KR20140087264A - Mesoporous Ni-X-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst - Google Patents
Mesoporous Ni-X-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The present invention relates to a mesoporous nickel-X-alumina controlled gel catalyst (X = active metal comprising nickel) using two active metals prepared in a single process, a process for their preparation and a catalyst for the methanation of carbon dioxide More specifically, X is at least one selected from the group consisting of Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, Mg and Ca, (Synthetic natural gas) by a methanation reaction of carbon dioxide in a continuous flow reactor using a nickel-X-alumina hybrid control hybrid catalyst having a carbon dioxide conversion of 50 to 70%.
The present invention provides a method of preparing a mesoporous nickel-X-alumina catalyst having excellent reproducibility by using a single sol-gel method. By using the above-described production method, a sintering reaction by heating of a methanation reaction, A catalyst excellent in the ability to re-oxidize the oxidized metal catalyst can be obtained. Further, the present invention provides a method for producing methane in which the dissociation energy of carbon monoxide, which is an important property of the methanation reaction, is suitable for methane production using the catalyst, and the conversion of carbon dioxide is excellent.
Description
The present invention relates to a mesoporous nickel-X-alumina controlled gel catalyst, a process for preparing the same, and a process for producing methane using the catalyst.
The securing of energy sources in modern society is an essential element for economic and industrial development. The importance of energy sources is getting bigger due to the rapid increase of energy consumption and the visualization of oil price limits. In addition, the consumption of fossil energy is soaring that air pollution is becoming serious. The development of alternative energy related technologies such as hydrogen energy, solar energy and bio energy has been continuously carried out in developed countries such as Europe and Japan, but it has not reached the level of replacing existing fossil fuels. Therefore, there is a growing need for technologies for processing and using existing fossil raw materials in an eco-friendly manner. In particular, natural gas is attracting attention as a clean energy source to replace conventional oil and coal. The proportion is also increasing. Natural gas, like petroleum, is a gaseous hydrocarbon that is produced naturally in the ground. Methane (CH 4 ) is the main component and it is a fuel that has the cleanliness, stability and convenience to prevent environmental pollution. Industrial and other sectors. However, in spite of the increase in demand for natural gas, there is a problem that supply and price are unstable due to limitation of natural gas reserves on the earth and interoperability of oil prices. To solve this problem, The research on synthetic natural gas is becoming important.
Synthetic natural gas (SNG) is an artificially produced natural gas called "Synthetic Natural Gas" or "Substitute Natural Gas." Currently, research on methane production, which is the main component of natural gas, is conducted from coal, biomass, and petroleum coke. have. Among them, the production of synthetic natural gas from coal is predicted as a major energy source in the future in terms of price stabilization of existing natural gas and diversification of fuel based on abundant reserves.
A method for obtaining synthetic natural gas from coal is a method (gasification method) which is obtained through a methane synthesis reaction using a catalyst, a method (hydrogen gasification method) which obtains a synthetic natural gas by reacting coal directly with hydrogen, There is a method (catalytic gasification method) of obtaining synthetic natural gas by reacting coal with steam at a low temperature. The synthesis of synthetic natural gas based on the gasification process is called indirect process because it synthesizes synthetic natural gas from synthesis gas (CO, H 2 ) obtained by gasification of coal. Hydrogen gasification process and catalytic gasification process are classified by direct method Currently, processes for producing synthetic natural gas through indirect methods are mainly studied. The indirect process for producing synthetic natural gas through the gasification of coal is mainly a synthetic gas production process (synthesis of CO → CO and H 2 as a main component) and a process for synthesizing synthetic natural gas using a catalyst (CO, H 2 , Synthetic gas → synthetic natural gas).
On the other hand, since H 2 / CO composition of the synthesis gas discharged from the coal gasifier is below 1.0, H 2 / CO ratio to increase the hydrogen concentration of 3.0 outside water
Carbon dioxide accounts for 93.5% of greenhouse gases. If global greenhouse gas regulations are implemented in earnest, carbon dioxide emissions from the synthetic natural gas production process can be directly linked to the competitiveness of the synthetic natural gas manufacturing industry. Domestic carbon dioxide emission reduction technologies are centered on CCS (Carbon Capture & Storage) technology, which collects and recovers carbon dioxide from mass emission sources and stores it before aquifers, strata, deep sea and waste oil. However, the carbon capture of carbon dioxide in the ground or under the seabed is considered to be not a fundamental measure because there is a serious danger like the nuclear waste repository, the economic efficiency and safety are low, and the storage space and the period are limited. Therefore, studies on the chemical conversion of carbon dioxide produced by methane, methanol, DMC and the like by chemically converting carbon dioxide have attracted more attention. Of these, the carbon dioxide methanation reaction is one of the chemical recycling technologies, in which methane is produced by catalytic reaction of carbon dioxide and hydrogen (Chemical Formula 1). The technology of converting carbon dioxide to methane, a major component of synthetic natural gas, rather than simply storing it with various limits, will not only reduce carbon dioxide emissions but also increase the economic ripple effect of the synthetic natural gas manufacturing industry.
[Chemical Formula 1]
CO 2 + 4H 2 → CH 4 + 2H 2 O, △ H o 298K = -164.1 KJ / mol
The methanation reaction of carbon dioxide requires a catalyst in order to attain a thermodynamically favorable reaction or a kinetic limitation as shown in the above formula (1), so as to achieve an appropriate reaction rate and selectivity. Therefore, the methanation reaction of carbon dioxide is mainly being studied in a metal-based catalyst system.
