Catalyst, method of its preparation and the process of obtaining ferromagnetic graphite carbon and hydrogen

 

(57) Abstract:

Use: in the production of graphite materials in the process of decomposition of methane and designed preimushestvenno for the preparation of ferromagnetic ink, graphite pigments to copy, synthetic rubbers and plastics. The inventive catalyst contains the following components, wt. NiO 70 90, CuO 2 16, Al(OH)3or Mg(OH)28 to 14. 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 process of obtaining ferromagnetic graphite material and hydrogen is carried out at 560 650C in the presence of the above catalyst, the contact time with the catalyst 3 10 2 10 S. 3 S. and 2 C. p. F.-ly, 3 tables.

The invention relates to the production of graphite materials in the process of decomposition of methane and intended primarily for the preparation of ferromagnetic ink, graphite pigments to copy, synthetic carbon KAU is in the smelting of steel, and also as a reducing agent in powder metallurgy. It should also be noted that in addition to the ferromagnetic graphite material produced hydrogen.

There are several catalysts and methods of implementation of the process of obtaining ferromagnetic graphite carbon and hydrogen (1,2):

the decomposition of methane in the presence of a solid metal catalyst (Fe, Co, Ni) at a temperature of 650-720aboutWITH (1);

decomposition of hydrocarbon gases on the surface of iron-containing catalyst at 850-900aboutWith pressure 1-35 atmospheres (2).

For achieved positive effect is the most perfect catalyst and method of implementation of the process (1), which is chosen for the prototype of the invention. The catalyst consists of a massive iron or cobalt, or Nickel with a metal content up to 100% while its disadvantage is the low yield of graphite material and hydrogen. The output of the carbon does not exceed 10 g with 1 g of catalyst.

The process is carried out by decomposition of methane at a temperature of 650-720aboutWith, and its disadvantage is the low yield of graphite material and hydrogen, as well as a relatively high temperature.

The closest-is (2) the catalyst is prepared by activation i.e. grinding sponge iron to the size of 3-5 mm

A common shortcoming of all three known objects is insufficient output of carbon and hydrogen, which is the object of the present invention.

The subject invention is a new catalyst, method of its preparation and the process of obtaining ferromagnetic graphite carbon and hydrogen. This is achieved by increasing the output of ferromagnetic material while reducing the temperature of the process with 650-720aboutTo 560-650aboutC.

The problem is solved by using a catalyst composition of 70-90 wt. Nickel oxide, 2-16 wt. copper oxide and 8-14 wt. aluminum hydroxide or magnesium hydroxide, and the following method of its preparation. A mixture of oxides of Nickel and copper loads in a planetary mill and subjected to mechanochemical activation. Planetary centrifugal mill, used in this work consists of two drum, which was loaded with steel balls and activated samples. Planetary mill works on the principle of gravitational grinding, which is implemented by the interaction of the two centrifugal fields. The reels in the apparatus involved in two dimethanol centrifugal mill is characterized by the parameters K and m. The value K= W2/W1(W2the number of turns around its own axis, W1the number of turns around a common axis) is called the kinematic characteristics of the mill. In the present work, W1=W2=10 Rev/s, hence K=1. The diameter of steel balls of 5 mm Weight 200 balls, the Weight of the activated sample 5,

After mechanical activation of a mixture of oxides of Nickel and copper for 30 min there was added aluminum hydroxide or magnesium hydroxide. If the system NiO-CuO-Al(OH)3necessary additional mechanochemical activation for 20-30 min, and in the case of the system NiO-CuO-Mg(OH)2within 90-120 minutes

The process of obtaining ferromagnetic graphite material is carried out in a flow reactor with weights poppy Ben and consists of three consecutive stages:

1) recovery of the catalyst with hydrogen during heating to the reaction temperature 575-650aboutC;

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

3) the cooling of the reactor in a stream of methane gas or inert gas to room temperature.

