CN107537536B - Sulfur-tolerant methanation catalyst, preparation method and application thereof - Google Patents
Sulfur-tolerant methanation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN107537536B CN107537536B CN201610495404.1A CN201610495404A CN107537536B CN 107537536 B CN107537536 B CN 107537536B CN 201610495404 A CN201610495404 A CN 201610495404A CN 107537536 B CN107537536 B CN 107537536B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- powder
- sulfur
- mass
- hypophosphite
- 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
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a sulfur-tolerant methanation catalyst and a preparation method thereof, and mainly solves the problems that the sulfur-tolerant methanation catalyst in the prior art has low CO conversion rate and CH4Poor selectivity. The invention adopts transition metal sulfide and phosphide as active components, and the catalyst comprises the following components in percentage by mass: a) 5-25% MoS2；b)0～3.5％Fe3P；c)0～5％Ni3P; d) the technical scheme of the aluminum oxide better solves the problem, and compared with the traditional sulfur-tolerant methanation catalyst, the catalyst has high CO conversion rate and CH4The selectivity solves the problems of low activity and poor selectivity of the traditional sulfur-tolerant methanation catalyst, and can be used for producing methane from synthesis gas.
Description
Technical Field
The invention relates to a sulfur-tolerant methanation catalyst, a preparation method and application thereof, mainly adopts transition metal sulfide and phosphide as sulfur-tolerant methanation active components, and can be used in the production of methane prepared from sulfur-containing synthesis gas.
Background
The coal-based natural gas (SNG) is the optimal mode of coal-based energy products and has good development prospect. At present, the international commercial coal-to-natural gas technology mainly comprises two steps, namely, synthesis gas production through coal gasification and substitute natural gas production through complete methanation of the synthesis gas. Two main process routes are provided for realizing the methanation of the synthesis gas, and one process is a non-sulfur-tolerant methanation process; and secondly, adopting a sulfur-tolerant methanation process.
The non-sulfur-tolerant methanation process adopts a nickel-based methanation catalyst, and because the catalyst has poor carbon deposition resistance and is extremely sensitive to sulfur, the raw material gas can be subjected to fine desulfurization until the concentration is less than 0.1 × 10 after being washed by low-temperature methanol-6The temperature of the methanation catalyst needs to be reduced from hundreds of degrees to-40 ℃, when the methanation catalyst enters a methanation reactor, the temperature of the methanation catalyst needs to be increased to 300-400 ℃, and the process is energy-wasting and large in equipment investment. In addition, H is adjusted by a shift process to meet the requirement of methanation2the/CO ratio is greater than 3, which increases both the process flow and the equipment investment.
The sulfur-tolerant methanation process adopts a sulfur-tolerant catalyst, has the greatest advantages that the raw material gas can not be desulfurized, and methanation and CO transformation reactions are simultaneously carried out on the same catalyst without adding water vapor to adjust H2The ratio of/CO is reduced, thereby simplifying the process flow, saving the investment, reducing the energy consumption, and reducing the heat consumption by about 40 percent compared with the traditional process.
Sulfur-tolerant methanation adopts sulfur-tolerant Mo-based catalyst, and this catalyst has steam shift and methanation function simultaneously, so water gas shift can go on in same reactor with methanation, and the synthetic gas that comes from behind the coal gasification directly gets into methanation reactor, takes place direct methanation reaction, as under:
CO+3H2→CH4+H2O (1)
CO+H2O→CO2+H2(2)
and (3) total reaction: 2CO +2H2→CH4+CO2△H＝-247kJ/mol
Compared with the traditional non-sulfur-tolerant methanation process, the sulfur-tolerant methanation process has the following characteristics:
(1) in the acid gas purification process, after the methanation process, the methanation reaction is a molecular reduction reaction, so that the gas treatment amount is remarkably reduced, and the process loads such as low-temperature methanol washing and the like are reduced;
(2) energy waste caused by temperature reduction and temperature rise of the raw material gas before and after the step of removing the acid gas is avoided;
(3) in natural gas pipelinesAllowing 20mg/m3H2S exists, so that H is not necessary in the purification step2S absorption to less than 0.1 × 10-6The process requirements and the corresponding operation cost are reduced;
(4) the water-vapor conversion process is omitted, and the equipment investment and the operation cost are reduced.
The sulfur-tolerant direct methanation catalyst is mainly represented by a molybdenum-based catalyst, and a Ce-Mo and Ce-Mo-Al catalyst is reported at present. Direct methanation studies were conducted by GRI in the united states. Patents US4151191 and US4260553 report GRI-C-284 and GRI-C-318 catalysts, respectively, with compositions of Ce-Mo and Ce-Mo-Al, respectively. However, the currently used molybdenum-based catalyst has low CO conversion rate and poor selectivity, is difficult to apply in actual industrial production, and has selectivity and conversion rate of less than 60 percent. The key to the realization of industrial application of the sulfur-tolerant methanation process is to improve the activity of sulfur-tolerant methanation.