In the methanation of carbon dioxide, metal catalysts of the VIIIB series such as Ru, Rh, Ni, Co, and Fe are supported on various oxide supports (SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 and CeO 2 ). Since the carbon dioxide methanation reaction is greatly influenced by the dispersion degree of the active metal, it is known that the support having a large surface area increases the reactivity of the catalyst. In addition, it is known that the interaction between the metal and the support, Many researches are actively being carried out. Since carbon dioxide adsorption on the surface of the catalyst is dissociated into CO and O, the reaction proceeds. Therefore, additives such as Cerium and Lanthanum may be used in order to improve the reducing ability of carbon dioxide. In addition, attempts have been made to find an optimal catalyst through the formation of alloys such as Pd-Mg / SiO 2 and Ni-Zr-Sm catalysts.
Nickel is the most widely used active metal for catalysts, but nickel-based catalysts have the problem that nickel carbonyl is formed due to the interaction between CO and metal and deactivation occurs at low temperatures. Precious metals such as Ru, Rh, and Pt show higher activity and stability than nickel-based catalysts under operating conditions. However, these catalysts are not effective for commercial use because they are low in price competitiveness.
The methanation of carbon dioxide is known to be the rate determining step of the dissociation of CO on the surface of the catalyst. This means that as the dissociation of CO proceeds rapidly, it is advantageous for methane production. Therefore, preparing a catalyst with dissociation energy of CO suitable for methane production plays an important role in increasing methane production.
In general, it is known that the methanation reaction of carbon dioxide proceeds at a temperature higher than 200 ° C, but the reverse reaction (CH 4 + 2H 2 O → CO 2 + 4H 2 ) of the methanation reaction proceeds at a temperature higher than 590 ° C. In addition, when a nickel catalyst is used, dissociation reaction (CH 4 → C + 2H 2 ) of methane generated at a constant temperature (about 345 ° C.) or higher proceeds. Therefore, the catalyst used in the methanation reaction of carbon dioxide should have high activity in the low temperature range of the temperature range in which the methanation reaction is possible.
On the other hand, since the methanation reaction of carbon dioxide proceeds in the course of reducing the carbon dioxide, the active metals present on the surface of the catalyst are oxidized by the oxygen released at this time. The oxidized catalyst must be recycled and reacted again with carbon dioxide and hydrogen to proceed the methanation reaction. Therefore, in order to improve the reactivity of the methanation reaction, a metal catalyst having excellent recycling ability is required.
One aspect of the present invention is to provide a process for producing a nickel-based catalyst by a single-process sol-gel process, wherein the sintering inhibition of the metal and the resistance to carbon deposition are improved and the interaction between the active metals by using the two metals as the active metal, X-alumina (X = metal) controlled catalyst having improved catalytic reactivity to methanation reaction of carbon dioxide and ability to recycle oxidized catalyst, and a process for producing the same.
Another aspect of the present invention is to provide a process for producing methane which is economical and highly reactive and which is simple to manufacture, using a gel catalyst under the control of the nickel-X-alumina (X = metal).
The present invention relates to a nickel-X-alumina hybrid controllable gel catalyst, wherein X is at least one selected from the group consisting of Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, Mg, A catalyst for methane synthesis comprising carbon dioxide and hydrogen having a conversion rate of carbon dioxide of 50 to 70% (based on 220 占 폚) as a reaction product in the methanation reaction.
The catalyst for producing methane may include 1 to 50 parts by weight of nickel and 1 to 20 parts by weight of X metal with respect to 100 parts by weight of the catalyst.
The present invention also relates to a process for producing an aluminum precursor sol, which comprises the steps of mixing a solution of an aluminum precursor dissolved in an alcohol solvent, water and an acid diluted with an alcohol solvent, and partially hydrating to form an aluminum precursor sol; A nickel-X-alumina sol forming step of mixing the aluminum precursor sol, the nickel precursor, and the X metal precursor thus prepared; A nickel-X-alumina gel forming step of mixing 50 to 70 parts by weight of alcohol and 200 to 420 parts by weight of water based on 100 parts by weight of the aluminum precursor by mixing nickel-X-alumina sol, water and an alcohol solvent; Drying and firing the nickel-X-alumina gel by aging, drying and calcining the nickel-X-alumina gel, wherein the X metal is Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, A1 A method for producing a nickel-X-alumina controlled gel catalyst for methane synthesis using carbon dioxide and hydrogen selected from the group consisting of carbon dioxide and hydrogen as a reaction product.
The alumina precursor may be aluminum alkoxide, which is at least one selected from the group consisting of aluminum ethoxide, aluminum tri-butoxide, aluminum tert-butoxide, aluminum isopropoxide and aluminum tri-sec-butoxide. have.
In the aluminum precursor sol forming step, 10 to 30 parts by weight of the aluminum precursor may be mixed with 100 parts by weight of the alcohol.
The nickel precursor and the X precursor in the nickel-X-alumina sol forming step may be in the form of metal acetate hydrate, metal chloride hydrate or metal sulfide.
In the nickel-X-alumina sol forming step, 1 to 50 parts by weight of the nickel precursor and 1 to 20 parts by weight of the X precursor may be mixed with 100 parts by weight of the catalyst.
The aging, drying and firing may be performed by aging the nickel-X-alumina gel at room temperature for 7 to 10 days, drying at 50 to 80 ° C, and calcining at 600 to 900 ° C for 3 to 10 hours.
The present invention also relates to a pretreatment step of pretreating a nickel-x-alumina controlled gel catalyst into a continuous flow reactor for methane-enriched application and pretreating it with a gas of hydrogen and nitrogen; And a methanation reaction step in which carbon dioxide, hydrogen and nitrogen are passed through a pretreated nickel-x-alumina controlled gel catalyst to carry out a methanation reaction.
The pretreatment may be carried out at 670 to 800 ° C for 3 to 10 hours by simultaneously supplying 30 ml / min of nitrogen and 3 to 15 ml / min of hydrogen to the methane fired continuous flow reactor.
The methanation reaction step may be carried out at a pressure of 0 to 20 bar and a reaction temperature of 200 to 250 ° C.
The volume ratio of carbon dioxide and hydrogen in the methanation reaction step may be 1: 2 to 5, and the volume ratio of carbon dioxide and nitrogen may be 1: 1 to 4.
