CN104475148A - Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof - Google Patents
Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof Download PDFInfo
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Abstract
The invention relates to a coal-oil hydrogenation co-processing catalyst as well as a preparation method and an application method thereof. The catalyst consists of a carrier, an active component and an additive, wherein the specific surface area of the carrier is 300 to 600 m<2>/g, the pore volume of the carrier is 0.5 to 1.0 cm<3>/g, the carrier is one or more of gamma zeolite, beta zeolite, ZSM-5 and KIT-6 powder with the particle size less than 200 micrometers, the active component is iron and nickel, and the additive is one or more of zinc chloride and tin chloride. The preparation method comprises the following steps of preparing the carrier, preparing the active component and preparing the additive. According to the application method of the catalyst, the catalyst and raw material coal powder are mixed and then added into a high pressure reaction kettle together with heavy oil, the addition amount of the catalyst is 0.5 to 5 parts by weight of the total mass of the coal and heavy oil, and the mass ratio of the coal to the oil is 1: 1. The catalyst is large in specific surface area, reasonable in preparation process, little in consumption, high in oil yield after the coal-oil hydrogenation co-processing and safe and convenient to use.
Description
Technical field
The present invention relates to coalification industrial technical field, especially a kind of kerosene hydrogenation refines Catalysts and its preparation method and methods for using them altogether.
Background technology
In recent years, along with development and the economic quick growth of science and technology, society is increasing to the dependence of oil product.But world today's petroleum resources worsening shortages, the heaviness of petroleum resources and in poor quality problem are more and more obvious, are badly in need of the energy and the exploitation efficiency utilization oil new technology that will find petroleum replacing.Heavy oil deep process technology not only effectively can utilize petroleum resources, and can improve the economic benefit of oil-processing enterprises.China is the country of rich coal oil starvation, how rich reserves and cheap coal resources are changed into the important development direction that fluid product becomes coal resources clean utilization, under these circumstances, coal liquefaction, the kerosene hydrogenation technology such as to refine altogether is arisen at the historic moment.
It is the process of the common hydrocracking under catalyst action coal and heavy oil that kerosene hydrogenation refines altogether.Owing to presenting a kind of interaction that heavy oil modification and coal liquefaction are worked in coordination with that promotes between coal and heavy oil, coal-heavy-oil hydrogenation refines altogether and adds separately liquid receipts raising in man-hour than coal or heavy oil, and hydrogen consumption reduces.Meanwhile, coal also promotes removing of metallic element in heavy oil, and high, the unmanageable heavy oil of content of beary metal is utilized.
Catalyst is kerosene hydrogenation one of core technology of refining process altogether, and for reduction reaction severity, improve reaction efficiency, thus reduction kerosene hydrogenation is smelt this altogether, improving its economic competitiveness has very important effect.Fe-series catalyst is due to wide material sources, cheap, can single use and not reclaiming, and discharges, does not form additional effect to environment, become the focus of research at present with liquefied residue.
Patent publication No. is that to be called that the Chinese invention patent application of the oily coal altogether smelting method of catalyst precursor " a kind of be " discloses a kind of take ferrous acetate as the oily coal smelting method altogether of catalyst precursor to CN102311750B name with ferrous acetate, the saturated solution of ferrous acetate is added coal dust, after stirring, through infiltration, dry obtained liquefaction coal sample.Coal sample after process, altogether oil refining, auxiliary agent are pulled an oar together, then carry out reacting under hydrogenation pressurized conditions, be separated and obtain product.The catalyst precursor carrying method of this invention is simple, and do not need precipitation, filter and pre-sulfiding step, catalyst precursor consumption is few, and product oil yield is higher.But product oil yield need further raising.Patent publication No. is that CN102309972B name is called that the Chinese invention patent application of " a kind of oily coal hydrogenation refines catalyst and common smelting method thereof altogether " discloses a kind of oily coal hydrogenation and refines catalyst and common smelting method thereof altogether.This catalyst is made up of major catalyst, secondary catalyst and auxiliary agent.The presoma of major catalyst is water miscible molysite, and the presoma of secondary catalyst is water-soluble and/or oil-soluble molybdenum salt, and the mol ratio of Fe and Mo is 50: 1-200: 1; Described auxiliary agent is Cosan or sulfur-containing compound.The catalyst that this invention provides is the obtained catalyst of method adopting pre-dispersed, solidification, decomposition in situ, has that particle size is little, consumption is few, is uniformly dispersed, activity is high and the oily yield of product is high advantage in system.But catalyst molybdenum not easily reclaims, product oil yield need further raising.