By conventional methods, e.g. as used in US4833112, with CeO2Improved sulfur-tolerant methanation catalyst prepared by taking molybdenum nickel as active component as carrier, and CO conversion rate and Al of improved sulfur-tolerant methanation catalyst2O3The supported molybdenum-based catalyst is improved to a certain extent, but the CH is4The selectivity of (a) is less than 50%.
Chinese patent CN102302929A discloses a MoSi2The sulfur-tolerant methanation catalyst is an active component, the first auxiliary agent is silicate, and the second auxiliary agent is La2O3The third additive is TiO2,ZrO2. The sulfur-tolerant catalyst has excellent sulfur tolerance and stability compared with the traditional high-temperature methanation catalyst, and can meet the requirement of high-temperature methanation. At H23/CO, water, H2The conversion rate of CO can reach 99% and the selectivity of CH4 is 90% under the condition of 500 deg.C when S is 100 ppm. Although it shows high catalytic activity, the sulfur content in the crude gas is higher than 0.1%, and the H content of the crude gas is higher than that of the crude gas2The ratio/CO is mostly less than 3. Therefore, the high sulfur resistance of the catalyst under practical industrial conditions is to be further improved.
Disclosure of Invention
One of the technical problems to be solved by the invention is the prior artIn the technology, the sulfur-tolerant methanation catalyst has low CO conversion rate and CH4Poor selectivity. Provides a sulfur-tolerant methanation catalyst which has the advantages of high CO conversion rate and high methane selectivity.
The second technical problem to be solved by the present invention is a method for preparing the catalyst.
The invention also provides a method for methanation of sulfur-tolerant catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows: the sulfur-tolerant methanation catalyst comprises the following components in percentage by mass: a) 5-25% MoS2；b)0～3.5％Fe3P；c)0～5％Ni3P; d) alumina; wherein components b) and c) are not all 0.
In the technical scheme, preferably, the content of the component b) is 0.5-3.5%; more preferably, the content of the component b) is 1-3%.
In the technical scheme, preferably, the content of the component c) is 0.1-5%; more preferably, the content of the component c) is 1-4%.
In the technical scheme, the content of the component a) is preferably 8-10%.
In order to solve the second technical problem, the technical scheme of the invention is as follows: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps:
(1) firstly, pseudo-boehmite powder is roasted to obtain powder alpha;
(2) mixing the powder alpha and the pseudo-boehmite powder according to the mass percentage of (95:5) - (50:50) to obtain powder beta; mixing the powder beta with a required amount of ammonium thiomolybdate aqueous solution, and drying to prepare powder gamma;
(3) forming the powder gamma to obtain a catalyst precursor I; (4) and mixing the catalyst precursor I with an acidic aqueous solution containing required amounts of ammonium hypophosphite, nickel hypophosphite and/or iron hypophosphite and a pH regulator to obtain a catalyst precursor II, and maintaining the pH value to be 3-6, wherein the molar ratio of the nickel hypophosphite or the iron hypophosphite to the ammonium hypophosphite in the acidic aqueous solution is 1: 0.5-1: 3.
(5) Heating the catalyst precursor II to 300-600 ℃ in a nitrogen atmosphere, maintaining the temperature for 3-10 hours, and then carrying out thermal decomposition treatment;
(6) and washing the thermal decomposition product by using an aqueous solution containing 0.5-30% of ammonia by mass percent, and removing the residual pH regulator to obtain the catalyst.
In the above technical solution, preferably, the step (6) may further include a step of washing with water until the washing solution is neutral.
In the technical scheme, the roasting temperature in the step (1) is preferably 600-1100 ℃; preferably, the roasting time is 2-16 hours.
In the above technical solution, the drying conditions in step (2) are not particularly limited, as long as the water content can be reduced, for example, but not limited to, the drying temperature is 30 to 120 ℃, and the drying time is 3 to 48 hours.
In the above technical solution, the pH adjusting agent in step (4) is preferably at least one of phosphoric acid, hypophosphorous acid, or phosphorous acid.
In the above technical scheme, the temperature raising speed in step (5) is not particularly limited, but slow temperature raising is beneficial to obtaining a carrier with better strength, and a person skilled in the art can flexibly grasp the carrier according to specific conditions, for example, but not limited to, the temperature raising speed is controlled to be 1-5 ℃/min.