The present invention provides a method of preparing a mesoporous nickel-X-alumina catalyst having excellent reproducibility by using a single sol-gel method. By using the above-described production method, a sintering reaction by heating of a methanation reaction, A catalyst excellent in the ability to re-oxidize the oxidized metal catalyst can be obtained. Further, the present invention provides a method for producing methane in which the dissociation energy of carbon monoxide, which is an important property of the methanation reaction, is suitable for methane production using the catalyst, and the conversion of carbon dioxide is excellent.
1 is a graph showing the results of X-ray diffraction analysis (a) and (b) before and after reduction of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention will be.
FIG. 2 is a graph showing the results of the temperature-reduction reduction test of the nickel-X-alumina-controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention.
FIG. 3 is a graph showing the results of carbon dioxide-temperature desorption experiments of the nickel-X-alumina controlled gel catalyst prepared in Preparation Examples 1 and 2 according to the present invention.
4 is a graph showing the results of the temperature-elevated surface reaction of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention.
FIG. 5 shows TEM analysis results of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention recovered after the reaction.
6 schematically shows a schematic view of a continuous flow reactor used in the present invention.
7 is a graph showing the conversion of carbon dioxide, the selectivity of methane, and the yield of methane by the methanation reaction of carbon dioxide using the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention FIG.
8 is a graph showing the relationship between the methane production temperature and the methane yield of the surface elevation reaction of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 according to the present invention, And the yield is shown in the graph.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
The present invention relates to a nickel-X-alumina hybrid controllable gel catalyst, wherein X is at least one selected from the group consisting of Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, Mg, A catalyst for methane synthesis comprising carbon dioxide and hydrogen having a conversion rate of carbon dioxide of 50 to 70% (based on 220 占 폚) as a reaction product in the methanation reaction.
In the present invention, the methanation reaction or the methanation reaction of carbon dioxide refers to a process for producing methane by reacting carbon dioxide and hydrogen. The nickel-X-alumina controlled gel catalyst can be used to produce methane by the methanation reaction of carbon dioxide.
In the present invention, a nickel-X-alumina gel is prepared, aged and dried, and then heat-treated at a high temperature to prepare a medium-porosity Nickel-X-alumina catalyst. The nickel-X-alumina refers to a mixture of nickel, X metal, and alumina. Specifically, nickel and X metal are uniformly dispersed in alumina having a low crystallinity.
The mesoporous nickel-X-alumina catalyst of the present invention can be produced by using a single-process sol-gel method to develop mesopores, and the formation of carbon species due to the metal particles dispersed on the catalyst surface is suppressed, Excellent resistance to deposition. In addition, catalyst deactivation due to sintering of the metal particles does not occur even during a long operation. Further, in addition to the properties of conventional nickel-alumina catalysts due to the interaction of nickel, X metals and alumina with the addition of the X metal, the nickel-X-alumina catalyst has a CO dissociation energy suitable for the methanation reaction, And improves the ability of the catalyst to recycle, resulting in a higher conversion of carbon dioxide than the existing methanation catalyst
When the nickel-X-alumina controlled gel catalyst according to the present invention is subjected to a methanation reaction at 220 ° C, the conversion of carbon dioxide ranges from 50 to 70%, the methane selectivity ranges from 95 to 99%, and the hydrocarbon selectivity other than methane Indicates a range of 1 to 5%. Thus, it can be seen that the nickel-X-alumina controlled gel catalyst is a catalyst suitable for methane production through the methanation reaction of carbon dioxide.
The present invention also provides a process for preparing a gel catalyst with nickel-X-alumina control. The method comprises: a solution in which an aluminum precursor is dissolved in an alcohol solvent; an aluminum precursor sol which forms an aluminum precursor sol by mixing and partially hydrating water and an acid diluted with an alcohol solvent; A nickel-X-alumina sol forming step of mixing the aluminum precursor sol, the nickel precursor, and the X metal precursor thus prepared; A nickel-X-alumina gel forming step of mixing 50 to 70 parts by weight of alcohol and 200 to 420 parts by weight of water based on 100 parts by weight of the aluminum precursor by mixing nickel-X-alumina sol, water and an alcohol solvent; Drying and firing the nickel-X-alumina gel by aging, drying and calcining the nickel-X-alumina gel, wherein the X metal is Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, And may be at least one selected from the group consisting of.
Hereinafter, the method of preparing the nickel-X-alumina catalyst according to the present invention will be described in detail in stages.
The alcohol solvent used in the aluminum precursor sol forming step is at least one alcohol solvent selected from the group consisting of ethanol, methanol, 1-propanol, isopropyl alcohol, 1-butanol and 2-butanol, It is preferable to add an aluminum precursor in an alcohol solvent and then dissolve by stirring. Further, it is necessary to keep the temperature of the alcohol solvent at 50 to 80 ° C because the aluminum precursor is difficult to completely dissolve in the alcohol solvent at 50 ° C or lower and the alcohol solvent rapidly evaporates at 80 ° C or higher.
In the aluminum precursor sol forming step, the aluminum precursor is at least one aluminum alkoxide selected from the group consisting of aluminum ethoxide, aluminum tri-butoxide, aluminum tert-butoxide, aluminum isopropoxide and aluminum tri-sec- Aluminum alkoxide).
The amount of the aluminum precursor added is preferably 10 to 30 parts by weight based on 100 parts by weight of the alcohol. When the amount of the alcohol is less than 10 parts by weight, it takes a long time to form the gel as the amount of alcohol becomes relatively large, and it is difficult to form a complete gel. When the amount of aluminum is more than 30 parts by weight, the amount of aluminum is relatively increased, so that the amount of alcohol present between aluminum is reduced during gel formation, and sufficient surface area and pores are not formed, so that the active metal is not evenly distributed.
