CN103120948A - Biomass heavy-oil hydrocracking catalyst and preparation method thereof - Google Patents
Biomass heavy-oil hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN103120948A CN103120948A CN2011103694082A CN201110369408A CN103120948A CN 103120948 A CN103120948 A CN 103120948A CN 2011103694082 A CN2011103694082 A CN 2011103694082A CN 201110369408 A CN201110369408 A CN 201110369408A CN 103120948 A CN103120948 A CN 103120948A
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a hydrocracking bifunctional catalyst and a preparation method thereof. A hydrogenation function in the catalyst is achieved by an active center composed of noble metal and non-noble metal, and a cracking function is achieved by an acid site on the surface of a catalyst carrier composed of a modification Y molecular screen, an SBA-15, magnesium oxide or boric acid, aluminium oxide and kaolin through pinching in a mixing manner; and the catalyst is characterized in that the noble metal and the non-noble metal can form a hydrogenation activity centre according to the proportion, surface acid concentration and acid strength are adjustable by controlling each component mixture ratio and a preparation process, the balance problem of the hydrogenation function and the cracking function in a hydrocracking reaction process is effectively solved, activity, selectivity, anti-carbon capability, antitoxic capability, and hydrogen consumption of the catalyst are improved, and the service life of the catalyst is prolonged. The catalyst is used for an overhydrocracking reaction of heavy fraction oil and biomass heavy oil.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for the hydrocracking of ether ring compounds, in particular for the Catalysts and its preparation method of bio-oil heavy constituent hydrocracking.
Background technology
Whole world living beings reserves are abundant, are clean renewable resources, and petroleum resources are wretched insufficiency but, develops reproducible biomass resource petroleum replacing resource, are to think at present an effective way that solves the not enough problem of petroleum resources.Living beings Fast Heating under complete anoxia condition makes the rapid pyrolysis of living beings, and the rapid condensation of pyrolysis gas is obtained primary liquid fuel---bio-oil (Bio-oil).The bio-oil that obtains through pyrolysis is the mixture of a kind of moisture and complicated oxygen-bearing organic matter, almost comprises the oxygen-bearing organic matter of all kinds, and oxygen content is up to 20%～40%; Compare with oil, bio-oil has high oxygen content and more complicated composition, and hydrogen, nitrogen, sulfur content are low than oil, do not contain the minor metallic elements such as Ni-V-Fe, antimony, and the bio-oil after upgrading has higher octane number.The bio-oil that hot tearing goes out has the shortcomings such as acid number is high, oxygen content is high, viscosity is large, can not directly use as automotive fuel.In order to reach the target of petroleum replacing resource, the researcher has carried out a large amount of research work to improving the bio-oil grade both at home and abroad.Through studying discovery for a long period of time, the bio-oil cutting that hot tearing is gone out is light component and heavy constituent, with reference to the hydrocracking technology in petrochemical industry, being saturated little molecule alkane with unsaturated lopps compound hydrogenation, cracking in heavy constituent, is an approach that realizes that bio-oil can use in internal combustion engine.Hydrocracking is in petrochemical industry, heavy distillate to be carried out one of main technique of deep processing, and hydrocracking reaction need to have the bifunctional catalyst of hydrogenating function and cracking function, generally is comprised of hydrogenation metal component, carrier, auxiliary agent three parts.The hydrogenation metal component is the main source of hydrotreatment, hydrocracking catalyst hydrogenation activity, and the metal that is fit to hydrogenation component all has cubic lattice or hexagonal lattice, can provide highly active hydrogenation sites in hydrogenation reaction.The hydrogenation component metal is VIB and VIII family metal in periodic table normally, noble metal has Pt, Pd, Rh, Ru etc., base metal has W, Mo, Cr, Fe, Co, Ni etc., and the bimetallic component catalyst of different metal combination preparation is better than monometallic component Hydrogenation.The cracking function that the hydrocracking bifunctional catalyst needs is to be provided by carrier, and cracking and the isomerization function of hydrocracking reaction realized at the solid acid center that mainly provides by acid carrier.To consider the equilibrium problem of feedstock oil characteristic and hydrogenating function and acid function in the hydrocracking catalyst design.Select to be fit to metal component and the suitable carrier of preparation acid centre of feedstock oil hydrogenation, by adding a small amount of conditioning agent (P, B, F, Ti, Zr, Mg, Zn), regulate support, metal component structure and character and active mutually dispersion and type, control the balance of hydrogenating function and acid function, just can improve the activity of catalyst, selective, carbon accumulation resisting ability, poison resistance, hydrogen and consume and the life-span.
Summary of the invention
The object of the present invention is to provide a kind of living beings heavy-oil hydrogenation Cracking catalyst and preparation method thereof.
Hydrocracking technology has the plurality of advantages such as adaptability to raw material is strong, product solution is flexible, liquid product yield is high, good product quality, the present invention is take the petrochemical industry hydrocracking technology as the reference basis, consider characteristic, process characteristic and the product requirement of bio-oil heavy constituent, be intended to develop the effective catalyst that is suitable for the hydrocracking of bio-oil heavy constituent.