In the above technical scheme, the thermal decomposition treatment in the step (5) may be performed under the condition of introducing O at 300-600 ℃ in percentage by volume20.1 to 1% of N26 to 24 hours.
The forming method is not particularly limited, and for example, rolling ball forming, tabletting forming, extrusion forming and the like can be performed, and in order to meet the needs of various forming methods, a person skilled in the art can select the commonly used forming aids. When extrusion molding is adopted, for example, a nitric acid aqueous solution (for example, a nitric acid aqueous solution with a concentration of 2-8 w%) can be used as a binder, and a pore-forming agent (for example, but not limited to, at least one of methyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, sesbania powder) can be added; when extrusion molding is used, those skilled in the art will appreciate that the composition may be dried (for example, but not limited to, drying at a temperature of 30 to 150 ℃), and fired (for example, but not limited to, firing at a temperature of 450 to 650 ℃).
To solve the third technical problem, the technical scheme of the invention is as follows: the method for methanation with sulfur tolerance takes synthetic gas as raw material to carry out methanation reaction in the presence of the catalyst in the technical scheme of one of the technical problems.
In the above technical scheme, the catalyst of the present invention can be used for synthesizing methane regardless of whether the synthesis gas contains impurity hydrogen sulfide, but the catalyst of the present invention has the outstanding characteristic of sulfur resistance, so the synthesis gas preferably contains impurity hydrogen sulfide, such as but not limited to H2The S content may be greater than 1% by volume, for example H2The S content is 0.5-3% (volume percentage).
In the above technical scheme, preferably, the content of impurity hydrogen sulfide in the synthesis gas is 0.5-5% (volume percentage); more preferably, the content of the impurity hydrogen sulfide in the synthesis gas is 0.5-3% (volume percentage); more preferably, the content of the impurity hydrogen sulfide in the synthesis gas is 0.8-3% (volume percentage).
In the technical scheme, the reaction temperature is preferably 200-700 ℃, and more preferably 300-600 ℃.
In the above-mentioned embodiment, the reaction pressure is preferably 2.0 to 6.0MPa, more preferably 3.0 to 5.0MPa in terms of gauge pressure.
In the technical scheme, the preferred volume airspeed of the raw materials is 3000-15000 hours-1More preferably 4000 to 8000 hours-1。
In the technical scheme, H in the raw material gas2The molar ratio of the carbon dioxide to CO is preferably 0.5 to 5, and the preferred molar ratio is 1 to 3.
The performance of the catalyst was evaluated as follows:
conversion of CO
CH4Selectivity is
In the formula (I), the compound is shown in the specification,
XCOCO conversion,%;
SCH4is CH4Selectivity,%;
qn in COis the molar flow (mol/min) of CO at the reactor inlet;
qn out COis the molar flow (mol/min) of CO at the outlet of the reactor;
qn out CH4is the reactor outlet CH4Molar flow (mol/min).
Evaluation conditions of the sulfur-tolerant methanation activity of the catalyst: the catalyst was carried out in a pressurized fixed bed reactor, and the loading of the catalyst was 30 mL. The catalyst needs to be subjected to pre-vulcanization treatment before activity evaluation, and the pre-treatment conditions are as follows: in the presence of 1% of H2H of S2Vulcanizing at 450 ℃ for 5 hours in atmosphere;
evaluation conditions were as follows: reaction space velocity of 8000h-1(ii) a The reaction pressure is 3.5 MPa; inlet temperature: at 450 ℃;
raw material gas composition (volume percentage): 38% CO, H236% of H2S is 1%, and the rest is N2。
The sulfur-resistant catalyst prepared by loading metal phosphide and molybdenum-based active components by using alumina as a carrier can obviously improve the conversion rate of CO and the selectivity of methane by utilizing the combined synergistic effect of the active components on the carrier. The catalyst of the present invention can be used under the condition that the content of sulfur impurities in the raw material is more than 1% (volume percentage), the CO conversion rate is more than 70%, and the methane selectivity is more than 50%.