In the step of forming the nickel-X-alumina sol, the aluminum precursor sol may be cooled to 40 to 60 ° C. The nickel precursor and the X precursor may be added to the aluminum precursor sol. The amount of the added metal may be 1 to 50 parts by weight of the nickel precursor and 1 to 20 parts by weight of the X precursor per 100 parts by weight of the catalyst. More preferably, 35 parts by weight of nickel and 5 parts by weight of X metal can be added to 100 parts by weight of the catalyst as a whole. When the content of the nickel precursor is out of the above range, the reactivity may be lowered. When the content of the X precursor is less than the above range, the size of the active metal participating in the reaction increases, so that the catalyst may be inactivated by the deposition reaction of the carbon species and the particle sintering reaction. Can be excessively reduced and the reactivity of the catalyst may be lowered.
The nickel precursor and the X metal precursor may be in the form of a metal acetate hydrate, a metal chloride hydrate or a metal sulfide.
The time for the nickel-x-alumina gel to be changed into the nickel-x-alumina gel in the step of forming the nickel-X-alumina gel is several hours to several tens of days. The nickel precursor and the X metal precursor . The metals to be added are combined with the branches of the aluminum precursor to form a gel, and the X metals occupy different positions in the periodic table, so that the size and electrical state of the atoms are different from each other. This affects the rate of condensation reaction that causes the nickel-x-aluminum sol to form a gel, and the formation time of the gel varies from several hours to several tens of days depending on the X metal to be added. Also, the pH of the gel changes depending on the salt form of the added precursor, and this change in pH also affects the gel formation time.
In order to adjust the condensation rate depending on the additive metal to within a few hours, the catalyst preparation method of the present invention comprises 50 to 70 parts by weight of alcohol, 200 to 420 parts by weight of water based on 100 parts by weight of the aluminum precursor contained in the nickel- By weight can be mixed. In this step, the reaction rate and the like can be determined according to the weight of the water to be mixed. When water is added in an amount of less than 200 parts by weight, the condensation reaction rate is slow and the gel formation time may be several days or tens of days. On the other hand, if the amount exceeds 420 parts by weight, the condensation rate becomes excessively high, so that the added metals do not form a net structure uniformly, or the metal contained in the nickel-X-alumina sol precipitates in the form of small particles, . The catalyst prepared from the opaque gel is difficult to expect high reactivity because the metals are not dispersed evenly.
Also, when nickel-X-alumina gel is formed by mixing 50 to 70 parts by weight of alcohol and 200 to 420 parts by weight of water based on 100 parts by weight of the aluminum precursor contained in the nickel-X-alumina sol. In addition to the alcohol used as a solvent, the nickel-X-alumina-controlled gel catalysts have a larger surface area and a larger pore size and porosity than the control gel prepared by conventional methods, because the water added during the condensation process exists between the net- A volume is formed. These physical properties improve the dispersibility of the active metal and thus favor the methanation reaction of carbon dioxide.
The aging of the nickel-X-alumina gel in the aging, drying and firing steps can be aged at room temperature for 7 to 10 days. The aging of the gel is a step in which the hydration and condensation reaction which are not completely completed in the step of forming the nickel-X-alumina gel is completed, which affects the physical and chemical properties of the catalyst. If the period is too short or too long, smaller surface area, pore volume and pore size are formed than desired.
Since the aged gel may vary in surface area, pore volume and pore size depending on the drying temperature, the opening of the container is closed with the punched aluminum foil It is preferable to carry out the reaction at 50 to 80 DEG C under the condition that the vapor pressure is controlled. The gel is dried at a controlled rate through 10 to 20 holes in the aluminum foil. When the number of the holes is less than 10, the drying time is prolonged, the contraction of the catalyst structure occurs and the pore size increases, but the surface area of the whole catalyst tends to decrease, so that the active metal is not smoothly dispersed. When the number of holes is more than 20, the drying speed is increased, and the gel is broken or collapsed during the drying process, so that the surface area, pore volume and pore size required in the present invention can not be obtained. In addition, if the drying is performed at a temperature lower than 50 캜, the time of exposure of the gel to heat is prolonged, and the condensation reaction continues during the drying process, thereby reducing the surface area of the catalyst and increasing the pore size. This is undesirable because of the nature of the methanation reaction of carbon dioxide, which exhibits greater conversion rates in evenly dispersed metals over a large surface area. When the gel is dried at a temperature higher than 80 ° C., the net structure formed due to the high temperature during the drying process is collapsed to lose the gel shape. In this state, the dried gel has the surface area, pore volume and pore size required in the present invention I can not.
The aged gel is fired at 600 to 900 ° C. for 3 to 10 hours. If the firing temperature is lower than 600 ° C., the thermal stability of the catalyst against heat generated during the methanation reaction of carbon dioxide, which is a heating process, can not be secured. If the heat treatment temperature exceeds 900 ° C, an undesirable alumina phase is formed and the dehydration reaction of alumina proceeds, so that the deformation of the catalyst structure and the collapse of the pores cause the desired catalytic activity to not be obtained.
Further, the present invention relates to a pretreatment step of pretreating a gel catalyst with a nickel-X-alumina control in a continuous flow type reactor for application to a methane incombination and pretreating it with hydrogen and nitrogen gas; And a methanation reaction step in which carbon dioxide, hydrogen, and nitrogen are passed through the pretreated nickel-X-alumina controlled gel catalyst under a constant pressure. The present invention also provides a method for producing methane from carbon dioxide.
