ink, graphite pigments to copy, synthetic and natural rubbers and plastics. Along with this, the carbon material can be used in the smelting of steel, and as a reducing agent in powder metallurgy.

There are several catalysts and methods for producing carbon and hydrogen:

1. Resloratadine hydrocarbon gases on the surface of iron-containing catalyst at 850 - 900oC under a pressure of 1 to 35 atmospheres [2].

3. Decomposition of methane or other hydrocarbons on the surface briketirovannogo carbon black with Nickel or carbon with iron at temperatures below the point of decomposition of these compounds [3].

4. Decomposition of methane on the surface of Ni/Al2O3or Ni/MgO catalysts at 500 - 550oC [4].

5. Decomposition of methane on the surface of Ni-Cu/Al2O3or Ni-Cu/MgO catalysts at temperatures of 560 - 650oC [5].

For achieved positive effect is the most perfect catalyst and method for producing carbon and hydrogen, which is chosen for the prototype [5].

The prototype catalyst has a composition, wt.%: 70 - 90 Nickel oxide with 2 - 16 copper oxide and 8 - 14 aluminum hydroxide or magnesium. The method of preparation of the catalyst includes the mechanochemical activation of the dual of a mixture of oxides of Nickel and copper, and then triple a mixture of Nickel and copper with aluminum hydroxide or magnesium in a planetary centrifugal mill with subsequent restoration of a mixture of hydrogen when heated to the reaction temperature of decomposition of methane. The method of producing carbon and hydrogen is passing methane over the above catalyst at 560 - 650oC and allerod and hydrogen are:

1. The relatively low overall outputs of carbon and hydrogen per gram of recovered catalyst.

2. The stability of the catalyst and, accordingly, the outputs of carbon and hydrogen sharply decrease with increasing operating temperature above 650oC and 560 - 650oC methane decomposes into carbon and hydrogen are not completely decay is limited by the equilibrium constant. The degree of conversion of 20 to 60%, i.e., a significant portion of the methane is not used. At the exit of the reactor is obtained methane-hydrogen mixture, which further complicates its use.

3. Impossible to recycle methane-hydrogen mixture with hydrogen consumption more than 60 - 70%.

The invention solves the problem of increasing the yield of carbon and hydrogen and increase the utilization of methane.

The problem is solved using the catalyst composition, wt.%: 69 - 74 Nickel oxide, 9,5 - 12 copper oxide, 9,5 - 12 aluminum hydroxide and 2 - 12 iron oxide and the next method of obtaining carbon and hydrogen from methane:

1) recovery of the catalyst with hydrogen during heating to the reaction temperature 651 - 800oC;

2) the replacement of hydrogen by methane and carrying out the decomposition reaction to a complete halt;

the features of the proposed catalyst is its composition, including, wt.%: 69 - 74 Nickel oxide, 9,5 - 12 copper oxide, 9,5 - 12 aluminum hydroxide and 2 - 12 iron oxide. The choice of the catalyst composition is dictated by considerations of maximum yield of carbon and hydrogen from methane with increasing the degree of utilization of methane. It turned out that this can be achieved if the composition of the catalyst from prototype to add iron oxide.

Distinctive features of the proposed method to obtain carbon and hydrogen from methane are: the composition of the catalyst and the temperature of the process. The choice of temperature range of the reaction is determined by the fact that at temperatures below 651oC dramatically reduces the reaction rate decreases the degree of decomposition of methane due to thermodynamic limitations, decreases the yield of the product, and the use of temperatures above 800oC does not increase the output of carbon and hydrogen and is disadvantageous from the energy point of view.

Unknown declare a collection of characteristics, leading to increased output of carbon and hydrogen while increasing the utilization of methane, so the catalyst and method of producing carbon and hydrogen can be classified as suitable for the Rami and supported by data shown in the table.

Examples 1 to 3 are shown for comparison.

Example 1. The catalyst consisting of 90 wt.% NiO and 10 wt.% Al(OH)3and obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0046 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 700oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 700oC for 1.5 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon amounted to 350 wt.% in relation to the weight of the recovered catalyst.

Example 2. The catalyst consisting of 75 wt.% NiO, 12.5 wt.% CuO and 12.5 wt. % Al(OH)3and obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0.0039 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 700oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 700oC for 1.5 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon was 2350 wt.% in relation to the weight of the recovered catalyst.

Example 3. The catalyst consisting of 77 wt.% NiO, 14 wt.% Al(OH)oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 700oC for 3 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon was 1018 wt.% in relation to the weight of the recovered catalyst.

Examples 4 to 13 illustrate the invention.

Example 4. The catalyst consisting of 74 wt.% NiO, 12 wt.% CuO, 12 wt.% Al(OH)3and 2 wt. % Fe2O3obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0029 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 700oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 700oC for 5 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon was 10548 wt.% in relation to the weight of the recovered catalyst.

Example 5. Similar to example 4, the only difference being the composition of the catalyst 73 wt. % NiO, 11.5 wt.% CuO, 11.5 wt.% Al(OH)3and 4 wt.% Fe2O3. The weight gain of the catalyst due to carbon was 16010 wt.% in relation to visitatore 72 wt. % NiO, 11% by weight CuO, 11 wt.% Al(OH)3and 6 wt.% Fe2O3. The weight gain of the catalyst due to carbon was 14370 wt.% in relation to the weight of the recovered catalyst.

