CN112517036A - Synthetic gas methanation catalyst and preparation method thereof - Google Patents
Synthetic gas methanation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112517036A CN112517036A CN201910873786.0A CN201910873786A CN112517036A CN 112517036 A CN112517036 A CN 112517036A CN 201910873786 A CN201910873786 A CN 201910873786A CN 112517036 A CN112517036 A CN 112517036A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- methanation
- hours
- sic
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/04—Methane
Abstract
The invention relates to a catalyst for methanation of synthesis gas, which comprises a carrier, an active component and an auxiliary agent, wherein the carrier is Al2O3And SiC, wherein the active components are NiO and Fe2O3The auxiliary agent is an oxide of at least one element of Mg, La and Ce; also relates to a preparation method of the catalyst, which comprises the following steps: (1) mixing SiC and Al2O3Spray-drying the mixed slurry with the binder to obtain carrier particles, and sequentially drying and roasting the carrier particles to obtain a catalyst carrier; (2) co-impregnating and loading auxiliary agent, NiO and Fe to the catalyst carrier step by step in sequence2O3Obtaining said synthesis gas methaneA catalyst is reacted; also relates to a method for producing methane by using synthesis gas, and the method uses the catalyst of the invention. The catalyst of the invention has high catalytic activity and high selectivity; good abrasion resistance and high mechanical strength.
Description
Technical Field
The invention relates to a synthesis gas methanation technology, in particular to a synthesis gas methanation catalyst, a preparation method thereof and a method for synthesizing methane by using the catalyst.
Background
With the increasing requirements for environmental protection, all countries begin to pay attention to and advance optimization of energy structures. The coal clean conversion is an important optimization means, and an important approach of the conversion is that coal gasification is carried out to obtain synthesis gas, and the synthesis gas is subjected to methanation to extract natural gas. The core of the coal-based synthetic natural gas is methanation, and one of the cores of the methanation technology is a methanation catalyst.
The syngas methanation reaction is a strongly exothermic reaction, typically producing a 74 ℃ temperature rise per 1% conversion of CO. Therefore, the high temperature resistance of the methanation catalyst is very required.
In the adiabatic fixed bed methanation process, in order to effectively control the temperature rise of the reactor and reduce the carbon deposit of the catalyst, the raw material gas is generally diluted, partial water vapor is introduced, and finally the synthetic natural gas is obtained through multistage methanation reactions.
Compared with a fixed bed reactor, the fluidized bed reactor has the advantages of remarkable quality and heat transfer, is more favorable for large-scale heat release, and can obtain good reaction effect without diluting raw gas, so that the fluidized bed reactor is adopted to implement the complete methanation of the synthesis gas to produce the natural gas, and is the first choice of most production enterprises.
On the other hand, although the advantages of fluidized bed reactors for methanation of synthesis gas are well established, the requirements for control of the production process, in particular the catalyst, are also relatively high. The synthetic gas methanation catalyst suitable for fluidized bed reaction needs to be balanced in various aspects such as catalytic activity, selectivity, mechanical strength, abrasiveness and the like, so that the catalyst can stably run for a long time while a good catalytic effect is obtained, and the catalyst is suitable for industrial popularization. Therefore, methanation catalysts suitable for use in fluidized bed reactors are also a focus of continuing attention and research in the industry.
CN105381803A discloses a fluidized bed catalyst for methanation of synthesis gas, a preparation method and application thereof. The disclosed catalyst comprises: 5-75% of active component Ni, 0.1-50% of auxiliary agent M (oxide of at least one element of Fe, Co, Mo, Si, Mg, Ca, Sc, Ti, Y, Zr, La, Ce, Yb and Sm) and the rest of carrier Al2O3(ii) a The preparation method comprises the steps of coprecipitating soluble salt solutions of nickel, aluminum and an auxiliary agent, washing the precipitated slurry, spray-drying, drying and roasting to obtain the microspheric methanation fluidized bed catalyst with a certain particle size. Through determination, the conversion rate of CO methanation of the catalyst product at a space velocity GHSV of 20000 ml/(h.g) is lower than 87%, and the selectivity is higher than 99.99%; in addition, the carrier is Al2O3When the catalyst is used for a fluidized bed reactor, the catalyst has poor abrasiveness and low mechanical strength. Therefore, the catalyst has relatively high selectivity when used for the methanation reaction of CO, but the conversion rate of methane is low, and the service life of the catalyst is not long.