Summary of the invention
First technical problem to be solved by this invention provides for above-mentioned prior art present situation the catalyst that a kind of kerosene hydrogenation refines altogether, this catalyst carrier has that specific area is large, catalyst activity component is evenly distributed, consumption is few, catalyst promoter is conducive to coal liquefaction, promotes that kerosene hydrogenation refines altogether.
The technical scheme that first technical problem to be solved by this invention adopts is: this kerosene hydrogenation refines catalyst altogether, and the formula of described catalyst is made up of carrier, active component and auxiliary agent, it is characterized in that: the specific area of described carrier is 300 ~ 600m
2/ g, pore volume is 0.5 ~ 1.0cm
3/ g, described carrier is γ zeolite, β zeolite, one or more in ZSM-5, KIT-6 powder that particle diameter is less than 200 microns, and described active component is iron and nickel, and described auxiliary agent is one or more in zinc chloride, stannic chloride, and above-mentioned is mass parts.
As improvement, described carrier is containing 80 ~ 95 parts of catalyst gross mass, and described active component is containing 5 ~ 15 parts of catalyst gross mass, and described auxiliary agent is containing 1 ~ 5 part of catalyst gross mass.
As improvement, in described active component, ferro element is containing 5 ~ 10 parts of catalyst gross mass, and nickel element is containing 1 ~ 5 part of catalyst gross mass, and above-mentioned is mass parts.
Second technical problem to be solved by this invention provides a kind of rational technology for above-mentioned prior art present situation, and catalyst amount is few, and kerosene hydrogenation refines the preparation method that the high kerosene hydrogenation of rear oil productivity refines catalyst altogether altogether.
The technical scheme that second technical problem to be solved by this invention adopts is: the preparation method of above-mentioned catalyst, is characterized in that: by following steps:
One, by the formula of carrier, carrier is joined in the Containing Zinc Chloride of amount of calculation or the weakly acidic solution of stannic chloride, washing after 1 ~ 4 hour is stirred in 30 ~ 90 DEG C, then by the carrier after washing in the temperature of 80 ~ 150 DEG C dry 1 ~ 6 hour, i.e. obtained carrier;
Two, by the formula of molysite and nickel salt, molysite and nickel salt are mixedly configured into the aqueous solution, carrier step one prepared is flood 1 ~ 8 hour in the aqueous solution of the molysite of 30 ~ 90 DEG C and nickel salt in temperature, then the carrier after dipping is filtered, weakly alkaline solution is added again by the carrier after filtration, stir 1 ~ 4 hour, then put into dry 4 ~ 18 hours of the temperature of 80 ~ 150 DEG C, namely make containing active component;
Three, the catalyst that step 2 is obtained is carried out sulfuration 1 ~ 4 hour under temperature 100 ~ 300 DEG C of vulcanizing agent effects, namely obtain the finished catalyst with hydrogenation activity.
As improvement, the weakly acidic solution of described Containing Zinc Chloride or stannic chloride can acetic acid preferably containing zinc chloride or stannic chloride, carbonic acid, one or more in hydrosulphuric acid solution, and the pH value of described weakly acidic solution can be preferably 5 ~ 7.
As improvement, described molysite may be selected to be in iron chloride, frerrous chloride, ferric sulfate, ferric nitrate, ferrous acetate one or more, one or more in described nickel salt nickel nitrate, nickelous sulfate, nickel acetate.
As improvement, described weakly alkaline solution may be selected to be in sodium carbonate, sodium acid carbonate, sodium acetate, sodium citrate aqueous solution one or more, the pH value of described weakly alkaline solution is 8 ~ 10..
As improvement, described vulcanizing agent may be selected to be in carbon disulfide, DMDS, dimethyl sulfide one or more.
Improve again, in described step one, the carrier after washing is in the baking oven of 80 ~ 150 DEG C dry 1 ~ 6 hour in temperature, in described step 2, stirring the carrier after 1 ~ 4 hour, to be placed on temperature be in the baking oven of 80 ~ 150 DEG C dry 4 ~ 18 hours, namely makes the catalyst containing active component.
