CN109908931B - Catalyst with Al modified activated carbon as carrier and preparation method thereof - Google Patents

Catalyst with Al modified activated carbon as carrier and preparation method thereof Download PDF

Info

Publication number
CN109908931B
CN109908931B CN201711325713.5A CN201711325713A CN109908931B CN 109908931 B CN109908931 B CN 109908931B CN 201711325713 A CN201711325713 A CN 201711325713A CN 109908931 B CN109908931 B CN 109908931B
Authority
CN
China
Prior art keywords
catalyst
temperature
solid
synthesis gas
roasting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711325713.5A
Other languages
Chinese (zh)
Other versions
CN109908931A (en
Inventor
张舒冬
孙晓丹
张庆军
宋永一
刘继华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201711325713.5A priority Critical patent/CN109908931B/en
Publication of CN109908931A publication Critical patent/CN109908931A/en
Application granted granted Critical
Publication of CN109908931B publication Critical patent/CN109908931B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention provides a catalyst taking Al modified activated carbon as a carrier and a preparation method thereof. The preparation method comprises the steps of firstly, uniformly mixing petroleum coke, metaaluminate and an activating agent, then activating, washing and separating to obtain a solid sample, introducing active metal and an auxiliary agent into the obtained sample, and finally washing and drying to obtain the synthesis gas methanation catalyst. The catalyst has the advantages of good dispersion of active components, high activity, difficult carbon deposition and the like, and also solves the problem of high-temperature aggregation of active metal of the active carbon carrier catalyst.