Distinctive features of the proposed catalyst is a composition comprising 70-90% of Nickel oxide, 2-16 wt. akinyemi maximum yield of graphite product and hydrogen: when the content of Nickel oxide in the mixture below 70 wt. as well as using 100% of Nickel oxide, the product yield is substantially less (see examples). As for the individual oxides of aluminum, magnesium and copper, they claimed conditions are inactive. The addition of copper oxide in the composition of the catalyst increases the yield of graphite product and hydrogen. The role of copper is in the formation of alloys with Nickel after recovery. Alloys of copper with Nickel have compared to pure Nickel higher stability and activity in the decomposition reaction of methane.

Distinctive features of the proposed method of preparation of the catalyst is the method of mechanochemical activation. In the proposed method is first activated dual mixture of Nickel oxide with copper oxide), and then the triple (plus aluminum hydroxide or magnesium). This is done in order to provide a more complete interaction of the oxides of copper and Nickel with the formation of solid solution of copper in Nickel oxide. Subsequent heating of the catalyst in hydrogen is recovered, the solid solution with the formation of an alloy of copper with Nickel, which improves the quality of the catalyst. The choice of the optimal time of mechanochemical activation is determined by the maximum output of the products of the carbon and hydrogen are the composition of the catalyst, no special recovery phase and temperature of the process 575-650aboutC. the Choice of temperature range of the process is determined by the fact that at temperatures below 575aboutWith a sharply reduced rate of the reaction decreases the degree of decomposition of methane due to thermodynamic limitations, decreases the yield of the product, and the use of temperatures above 650aboutWith does not increase the output of carbon and hydrogen and is disadvantageous from the energy point of view. As follows from the table. 3, the output of the ferromagnetic graphite material and hydrogen depends on the volumetric feed rate of methane. The greatest removal of carbon with 1 g of the catalyst was observed at volumetric flow rates of methane 3-12 l/h or when the contact time between 310-4-210-3(the ratio of the amount of the catalyst to the feed rate of methane).

Authors unknown to declare a collection of characteristics, leading to increased output of graphite material and hydrogen, to create environmentally friendly method of preparation of the catalyst, to the increased use of methane and simplification of the process of obtaining a ferromagnetic graphite carbon and hydrogen, therefore, offer the appropriate criterion of "Significant differences".

The invention is illustrated by the following examples and confirmed by the data given in table. 1-3.

P R I m e R 1. The catalyst consisting of 90 wt. Nickel oxide and 10 wt. aluminum hydroxide and the resulting 5-minute mechanochemical activation in a planetary centrifugal mill in the number 0.0024 g load in a flow quartz reactor with weights Mak Ben, heated for 20-30 minutes in a hydrogen flow of 20 l/h up to 560aboutC. Then cooling the reactor, the hydrogen is replaced by methane and carry out the decomposition reaction at 560aboutC for 1 h and the flow rate of methane 12 l/h Superagency product is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and discharged. The weight gain of the catalyst due to carbon is 1530% relative to the weight of the recovered catalyst.

P R I m e R s 2-5. Similar to example 1, the only difference is the time of mechanochemical activation ( see tab. 1).

P R I m e R 6. A catalyst consisting of 80 wt. NiO, 10 wt. CuO and 10 wt. Al(OH)3and received a 20-minute mechanochemical activation in a planetary centrifugal mill in the number 0.0027 g load in a flow quartz reactor with weights Mak Ben, heated for 20-30 minutes in a hydrogen flow of 20 l/h to /SUP>C for 90 min and the flow rate of methane 12 l/h After termination of the reaction superagency product is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and discharged. The weight gain of the catalyst due to carbon is 5140% relative to the weight of the recovered catalyst.

P R I m e R 7. A catalyst consisting of 80 wt. NiO 8 wt. CuO and 12 wt. aluminum hydroxide and obtained first 30 minutes of mechanochemical activation dual mixture of NiO+CuO, and then a 10-minute activation of ternary mixtures of NiO+CuO+Al(OH)3in a planetary centrifugal mill in the number 0.0024 g load in a flow quartz reactor with weights Mak Ben, heated for 20-30 minutes in a hydrogen flow of 20 l/h to a temperature of 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 2 h, and the flow rate of methane 12 l/h Weight of the catalyst due to carbon is 7200% relative to the weight of the recovered catalyst. Superagency the catalyst is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and discharged.