3rd technical problem to be solved by this invention is the application process of catalyst providing a kind of simple to operate, preparation safety for above-mentioned prior art present situation.
The technical scheme that 3rd technical problem to be solved by this invention adopts is: the application process of above-mentioned catalyst, it is characterized in that: described catalyst adds autoclave after mixing with raw material coal dust together with heavy oil, described raw material coal dust is one or more in brown coal, jet coal, bottle coal, gas-rich coal, described heavy oil is one or more in reduced crude, decompression residuum, tar asphalt, the addition of described catalyst is 0.5 ~ 5 part of coal and oily gross mass, the mass ratio of described coal and oil is 1: 1, and above-mentioned is mass parts.
Compared with prior art, the advantage of catalyst of the present invention is: carrier selects molecular sieve, and specific area is large, mild acidity, and the catalyst made not only has good hydrogenation cracking activity, and the easily separated recovery of catalyst; Selection of auxiliary zinc chloride or stannic chloride, have and utilize promotion lique faction of coal, improve the production rate of coal liquifaction; Active component selects the compound of iron and nickel, and hydrogenation cracking activity is high, and consumption is few, and this catalyst has excellent kerosene hydrogenation and refines the performance generating light oil altogether.Auxiliary agent zinc chloride or stannic chloride are first immersed on molecular sieve carrier by the preparation method of catalyst of the present invention under mildly acidic conditions, the presoma of impregnated activated component of iron and nickel after washing drying, and with weakly alkaline solution, iron and nickel are fixed on carrier, obtain the catalyst containing active component after drying, finally by obtaining the finished catalyst with hydrogenation cracking activity after vulcanizing treatment.The method is rational technology not only, and obtained catalyst activity is high, and consumption is few, and it is high that kerosene hydrogenation refines rear product oil yield altogether.The present invention also provides a kind of application process of catalyst of simple to operate, preparation safety.
Detailed description of the invention
Below the present invention is described in further detail;
The kerosene hydrogenation of the present embodiment refines catalyst altogether, and the formula of described catalyst is made up of carrier, active component and auxiliary agent, and the specific area of described carrier is 300 ~ 600m
2/ g, pore volume is 0.5 ~ 1.0cm
3/ g, described carrier is γ zeolite, β zeolite, one or more in ZSM-5, KIT-6 powder that particle diameter is less than 200 microns, described active component is iron and nickel, described auxiliary agent is one or more in zinc chloride, stannic chloride, described carrier is containing 80 ~ 95 parts of catalyst gross mass, described active component is containing 5 ~ 15 parts of catalyst gross mass, described auxiliary agent is containing 1 ~ 5 part of catalyst gross mass, in described active component, ferro element is containing 5 ~ 10 parts of catalyst gross mass, nickel element is containing 1 ~ 5 part of catalyst gross mass, and above-mentioned is mass parts.The specific area of described carrier refers to the surface area that unit mass carrier has, described pore volume refers to the pore total measurement (volume) that unit mass carrier has, described Y zeolite refers to that one has three-dimensional supercage structure, the Si-Al zeolite of cubic system, described β zeolite refers to a kind of silica-rich zeolite with three-dimensional twelve-ring pore structure, its design feature is two four-membered rings and four pentacyclic pair hexatomic ring unit bug hole structure, described ZSM-5 powder refer to a kind of form complexity and there is special crystalline form select shape zeolite molecular sieve, it is the known technology of the art, industrially just be this name.KIT-6 powder refers to a kind of porous silica material with nanostructured, is also the known technology of the art, is industrially just this name.