The catalyst of the invention has the reaction pressure of 3.5MPa, the reaction temperature of 450 ℃ and the space velocity of 8000h-1(ii) a Raw material gas composition (volume percentage): 38% CO, H236% of H2S is 1%, and the rest is N2When the conversion rate of CO is more than 70 percent, CH4Selectivity greater than 50%, whereas prior art CO conversionRate less than 60%, CH4The selectivity is less than 50 percent, and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weighing 300 g of pseudo-boehmite raw powder, roasting at 850 ℃ for 8 hours to obtain α g of powder, weighing 160 g of powder α, mixing the powder α and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain β g of powder, weighing 148 g of powder β, adding MoS in mass percentage2160 g of 25.0 percent ammonium thiomolybdate solution, drying for 24 hours at 80 ℃, dehydrating, and preparing powder gamma again; adding 5 g of sesbania powder into the powder gamma and an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4 percent and Fe in percentage by mass3100 g of an acidic aqueous solution of 2% of ferric hypophosphite and ammonium hypophosphite P is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0.85, the pH value of the solution is 4 (adjusted by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst to 20 deg.C in nitrogen atmosphere, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; and washing the thermal decomposition product by using an aqueous solution containing 3% of ammonia by mass percent, removing an acidic compound in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity:
the catalyst is carried out on a pressurized fixed adiabatic bed reaction device, and the loading amount of the catalyst is 30 mL;
catalyst in situPre-vulcanization treatment is needed before the evaluation of the performance, and the pre-treatment conditions are as follows: in the presence of 1% of H2H of S2Vulcanizing at 450 ℃ for 5 hours in atmosphere;
evaluation conditions were as follows: reaction space velocity of 8000h-1(ii) a The reaction pressure is 3.5 MPa; inlet temperature: at 450 ℃;
raw material gas composition (volume percentage): 38% CO, H236% of H2S is 1%, and the rest is N2。
The catalyst evaluation results are shown in tables 7 and 8.
[ example 2 ]
Weighing 300 g of pseudo-boehmite raw powder, roasting at 850 ℃ for 8 hours to obtain α g of powder, weighing 160 g of powder α, mixing the powder α and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain β g of powder, weighing 124 g of powder β, adding MoS in mass percentage2150 g of 20.0 percent ammonium thiomolybdate solution, drying for 24 hours at 80 ℃, dehydrating, and preparing powder gamma again; adding 3 g of sesbania powder into the powder gamma and an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst precursor I; weighing 92 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4.5 percent and Fe contained in percentage by mass3100 g of an acidic aqueous solution of ferric hypophosphite and ammonium hypophosphite with the P content of 3 percent is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0.85, the pH value of the solution is 4 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst to 20 deg.C in nitrogen atmosphere, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; and washing the thermal decomposition product by using an aqueous solution containing 3% of ammonia by mass percent, removing an acidic compound in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The preparation conditions and the composition of the catalyst are shown in Table 1,Tables 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity:
the catalyst is carried out on a pressurized fixed adiabatic bed reaction device, and the loading amount of the catalyst is 30 mL;
the catalyst needs to be subjected to pre-vulcanization treatment before activity evaluation, and the pre-treatment conditions are as follows: in the presence of 1% of H2H of S2Vulcanizing at 450 ℃ for 5 hours in atmosphere;
evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 3 ]
Weighing 300 g of pseudo-boehmite raw powder, roasting at 850 ℃ for 8 hours to obtain α g of powder, weighing 160 g of powder α, mixing the powder α and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain β g of powder, weighing 140 g of powder β, adding MoS in mass percentage2150 g of 20.0 percent ammonium thiomolybdate solution, drying for 24 hours at 80 ℃, dehydrating, and preparing powder gamma again; adding 3 g of sesbania powder into the powder gamma and an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst precursor I; weighing 100 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 0.1 percent and Fe contained in percentage by mass3100 g of an acidic aqueous solution of ferric hypophosphite and ammonium hypophosphite with the P content of 0.5 percent is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0.83, the pH value of the solution is 4 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst to 20 deg.C in nitrogen atmosphere, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; washing the thermal decomposition product with an aqueous solution containing 3% by mass of ammonia to remove acidic compounds in the catalyst, and washing the catalyst with deionized water to neutralAnd (5) carrying out esterification to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 4 ]
Weighing 300 g of pseudo-boehmite raw powder, roasting at 850 ℃ for 8 hours to obtain α g of powder, weighing 160 g of powder α, mixing the powder α and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain β g of powder, weighing 90 g of powder β, adding MoS in mass percentage280 g of 5.0 percent ammonium thiomolybdate solution are mixed, and then the mixture is dried for 24 hours at 80 ℃ for dehydration to prepare powder gamma again; adding 3 g of sesbania powder into the powder gamma and an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst precursor I; weighing 47 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 5 percent and Fe in percentage by mass3100 g of an acidic aqueous solution of ferric hypophosphite and ammonium hypophosphite with the P content of 0.5 percent is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0.83, the pH value of the solution is 4 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst to 20 deg.C in nitrogen atmosphere, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; and washing the thermal decomposition product by using an aqueous solution containing 3% of ammonia by mass percent, removing an acidic compound in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 5 ]