Description

Catalyst with Al modified activated carbon as carrier and preparation method thereof
Technical Field
The invention relates to a synthesis gas methanation catalyst and a preparation method thereof, in particular to a synthesis gas methanation catalyst taking Al modified activated carbon as a carrier and a preparation method thereof.
Background
Methanation refers to CO/CO2And H2Under the action of certain temp., pressure and catalyst, CH is generated4At present, the reaction is widely applied to the technical processes of removing trace carbon, methanation of coke oven gas, coal-to-natural gas and the like in the process of synthesizing ammonia or producing hydrogen. Methanation is an important catalytic technique, particularly in the field of fuel applications, which can be used to increase the calorific value of fuel gas and allow the conversion of coke oven gas, coal or biomass to natural gasAnd (4) transforming. In recent years, with the rapid development of the coal substitute natural gas industry in China, methanation, which is one of the core technologies, receives more and more attention.
For the reaction of preparing natural gas by methanation of synthesis gas, the commonly used catalysts comprise Ni-based catalyst, Fe-based catalyst, Co-based catalyst and Ru-based catalyst, and the adopted auxiliary agents or carrier materials comprise alumina, titanium oxide, silicon oxide, cerium oxide, lanthanum oxide, zirconium oxide, calcium oxide, magnesium oxide and the like. Design of synthetic gas methanation catalyst needs to take active center into consideration for CO and H2The degree of activation of, in general, CO and H are activated for heterogeneous catalyst transition metal active sites2The modulation of the electronic property of the active center is just opposite, and according to the metal energy band theory, CO dissociation and adsorption requires that the active center has more d-band holes and H2Less d-band holes are needed for dissociative adsorption. The selectivity of methane can be reduced due to the over-strong CO activation capability, and the disproportionation reaction is easy to occur, so that carbon deposition and inactivation of the catalyst are caused; h2If the activation capability is too strong, the conversion rate of CO is low and the activity of the catalyst is poor. Therefore, the delicate design of the catalyst is the key to the high performance syngas methanation catalyst.
CN101380581A discloses a novel methanation catalyst and a preparation method thereof, wherein the catalyst comprises NiO, MgO, La2O3, CeO2, CaO and Na2O, BaO and Al2O3The anti-carbon deposition property and the high-temperature stability of the catalyst are improved to a certain extent. Methanation catalyst disclosed in US3933883 for purification of gamma-Al2O3Is used as a carrier and loaded with active components of nickel oxide and cobalt oxide. In the methanation catalyst disclosed in the Chinese patent CN1043449A, nickel is used as an active component, rare earth metal and magnesium are used as promoters, and the balance is alumina. The above patents all adopt alumina carriers commonly used in methanation catalysts, and although the dispersion degree of active metals is improved and the aggregation of the active metals is inhibited under the high temperature condition, the defects of easy carbon deposition and poor low-temperature activity exist, and the preparation method is particularly difficult to be applied to the methanation of synthesis gas with low hydrogen-carbon ratio.
CN106492864A discloses a methanation catalyst of a silicon carbide and carbon composite carrier loaded Raney alloy, which has the advantage of high low-temperature activity. The patent adopts the silicon carbide and carbon composite carrier, reduces the interaction between metals of the carrier, inhibits CO disproportionation reaction and reduces carbon deposition, but because the carrier is relatively inert and has low specific surface area, the active metal is easy to sinter at high temperature.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the synthesis gas methanation catalyst and the preparation method thereof, the catalyst takes Al modified petroleum coke-based active carbon as a carrier, overcomes the problem of high-temperature aggregation of active metal of the active carbon carrier catalyst, and has the advantages of good dispersion of active components, sintering resistance, high activity, difficult carbon deposition and the like.
The invention provides a synthesis gas methanation catalyst, which comprises an active component, an auxiliary agent and a carrier, wherein the active component is selected from Ni or Co, and is preferably Ni; the auxiliary agent is selected from one or more of alkaline earth metal, rare earth metal and IVB subgroup metal, preferably one or more of Ca, Mg, Zr, La and Ce; the carrier is Al modified petroleum coke-based activated carbon.
According to the synthesis gas methanation catalyst, the mass content of active components is 5-30 wt%, preferably 10-20 wt% calculated by elements; the mass content of the auxiliary agent is 1wt% -10 wt%, preferably 2wt% -4 wt% calculated by element; calculated by element, the mass content of Al is 1wt% -10 wt%, preferably 2wt% -4 wt%; the carrier content is 40wt% to 85wt%, preferably 60wt% to 80 wt%.
The specific surface of the synthetic gas methanation catalyst is 500-1500 m2Preferably 600 to 1000 m/g2(ii)/g; the pore size distribution is such that the pores smaller than 2nm are larger than 60%, preferably larger than 80%.
In the synthesis gas methanation catalyst, active components are combined with amorphous defects of active carbon embedded in petroleum coke-based and alumina in an active carbon graphite microchip layer, and the size of active metal crystal grains is 0.5-5 nm, preferably 1-3 nm.
The second aspect of the invention provides a preparation method of a synthesis gas methanation catalyst, which comprises the following steps:
(1) mixing petroleum coke, metaaluminate and an activating agent, and activating after uniformly mixing;
(2) washing and carrying out solid-liquid separation on the sample obtained in the step (1) until the filtrate is neutral;
(3) mixing the solid sample obtained by solid-liquid separation in the step (2) with water for low-temperature treatment, standing for solid-liquid separation, and drying and roasting the solid sample obtained by separation;
(4) and (4) introducing active metal and an auxiliary agent into the sample obtained in the step (3), and then drying and roasting to obtain the synthesis gas methanation catalyst.
In the preparation method of the synthesis gas methanation catalyst, the metaaluminate in the step (1) is one or more of potassium metaaluminate, sodium metaaluminate and lithium metaaluminate, and preferably potassium metaaluminate.
In the preparation method of the synthesis gas methanation catalyst, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and potassium hydroxide is preferred.
In the preparation method of the synthesis gas methanation catalyst, in the step (1), the mass ratio of petroleum coke, metaaluminate (calculated by the mass of Al element) and an activating agent is 1: 0.005-0.05: 1-5, preferably 1: 0.01-0.02: 2 to 4.
In the preparation method of the synthesis gas methanation catalyst, the activation process in the step (1) is as follows: grinding petroleum coke into powder, then uniformly mixing the powder with metaaluminate and an activating agent, heating to an activation temperature, cooling to room temperature after activation is completed, and performing subsequent treatment, wherein the activation temperature is 600-1000 ℃, preferably 700-900 ℃, and the activation time is 5-240 min, preferably 10-120 min. The activation process is further preferably carried out under microwave irradiation conditions, the microwave frequency being 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke, and preferably 2-4 kw. When the activation is carried out under the microwave radiation condition, the activation is further preferably carried out in two sections, the first section is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
In the preparation method of the synthesis gas methanation catalyst, the washing in the step (2) is washing with water, the washing temperature is 50-95 ℃, and preferably 70-90 ℃, and the specific operation can be that firstly, the solid sample obtained in the step (1) is heated and washed at the washing temperature, then, the solid sample is mixed with water at the same temperature, and after uniform mixing, solid-liquid separation is carried out until the filtrate is neutral.
In the preparation method of the synthesis gas methanation catalyst, the low-temperature treatment temperature in the step (3) is 1-20 ℃, preferably 5-10 ℃, the mixture is uniformly mixed and then placed for 2-16 hours, preferably 4-8 hours, and then solid-liquid separation is carried out.
In the preparation method of the synthesis gas methanation catalyst, the drying temperature in the step (3) is 80-200 ℃, the drying time is 2-10 hours, the preferable drying temperature is 120-180 ℃, and the drying time is 4-8 hours. The drying is preferably carried out under vacuum.
In the preparation method of the synthesis gas methanation catalyst, the roasting in the step (3) is carried out in an inert atmosphere or a nitrogen atmosphere, the roasting temperature is 500-700 ℃, the preferred roasting temperature is 540-650 ℃, the roasting time is 2-10 hours, and the preferred roasting time is 4-8 hours.
In the preparation method of the synthesis gas methanation catalyst, the sample obtained in the step (3) can be further molded according to a method generally used in the field, such as extrusion, tabletting and the like, and can be prepared or selected into a proper particle form according to the use requirement, such as strip, tablet and the like.
In the preparation method of the synthesis gas methanation catalyst, the method for introducing the active metal and the auxiliary agent into the sample obtained in the step (3) in the step (4) is carried out by a method known in the art, and the solid obtained in the step (4) is impregnated by using a soluble salt solution containing the active metal and a soluble salt solution containing the auxiliary agent, and the method comprises an equal-volume impregnation method, a supersaturated impregnation method and a kneading method, and preferably an equal-volume impregnation method; when the active metal and the auxiliary are introduced, they may be introduced simultaneously or in multiple portions.
In the preparation method of the synthesis gas methanation catalyst, the soluble salt containing the active metal in the step (4) can be one or more of nitrate, sulfate and hydrochloride, and preferably nitrate.
In the preparation method of the synthesis gas methanation catalyst, the soluble salt containing the auxiliary agent in the step (4) can be one or more of nitrate, sulfate and hydrochloride, and is preferably nitrate.
In the preparation method of the synthesis gas methanation catalyst, the drying temperature in the step (4) is 60-160 ℃, the preferred drying temperature is 80-120 ℃, the drying time is 2-10 hours, and the preferred drying time is 4-8 hours. The drying is preferably carried out under vacuum.
In the preparation method of the synthesis gas methanation catalyst, the roasting in the step (4) is carried out in an inert atmosphere or a nitrogen atmosphere, the roasting temperature is 500-700 ℃, the preferred roasting temperature is 540-650 ℃, the roasting time is 2-10 hours, and the preferred roasting time is 4-8 hours.
The synthesis gas methanation catalyst prepared by the method is applied to the reaction of preparing natural gas by methanation of synthesis gas.
Compared with the prior art, the synthesis gas methanation catalyst and the preparation method thereof have the following advantages:
1. the synthesis gas methanation catalyst provided by the invention has the advantages of large specific surface area, good dispersion of active metal, high reaction activity, sintering resistance, difficult carbon deposition and the like, and the preparation method is simple.
2. According to the preparation method of the catalyst, Al is introduced in the petroleum coke activation process, an activating agent enters a diffusion path generated by petroleum coke bulk phase, and is combined with amorphous carbon defects and graphite carbon sheet layers to form aluminum carbide under the action of microwave catalysis, and the activated carbon/alumina composite carrier is formed through low-temperature hydrolysis. The loaded active metal is combined with the amorphous defect of the petroleum coke-based active carbon and the alumina embedded in the active carbon graphite microchip layer to obtain the catalyst with high dispersion and high temperature stability, and the problems that the active metal is aggregated and loses activity due to dehydration and condensation of oxygen-containing groups at high temperature when the metal catalyst taking the active carbon as a carrier is applied to high-temperature reaction are solved.
3. According to the preparation method of the catalyst, unreacted activating agents are removed through high-temperature water washing, the elution rate of the unreacted activating agents is increased, hydrolysis of carbides is inhibited, and then aluminum carbide is fully hydrolyzed under the low-temperature condition to form the activated carbon/alumina composite carrier.
4. The catalyst takes the Al modified activated carbon as a carrier, and improves the carbon deposition resistance of the catalyst by utilizing the intermiscibility of the activated carbon carrier and carbon deposition generated in the application process and abundant micropores.
5. According to the preparation method of the catalyst, the modification metal introduced in the petroleum coke activation process takes aluminate as a precursor, and can more easily enter the petroleum coke-based activated carbon. The reason is that under the action of the activator, active sites of the petroleum coke react to generate positive charged cavities, and aluminate anions are more easily combined and intercalated.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto.
In the following examples and comparative examples, low-temperature N was used for the specific surface area and pore size distribution of the catalyst2Measuring by an adsorption method; the grain size of the active component of the catalyst is measured by an X-ray broadening method; catalyst composition was determined using XRF analysis techniques.
Example 1
Grinding 100g of petroleum coke into powder, uniformly mixing with 5.06g of potassium metaaluminate and 200g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.2kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.2kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 4%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percentage contents of 10% of Ni, 4% of Zr and 2% of Al in terms of elements, wherein the mass percentage content is marked as C-1.
Example 2
Grinding 100g of petroleum coke into powder, uniformly mixing with 6.77g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition of microwave power of 0.3kw for activation for 30 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 8 ℃, uniformly mixing, keeping the system at 8 ℃ and standing for 6h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 120 ℃ for 8h under a vacuum condition, and roasting at 540 ℃ for 8h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 3 percent of Zr and 3 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-2.
Example 3
Grinding 100g of petroleum coke into powder, uniformly mixing with 9.94g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition of microwave power of 0.4kw, keeping the temperature constant for 10min, introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition of microwave power of 0.4kw for activation for 10 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 90 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 10 ℃, uniformly mixing, keeping the system at 10 ℃ and standing for 8h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 180 ℃ for 4h under a vacuum condition, and roasting at 650 ℃ for 4h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 2%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying the sample for 8 hours at 80 ℃ under a vacuum condition, and roasting the sample for 8 hours at 540 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises the following components in percentage by mass of 20% of Ni, 2% of Zr and 4% of Al, and marking the catalyst as C-3.
Example 4
Grinding 100g of petroleum coke into powder, uniformly mixing with 6.77g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition of microwave power of 0.3kw for activation for 30 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the content of Co and the content of Zr of the final catalyst of 15 percent and 3 percent, dissolving the nickel nitrate hexahydrate and the zirconium nitrate pentahydrate in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percentage of the elements of 15 percent of Co, 3 percent of Zr and 3 percent of Al, and marking as C-4.
Example 5
Grinding 100g of petroleum coke into powder, uniformly mixing with 5.22g of potassium metaaluminate and 400g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.4kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.4kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and lanthanum nitrate hexahydrate according to the Ni content of the final catalyst and the La content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying at 120 ℃ for 4h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 3 percent of La and 3 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-5.
Example 6