The preparation method of above-mentioned catalyst, by following steps:
One, by the formula of carrier, carrier is joined in the Containing Zinc Chloride of amount of calculation or the weakly acidic solution of stannic chloride, washing after 1 ~ 4 hour is stirred in 30 ~ 90 DEG C, then by the carrier after washing in the temperature of 80 ~ 150 DEG C dry 1 ~ 6 hour, i.e. obtained carrier;
Two, by the formula of molysite and nickel salt, molysite and nickel salt are mixedly configured into the aqueous solution, carrier step one prepared is flood 1 ~ 8 hour in the aqueous solution of the molysite of 30 ~ 90 DEG C and nickel salt in temperature, then the carrier after dipping is filtered, weakly alkaline solution is added again by the carrier after filtration, stir 1 ~ 4 hour, then put into dry 4 ~ 18 hours of the temperature of 80 ~ 150 DEG C, namely make the catalyst containing active component;
Three, the catalyst that step 2 is obtained is carried out sulfuration 1 ~ 4 hour under temperature 100 ~ 300 DEG C of vulcanizing agent effects, namely obtain the finished catalyst with hydrogenation activity.The weakly acidic solution of described Containing Zinc Chloride or stannic chloride is one or more in acetic acid containing zinc chloride or stannic chloride, carbonic acid, hydrosulphuric acid solution, and the pH value of described weakly acidic solution is 5 ~ 7.Described molysite is one or more in iron chloride, frerrous chloride, ferric sulfate, ferric nitrate, ferrous acetate, one or more in described nickel salt nickel nitrate, nickelous sulfate, nickel acetate.Described weakly alkaline solution is one or more in sodium carbonate, sodium acid carbonate, sodium acetate, sodium citrate aqueous solution, and the pH value of described weakly alkaline solution is 8 ~ 10.Described vulcanizing agent is one or more in carbon disulfide, DMDS, dimethyl sulfide, in described step one, carrier after washing is in the baking oven of 80 ~ 150 DEG C dry 1 ~ 6 hour in temperature, in described step 2, stirring the carrier after 1 ~ 4 hour, to be placed on temperature be in the baking oven of 80 ~ 150 DEG C dry 4 ~ 18 hours, namely makes the catalyst containing active component.
The application process of above-mentioned catalyst, described catalyst adds autoclave after mixing with raw material coal dust together with heavy oil, described raw material coal dust is one or more in brown coal, jet coal, bottle coal, gas-rich coal, described heavy oil is one or more in reduced crude, decompression residuum, tar asphalt, the addition of described catalyst is 0.5 ~ 5 part of coal and oily gross mass, the mass ratio of described coal and heavy oil is 1: 1, and above-mentioned is mass parts.
Below in conjunction with embodiment, the present invention is described in further detail.
Below in an example, the kerosene hydrogenation of catalyst C1 ~ C4 obtained by application the present invention refines catalyst altogether.Embodiment 1 ~ 4 is the preparation of hydrocracking catalyst of the present invention, and embodiment 5 is that the kerosene hydrogenation of catalyst refines performance evaluation altogether.
Embodiment 1
Get amount of calculation γ zeolite, join (pH is 6.0) in the acetum of the Containing Zinc Chloride of amount of calculation, in 60 DEG C, stir washing after 2 hours, to put in 120 DEG C of baking ovens dry 2 hours, obtain the carrier containing auxiliary agent.
Get iron chloride and the nickelous sulfate of amount of calculation, be mixedly configured into the aqueous solution, by the carrier containing auxiliary agent of above-mentioned preparation, be flood 4 hours in the aqueous solution of the iron chloride of 80 DEG C and nickelous sulfate in temperature, a small amount of sodium carbonate liquor (pH is 10.0) is added in carrier after filtering, stir 2 hours, then put into 150 DEG C of baking ovens dry 8 hours, namely make the catalyst containing active component.
Above-mentioned obtained catalyst is carried out sulfuration under temperature 200 DEG C of carbon disulfide effects, finally obtains the finished catalyst C1 with hydrogenation activity.
Embodiment 2
Get amount of calculation β zeolite, join (pH is 6.0) in the acetum of the Containing Zinc Chloride of amount of calculation, in 60 DEG C, stir washing after 3 hours, to put in 120 DEG C of baking ovens dry 3 hours, obtain the carrier containing auxiliary agent.
Get frerrous chloride and the nickel nitrate of amount of calculation, be mixedly configured into the aqueous solution, by the carrier containing auxiliary agent of above-mentioned preparation, be flood 4 hours in the aqueous solution of the frerrous chloride of 70 DEG C and nickel nitrate in temperature, a small amount of sodium carbonate liquor (pH is 10.0) is added in carrier after filtering, stir 3 hours, then put into 150 DEG C of baking ovens dry 12 hours, namely make the catalyst containing active component.
Above-mentioned obtained catalyst is carried out sulfuration under temperature 250 DEG C of DMDS effects, finally obtains the finished catalyst C2 with hydrogenation activity.