Weighing 300 g of pseudo-boehmite raw powder, roasting at 1000 ℃ for 2 hours to obtain α g of powder, weighing 160 g of powder α, mixing the powder α and the pseudo-boehmite powder according to a mass percentage of 50:50 to obtain β g of powder, weighing 140 g of powder β, adding MoS in mass percentage280 g of 5.0 percent ammonium thiomolybdate solution are mixed, and then the mixture is dried for 24 hours at 80 ℃ for dehydration to prepare powder gamma again; adding 3 g of sesbania powder into the powder gamma and an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 3 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4 percent and Fe in percentage by mass3100 g of an acidic aqueous solution of ferric hypophosphite and ammonium hypophosphite with the P content of 3.5 percent is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0.83, the pH value of the solution is 4 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst to 20 deg.C in nitrogen atmosphere, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; and washing the thermal decomposition product by using an aqueous solution containing 3% of ammonia by mass percent, removing an acidic compound in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 6 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 700 ℃ for 16 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 75:25 to obtain raw powder II; weighing 146 g of raw powder II2 g of calcium oxide powder, and adding the calcium oxide powder160 g of ammonium thiomolybdate solution containing 25.0% of MoS2 in percentage by weight are mixed, and then dried and dehydrated for 48 hours at 30 ℃ to prepare powder III again; adding 6 g of hydroxymethyl cellulose into the powder III and an aqueous solution containing 2% of nitric acid in mass percent according to the mass ratio of 100:120, kneading, extruding and forming, drying at 150 ℃ for 3 hours, and roasting at 650 ℃ for 2 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4 percent and Fe in percentage by mass3100 g of an acidic aqueous solution of 0.5% P of hypophosphorous acid and ammonium hypophosphite is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:1, the pH value of the solution is 6 (hypophosphorous acid or ammonia water is used), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 100 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a heating rate of 3 deg.C/min, cooling the catalyst in nitrogen atmosphere to 20 deg.C for 1 hr, and introducing O at 20 deg.C2Is 2% of N2Passivating for 1 hour in atmosphere; and washing the passivation product for 2 times by using an aqueous solution containing 0.5% of ammonia by mass percent, removing an acidic compound in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 7 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 1000 ℃ for 3 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 60:40 to obtain raw powder II; weighing 148 g of raw powder II, adding 160 g of ammonium thiomolybdate solution containing 20.0% of MoS2 in mass percent, mixing, drying and dehydrating at 110 ℃ for 9 hours, and preparing powder III again; mixing the powder III with an aqueous solution containing 4% nitric acid in a mass ratio of 100:90, adding 5 g carboxymethyl cellulose, kneading, extruding, drying at 100 deg.C for 5 hr, and baking at 600 deg.CBurning for 2 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4 percent and Fe in percentage by mass3100 g of an acidic aqueous solution of ferric hypophosphite and ammonium hypophosphite with the P content of 0.5 percent is soaked, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:3, the pH value of the solution is 5 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after soaking; drying the catalyst precursor II at 80 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 5 deg.C/min for 6 hr, cooling the catalyst in nitrogen atmosphere to 50 deg.C, and introducing O at 50 deg.C20.5% of N2Passivating for 18 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 1% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 8 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 900 ℃ for 5 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 70:30 to obtain raw powder II; 148 g of raw powder II are weighed and added with MoS by mass percentage2160 g of 20.0 percent ammonium thiomolybdate solution, drying for 12 hours at 100 ℃, dehydrating, and preparing powder III again; adding 3 g of sesbania powder and 2 g of methylcellulose into the powder III and a water solution containing 7% of nitric acid in mass percent according to a mass ratio of 100:70, kneading, extruding and forming, drying at 80 ℃ for 10 hours, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 4 percent and Fe in percentage by mass3100 g of an aqueous acidic solution of iron hypophosphite and ammonium hypophosphite having a P content of 2%, in which aqueous acidic solution hypophosphorous acid is presentThe mol ratio of nickel to ammonium hypophosphite is 1:2, the pH value of the solution is 3 (regulated by hypophosphorous acid or ammonia water), and a catalyst precursor II is obtained after impregnation; drying the catalyst precursor II at 60 deg.C to remove water, heating the catalyst in nitrogen atmosphere at 4 deg.C/min, cooling the catalyst in nitrogen atmosphere to 10 deg.C for 4 hr, and introducing O at 10 deg.C21.5% of N2Passivating for 20 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 2% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 9 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 600 ℃ for 10 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 95:5 to obtain raw powder II; weighing 148 g of raw powder II, adding 160 g of ammonium thiomolybdate solution containing 25.0% of MoS2 in mass percent, mixing, drying at 60 ℃ for 20 hours, dehydrating, and preparing powder III again; adding 3 g of sesbania powder and 2 g of carboxymethyl cellulose into the powder III and an aqueous solution containing 5% of nitric acid in percentage by mass according to the mass ratio of 100:80, kneading, extruding and forming, drying