The pretreatment may be carried out by feeding the hydrogen-containing catalyst into the nickel-x-alumina controlled-flow continuous-flow reactor, and supplying hydrogen and nitrogen to the reactor. Without any particular limitation, Can be carried out for 3 to 10 hours while simultaneously flowing hydrogen at 3 to 15 ml / min. Since the calcined nickel-X-alumina catalyst exists in an oxidized state and has no reactivity to the methanation reaction of carbon dioxide, it must be activated to react with the methanation reaction through reduction with hydrogen. The catalyst reduction method includes a method of flowing only hydrogen and a method of simultaneously flowing nitrogen and hydrogen. Among them, the method of reducing nitrogen while flowing at a flow rate of 30 ml / min and hydrogen at a rate of 3 to 15 ml / min is preferable to the methanation reaction of carbon dioxide because the smaller amount of active metal is distributed on the catalyst surface compared with the method of flowing only hydrogen .
If the reduction temperature is lower than 670 ° C, the metal oxide forming the alumina and the spinel structure is not reduced and remains in an oxidized state, so that the reactivity is lost due to the inability to participate in the methanation reaction of carbon dioxide. If the reduction temperature is higher than 800 ° C, the sintering reaction of the metal proceeds along with the reduction of the metal oxide species, the active sites of the metal are reduced, and the reactivity of the catalyst is deteriorated. Preferably 700 < 0 > C.
The reduction time also determines the degree of reduction of the metal oxide. In order to reduce the oxidized species present on the surface, a reduction process must be performed over a certain period of time. May be carried out for 3 to 10 hours, although not particularly limited. However, after a certain period of time, all the metals in the oxidation state present on the surface are reduced, so that the reduction process is meaningless.
Next, in the method for producing methane by using the nickel-X-alumina controlled gel catalyst according to the present invention, the methanation reaction step is a step of introducing carbon dioxide into the gel catalyst pre- Passing the hydrogen through the methanation reaction.
The methanation reaction in the methanation reaction step is carried out at a reaction temperature of 200 to 250 ° C under a pressure of 0 to 20 bar while flowing nitrogen dioxide-containing carbon dioxide and hydrogen at a space velocity of 1,000 to 10,000 ml / Can be performed.
At this time, the volume ratio of carbon dioxide and hydrogen may be 1: 2 to 5, preferably 1: 3 to 4, in order to secure sufficient methane yield and minimize carbon deposition. When the volume ratio of carbon dioxide and hydrogen is less than 1: 2, hydrocarbon selectivity of methane or higher is slightly increased, and carbon deposition proceeds on the surface of the catalyst. This means that the Fischer-Tropsch reaction as well as the methanation reaction proceeds. When the volume ratio of carbon dioxide and hydrogen exceeds 1: 5, hydrogen is present in an excess of stoichiometric ratio, and hydrogen that has not participated in the reaction remains after the methanation reaction. Hydrogen present with methane is difficult to separate and should contain as little as possible of the final product, methane.
The volume ratio of nitrogen added to the reactant is 1 to 4 times the volume of carbon dioxide. Since the methanation reaction is an exothermic reaction having a large reaction formation heat, the reaction heat can not be effectively dispersed above a certain conversion rate. In order to effectively disperse the heat of reaction, an inert gas must be added together with the reaction gas to dilute the reaction product. When the volume ratio is 1 or less, it is difficult to effectively disperse the heat of reaction. When the volume ratio is 4 or more, the conversion rate of carbon dioxide is lowered. Therefore, the volume ratio of nitrogen is preferably 1 to 4 in terms of the volume of carbon dioxide.
In the methanation reaction of carbon dioxide, the conversion rate of carbon dioxide is low when the space velocity is high, and conversely, when the space velocity is low, the conversion rate of carbon dioxide is increased. However, since the conversion of carbon dioxide has a maximum value, the space velocity of 8,000 to 15,000 ml / h · g-catalyst is preferable for producing methane.
On the other hand, carbon monoxide, C 2 , C 3 , C 4 and the like can be produced through the methanation reaction of carbon dioxide, but the catalyst prepared by the present invention is more than 95% methane. In the methanation reaction of carbon dioxide, the conversion rate of carbon dioxide tends to increase as the reaction pressure increases. However, above 20 bar, the conversion rate reaches its maximum and the increase in pressure beyond that point is meaningless.
In addition, the catalyst for methanation of carbon dioxide requires heat above a certain temperature in order to have activity. At temperatures below 200 ° C, the catalyst does not have activity and the methanation reaction of carbon dioxide does not occur. At 250 ° C or higher, the conversion of carbon dioxide is at its maximum. Therefore, it is preferable to carry out the methanation reaction of carbon dioxide at a reaction temperature of 200 to 250 ° C.
Hereinafter, the present invention will be described in more detail with reference to the following Production Examples and Examples. However, the following examples and examples are illustrative of the invention, and the content of the present invention is not limited by the following production examples and examples.
[Preparation Example 1] Preparation of gel catalyst with nickel-Fe-alumina control
The ethanol solvent was heated to 80 캜 with stirring, and then aluminum tri-sec-butoxide (Al [OCH (CH 3 ) C 2 H 5 ] 3 , Aldrich) was dissolved in a heated ethanol solvent. Then, while maintaining the above solution at 80 占 폚, a mixed solution of ethanol (40 ml), nitric acid (0.1 ml) and water (0.3 ml) was slowly added to progress the partial hydration reaction to obtain a transparent aluminum sol. Then the aluminum sol is cooled to 50 ℃, the nickel acetate tetrahydrate (C 4 H 6 NiO 4 · H 2 O, Aldrich) and
The aged gel was covered with a punched aluminum foil and dried slowly in a drier maintained at 70 DEG C until the ethanol was completely removed to obtain gel nickel-Fe-aluminum. The resulting nickel-Fe-alumina catalyst was heat-treated at 700 ° C for 5 hours using an electric furnace to prepare a gel nickel-Fe-alumina catalyst. The catalyst thus prepared was named 35 Ni5FeAl . In this case, 35 and 5 in front of Ni and Fe mean the parts by weight of nickel and iron with respect to 100 parts by weight of the whole catalyst.