Embodiment 3
Get amount of calculation KIT-6 powder, join (pH is 5.0) in the acetum of the chloride containing tin of amount of calculation, in 60 DEG C, stir washing after 2 hours, to put in 130 DEG C of baking ovens dry 3 hours, obtain the carrier containing auxiliary agent.
Get ferric nitrate and the nickel nitrate of amount of calculation, be mixedly configured into the aqueous solution, by the carrier containing auxiliary agent of above-mentioned preparation, be flood 6 hours in the aqueous solution of the ferric nitrate of 80 DEG C and nickel nitrate in temperature, a small amount of SAS (pH is 10.0) is added in carrier after filtering, stir 4 hours, then put into 150 DEG C of baking ovens dry 12 hours, namely make the catalyst containing active component.
Above-mentioned obtained catalyst is carried out sulfuration under temperature 200 DEG C of carbon disulfide effects, finally obtains the finished catalyst C3 with hydrogenation activity.
Embodiment 4
Get amount of calculation γ zeolite and ZSM-5, join (pH is 5.0) in the Containing Zinc Chloride of amount of calculation and the hydrosulphuric acid solution of stannic chloride, in 80 DEG C, stir washing after 2 hours, to put in 120 DEG C of baking ovens dry 4 hours, obtain the carrier containing auxiliary agent.
Get ferric sulfate and the nickelous sulfate of amount of calculation, be mixedly configured into the aqueous solution, by the carrier containing auxiliary agent of above-mentioned preparation, be flood 4 hours in the aqueous solution of the ferric sulfate of 80 DEG C and nickelous sulfate in temperature, a small amount of SAS (pH is 9.5) is added in carrier after filtering, stir 3 hours, then put into 150 DEG C of baking ovens dry 12 hours, namely make the catalyst containing active component.
Above-mentioned obtained catalyst is carried out sulfuration under temperature 250 DEG C of carbon disulfide effects, finally obtains the finished catalyst C4 with hydrogenation activity.
In above-mentioned four embodiments, the main physical and chemical of catalyst C1, C2, C3, C4 is shown in as following table 1.
In table 1 embodiment, kerosene hydrogenation refines the main physical and chemical of catalyst altogether
Embodiment 5
Kerosene hydrogenation of the present invention refines the performance evaluation of catalyst altogether, take autoclave as evaluating apparatus.With brown coal and decompression residuum for raw material, feedstock property is in table 2, and the mass ratio of coal and oil is 1: 1, and catalyst charge is 1% of coal and oily gross mass.The evaluation method that kerosene hydrogenation refines altogether is: import autoclave after being mixed with coal dust by catalyst together with decompression residuum, after displacement gas reactor, fills hydrogen and closes to 10.0MPa.Be warmed up to 450 DEG C of reactions cooling after 2 hours, collect gas reactor and liquid and analyze, still inner catalyst centrifuge washing reclaims, and adopt said method evaluate catalysts C1, C2, C3, C4 respectively, evaluation result is in table 3.Conversion ratio in table and oily yield data are all with coal and refine oil sum altogether for Calculation Basis.
Conversion ratio=(tetrahydrofuran insoluble SOLID ORGANIC matter in 1-product/(coal+oil refining altogether)) × 100%
N-hexane organic matter/(coal+oil refining altogether) × 100% is dissolved in oil yield=product
Table 2 feed coal and character of refining oil altogether
| Analysis project | Brown coal | Decompression residuum |
| C，wt％ | 71.3 | 81.5 |
| H，wt％ | 6.8 | 11.8 |
| O，wt％ | 18.5 | 3.2 |
| N，wt％ | 2.4 | 1.3 |
| S，wt％ | 1.0 | 2.1 |
| Density (20 DEG C), g/cm 3 | 1.31 | 0.998 |
Table 3 kerosene hydrogenation refines evaluation result altogether
| Catalyst | Conversion ratio, wt% | Oil yield, wt% |
| C1 | 95.6 | 75.4 |
| C2 | 94.5 | 72.3 |
| C3 | 98.7 | 79.6 |
| C4 | 97.2 | 77.5 |
As can be seen from Table 3, catalyst of the present invention has good kerosene hydrogenation and refines catalytic cracking activity altogether, conversion rate of products and oily yield high.