Example 7. Similar to example 4, the only difference being the composition of the catalyst 71 wt. % NiO, and 10.5 wt.% CuO, 10.5 wt.% Al(OH)3and 8 wt.% Fe2O3. The weight gain of the catalyst due to carbon was 11868 wt.% in relation to the weight of the recovered catalyst.

Example 8. Similar to example 4, the only difference being the catalyst composition 70 wt.% NiO, 10 wt.% CuO, 10% by weight Al(OH)3and 10 wt.% Fe2O3. The weight gain of the catalyst due to carbon was 9218 wt.% in relation to the weight of the recovered catalyst.

Example 9. Similar to example 4, the only difference being the composition of the catalyst 69 wt. % NiO, and 9.5 wt.% CuO, and 9.5 wt.% Al(OH)3and 12 wt.% Fe2O3. The weight gain of the catalyst due to carbon was 6346 wt.% in relation to the weight of the recovered catalyst.

Example 10. The catalyst composed of 72 wt.% NiO, 11% by weight CuO, 11 wt. % Al(OH)3and 6 wt.% Fe2O3obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0033 g load in a flow reactor with weigh Tank-Bains, heated in t the share of decomposition at 651oC for 4 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon was 5433 wt. % relative to the weight of the recovered catalyst.

Example 11. The catalyst consisting of 73 wt.% NiO, 11.5 wt.% CuO, 11.5 wt.% Al(OH)3and 4 wt.% Fe2O3obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0023 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 725oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 725oC for 3 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon was 15916 wt.% in relation to the weight of the recovered catalyst.

Example 12. The catalyst consisting of 73 wt. NiO, 11.5 wt.% CuO, 11.5 wt.% Al(OH)3and 4 wt.% Fe2O3obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0023 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 750oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 750oC for 3 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon accounted for the C 73 wt.% NiO, 11.5 wt.% CuO, 11.5 wt.% Al(OH)3and 4 wt.% Fe2O3obtained 30 min mechanochemical activation in a planetary centrifugal mill, in the amount of 0,0034 g load in a flow reactor with weights Mak Ben, heated for 30 - 35 min in a stream of hydrogen is 20 l/h to a temperature of 800oC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 800oC for 3 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon amounted to 423 wt.% in relation to the weight of the recovered catalyst.

As can be seen from the description of the examples and tables, the invention allows to obtain a filamentary carbon and hydrogen from methane and can find industrial application in the recycle gas to hydrocarbon emissions.

1. The catalyst obtain carbon and hydrogen from methane, consisting of the oxides of Nickel, copper, aluminum hydroxide, characterized in that the catalyst composition additionally injected iron oxide in the following ratio, wt.%:

NiO - 69,0 - 74,0

CuO - 9,5 - 12,0

Al(OH)3- 9,5 - 12,0

Fe2O3- 2,0 - 12,0

2. The method of producing carbon and hydrogen, including the decomposition of methane on Nickel-containing catalyst at elevated tempera aluminum, the recovered hydrogen when heated to 651 - 800oC, in the following ratio, wt.%:

NiO - 69,0 - 74,0

CuO - 9,5 - 12,0

Al(OH)3- 9,5 - 12,0

Fe2O3- 2,0 - 12,0

3. The method according to p. 2, characterized in that the decomposition of methane is carried out at 651 - 800oC.

 

Same patents:

The invention relates to a method of catalytic partial oxidation of hydrocarbons
The invention relates to chemistry and may find application in the production of hydrogen by methane
The invention relates to chemistry and may find application in the production of hydrogen by methane

The invention relates to the oil industry, more specifically to chemical treatment processes-gas by-products of oil processing, and more particularly to a method of decomposition of hydrogen sulfide contained in the gas feed stream

The invention relates to the processing and disposal of hydrocarbon gases and can be used in gas processing, chemical, petrochemical and other industries

The invention relates to the manufacture of carbon products, in particular, plates coke fired for anodes fluorous medium-temperature electrolyzers

The invention relates to the production of carbon materials, in particular to the production technology of penografit used for manufacturing flexible graphite foil and products on its basis

The invention relates to the technology of carbon materials, in particular, to obtain penografit, which can be used as a component of composite materials for the manufacture of flexible graphite foil and so on

The invention relates to the technology of carbon materials, in particular, to a method for the oxidized graphite by heat treatment which receive penografit used for the production of flexible graphite tape, and various composite materials based on it

The invention relates to the production of uglerodsoderzhashchih structural materials, and more particularly to methods of regulating their production process, and may find application in the manufacture of crucibles, heaters in metallurgy, parts, vacuum devices, electronic and other engineering industries

The invention relates to the technology of carbon materials, in particular to electrochemical method of producing graphite bisulfate with a high degree of expansion
The invention relates to solid compositions for storage and transportation of hydrocarbon gases, namely clathrate compounds include natural gas on the basis of the fluorinated graphite of the total composition CxFClyzCnH2n+2where x=1.8 to 2.5, y=0,08-0,09, z=0,12-0,22, CnH2n+2methane, ethane, propane and butane

The invention relates to destructive distillation of carbonaceous materials for receiving the expanded graphite from its oxidized forms, which can be used in ferrous and nonferrous metallurgy, nuclear, aviation, automotive, shipbuilding and chemical industries, construction and solution of problems of environmental protection of the natural environment
The invention relates to the field of inorganic chemistry, namely to obtain expanded graphite

The invention relates to methods for Nickel catalysts for the hydrogenation of oxides of carbon, oxygen and aromatic hydrocarbons
Up!