Grinding 100g of petroleum coke into powder, uniformly mixing with 6.92g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of cobalt nitrate hexahydrate and magnesium nitrate according to the content of Co and the content of Mg of the final catalyst of 15 percent and 3 percent, dissolving the cobalt nitrate hexahydrate and the magnesium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percentage of Co, Mg and Al accounting for 15%, 3% and 3% of the catalyst by element, and marking as C-6.
Example 7
Grinding 100g of petroleum coke into powder, uniformly mixing with 5.74g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at the temperature of 8 ℃, uniformly mixing, keeping the system at the temperature of 8 ℃ and standing for 6h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at the temperature of 150 ℃ for 6h under a vacuum condition, and roasting at the temperature of 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst of 5% and the Zr content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percentage of 5% of Ni, 3% of Zr and 3% of Al in terms of elements, wherein the mass percentage is marked as C-7.
Example 8
Grinding 100g of petroleum coke into powder, uniformly mixing with 9.27g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 1 ℃ and standing for 2h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percentage contents of 30% of Ni, 3% of Zr and 3% of Al in terms of elements, wherein the mass percentage content is marked as C-8.
Example 9
Grinding 100g of petroleum coke into powder, then uniformly mixing with 2.07g of sodium metaaluminate and 300g of sodium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition of microwave power of 1kw, keeping the temperature constant for 10min, then introducing nitrogen to normal pressure, and continuously heating to 900 ℃ under the condition of microwave power of 1kw for activation for 10 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 10%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 10 percent of Zr and 1 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-9.
Example 10
Grinding 100g of petroleum coke into powder, uniformly mixing with 18.38g of potassium metaaluminate and 500g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition of microwave power of 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to normal pressure, and continuously heating to 800 ℃ under the condition of microwave power of 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel chloride hexahydrate and zirconium chloride according to the Ni content of the final catalyst and the Zr content of 1%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 1 percent of Zr and 10 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-10.
Example 11
Grinding 100g of petroleum coke into powder, uniformly mixing with 6.02g of potassium metaaluminate and 300g of potassium hydroxide, placing in a microwave heating furnace with the microwave frequency of 2450MHz, vacuumizing, heating to 800 ℃ under the condition that the microwave power is 0.3kw, and keeping the temperature constant for 60 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 3 percent of Zr and 3 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-11.
Example 12
Grinding 100g of petroleum coke into powder, then uniformly mixing with 7.53g of potassium metaaluminate and 200g of potassium hydroxide, placing in a high-temperature vacuum roasting furnace, heating to 800 ℃ under a vacuum condition, and activating for 60 min. And after the activation is finished, cooling to normal temperature, taking out the obtained sample, placing the sample in a drying box, heating to 80 ℃, then mixing the sample with deionized water at the same temperature, uniformly stirring, carrying out solid-liquid separation, and repeating for several times until the filtrate is neutral. And (3) placing the solid sample obtained after solid-liquid separation into deionized water at 5 ℃, uniformly mixing, keeping the system at 5 ℃ and standing for 4h, then carrying out solid-liquid separation, drying the solid sample obtained after separation at 150 ℃ for 6h under a vacuum condition, and roasting at 600 ℃ for 6h under a nitrogen atmosphere to obtain the Al modified activated carbon carrier.
Weighing 20g of Al modified activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate and zirconium nitrate pentahydrate according to the Ni content of the final catalyst and the Zr content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading the Al modified activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 3 percent of Zr and 3 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as C-12.
Comparative example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing the powder with 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15, adding the mixture into an acetic acid solution with the concentration of 30wt%, fully stirring, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 20g of the activated carbon carrier, weighing a proper amount of nickel nitrate hexahydrate, zirconium nitrate pentahydrate and aluminum nitrate nonahydrate according to the Ni content of 15%, the Zr content of 3% and the Al content of 3% of the final catalyst, dissolving in a proper amount of deionized water, fixing the volume to 26mL, loading on the activated carbon carrier by adopting an isometric impregnation method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst with the mass percent of 15 percent of Ni, 3 percent of Zr and 3 percent of Al in terms of elements, wherein the mass percent of the catalyst is marked as D-1.
Evaluation of catalyst reaction Performance: the reaction performance was examined with samples of the catalysts prepared in examples 1 to 12 and comparative example 1, respectively, and the reaction was carried out in a continuous flow fixed bed reactor with a catalyst loading of 3g, H2The reaction temperature is 300 ℃, the reaction pressure is 2MPa, and the volume space velocity is 8000h-1(ii) a The product was analyzed on-line by gas chromatography and the results are shown in Table 1.
TABLE 1 catalyst Properties and reaction Performance
Figure DEST_PATH_IMAGE002