CN106391028A discloses a methanation catalyst for a fluidized bed and a preparation method thereof. The catalyst disclosed by the method comprises a carrier, an active component and an auxiliary agent which are loaded on the carrier. The carrier may be one of two, Al2O3－ZrO2-NiO complex, and Al2O3－TiO2-a complex of NiO; the active component is nickel oxide; the auxiliary agent is an oxide of at least one element of Mg, Ca, La, Ce, Mn, Fe, Cu, Cr and Co. The preparation method of the catalyst comprises the following steps: 1) adding a precipitator into a nitrate solution of Al, Zr and Ni or a nitrate solution of Al, Ti and Ni, adjusting the pH value to 8.0-9.0, and reacting to obtain a precipitate; 2) mixing the precipitate with silica sol or silicon-aluminum composite sol, pulping, and then performing spray drying to obtain spherical particles, wherein the spherical particles are sequentially dried and roasted to obtain microsphere carrier particles; 3) dipping the microsphere carrier particles into a nickel nitrate solution and a nitrate solution of metal elements in the auxiliary agent; and after the impregnation is finished, drying and roasting are sequentially carried out to obtain the methanation catalyst. Although the selectivity of the catalyst is more than 99 percent, the problem of low conversion rate still exists, the measurement result shows that the feeding amount of the synthesis gas is 8000h-1Also the CO conversion is below 86% at lower space velocity.
Disclosure of Invention
The technical problem solved by the invention is to provide a synthesis gas methanation catalyst, which can run at high airspeed, and has high catalytic activity and high selectivity; and has good abrasion resistance and high mechanical strength.
The invention also provides a preparation method of the catalyst, and the preparation method has mild operation conditions, is easy to control and is beneficial to large-scale production of the catalyst.
The invention also provides a method for producing methane from synthesis gas by using the catalyst.
The invention provides a synthesis gas methanation catalyst, which comprises a carrier, an active component and an auxiliary agent, wherein the carrier is Al2O3And SiC, wherein the active components are NiO and Fe2O3The auxiliary agent is an oxide of at least one element of Mg, La and Ce.
In one embodiment of the present invention, Al is2O3SiC is doped in the carrier and is used as a composite carrierAnd (3) a body. The research of the applicant finds that the addition of SiC reduces the acidity of the carrier, and reduces the generation of carbon deposition in application, thereby improving the activity of the catalyst; the SiC has the characteristic of high heat conductivity, so that the generation of local hot spots of the catalyst can be avoided, the thermal stability of the catalyst is improved, and the high activity of the catalyst is favorably maintained; meanwhile, the SiC has high hardness, so that the abrasiveness of the catalyst is improved. Therefore, the proper amount of silicon carbide is doped into the aluminum oxide to form the composite carrier, and the composite carrier is matched with the selected active component and the auxiliary agent component to obtain the methanation catalyst with improved catalytic activity and mechanical property, and the methanation catalyst is particularly suitable for the synthesis gas methanation reaction of a fluidized bed reactor.
The SiC used in the present invention may be high specific surface area SiC. The specific surface area of the high specific surface area SiC measured by a BET method is more than or equal to 60m2/g。
In the present invention, the Al2O3Has a specific surface area of 250m or more as measured by the BET method2(iii) g of said Al2O3May be selected from, for example, gamma-Al2O3。
In the present invention, the NiO may be derived from nickel salts commonly used in the art, such as nickel nitrate, nickel sulfate, or nickel phosphate, but is not limited thereto; said Fe2O3Can be derived from iron salts commonly used in the art, such as, but not limited to, iron nitrate, iron sulfate, or iron phosphate.
The catalyst is used for methanation of catalytic synthesis gas, NiO mainly provides CO methanation activity and is a main active component; fe2O3As another active component, has better CO2The methanation activity can better convert CO in the raw material2Component Fe2O3The catalyst can form an alloy with NiO to reduce NiO crystal grains, thereby enhancing the methanation performance of NiO and being beneficial to improving the conversion rate of CO in methanation reaction; in addition, with Fe2O3As part of the active component, the catalyst feed cost may also be reduced.
In one embodiment of the invention, the catalyst is based onThe content of the carrier is 62-80 wt%, and the active components NiO and Fe2O3The sum of the contents of the components is 15 to 35 weight percent, and the content of the auxiliary agent is 3 to 8 weight percent; the content of the SiC is 30 wt% -70 wt% based on the carrier.