at 60 ℃ for 24 hours, and roasting at 580 ℃ for 3 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Nickel hypophosphite with P of 5 percent and Fe in percentage by mass3Performing equal-volume impregnation on an acidic aqueous solution of 2% of hypophosphorous acid and ammonium hypophosphite P, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:1.5, the pH value of the solution is 5 (adjusted by hypophosphorous acid or ammonia water), and obtaining a catalyst precursor II after impregnation; drying the catalyst precursor II at 40 deg.C to remove water, heating the catalyst in nitrogen atmosphere at 3 deg.C/min for 2 hr,the catalyst was cooled to 60 ℃ in a nitrogen atmosphere and then passed at 60 ℃ with an O-containing gas20.8% of N2Passivating for 10 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 30% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 10 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 600 ℃ for 8 hours to obtain powder I; weighing 160 g of the powder I and the pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 90:10 to obtain raw powder II; 148 g of raw powder II are weighed and added with MoS by mass percentage2160 g of 20.0 percent ammonium thiomolybdate solution are mixed, and then dried for 20 hours at 60 ℃ for dehydration to prepare powder III again; adding 3 g of sesbania powder and 2 g of carboxymethyl cellulose into the powder III and an aqueous solution containing 5% of nitric acid in percentage by mass according to the mass ratio of 100:80, kneading, extruding and forming, drying at 60 ℃ for 24 hours, and roasting at 580 ℃ for 3 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Ni in percentage by mass3Soaking nickel hypophosphite with P being 4% and an acidic aqueous solution of ammonium hypophosphite in an equal volume, wherein the molar ratio of the nickel hypophosphite to the ammonium hypophosphite in the acidic aqueous solution is 0:0.85, the pH value of the solution is 4 (adjusted by hypophosphorous acid or ammonia water), and obtaining a catalyst precursor II after soaking; drying the catalyst precursor II at 40 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a heating rate of 3 deg.C/min, cooling the catalyst in nitrogen atmosphere to 60 deg.C for 2 hr, and introducing O at 60 deg.C20.8% of N2Passivating for 10 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 30% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst.The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ example 11 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 600 ℃ for 10 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain raw powder II; 148 g of raw powder II are weighed and added with MoS by mass percentage2160 g of 20.0 percent ammonium thiomolybdate solution are mixed, and then dried for 20 hours at 60 ℃ for dehydration to prepare powder III again; adding 3 g of sesbania powder and 2 g of carboxymethyl cellulose into the powder III and an aqueous solution containing 5% of nitric acid in percentage by mass according to the mass ratio of 100:80, kneading, extruding and forming, drying at 60 ℃ for 24 hours, and roasting at 580 ℃ for 3 hours to obtain a catalyst precursor I; weighing 94 g of catalyst precursor I and Fe in percentage by mass3Performing equal-volume impregnation on an acidic aqueous solution of 2% of P and ammonium hypophosphite, wherein the molar ratio of nickel hypophosphite to ammonium hypophosphite in the acidic aqueous solution is 1:0, the pH value of the solution is 4 (adjusted by hypophosphorous acid or ammonia water), and obtaining a catalyst precursor II after impregnation; drying the catalyst precursor II at 40 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a heating rate of 3 deg.C/min, cooling the catalyst in nitrogen atmosphere to 60 deg.C for 2 hr, and introducing O at 60 deg.C20.8% of N2Passivating for 10 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 30% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ COMPARATIVE EXAMPLE 1 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 850 ℃ for 8 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain raw powder II; 148 g of raw powder II are weighed and added with MoS by mass percentage2208 g of 25.0 percent ammonium thiomolybdate solution are mixed, and then dried and dehydrated at 80 ℃ to prepare powder III again; and adding 3 g of sesbania powder into the powder III and an aqueous solution containing 3% of nitric acid in percentage by mass according to a mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃, and roasting at 550 ℃ to obtain the catalyst. The catalyst preparation conditions and catalyst compositions are shown in tables 1, 2, 3, 4, 5 and 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
[ COMPARATIVE EXAMPLE 2 ]
Weighing 300 g of pseudo-boehmite powder, and roasting at 850 ℃ for 8 hours to obtain powder I; weighing 160 g of the powder I and pseudo-boehmite powder, and mixing the powder I and the pseudo-boehmite powder according to a mass ratio of 80:20 to obtain raw powder II; weighing 148 g of raw powder II, adding 3 g of sesbania powder into an aqueous solution containing 3% of nitric acid in percentage by mass according to the mass ratio of 100:85, kneading, extruding and forming, drying at 120 ℃, and roasting at 550 ℃ to obtain a catalyst carrier; weighing 74 g of catalyst carrier and Ni in percentage by mass3Mixing nickel hypophosphite with P being 6% with 433 g of an acidic aqueous solution of ammonium hypophosphite, wherein the molar ratio of the nickel hypophosphite to the ammonium hypophosphite in the acidic aqueous solution is 1:0.83, the pH value of the solution is 4 (adjusted by hypophosphorous acid), and dipping to obtain a catalyst precursor; drying the catalyst precursor at 50 deg.C to remove water, heating the catalyst in nitrogen atmosphere at a temperature of 2 deg.C/min for 8 hr, cooling the catalyst in nitrogen atmosphere to 20 deg.C, and introducing O at 20 deg.C2Is 1% of N2Passivating for 16 hours in atmosphere; and washing the passivation product by using an aqueous solution containing 3% of ammonia by mass percent to remove acidic compounds in the catalyst, and washing the catalyst to be neutral by using deionized water to obtain the catalyst. Catalyst preparation conditions and catalyst compositionSee tables 1, 2, 3, 4, 5, 6.