Claims (36)

1. A catalyst for methanation of synthesis gas comprises an active component, an auxiliary agent and a carrier, wherein the active component is selected from Ni or Co, the auxiliary agent is selected from one or more of alkaline earth metals, rare earth metals and IVB subgroup metals, and the carrier is Al-modified petroleum coke-based activated carbon, wherein the mass content of the active component is 5wt% -30 wt% in terms of elements, the mass content of the auxiliary agent is 1wt% -10 wt% in terms of elements, the mass content of Al is 1wt% -10 wt% in terms of elements, and the mass content of the carrier is 40wt% -85 wt%
The preparation method of the synthesis gas methanation catalyst comprises the following steps:
(1) mixing petroleum coke, metaaluminate and an activating agent, and activating after uniformly mixing;
(2) washing and carrying out solid-liquid separation on the sample obtained in the step (1) until the filtrate is neutral;
(3) mixing the solid sample obtained by solid-liquid separation in the step (2) with water for low-temperature treatment, standing for solid-liquid separation, and drying and roasting the solid sample obtained by separation;
(4) and (4) introducing active metal and an auxiliary agent into the sample obtained in the step (3), and then drying and roasting to obtain the synthesis gas methanation catalyst.
2. The synthesis gas methanation catalyst of claim 1, wherein: the catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is selected from Ni; the auxiliary agent is one or more of Ca, Mg, Zr, La and Ce; the carrier is Al-modified petroleum coke-based activated carbon, wherein the mass content of active components in terms of elements is 10-20 wt%; the mass content of the auxiliary agent is 2wt% -4 wt% calculated by element; calculated by element, the mass content of Al is 2wt% -4 wt%; the content of the carrier is 60wt% -80 wt%.
3. The synthesis gas methanation catalyst of claim 1, wherein: the specific surface area of the catalyst is 500-1500 m2/g。
4. The synthesis gas methanation catalyst of claim 1, wherein: the specific surface area of the catalyst is 600-1000 m2/g。
5. The synthesis gas methanation catalyst of claim 1, wherein: in the pore size distribution of the catalyst, micropores smaller than 2nm are larger than 60%.
6. The synthesis gas methanation catalyst of claim 1, wherein: in the pore size distribution of the catalyst, micropores smaller than 2nm are larger than 80%.
7. The synthesis gas methanation catalyst of claim 1, wherein: the active component is combined with the amorphous defects of the petroleum coke-based active carbon and alumina embedded in the active carbon graphite microchip layer, and the size of active metal crystal grains is 0.5-5 nm.
8. The synthesis gas methanation catalyst of claim 1, wherein: the active component is combined with the amorphous defects of the petroleum coke-based active carbon and alumina embedded in the active carbon graphite microchip layer, and the size of active metal crystal grains is 1-3 nm.
9. The process for the preparation of a synthesis gas methanation catalyst as claimed in any of claims 1 to 8, characterized in that: the preparation method comprises the following steps:
(1) mixing petroleum coke, metaaluminate and an activating agent, and activating after uniformly mixing;
(2) washing and carrying out solid-liquid separation on the sample obtained in the step (1) until the filtrate is neutral;
(3) mixing the solid sample obtained by solid-liquid separation in the step (2) with water for low-temperature treatment, standing for solid-liquid separation, and drying and roasting the solid sample obtained by separation;
(4) and (4) introducing active metal and an auxiliary agent into the sample obtained in the step (3), and then drying and roasting to obtain the synthesis gas methanation catalyst.
10. The method of claim 9, wherein: the metaaluminate in the step (1) is one or more of potassium metaaluminate, sodium metaaluminate and lithium metaaluminate.
11. The production method according to claim 9 or 10, characterized in that: the metaaluminate in the step (1) is potassium metaaluminate.
12. The method of claim 9, wherein: the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate.
13. The production method according to claim 9 or 12, characterized in that: the activating agent in the step (1) is potassium hydroxide.