In the present invention, the catalyst support contains SiC in an appropriate amount, which may be 30 to 70%, for example 30 wt%, 40%, 60 wt% or 70 wt%, based on the support.
In general, in Al2O3The addition of other substances into the carrier is equivalent to the dilution of Al2O3Also reduce Al2O3Content in the monolithic catalyst which weakens Al2O3Contribution to catalytic performance. However, in the present invention, by controlling the amount of SiC added to the carrier, CH of the catalyst is obtained4The selectivity is maintained not lower than 99% and is not caused by Al2O3Reduction or dilution of; meanwhile, the CO conversion rate on the catalyst is higher than 90 percent and is generally not lower than 92 percent; at the same time, the attrition of the catalyst is good and the higher mechanical strength can meet the requirement of operating in a fluidized bed at high space velocity.
In the present invention, the catalytically active components NiO and Fe2O3The sum of the amounts of (B) may be from 17% to 33% by weight, or from 20% to 30% by weight, for example 23% by weight, 26% by weight.
In the catalyst of the present invention, SiC and Al2O3With active components NiO and Fe2O3Are matched with each other in a specific content, so that SiC favorably regulates Al2O3With active components NiO and Fe2O3And further the activity of the catalyst is improved.
In one embodiment of the invention, the content of the active component NiO is 12 wt% to 18 wt% based on the catalyst, and the active component Fe2O3The content of (B) is 5 wt% -12 wt%.
The composite carrier containing SiC is matched with and loaded with a proper amount of bimetal active components, so that the obtained synthetic gas methanation catalyst has high activity and selectivity and high mechanical strength.
In one embodiment of the invention, the catalyst is obtained by sequentially impregnating salt solutions loaded with the auxiliary element, the nickel element and the iron element on a carrier, and then standing at a constant temperature, drying and roasting.
The catalyst is a nickel-iron bimetallic catalyst, and two active components are matched with each other to play a role. Through step-by-step impregnation, the auxiliary agent, the nickel and the iron elements occupy the space on the carrier in sequence, favorable distribution of the active components can be controlled, and favorable conditions are provided for mutual matching of the two active components, so that the catalyst has higher catalytic performance.
In another aspect of the invention, a preparation method of a synthesis gas methanation catalyst is provided, and the method comprises the following steps
(1) Mixing SiC and Al2O3Mixing the slurry with a binder, pulping, spray-drying the slurry to obtain carrier particles, and drying and roasting the carrier particles in sequence to obtain a catalyst carrier;
(2) impregnating the catalyst support, the impregnation being carried out in the following order:
firstly, dipping a salt solution of at least one metal of magnesium, cerium and lanthanum, drying and roasting;
secondly, dipping a nickel salt solution, drying and roasting;
thirdly, dipping the ferric salt solution, drying and roasting;
obtaining the synthesis gas methanation catalyst.
In one embodiment of the invention, the binder is an aqueous nitric acid solution with HNO in the aqueous nitric acid solution3The amount of the catalyst accounts for 0.1 to 3 percent of the mass of the catalyst carrier. The nitric acid aqueous solution is used as the adhesive, so that the introduction of heteroatoms in the preparation process is reduced, and the catalytic performance of the catalyst is improved.
In one embodiment of the present invention, the slurry is subjected to spray drying so that the carrier particles obtained have an average particle diameter of 60um to 200 um. In the average particle size range, the fluidity of the catalyst particles is good, so that the catalyst particles are suitable for a fluidized bed reactor, the catalytic performance of the catalyst particles is favorably exerted, and the catalytic reaction has higher activity and selectivity.
In one embodiment of the invention, the impregnation of the catalyst support is carried out at room temperature in each step, and the temperature is kept constant at 70-80 ℃ for more than 2 hours after each impregnation.
The temperature is kept at 70-80 ℃, and the self fluidity of the impregnation liquid is better at a higher temperature higher than the room temperature, so that the metal elements (auxiliary agents and active component metal elements) in the impregnation liquid can be deeper into the pores of the carrier, the favorable loading of the metal elements is realized, and the catalyst with better catalytic performance is obtained.