[Preparation Example 2] Preparation of gel catalyst with nickel-X-alumina control with different metal (x) added
A gel catalyst having a different mesoporous nickel-X-alumina structure with X metal was prepared according to the preparation method of Preparation Example 1 by changing the kind of X metal added to nickel. More specifically, nickel acetate tetrahydrate (C 4 H 6 NiO 4 .H 2 O, Aldrich), zirconium acetate hydroxide ((CH 3 CO 2 ) x Zr (OH) y , x + y using ~ 4, Aldrich), yttrium acetate ha deureyiteu ((CH 3 CO 2) 3 Y · H 2 O, Aldrich), magnesium acetate tetrahydrate ((CH 3 COO) 2 Mg · H 2 O, Aldrich) of nickel Gel catalysts (M = Ni, Zr, Y and Mg) were prepared with -X-alumina control. The thus-prepared catalyst was designated as 35 Ni5NiAl , 35 Ni5ZrAl , 35 Ni5YAl And 35Ni5MgAl , where 35 and 5 in front of Ni and metal X represent the parts by weight of nickel and metal X relative to 100 parts by weight of the catalyst, respectively.
[Preparation Example 3] Preparation of a gel catalyst with nickel-Fe-alumina control by controlling the ratio of nickel to iron
A nickel-Fe-alumina controlled gel catalyst was prepared by varying the amount of iron added to nickel and adjusting the ratio of nickel to iron according to the preparation method of Preparation Example 1. The amount of the nickel precursor added was calculated such that the nickel content was 30 parts by weight and 25 parts by weight based on 100 parts by weight of the prepared catalyst, and the amount of the precursor of the Fe metal was calculated based on 100 parts by weight of the prepared catalyst, Is calculated to be 10 parts by weight and 15 parts by weight. Thus it was named the catalyst prepared in each of 30 Ni10FeAl, 25 Ni15FeAl, wherein the Ni and Fe front number represents parts by weight of nickel and iron to the total 100 parts by weight of the catalyst.
[Experimental Example 1] ICP-AES analysis and physical properties of nickel-X-alumina controlled gel catalyst
ICP-AES analysis, specific surface area, pore volume, and average pore size were measured in order to examine the basic properties of the prepared nickel-X-alumina catalyst, and the results are shown in Table 1.
From the results of ICP-AES analysis in Table 1, it can be confirmed that a nickel-X-alumina catalyst containing 35 parts by weight of nickel and 5 parts by weight of X metal was produced with respect to 100 parts by weight of the catalyst as a production target. Also, it can be seen from Table 1 that the 35 Ni5FeAl , 35Ni5ZrAl, 35 Ni5NiAl , 35 Ni5YAl, and 35 Ni5MgAl catalysts produced by the present invention are nickel-X-alumina controlled gels having a mesoporous structure in the skeleton structure. In Table 1, it can be seen that different kinds of metals such as Fe , Zr , Y and Mg , which are X metals, have different specific surface area, pore volume and average pore size when compared with 35Ni5NiAl catalyst added with only a single metal , There is no tendency between catalysts. However, it can be seen that both of the produced catalysts have a large surface area and a large pore size.
(Parts by weight) a
(Parts by weight) a
(M < 2 > / g) b
(Cm < 3 > / g) c
Size (nm) d
a Determined by ICP-AES measurement
b Calculated by the BET equation
c BJH desorption pore volume
d BJH desorption average pore diameter
[Experimental Example 2] X-ray diffraction analysis of gel catalyst using nickel-X-alumina control
FIG. 1 shows the results of X-ray diffraction analysis of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 before and after reduction. 1 (a) showing the results of the X-ray diffraction analysis before reduction show no metal oxide species characteristic peaks of nickel and X metals in all of the prepared catalysts, but the peaks of nickel, X metals and aluminates formed by alumina Was confirmed. Exceptionally, in the case of the 35Ni5ZrAl catalyst with zirconium addition, the characteristic peak of zirconia was confirmed in addition to the characteristic peak of aluminate.
1 (b), which is the result of X-ray diffraction analysis after the reduction of each catalyst (700 ° C.), the characteristic peaks of aluminate of each catalyst disappear after reduction and the characteristic peaks of nickel metal are formed, It was found that all of the existing nickel oxide species was reduced. In the case of 35Ni5ZrAl catalyst, zirconia formed on the catalyst surface was not reduced because the characteristic peak of zirconia still existed. In the case of the catalysts other than the 35Ni5ZrAl catalyst, all of the aluminate phase disappeared, but the characteristic peak of the added X metal was not confirmed. It can be seen that the added X metal was reduced but existed in a small size or in an amorphous state so as not to be analyzed by X-ray diffraction analysis.
[Experimental Example 3] Heating and reduction experiments of gel catalyst with nickel-X-alumina control
Temperature-Programmed Reduction experiments were conducted to examine the characteristics of the nickel-X-alumina controlled gel catalysts prepared in Preparation Examples 1 and 2. The nickel-X-alumina controlled gel catalyst prepared in Preparation Example 1 and Preparation Example 2 was charged into a U-shaped quartz tube in an amount of 0.05 g, and then nitrogen (20 ml / min) and hydrogen (2 ml / min) And the reduction reaction was proceeded at a rate of 5 ° C / min to measure the consumption of hydrogen gas according to the temperature. The results are shown in FIG. Each of the catalysts exhibited one peak for consumption of hydrogen gas at around 650 to 720 ° C. The fact that the reduction peak differs depending on the type of the metal to which it is added means that the degree of interaction between the metal and the carrier varies depending on the added metal. The temperature at which the reduction peak appears is in the order of 35Ni5MgAl>35Ni5YAl>35Ni5NiAl>35Ni5ZrAl> 35Ni5FeAl. Catalysts with reduction peaks at low temperatures are more excellent in reducing ability and ability to recycle oxidized metals during methanation of carbon dioxide.