P R I m e R s 8-12. Similar to example 7, different catalyst composition and time of mechanochemical activation of ternary mixtures of NiO+CuO+Al(OH)3(see tab. 1).

P R I m e is 0.0024 g load in a flow quartz reactor with weights Mac-Bains. Next, the sample is heated for 20-30 minutes in a hydrogen flow of 20 l/h to 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 1 h and the flow rate of methane 12 l/h Weight of the catalyst due to carbon is 10% of the weight of the recovered catalyst. Superagency the catalyst is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and discharged.

P R I m e R 14. The catalyst consisting of 75 wt. NiO to 12.5 wt. CuO and 12.5 wt. magnesium hydroxide and received 120 minutes of mechanochemical activation in a planetary centrifugal mill in the number 0.0024 g load in a flow quartz reactor with weights Mak Ben, heated for 20-30 minutes in a hydrogen flow of 20 l/h to 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 2 h and the flow rate of methane 12 l/h Weight of the catalyst due to carbon is 4870% relative to the weight of the recovered catalyst. Superagency the catalyst is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and discharged.

P R I m e R 15. Analogous to example 15, differs in the previous 15-minute mechanochemical activation dual mixture of NiO+CuO before the 20-minute activation troino the-minute mechanochemical activation dual mixture of NiO+CuO before the 120-minute activation of ternary mixtures of NiO+CuO+Mg(OH)2(see tab. 1).

P R I m e R 17. Analogous to example 14, differs preliminary 45-minute mechanochemical activation dual mixture of NiO+CuO before the 120-minute activation of ternary mixtures of NiO+CuO+MgO(OH)2(see tab. 1).

P R I m e R 18. Analogous to example 14, differs preliminary 45-minute mechanochemical activation dual mixture of NiO+CuO before a 90-minute activation of ternary mixtures of NiO+CuO+Mg(OH)2(see PL. 1).

P R I m e R 19. Analogous to example 14, differs preliminary 45-minute mechanochemical activation dual mixture of NiO+CuO before the 60-minute activation of ternary mixtures of NiO+CuO+MgO(OH)2(see tab. 1).

P R I m e R 20. Analogous to example 14, differs preliminary 30-minute mechanochemical activation dual mixture of NiO+CuO before a 90-minute activation of ternary mixtures of NiO+CuO+MgO2(see tab. 1).

P R I m e R 21. Analogous to example 14, differs by mechanochemical activation of ternary mixtures of NiO+CuO+Mg(OH)2for 150 min (see table. 1).

P R I m e R 22. Similar to example 16.

P R I m e R s 23-29. Similar to example 16, are compositions of catalysts and time of mechanochemical activation of ternary mixtures of NiO+CuO+hydroxide.

P R I m e R 30. Katal is the first mill in the number 0,0033 g load in a flow reactor with weights Mac-Bains heat for 20-30 minutes in a hydrogen flow of 20 l/h to 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 30 min and the flow rate of methane 12 l/h Weight of the catalyst due to carbon amounted to 1% relative to the weight of the recovered catalyst. After termination of the reaction the reactor is cooled in a stream of argon (the flow rate of 75 l/h) to room temperature and superagency the catalyst is unloaded.

P R I m e R 31. Similar to example 30, is the catalyst composition 90% NiO+Mg(OH)2and time of mechanochemical activation (see tab. 2).

P R I m e R 32. Analogous to example 30. Different catalyst composition 90% NiO+10% Al(OH)3and time of mechanochemical activation 20 min (see table. 2).

P R I m e R 33. Similar to example 32, is the catalyst composition 100% NiO (see tab. 2).

P R I m e R 34. The catalyst consisting of 90% NiO+10% Al(OH)3and cooked by the prototype (3) 0.0024 g load in a flow quartz reactor with weights Mac-Ben and heated for 20-30 minutes in a hydrogen flow of 20 l/h to 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 30 min and the flow rate of methane 12 l/h Gain catalyst for schedu in a stream of argon (the flow rate of 75 l/h) to room temperature and the resulting product being unloaded.