The impregnated catalyst particles may be held at a temperature of from 70 ℃ to 80 ℃ for a period of from 2 to 6 hours, for example 4 or 5 hours. The time is too short, which is not beneficial to the impregnation liquid to fully permeate into the pores of the carrier; if the time is too long, the solvent in the immersion liquid is greatly evaporated, and the function of conveying metal elements is greatly weakened.
Therefore, the constant temperature for a certain time higher than the room temperature is more beneficial to fully soaking and loading the loaded components, the distribution condition is better, and the energy is saved.
In the present invention, the impregnation in each step of (2) may be the same impregnation manner, or may be different impregnation manners, for example, equal volume impregnation or excess impregnation; the immersion time is 2-3 hours.
In the present invention, the salt solutions described in the respective steps of (2) are, for example, aqueous salt solutions.
In the present invention, the drying described in each step of (2) may be carried out at a conventional drying temperature, for example, 100 ℃ to 110 ℃; the drying time is 10-12 hours.
In the present invention, the calcination described in each step of (2) may be carried out at a conventional calcination temperature, for example, 350 ℃ to 550 ℃; the roasting time is 4-5 hours.
In a further aspect of the invention there is provided a process for the production of methane from synthesis gas, the process comprising subjecting a synthesis gas feedstock to a methanation reaction in a fluidized bed reactor over a methanation catalyst, the methanation catalyst being a catalyst as hereinbefore described.
In one embodiment of the invention, the space velocity of the methanation reaction is 15000h-1To 25000h-1. Namely, the catalyst of the present invention can control a high space velocity to carry out methanation reaction.
As used herein, the term "space velocity" refers to the amount of gas treated per unit volume of catalyst per unit time under specified conditions, and is expressed in units of (m)3Gas)/(m3Catalyst h) can be simplified to h-1. For a given plant, the feed rate is increased by an increase in hourly space velocity, with a large space velocity meaning more feedstock passes over the catalyst per unit time, short residence time of the feedstock on the catalyst, and shallow depth of reaction. Conversely, a small space velocity means a long reaction time, and decreasing the space velocity is advantageous for increasing the conversion of the reaction.
By using the catalyst of the invention, the methanation reaction has higher conversion rate at higher space velocity.
In the present invention, the term "wt%" is understood to mean "wt%" unless otherwise specified.
The synthesis gas methanation catalyst provided by the invention is used for 15000h-1-25000h-1Can simultaneously meet the requirement that the CO conversion rate is more than 92 percent, even can reach 97 percent or higher under the condition of operation at high space velocity, and CH4The selectivity is not lower than 99 percent; and the abrasion index of the catalyst is not higher than 0.5%, and the catalyst has higher mechanical strength, so that the catalyst can stably run for a long time when being applied to a fluidized bed reactor. The catalyst of the invention has excellent conversion rate and selectivity and high mechanical strength, and is very suitable for industrial popularization and application.
The method for producing methane by using synthesis gas provided by the invention has the advantages that the reaction conversion rate is obviously improved by using the catalyst provided by the invention, and high CH (carbon-oxygen) is kept4And (4) selectivity.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments.
All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Raw materials
High specific surface area SiC powder BET specific surface area>60m2Per g, purity greater than 99.5%, average
The grain diameter is 20nm-40 nm.
γ-Al2O3Pseudo-boehmite with a trade name of P-DF-03-LS, purchased from Zhongai Shandong Co Ltd, was calcined at 550 ℃ for 2 hours for use.
Spray drying tower operating parameters
The air inlet temperature is 250-280 DEG C
The air exhaust temperature is about 90 DEG C
Spraying pressure 0.2MPa
Method for measuring abrasion index of catalyst
The abrasion index is determined by adopting the method for determining the abrasion index of the catalytic cracking catalyst of NB/SH/T0964-2017.
EXAMPLE 1 preparation of SiC/γ -Al2O3Composite supported catalyst
1) 60 g of SiC and 140 g of gamma-Al2O3And 400 g of 0.5% nitric acid aqueous solution, pulping at 60-80 ℃ for 2 hours, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 80 um, namely composite carrier particles, wherein SiC accounts for 30% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
55.4 g of magnesium nitrate hexahydrate and 14.6 g of cerium nitrate hexahydrate were weighed, dissolved in deionized water and diluted to 260ml to obtain a maceration extract. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
180.5 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 260ml by deionized water to obtain impregnation liquid. Adding 214 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
thirdly, impregnating and loading the active component Fe in equal volume2O3：
146.5 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 260ml by deionized water to obtain a steeping fluid. Adding 261 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 3 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven and dried for 12 hours at the temperature of 100-110 ℃,
the sample was placed in a muffle furnace and fired at a temperature of 350 ℃ for about 5 hours.