Evaluation of catalyst Activity and feed gas composition [ example 1 ]
The catalyst evaluation results are shown in tables 7 and 8.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
[ examples 12 to 16 ]
The catalyst obtained in example 1 was used for the sulfur tolerant methanation reaction, and the reaction conditions and results are shown in Table 9.
TABLE 9
| Temperature of | Pressure of | Airspeed | Percent conversion of CO% | CH4Selectivity% | |
| Example 12 | 400 | 3.0 | 5000 | 68 | 51 |
| Example 13 | 450 | 5.0 | 4000 | 71 | 53 |
| Example 14 | 500 | 4.0 | 4000 | 73 | 56 |
| Example 15 | 550 | 4.0 | 6000 | 74 | 57 |
| Example 16 | 550 | 4.0 | 6000 | 74 | 51 |
[ examples 17 to 20]
The catalysts prepared in example 1 and the reaction conditions were used, and the catalysts were evaluated under different hydrogen sulfide contents (fixed under other conditions), and the evaluation results are shown in Table 10.
Watch 10
Claims (9)
1. A sulfur-tolerant methanation catalyst comprises the following components in percentage by mass:
a)5～25％MoS2；
b)0.5-3.5％Fe3P；
c)0～5％Ni3P；
d) 75-95% alumina.
2. The sulfur-tolerant methanation catalyst according to claim 1, characterized in that the content of component b) is 1 to 3%.
3. The sulfur-tolerant methanation catalyst according to claim 1, characterized in that the content of component c) is 0.1 to 5%.
4. The sulfur-tolerant methanation catalyst according to claim 3, characterized in that the content of component c) is 1 to 4%.
5. Process for the preparation of a sulfur-tolerant methanation catalyst as claimed in any of claims 1 to 4, comprising the steps of:
(1) pre-roasting pseudo-boehmite powder to obtain powder alpha;
(2) mixing the powder alpha and the pseudo-boehmite powder according to the mass percentage of (95:5) - (50:50) to obtain powder beta; mixing the powder beta with a required amount of ammonium thiomolybdate aqueous solution, and drying to prepare powder gamma;
(3) forming the powder gamma to obtain a catalyst precursor I;
(4) mixing a catalyst precursor I with an acidic aqueous solution containing required amounts of ammonium hypophosphite, nickel hypophosphite, iron hypophosphite and a pH regulator to obtain a catalyst precursor II, and maintaining the pH value to be 3-6, wherein the molar ratio of the nickel hypophosphite or the iron hypophosphite to the ammonium hypophosphite in the acidic aqueous solution is 1 (0.5-3);
(5) heating the catalyst precursor II to 300-600 ℃ in a nitrogen atmosphere, maintaining the temperature for 3-10 hours, and then carrying out thermal decomposition treatment;
(6) and washing the thermal decomposition product by using an aqueous solution containing 0.5-30% of ammonia by mass percent, and removing the residual pH regulator to obtain the catalyst.
6. A sulfur tolerant methanation process wherein a synthesis gas containing hydrogen sulfide as an impurity is subjected to methanation in the presence of the catalyst as claimed in any one of claims 1 to 4.
7. The sulfur-tolerant methanation process according to claim 6, wherein the reaction temperature is 300 to 600 ℃.
8. The sulfur-tolerant methanation process according to claim 6, characterized in that the reaction pressure is from 3.0MPa to 5.0 MPa.