P R I m e R s 35-41. Similar to example 16, are temperature decomposition reaction of methane and bulk velocities of its submission (see tab. 3).

P R I m e R s 42-43. Analogous to example 34, differ in the composition of the catalyst 90% NiO+10% Mg(OH)2and volumetric feed rate and methane (see table. 3).

P R I m e R s 44-47. Analogous to example 11. Different temperatures of decomposition of methane and bulk velocities of its submission (see tab. 3).

P R I m e R 48. The catalyst consisting of 75 wt. NiO to 12.5 wt. CuO and 12.5 wt. aluminum hydroxide and obtained first 30 minutes of mechanochemical activation dual mixture of NiO+CuO, and then a 20-minute activation of ternary mixtures of NiO+CuO+Al(OH)3in a planetary centrifugal mill in the amount of 0.05 g load in a flow quartz reactor, heated for 20-30 minutes in a hydrogen flow of 20 l/h up to 625aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 625aboutC for 4 h and the flow rate of methane 3 l/h Analysis of methane at the outlet of the reactor showed that a significant portion of the methane is decomposed into carbon and hydrogen. At the beginning of the reaction (during the first 15 min) degree of conversion of methane is 49% and then increased to 65% and remains approximately constant within 1 h superagency the catalyst is cooled in a stream of argon (flow rate 10 l/h) to room temperature and discharged. The weight gain of the catalyst due to carbon is 4600% relative to the weight of the recovered catalyst.

P R I m e R 49. The catalyst consisting of 84 wt. NiO, 2 wt. CuO and 14 wt. Al(OH)3and received since the beginning of the 30-minute dual activation of a mixture of NiO+CuO, and then a 30-minute activation of ternary mixtures of NiO+CuO+Al(OH)3in a planetary centrifugal mill in the number of 0.004 g load in a flow quartz reactor with weights Mak Ben, heated for 20-30 minutes in a hydrogen flow of 20 l/h to 600aboutC. Then hydrogen is replaced by methane and carry out the decomposition reaction at 600aboutC for 2 h and the flow rate of methane 3 l/h Weight of the catalyst due to carbon is 4700% relative to the weight of the recovered catalyst.

P R I m e R 50. Analogous to example 49, differing only in the composition of the catalyst 83 wt.NiO, 5 wt. CuO and 12 wt. Al(OH)3. The weight gain of the catalyst due to carbon is 6700% relative to the weight of the recovered catalyst.

As follows from the above examples, we have developed a new catalyst, environmentally friendly way of cooking and the process of obtaining ferromagnetic graphite carbon and hydrogen. When this is achieved, compared with the prototype to increase the output of the surveillance process 3-4 times and increased use of methane in 2-3 times.

1. The catalyst obtain ferromagnetic graphite carbon and hydrogen from methane, including Nickel-containing component, characterized in that as the Nickel component of the catalyst contains Nickel oxide and optionally copper oxide and aluminum hydroxide or magnesium in the following ratio, wt.

NiO 70 90

CuO 2 16

Al(OH)3or Mg(OH)28 14

2. The method of preparation of the catalyst obtain ferromagnetic graphite carbon and hydrogen, including the activation of a catalyst, characterized in that the conduct of mechanochemical activation dual mixture of oxides of Nickel and copper, and then triple a mixture of oxides 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 in the following ratio of components in the catalyst, wt.

NiO 70 90

CuO 2 16

Al(OH)3or Mg(OH)28 14

3. The process of obtaining ferromagnetic graphite carbon and hydrogen, including the decomposition of methane on Nickel-containing catalyst by heating, characterized in that as the catalyst espulso 560 650oWith, in the following ratio of components in the catalyst, wt.

NiO 70 90

CuO 2 16

Al(OH)3or Mg(OH)28 14

4. The process under item 3, characterized in that the decomposition of methane is carried out at 560 650oC.

5. The process under item 3, characterized in that the contact time of methane with the catalyst is 3 to 10-42 10-3C.

 

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