In the obtained catalyst sample, the content of the active component nickel oxide is 16%, the content of the iron oxide is 10%, the content of the auxiliary agent magnesium oxide is 3%, and the content of the cerium oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 96.1%, CH4The selectivity of (3) was 99%. The catalyst attrition index was 0.5%.
EXAMPLE 2 preparation of SiC/γ -Al2O3Composite supported catalyst
1) 120 g of SiC and 80 g of gamma-Al2O3And 500 g of 1% nitric acid aqueous solution, pulping for 2 hours at the temperature of 60-80 ℃, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 150 um, namely composite carrier particles, wherein SiC accounts for 60% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
72.9 g of magnesium nitrate hexahydrate, 7.2 g of cerium nitrate hexahydrate and 15.2 g of lanthanum nitrate hexahydrate are weighed, dissolved by deionized water and diluted to 200ml to obtain an impregnation liquid. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 2 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
placing the sample in a muffle furnace and roasting at 450 ℃ for about 4 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
200.3 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 200ml by deionized water to obtain impregnation liquid. Adding 220 g of the composite carrier particles into the impregnation liquid, impregnating for about 2 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
placing the sample in a muffle furnace and roasting at 450 ℃ for about 4 hours;
thirdly, impregnating and loading the active component Fe in equal volume2O3：
72.2 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 200ml by deionized water to obtain a steeping fluid. Adding 271 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 2 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
the sample was placed in a muffle furnace and fired at a temperature of 450 ℃ for approximately 4 hours.
In the obtained catalyst sample, the content of the active component nickel oxide is 18%, the content of the iron oxide is 5%, the content of the auxiliary agent magnesium oxide is 4%, the content of the cerium oxide is 1%, and the content of the lanthanum oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 95.4%, CH4The selectivity of (3) was 99%. The catalyst attrition index was 0.4%. EXAMPLE 3 preparation of SiC/γ -Al2O3Composite supported catalyst
1) 140 g of SiC and 60 g of gamma-Al2O3And 470 g of 0.4% nitric acid aqueous solution, pulping at 60-80 ℃, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 190um, namely composite carrier particles, wherein SiC accounts for 70% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
72.9 g of magnesium nitrate hexahydrate, 7.2 g of cerium nitrate hexahydrate and 15.2 g of lanthanum nitrate hexahydrate are weighed, dissolved by deionized water and diluted to 200ml to obtain an impregnation liquid. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 2 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
placing the sample in a muffle furnace, and roasting at 550 ℃ for about 3 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
200.3 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 200ml by deionized water to obtain impregnation liquid. Adding 220 g of the composite carrier particles into the impregnation liquid, impregnating for about 2 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
placing the sample in a muffle furnace, and roasting at 550 ℃ for about 3 hours;
thirdly, impregnating and loading the active component Fe in equal volume2O3：
72.2 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 200ml by deionized water to obtain a steeping fluid. Adding 271 g of the composite carrier particles into the impregnation solution, impregnating for about 2 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 10 hours,
the sample was placed in a muffle furnace and fired at a temperature of 550 ℃ for about 3 hours.
In the obtained catalyst sample, the content of the active component nickel oxide is 18%, the content of the iron oxide is 5%, the content of the auxiliary agent magnesium oxide is 4%, the content of the cerium oxide is 1%, and the content of the lanthanum oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as the airspeed of 20000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. Measured out ofConversion of CO was 92.2%, CH4The selectivity of (3) was 99%. The catalyst attrition index was 0.4%.
In examples 1 to 3 of the present invention, the selectivity of the catalyst was higher than 99%, and for the sake of simplicity, it was collectively referred to as "99%".