Experimental Example 4 Carbon Dioxide of Nickel-X-alumina Controlled Gel Catalyst - Temperature Deposition Experiment
In order to investigate the difference in the characteristics of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2, carbon dioxide as a reactant was adsorbed on the catalyst, and a temperature elevation desorption experiment was conducted.
The nickel-X-alumina controlled gel catalyst prepared in Preparation Example 1 and Preparation Example 2 was filled in a U-shaped quartz tube in an amount of 0.1 g, and then a mixed gas of helium and hydrogen containing 5% of hydrogen (50 ml / min), followed by reduction at 700 ° C for 5 hours, followed by cooling to 40 ° C. In this process, hydrogen remaining on the catalyst surface was removed with helium (40 ml / min). After that, a mixed gas of helium and carbon dioxide containing 5% of carbon dioxide (50 ml / min) was supplied and carbon dioxide was adsorbed on the activated metal surface for 60 minutes. After the carbon dioxide adsorption process, He (50 ml / min) was flowed for 30 minutes in order to remove carbon dioxide adsorbed on the surface. The preheated nickel-X-alumina catalyst layer was heated at a rate of 10 ° C / min in a helium gas (30 ml / min) atmosphere to carry out the temperature elevated desorption reaction. The experimental results are shown in Fig. Table 2 shows the amount of carbon dioxide that has been desorbed during the temperature desorption experiment. The desorption curve of carbon dioxide in each catalyst is formed over a wide range of two peaks. Each peak is related to the adsorption strength of carbon dioxide. The amount of desorbed carbon dioxide in each catalyst is lowered in the order of 35Ni5MgAl> 35Ni5YAl> 35Ni5NiAl> 35Ni5ZrAl> 35Ni5FeAl.
(mmol-CO 2 / g-catalyst)
[Experimental Example 5] Experimental study on the surface reaction of nickel catalyst with gel catalyst of nickel-X-alumina
The temperature-programmed surface reaction (TPSR) was performed to examine the characteristics of the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2. The results are shown in FIG. 4 . The gel catalysts prepared in Preparative Example 1 and Preparation Example 2 were charged into a U-shaped quartz tube in an amount of 0.1 g each, and helium (30 ml / min) and hydrogen (3 ml / min) at 700 ° C for 5 hours. After cooling to room temperature, hydrogen remaining on the catalyst surface was removed with helium (40ml / min). Then, helium (5 ml / min) was poured while carbon dioxide (20 ml) was injected 10 times to adsorb carbon dioxide on the activated metal surface in a saturated state. After the carbon dioxide adsorption process, helium (30 ml / min) was flowed for 30 minutes in order to remove carbon dioxide physically adsorbed on the surface. The preheated nickel-X-alumina catalyst layer was heated in a mixed gas atmosphere of hydrogen (1 ml / min) and helium (9 ml / min) at a rate of 10 ° C / min. The gas released after passing through the catalyst was analyzed through a mass spectrometer to measure the methane produced during the heating process and the characteristics of the methanation reaction of the carbon dioxide of each catalyst were confirmed. The results are shown in FIG. 4 .
In FIG. 4, it can be seen that each catalyst has a peak for methane production at a specific temperature. The methanation of carbon dioxide is an important step in determining the reaction rate by the step in which CO is dissociated and separated into C and O. The peak at the specific temperature in the result of the temperature elevation reaction is that the CO present on the surface of the catalyst is C O and dissociated into a series of methanogenic reactions. Therefore, it is advantageous for the methanation reaction of carbon dioxide because the methane - producing peak at low temperature means that the dissociation energy of CO suitable for methane production is small. The methane generation peak is lowered in the order of 35Ni5MgAl>35Ni5YAl>35Ni5Ni>35Ni5Zr> 35Ni5Fe.
[Experimental Example 6] TEM analysis results of nickel-X-alumina controlled gel catalyst recovered after the reaction
The nickel-X-alumina controlled gel catalyst prepared in Preparation Example 1 and Preparation Example 2 was recovered after the methanation reaction and confirmed by scanning transmission microscopy. The results are shown in FIG. The active metals of the catalyst can be identified in the form of black spots. The active metals of these catalysts are dispersed evenly on the catalyst surface at a size of about 5-10 nm. No carbon deposition was observed on the surface of all the catalysts recovered after the reaction experiment. Through the scanning transmission microscope analysis, it is confirmed that the active metals of the catalyst are evenly dispersed in a comparatively small size even after the methanation reaction of carbon dioxide and exist on the catalyst surface. The results show that the nickel - X - alumina controlled gel catalyst prepared by the single - process sol - gel method is suitable for the methanation reaction of carbon dioxide.
[Example 1] Methanation of carbon dioxide using a gel catalyst with nickel-X-alumina control
Methane production by the methanation reaction of a mixed gas composed of carbon dioxide and hydrogen was performed using the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2.
Before the reaction, the prepared catalysts were reduced at 700 ° C. for 5 hours while flowing nitrogen (30 ml / min) and hydrogen (3 ml / min) at the same time in a continuous flow reactor using methane. The reactor was a stainless steel reactor, installed in an electric furnace, maintained at a constant temperature through a temperature controller, and allowed to proceed while the reactant continuously passed through the catalyst bed in the reactor. The amount of carbon dioxide, hydrogen, and nitrogen used in the reaction was controlled using a mass flow controller, and the reaction was carried out at a constant pressure through a pressure regulator.
The composition of the reactants was such that the volume ratio of nitrogen: carbon dioxide: hydrogen was 1.67: 1: 4, and the space velocity was set to 9,600 ml / h · g-catalyst. The reaction temperature was maintained at 220 ° C and the reaction pressure was maintained at 10 bar. The schematic diagram of the reactor used in the reaction is shown in Fig.
The products after the methanation reaction of carbon dioxide by the nickel-X-alumina controlled gel catalyst prepared in Production Example 1 and Production Example 2 were analyzed by gas chromatography, and the conversion of carbon dioxide, the conversion rate of hydrogen, the selectivity of hydrocarbon, And the yield of methane were calculated and shown in Table 3 and FIG. 7 (after 600 minutes of reaction time).