14. The method of claim 9, wherein: in the step (1), the mass ratio of petroleum coke, metaaluminate and an activating agent is 1: 0.005-0.05: 1 to 5.
15. The production method according to claim 9 or 14, characterized in that: in the step (1), the mass ratio of petroleum coke, metaaluminate and an activating agent is 1: 0.01-0.02: 2 to 4.
16. The method of claim 9, wherein: the activation process in the step (1) is as follows: grinding the petroleum coke into powder, then uniformly mixing the powder with metaaluminate and an activating agent, heating to the activation temperature, and cooling to room temperature for subsequent treatment after the activation is finished.
17. The production method according to claim 9 or 16, characterized in that: the activation temperature is 600-1000 ℃, and the activation time is 5-240 min.
18. The production method according to claim 9 or 16, characterized in that: the activation temperature is 700-900 ℃, and the activation time is 10-120 min.
19. The method of claim 9, wherein: the activation process is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke.
20. The method of claim 9, wherein: the activation process is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 2-4 kw per kg of petroleum coke.
21. The production method according to claim 19 or 20, wherein: when the activation is carried out under the microwave radiation condition, two-stage activation is carried out, wherein the first stage is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
22. The method of claim 9, wherein: and (3) washing in the step (2) is washing with water, and the washing temperature is 50-95 ℃.
23. The production method according to claim 9 or 22, characterized in that: and (3) washing in the step (2) is washing with water, and the washing temperature is 70-90 ℃.
24. The method of claim 9, wherein: and (3) uniformly mixing the materials at the low-temperature treatment temperature of 1-20 ℃, standing for 2-16 h, and then carrying out solid-liquid separation.
25. The production method according to claim 9 or 24, characterized in that: and (3) uniformly mixing the materials at the low-temperature treatment temperature of 5-10 ℃, standing for 4-8 hours, and then carrying out solid-liquid separation.
26. The method of claim 9, wherein: and (3) drying at the temperature of 80-200 ℃ for 2-10 h.
27. The production method according to claim 9 or 26, characterized in that: and (4) drying at the temperature of 120-180 ℃ for 4-8 h.
28. The method of claim 9, wherein: and (3) roasting in an inert atmosphere at the roasting temperature of 500-700 ℃ for 2-10 h.
29. The method of claim 9, wherein: and (3) roasting in an inert atmosphere at 540-650 ℃ for 4-8 h.
30. The method of claim 9, wherein: step (4) the method for introducing the active metal and the auxiliary into the sample obtained in step (3) is to impregnate the sample obtained in step (3) with a soluble salt solution containing the active metal and a soluble salt solution containing the auxiliary.
31. The method of claim 30, wherein: the soluble salt containing active metal is one or more of nitrate, sulfate and hydrochloride.
32. The production method according to claim 30 or 31, wherein: the soluble salt containing the auxiliary agent is nitrate.
33. The method of claim 9, wherein: and (4) drying at the temperature of 60-160 ℃ for 2-10 h.
34. The method of claim 9, wherein: and (4) drying at the temperature of 80-120 ℃ for 4-8 h.
35. The method of claim 9, wherein: and (4) roasting in an inert atmosphere at the roasting temperature of 500-700 ℃ for 2-10 h.
36. The production method according to claim 9 or 35, wherein: and (4) roasting in an inert atmosphere at 540-650 ℃ for 4-8 h.
CN201711325713.5A 2017-12-13 2017-12-13 Catalyst with Al modified activated carbon as carrier and preparation method thereof Active CN109908931B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711325713.5A CN109908931B (en) 2017-12-13 2017-12-13 Catalyst with Al modified activated carbon as carrier and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711325713.5A CN109908931B (en) 2017-12-13 2017-12-13 Catalyst with Al modified activated carbon as carrier and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109908931A CN109908931A (en) 2019-06-21
CN109908931B true CN109908931B (en) 2021-10-08