Comparative example 1 preparation of gamma-Al2O3Supported catalyst
1) 200 g of gamma-Al2O3And 400 g of 0.5% nitric acid aqueous solution, then pulping for 2 hours at 60-80 ℃, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microsphere particles with the average particle size of 70um, namely composite carrier particles;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
55.4 g of magnesium nitrate hexahydrate and 14.6 g of cerium nitrate hexahydrate were weighed, dissolved in deionized water and diluted to 300ml to obtain a maceration extract. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
180.5 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 300ml by deionized water to obtain impregnation liquid. Adding 214 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
thirdly, impregnating and loading the active component Fe in equal volume2O3：
146.5 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 300ml by deionized water to obtain a steeping fluid. Adding 261 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 3 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven and dried for 12 hours at the temperature of 100-110 ℃,
the sample was placed in a muffle furnace and fired at a temperature of 350 ℃ for about 5 hours.
In the obtained catalyst sample, the content of the active component nickel oxide is 16%, the content of the iron oxide is 10%, the content of the auxiliary agent magnesium oxide is 3%, and the content of the cerium oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 87.1%, CH4The selectivity of (A) was 98.8%. The catalyst attrition index was 2.3%. Comparative example 2 preparation of SiC/γ -Al2O3Composite supported catalyst
1) 40 g of SiC and 160 g of gamma-Al2O3And 400 g of 0.5% nitric acid aqueous solution, pulping at 60-80 ℃ for 2 hours, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 80 um, namely composite carrier particles, wherein SiC accounts for 20% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
55.4 g of magnesium nitrate hexahydrate and 14.6 g of cerium nitrate hexahydrate were weighed, dissolved in deionized water and diluted to 260ml to obtain a maceration extract. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
180.5 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 260ml by deionized water to obtain impregnation liquid. Adding 214 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
thirdly, impregnating and loading the active component Fe in equal volume2O3：
146.5 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 260ml by deionized water to obtain a steeping fluid. Adding 261 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 3 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven and dried for 12 hours at the temperature of 100-110 ℃,
the sample was placed in a muffle furnace and fired at a temperature of 350 ℃ for about 5 hours.
In the obtained catalyst sample, the content of the active component nickel oxide is 16%, the content of the iron oxide is 10%, the content of the auxiliary agent magnesium oxide is 3%, and the content of the cerium oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 90.2%, CH4The selectivity of (A) was 98.1%. The catalyst attrition index was 1.5%. Comparative example 3 preparation of SiC/γ -Al2O3Composite supported catalyst
1) 60 g of SiC and 140 g of gamma-Al2O3And 400 g of 0.5% nitric acid aqueous solution, pulping at 60-80 ℃ for 2 hours, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 80 um, namely composite carrier particles, wherein SiC accounts for 30% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, equal volume impregnation and assistant loading:
48.3 g of magnesium nitrate hexahydrate and 12.8 g of cerium nitrate hexahydrate were weighed, dissolved in deionized water and diluted to 260ml to obtain a maceration extract. Adding 200 g of the composite carrier particles into the impregnation liquid, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
and secondly, impregnating in equal volume and loading an active component NiO:
157.7 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 260ml by deionized water to obtain impregnation liquid. Adding 213 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 3 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
in the obtained catalyst sample, the content of the active component nickel oxide is 16%, the content of the auxiliary agent magnesium oxide is 3%, and the content of the cerium oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 88.4%, CH4The selectivity of (a) was 92%. The catalyst attrition index was 0.5%. Comparative example 4 preparation of SiC/γ -Al2O3Catalyst of composite carrier (active component impregnation sequence is different)
1) 60 g of SiC and 140 g of gamma-Al2O3And 400 g of 0.5% nitric acid aqueous solution, pulping at 60-80 ℃ for 2 hours, and then feeding the slurry into a spray drying tower (self-made) for spray drying to obtain carrier particles. Then, drying and roasting the carrier particles in sequence to obtain microspherical particles with the average particle size of 80 um, namely composite carrier particles, wherein SiC accounts for 30% of the weight of the carrier;
2) the obtained composite carrier particles are impregnated step by step according to the following processes:
step one, impregnating and loading an active component NiO in equal volume:
180.5 g of nickel nitrate hexahydrate is weighed and dissolved and diluted to 260ml by deionized water to obtain impregnation liquid. Adding 200 g of the composite carrier particles into the impregnation solution, impregnating for about 3 hours at room temperature, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
second, the active component Fe is impregnated and loaded in equal volume2O3：
146.5 g of ferric nitrate nonahydrate are weighed and dissolved and diluted to 260ml by deionized water to obtain a steeping fluid. Adding 246 g of the composite carrier particles into the impregnation solution, impregnating at room temperature for about 3 hours, keeping the temperature at 70-80 ℃ for about 4 hours,
the sample is placed in an oven and dried for 12 hours at the temperature of 100-110 ℃,
the sample was placed in a muffle furnace and fired at a temperature of 350 ℃ for about 5 hours.