The conversion of carbon dioxide, the conversion of hydrogen, the selectivity of hydrocarbons and the selectivity of carbon monoxide by the gel catalyst with nickel-X-alumina control were calculated by the following
(mole%)
As can be seen from Table 3 and FIG. 7, it can be seen that the conversion of carbon dioxide and the yield of methane are high in the order of 35Ni5FeAl>35Ni5ZrAl>35Ni5NiAl>35Ni5YAl> 35Ni5MgAl catalyst. The selectivity of each catalyst to methane was over 99%, and small amounts of C 2 and C 3 were produced.
In the methanation reaction of carbon dioxide, the step of determining the reaction rate is the dissociation step of CO. The CO present on the catalyst surface is dissociated into C and O, which reacts with hydrogen and converts to methane. The elevated surface reaction experiment indirectly shows the CO dissociation energy of each catalyst. As the catalysts in which the methane peak is generated at a low temperature, the CO is dissociated more rapidly and the intermediate carbon form appears on the surface of the catalyst. Therefore, the 35Ni5FeAl catalyst formed at low methane production peak temperature yielded a high methane yield in the methanation reaction of carbon dioxide.
From the results of the methanation reaction and the temperature elevation desorption experiment of carbon dioxide as a reactant, it can be seen that the yield of methane decreases with the amount of desorption of carbon dioxide. In general, electron-deficient metals are known to have higher reactivity in the COx methanation reaction than electron-rich metals. The carrier having a basic character is a strong metal-carrier interaction, Thereby producing an electron-rich metal. This means that the metal-carrier interaction due to the base nature of the catalyst has a great influence on the catalytic activity of the carbon dioxide methanation reaction. The interaction between the metal and the support by the base nature of these catalysts can be seen from the results of the temperature desorption experiments of carbon dioxide. The metal-support interaction of each catalyst decreases in the order of 35Ni5MgAl>35Ni5YAl>35Ni5Ni>35Ni5Zr> 35Ni5Fe. Therefore, the 35Ni5FeAl catalyst among the prepared catalysts has the highest methane yield due to the weakest metal-carrier interaction.
On the other hand, when the results of the temperature raising and lowering test are compared with those of the methanation reaction, it can be seen that the yield of methane is higher for the catalyst having a reduction peak at a lower temperature. The fact that the reduction peak is low means that the metals oxidized after the methanation reaction of carbon dioxide react with the hydrogen in the reactant again and have excellent ability to be recycled. This means that the number of active sites participating in the new reaction is increased, and the recycling ability plays an important role in enhancing the reactivity of the catalyst. Therefore, the 35Ni5FeAl catalyst formed at the lowest temperature of the reduction peak in the temperature reduction experiment showed high methane yield in the methanation reaction of carbon dioxide.
Figure 8 shows the yields of methane produced after the reaction, the results of the heating surface reaction, the yield of methane, and the results of heating and reducing experiments. As a result of the surface temperature reaction of the prepared catalyst, the catalyst formed at a low methane formation temperature showed a high methane yield in the methanation reaction. This result is related to the dissociation energy of CO, which determines the reaction rate. The lower the dissociation energy, the better the yield of methane. The results of the temperature reduction test are related to the ability to rapidly recycle the oxidation of the active metal during the methanation of carbon dioxide. The result is that the yield of methane increases as the number of active sites participating in the methanation reaction increases . All the results show that the 35Ni5FeAl catalyst among the prepared catalysts is the best catalyst for the carbonation of carbon dioxide.
Example 2 Methanation of Carbon Dioxide Using Gel-Catalyzed Nickel-Fe-Alumina Controlled Nickel-Iron Ratio
In Example 1, it was confirmed that the gel catalyst with nickel-Fe-alumina control had excellent performance in the carbonation reaction of carbon dioxide. The nickel-Fe-alumina controlled gel catalyst was further tested to determine the optimum composition of nickel and iron having the maximum methane yield. Methane production by a methanation reaction of a synthesis gas composed of carbon dioxide and hydrogen was carried out by using a nickel-Fe-alumina controlled gel catalyst in which the ratio of nickel to iron produced in Production Example 3 was controlled. The methanation reaction was carried out in the same manner as in Example 1, and the results are shown in Table 4. As can be seen from the following Table 4, 35 Ni5FeAl catalyst containing 35 parts by weight of iron and 5 parts by weight of iron based on 100 parts by weight of the total catalyst was found to be the most excellent catalyst for the carbonization of carbon dioxide.
(mole%)
Claims (13)
A nickel-X-alumina sol forming step of mixing the aluminum precursor sol, the nickel precursor, and the X metal precursor thus prepared;
A nickel-X-alumina gel forming step of mixing 50 to 70 parts by weight of alcohol and 200 to 420 parts by weight of water based on 100 parts by weight of the aluminum precursor by mixing nickel-X-alumina sol, water and an alcohol solvent; And
Drying and calcining the nickel-X-alumina gel for aging, drying and firing,
Wherein the X metal is nickel-X-alumina control for methane synthesis using at least one selected from the group consisting of Fe, Co, Ni, Zr, Y, Zn, Ce, La, Sm, Mg and Ca, Process for preparing rosel catalyst.
A methanation reaction step in which carbon dioxide, hydrogen, and nitrogen are passed through a pretreated nickel-X-alumina controlled gel catalyst to carry out a methanation reaction
Wherein the reaction product is carbon dioxide and hydrogen.
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| CN104028270A (en) * | 2014-06-10 | 2014-09-10 | 中国华能集团清洁能源技术研究院有限公司 | Methanation catalyst and preparation method thereof |
| CN105664948A (en) * | 2016-01-06 | 2016-06-15 | 江苏大学 | Preparation method and application of nickel-based dried gel catalyst |
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