Family

ID=66958339

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711325713.5A Active CN109908931B (en) 2017-12-13 2017-12-13 Catalyst with Al modified activated carbon as carrier and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109908931B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479280B (en) * 2019-07-17 2022-09-13 华南理工大学 CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof
CN113120900B (en) * 2019-12-31 2022-10-11 中国石油化工股份有限公司 Preparation process of petroleum coke-based activated carbon with high specific surface area
CN113797908B (en) * 2020-06-11 2023-09-01 中国石油化工股份有限公司 Catalyst carrier material and preparation method and application thereof
CN114477173B (en) * 2020-10-27 2023-08-01 中国石油化工股份有限公司 Petroleum coke-based activated carbon for methane adsorption and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527399A (en) * 2010-12-29 2012-07-04 中国科学院大连化学物理研究所 Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst
CN102861572A (en) * 2012-10-12 2013-01-09 李建修 Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene
CN104609421A (en) * 2013-11-04 2015-05-13 郭晶晶 Preparation method of active carbon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527399A (en) * 2010-12-29 2012-07-04 中国科学院大连化学物理研究所 Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst
CN102861572A (en) * 2012-10-12 2013-01-09 李建修 Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene
CN104609421A (en) * 2013-11-04 2015-05-13 郭晶晶 Preparation method of active carbon

Also Published As

Publication number Publication date
CN109908931A (en) 2019-06-21

Similar Documents

Publication Publication Date Title
CN109908931B (en) Catalyst with Al modified activated carbon as carrier and preparation method thereof
CN109912372B (en) Synthetic gas methanation catalyst and preparation method thereof
CN108855109A (en) A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application
CN111375373B (en) Adsorbent using active carbon as carrier and preparation method thereof
CN105013506A (en) Bifunctional catalyst for methane catalytic cracking, preparation method thereof and hydrogen production method
An et al. Co0− Coδ+ active pairs tailored by Ga-Al-O spinel for CO2-to-ethanol synthesis
CN104984769B (en) A kind of method of synthesizing gas by reforming methane with co 2 carbon base catalyst
CN106944159B (en) A kind of preparation method of catalyst for hydrogen production from methane vapor reforming
CN110721690B (en) Ni-Fe bimetal multifunctional catalyst for biological oil steam reforming hydrogen production
CN109908906B (en) Catalyst for preparing synthetic gas and preparation method thereof
CN111377443B (en) Copper-doped activated carbon composite material and preparation method thereof
CN109908909B (en) Synthetic gas methanation catalyst and preparation method thereof
Tri et al. High activity and stability of nano‐nickel catalyst based on LaNiO3 perovskite for methane bireforming
CN111375400B (en) Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof
CN108097237B (en) Modified manganese sand, transformation methanation catalyst using modified manganese sand as carrier and preparation method
CN114917929B (en) Catalyst for hydrogenation and dehydrogenation of organic liquid hydrogen storage material and preparation method and application thereof
CN109908907B (en) Catalyst for reforming methane and carbon dioxide to produce synthetic gas and its preparing process
CN109908898B (en) Fischer-Tropsch synthesis catalyst and preparation method thereof
CN109908930B (en) Fischer-Tropsch synthesis catalyst and preparation method thereof
CN111375417B (en) Catalyst for preparing high-carbon alcohol by CO hydrogenation and preparation method thereof
CN109261183B (en) Cobalt-based catalyst for methanation of carbon dioxide and application thereof
CN109569617A (en) Dual whole catalyst for preparing synthesized gas of coke-stove gas and its preparation method and application
CN111375414B (en) Methanol carbonylation catalyst and preparation method thereof
CN109651030B (en) Method for directly preparing low-carbon olefin from synthesis gas
CN109305871B (en) Method for producing low-carbon olefin by synthesis gas one-step method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231009

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right