Step three, equal-volume impregnation and auxiliary agent loading:
55.4 g of magnesium nitrate hexahydrate and 14.6 g of cerium nitrate hexahydrate are weighed, dissolved and diluted to 260ml with deionized water to obtain a mixed impregnation liquid. 275 g of the composite carrier particles were added to the impregnation solution, impregnated at room temperature for about 3 hours, maintained at a constant temperature of 70 ℃ to 80 ℃ for about 4 hours,
the sample is placed in an oven, dried at 100-110 c for about 12 hours,
placing the sample in a muffle furnace, and roasting at 350 ℃ for about 5 hours;
in the obtained catalyst sample, the content of the active component nickel oxide is 16%, the content of the iron oxide is 10%, the content of the auxiliary agent magnesium oxide is 3%, and the content of the cerium oxide is 2%.
And carrying out a fluidized bed methanation evaluation experiment on the obtained catalyst sample in a fluidized bed synthesis gas complete methanation reaction evaluation system.
Set as airspeed 18000h-1System pressure 3.0MPa, H23.1/CO, reaction temperature 550 ℃. The conversion of CO was found to be 85.1%, CH4The selectivity of (a) was 96.3%. The catalyst attrition index was 0.5%.
Claims (10)
1. A catalyst for methanation of synthesis gas is characterized by comprising
A carrier, a carrier and a water-soluble polymer,
an active ingredient, and
an auxiliary agent, wherein the auxiliary agent is a mixture of,
wherein the carrier is Al2O3And SiC, wherein the active components are NiO and Fe2O3The auxiliary agent is an oxide of at least one element of Mg, La and Ce.
2. The catalyst according to claim 1,
based on the catalyst, the content of the carrier is 62-80 wt%, and the active components NiO and Fe2O3The sum of the contents of the components is 15 to 35 weight percent, and the content of the auxiliary agent is 3 to 8 weight percent;
the content of the SiC is 30 wt% -70 wt% based on the carrier.
3. The catalyst according to claim 1 or 2,
based on the catalyst, the content of the active component NiO is 12 to 18 weight percent, and the active component Fe2O3The content of (B) is 5 wt% -15 wt%.
4. The catalyst of claim 1 or 3, wherein the catalyst is in Al2O3And sequentially dipping salt solution loaded with the auxiliary element, the nickel element and the iron element on the SiC compound carrier, standing at constant temperature, drying and roasting to obtain the SiC/SiC composite material.
5. A process for the preparation of a synthesis gas methanation catalyst as claimed in any of claims 1 to 4, characterized in that the process comprises
(1) Mixing SiC and Al2O3Mixing the slurry with a binder, pulping, spray-drying the slurry to obtain carrier particles, and drying and roasting the carrier particles in sequence to obtain a catalyst carrier;
(2) impregnating the catalyst support, the impregnation being carried out in the following order:
firstly, dipping a salt solution of at least one metal of magnesium, cerium and lanthanum, drying and roasting;
secondly, dipping a nickel salt solution, drying and roasting;
thirdly, dipping the ferric salt solution, drying and roasting;
obtaining the synthesis gas methanation catalyst.
6. The method according to claim 5, characterized in that the binder is an aqueous nitric acid solution, the HNO of which is an aqueous nitric acid solution3The amount of (B) is 0.1 wt% -3 wt% of the mass of the catalyst carrier.
7. A method according to claim 5 or 6, characterized in that the slurry is spray-dried to obtain carrier particles having an average particle size of 60-200 um.
8. The method according to claim 5 or 7,
the impregnation of the catalyst carrier in each step is room temperature impregnation, and the constant temperature of 70-80 ℃ is kept for more than 2 hours after each impregnation.
9. A process for the production of methane from synthesis gas, comprising subjecting a synthesis gas feedstock to methanation in a fluidized bed reactor over a methanation catalyst, the methanation catalyst being as defined in any one of claims 1 to 4.