Claims (10)
1. kerosene hydrogenation refines a catalyst altogether, and the formula of described catalyst is made up of carrier, active component and auxiliary agent, it is characterized in that: the specific area of described carrier is 300 ~ 600m
2/ g, pore volume is 0.5 ~ 1.0cm
3/ g, described carrier is γ zeolite, β zeolite, one or more in ZSM-5, KIT-6 powder that particle diameter is less than 200 microns, and described active component is iron and nickel, and described auxiliary agent is one or more in zinc chloride, stannic chloride, and above-mentioned is mass parts.
2. catalyst according to claim 1, is characterized in that: described carrier is containing 80 ~ 95 parts of catalyst gross mass, and described active component is containing 5 ~ 15 parts of catalyst gross mass, and described auxiliary agent is containing 1 ~ 5 part of catalyst gross mass.
3. catalyst according to claim 1, is characterized in that: in described active component, ferro element is containing 5 ~ 10 parts of catalyst gross mass, and nickel element is containing 1 ~ 5 part of catalyst gross mass, and above-mentioned is mass parts.
4. the preparation method of arbitrary described catalyst in claims 1 to 3, is characterized in that: by following steps:
One, by the formula of carrier, carrier is joined in the Containing Zinc Chloride of amount of calculation or the weakly acidic solution of stannic chloride, washing after 1 ~ 4 hour is stirred in 30 ~ 90 DEG C, then by the carrier after washing in the temperature of 80 ~ 150 DEG C dry 1 ~ 6 hour, i.e. obtained carrier;
Two, by the formula of molysite and nickel salt, molysite and nickel salt are mixedly configured into the aqueous solution, carrier step one prepared is flood 1 ~ 8 hour in the aqueous solution of the molysite of 30 ~ 90 DEG C and nickel salt in temperature, then the carrier after dipping is filtered, weakly alkaline solution is added again by the carrier after filtration, stir 1 ~ 4 hour, then put into dry 4 ~ 18 hours of the temperature of 80 ~ 150 DEG C, namely make the catalyst containing active component;
Three, the catalyst that step 2 is obtained is carried out sulfuration 1 ~ 4 hour under temperature 100 ~ 300 DEG C of vulcanizing agent effects, namely obtain the finished catalyst with hydrogenation activity.
5. preparation method according to claim 4, it is characterized in that: the weakly acidic solution of described Containing Zinc Chloride or stannic chloride is one or more in acetic acid containing zinc chloride or stannic chloride, carbonic acid, hydrosulphuric acid solution, and the pH value of described weakly acidic solution is 5 ~ 7.
6. preparation method according to claim 4, is characterized in that: described molysite is one or more in iron chloride, frerrous chloride, ferric sulfate, ferric nitrate, ferrous acetate, one or more in described nickel salt nickel nitrate, nickelous sulfate, nickel acetate.
7. preparation method according to claim 4, is characterized in that: described weakly alkaline solution is one or more in sodium carbonate, sodium acid carbonate, sodium acetate, sodium citrate aqueous solution, and the pH value of described weakly alkaline solution is 8 ~ 10..
8. preparation method according to claim 4, is characterized in that: described vulcanizing agent is one or more in carbon disulfide, DMDS, dimethyl sulfide.
9. preparation method according to claim 4, it is characterized in that: in described step one, carrier after washing is in the baking oven of 80 ~ 150 DEG C dry 1 ~ 6 hour in temperature, in described step 2, stirring the carrier after 1 ~ 4 hour, to be placed on temperature be in the baking oven of 80 ~ 150 DEG C dry 4 ~ 18 hours, namely makes the catalyst containing active component.
10. the application process according to described catalyst arbitrary in claims 1 to 3, it is characterized in that: described catalyst adds autoclave after mixing with raw material coal dust together with heavy oil, described raw material coal dust is one or more in brown coal, jet coal, bottle coal, gas-rich coal, described heavy oil is one or more in reduced crude, decompression residuum, tar asphalt, the addition of described catalyst is 0.5 ~ 5 part of coal and oily gross mass, the mass ratio of described coal and heavy oil is 1: 1, and above-mentioned is mass parts.
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| CN112973718A (en) * | 2021-02-22 | 2021-06-18 | 安徽工业大学 | Kerosene co-hydrogenation catalyst and preparation method thereof |
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