9. The sulfur-tolerant methanation process according to claim 6, characterized in that the volume space velocity of the feedstock is 4000-8000 hours-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495404.1A CN107537536B (en) | 2016-06-29 | 2016-06-29 | Sulfur-tolerant methanation catalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610495404.1A CN107537536B (en) | 2016-06-29 | 2016-06-29 | Sulfur-tolerant methanation catalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107537536A CN107537536A (en) | 2018-01-05 |
| CN107537536B true CN107537536B (en) | 2020-09-04 |
Family
ID=60965516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610495404.1A Active CN107537536B (en) | 2016-06-29 | 2016-06-29 | Sulfur-tolerant methanation catalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107537536B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085225B (en) * | 2018-10-24 | 2022-10-14 | 中国石油化工股份有限公司 | Pre-vulcanized sulfur-tolerant shift methanation catalyst and preparation method thereof |
| US11413611B2 (en) | 2019-12-09 | 2022-08-16 | King Fahd University Of Petroleum And Minerals | Molybdenum sulfide nanosheets decorated with iron phosphide for hydrogen gas evolution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540482A (en) * | 1982-07-20 | 1985-09-10 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
| US4853359A (en) * | 1986-04-23 | 1989-08-01 | Simon Fraser University | Novel transition metal dichalcogenide catalysts |
| CN105582969A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Sulfur-tolerant methanation catalyst and preparation method thereof |
-
2016
- 2016-06-29 CN CN201610495404.1A patent/CN107537536B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540482A (en) * | 1982-07-20 | 1985-09-10 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
| US4853359A (en) * | 1986-04-23 | 1989-08-01 | Simon Fraser University | Novel transition metal dichalcogenide catalysts |
| CN105582969A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Sulfur-tolerant methanation catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘理华等.磷化镍调变MoS2/γ-Al2O3催化剂加氢脱硫性能.《化工学报》.2011,第62卷(第5期),第1296-1301页. * |
| 硫化钼催化剂上甲烷化反应的研究-合成气在MoS2/Al2O3上甲烷化反应的特征;庄叔贤等;《染料化学学报》;19880930;第16卷(第8期);第205-211页 * |
| 磷化镍调变MoS2/γ-Al2O3催化剂加氢脱硫性能;刘理华等;《化工学报》;20110531;第62卷(第5期);第1296-1301页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107537536A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3119667A (en) | Process for hydrogen production | |
| KR101529906B1 (en) | Process for operating hts reactor | |
| CN100551888C (en) | The method of rich hydrocarbon industrial tail gas combined production of methanol, natural gas used for automobile and synthetic ammonia | |
| CN107971026B (en) | Combined catalyst for preparing low-carbon olefin | |
| CN111644175B (en) | Ni-gangue ash catalyst, preparation method thereof and application thereof in tar steam reforming reaction | |
| KR20060132446A (en) | Process for the production of dimethylether from hydrocarbon | |
| CN103864644B (en) | A kind of method preparing cyanobenzene by phenylformic acid gas phase ammonification | |
| KR20130005848A (en) | Iron-cobalt catalyst, manufacturing method same and method for obtaining water-gas shift reaction activity and for highly selective liquid fuel production in fischer-tropsch synthesis using iron-cobalt catalyst | |
| JPS6317118B2 (en) | ||
| CN103769116A (en) | Sulfur tolerant shift catalyst and preparation method | |
| GB1472595A (en) | Process for the preparation of a hydrogenrich gas | |
| JP2014506183A (en) | Method for producing methane synthesis catalyst and catalyst precursor | |
| CN107537536B (en) | Sulfur-tolerant methanation catalyst, preparation method and application thereof | |
| CN111013598A (en) | Catalyst for preparing H2 through methanol steam conversion and application thereof | |
| CN109174110B (en) | Pre-vulcanized sulfur-tolerant methanation catalyst and preparation method thereof | |
| CN103157475B (en) | For the Catalysts and its preparation method of coke-stove gas tri-reforming | |
| CN101703934A (en) | Natural gas catalyst manufactured by coal and manufacturing method thereof | |
| CA1138477A (en) | Methanation of carbon monoxide with improved catalyst regeneration | |
| CN101468311A (en) | Catalyst for methanation of coal gas and preparation method thereof | |
| KR101386418B1 (en) | Catalyst for the steam reforming of methane, method for preparing thereof and method for the steam reforming of methane included in by-product gas of iron manufacture using the catalyst | |
| CN107043089B (en) | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals | |
| CN105582969B (en) | Catalyst for methanation in presence of sulfur and preparation method | |
| CN110015939B (en) | Method and device for producing hydrogen and co-producing methane by coal | |
| CN103897747B (en) | Treatment of water gas from gasification plants | |
| CN107952469B (en) | Bifunctional catalyst and preparation method and application thereof |
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 |