10. The process according to claim 9, characterized in that the space velocity of the methanation reaction is 15000h-1To 25000h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873786.0A CN112517036A (en) | 2019-09-17 | 2019-09-17 | Synthetic gas methanation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873786.0A CN112517036A (en) | 2019-09-17 | 2019-09-17 | Synthetic gas methanation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112517036A true CN112517036A (en) | 2021-03-19 |
Family
ID=74974394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910873786.0A Pending CN112517036A (en) | 2019-09-17 | 2019-09-17 | Synthetic gas methanation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112517036A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499763A (en) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | Coke-oven gas isothermal methanation catalyst and preparation method thereof |
| CN114260007A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
| CN102600860A (en) * | 2012-02-15 | 2012-07-25 | 华东理工大学 | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Nickel iron bimetallic methanation catalyst and preparation and application thereof |
| WO2018141648A1 (en) * | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
-
2019
- 2019-09-17 CN CN201910873786.0A patent/CN112517036A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
| CN102600860A (en) * | 2012-02-15 | 2012-07-25 | 华东理工大学 | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof |
| CN104174420A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院大连化学物理研究所 | Silicon carbide based monolithic catalyst for synthetic gas methanation and preparation method |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Nickel iron bimetallic methanation catalyst and preparation and application thereof |
| WO2018141648A1 (en) * | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
Non-Patent Citations (2)
| Title |
|---|
| MINGZHENG LIAO，ET AL.: "Hydrogen production from partial oxidation of propane: Effect of SiC addition on Ni/Al2O3 catalyst", 《APPLIED ENERGY》 * |
| 靳永勇: "碳化硅负载镍基催化剂高温甲烷化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(月刊)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499763A (en) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | Coke-oven gas isothermal methanation catalyst and preparation method thereof |
| CN114260007A (en) * | 2021-12-13 | 2022-04-01 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2477654C1 (en) | Fischer-tropsh synthesis catalyst, its production and application | |
| JP5458088B2 (en) | Method for producing nanocrystalline bismuth-molybdenum mixed oxide | |
| CN101829580B (en) | Fischer-Tropsch synthetic catalyst, preparation method and application thereof | |
| CN111085199A (en) | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof | |
| CN105817222B (en) | A kind of preparation method and application of hydro carbons catalyst for fischer-tropsch synthesis composition | |
| CN111330586A (en) | Novel ethynylation catalyst and method for producing same | |
| CN106391028A (en) | Methanation catalyst for fluidized bed and preparation method of methanation catalyst for fluidized bed | |
| CN105921147B (en) | A kind of hydro carbons catalyst for fischer-tropsch synthesis composition and its application | |
| EP2673081B1 (en) | Method of preparing a catalyst precursor, method of preparing a catalyst and a hydrocarbon synthesis process | |
| WO2002018043A1 (en) | Attrition resistant bulk iron catalysts and processes for preparing and using same | |
| CN108136369A (en) | Catalyst for oxidative dehydrogenation and preparation method thereof | |
| EP2318131B1 (en) | Catalyst for direct production of light olefins and preparation method thereof | |
| CN112517036A (en) | Synthetic gas methanation catalyst and preparation method thereof | |
| CN109317192B (en) | CO (carbon monoxide)2Core-shell catalyst for preparing low-carbon olefin by hydrogenation coupling and preparation thereof | |
| CN111589449A (en) | Cobalt-based catalyst for propane dehydrogenation, preparation method and application | |
| CN101966460A (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| KR101405517B1 (en) | Process for preparing nickel based catalysts for SCR of natural gas | |
| CN103071491B (en) | Hydrogenation catalyst with large specific surface and low acid amount, and application thereof | |
| CN105582931B (en) | Cobalt-based Fischer-Tropsch synthesis catalyst loaded by mixed oxide carrier and preparation method thereof | |
| CN108014795A (en) | A kind of propane dehydrogenation catalyst and its preparation method and application | |
| WO2019148551A1 (en) | Method for preparing ni-based catalyst microspheres and use thereof | |
| CN109422638B (en) | Method for preparing ketone compound by ABE fermentation liquor conversion | |
| CN106540729B (en) | Loaded catalyst and application thereof | |
| CN115634678A (en) | Ethane dehydrogenation catalyst and method for simultaneously preparing ethylene and hydrogen by ethane dehydrogenation | |
| CN112742385B (en) | Catalyst for catalytic conversion of gasoline, preparation method thereof and catalytic conversion method of gasoline |
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 |