At first the present invention considers bio-oil heavy constituent and the difference of oil on forming in Catalyst Design, oil mainly is comprised of the hydrocarbon that accounts for 95%～99%, carbon content 83%～87%, hydrogen content 11%～14%, all the other are sulphur (0.06%～0.8%), nitrogen (0.02%～1.7%), oxygen (0.08%～1.82%) and minor metallic element (Ni-V-Fe etc.), living beings heavy oil carbon content is 60% left and right, oxygen content 20%～40%, hydrogen content 6% left and right, sulphur, nitrogen content are extremely low, substantially do not contain minor metallic element.Living beings heavy oil has that hydrogen content is low, oxygen content is high, viscosity is large, poor stability, composition is take aromatic hydrocarbons and derivative thereof as the shortcoming such as main, by hydrotreatment, can improve hydrogen content and the C/Hratio of living beings heavy oil, increase energy density, strengthen stability and than low viscosity, so the living beings heavy-oil hydrogenation needs the high hydrogenation sites of hydrogenation efficiency, and extremely low sulphur, the nitrogen content of living beings heavy oil can not considered sulphur, the poisoning problem of nitrogen in Catalyst Design, therefore this patent selects VIII family metal as the hydrogenation activity component.
The raw material that the present invention uses is the bio-oil heavy constituent, and mainly by the compositions of mixtures of complicated oxygen-bearing organic matter, molecule is larger, and target product is little molecule monocyclic naphthenes or linear paraffin.Require catalyst to have good cracking function, isomery, cycloreversion reaction occur in the above cyclic hydrocarbon of dicyclo under hydrocracking condition, generate more micromolecular alkane.By control each component proportion of carrier and preparation process and by additive prepare that specific area is large, the aperture is suitable, the catalyst carrier of middle strong acidity, multi-stage artery structure.Catalyst of the present invention and carrier preparation process are: modified Y molecular sieve, SBA-15, auxiliary agent are mixed by proportioning, contact after adding peptizing agent, drying grinds to form powdery, prepares catalyst precarsor A.Aluminium oxide, kaolin, conditioning agent are mixed by proportioning, be placed in successively and contain VIII family's noble metal and non-noble metal water-soluble salt solution floods, drying grinds to form powdery, prepares catalyst precarsor B.Precursor A and B are mixed, add peptizing agent, the extrusion aid kneading; Extruded moulding, drying, roasting is crushed to 10 orders～18 orders, namely gets catalyst sample after low-temperature reduction.It is characterized in that: the acid carrier of cracking function will be provided in catalyst preparation process and provide the activated centre of hydrogenating function to separate preparation.Be that precursor A is the part carrier that the cracking acid site can be provided, precursor B loads on the hydrogenation activity component on this part carrier in Kaolinite Preparation of Catalyst part carrier, and adds simultaneously the conditioning agent of regulating hydrogenation and cracking function balance.
Catalyst activity component of the present invention is VIII family metal, and noble metal is selected one or both in Pt, Pd, Rh, Ru, and base metal is selected a kind of in Fe, Co, Ni; Molybdenum trioxide or tungstic acid in selection of auxiliary group vib metal oxide.
Catalyst carrier of the present invention is comprised of modified Y molecular sieve, SBA-15, aluminium oxide, kaolin, conditioning agent compounding ingredients.
Catalyst of the present invention is take catalyst weight percentage as benchmark, bullion content 0.7%～1.5%, base metal content 2%～7%, auxiliary agent 3%～10%, Y zeolite content 30%～45%, SBA-15 content 11%～20%, alumina content 20%～35%, kaolin content 4%～9%, conditioning agent content 2%～5%.
The present invention utilizes the acidic character of Y zeolite and the meso-hole structure of SBA-15, regulates acid strength and acid concentration by adding conditioning agent, improves the uniformity that the acid site disperses.
The catalyst that the present invention prepares is the bifunctional catalyst with hydrogenation and cracking function, hydrogenating function is by metal active center realization, the cracking function realizes by the acid site on carrier, is the key of this catalyst by adding conditioning agent control hydrogenation activity and lytic activity Proper Match.
The peptizing agent that uses in catalyst preparation process of the present invention is inorganic acid well known in the art, comprises hydrochloric acid, sulfuric acid, nitric acid, oxalic acid.
The concrete preparation process of catalyst precarsor B of the present invention is, first aluminium oxide, kaolin, conditioning agent homogeneous mixture and noble metal water-soluble salt solution flooded, and drying is flooded with the base metal water-soluble salt solution after grinding again, and drying is ground.
The conditioning agent that uses in catalyst preparation process of the present invention is selected magnesia or boric acid.
The extrusion aid that uses in catalyst preparation process of the present invention is selected a kind of in sesbania powder well known in the art, citric acid, cellulose, starch.
In catalyst preparation process of the present invention, the catalyst roasting divides the roasting of two temperatures section, respectively 180 ℃～250 ℃ roastings 1～3 hour and 480 ℃～650 ℃ roastings 2～5 hours.
In catalyst preparation process of the present invention, the catalyst low-temperature reduction is to adopt temperature-programmed mode to carry out under nitrogen atmosphere, it is characterized in that: during reduction, temperature programming is 8 ℃/minute and is raised to 180 ℃, kept 30 minutes, then be raised to 200 ℃～300 ℃ maintenances 2～5 hours with 5 ℃/minute.
The granularity that catalyst of the present invention is fit to the cracking reaction of living beings heavy-oil hydrogenation is 10 orders～18 orders.
Catalyst sample parameter of the present invention is: specific area 690m
2/ g～850m
2/ g, pore volume 0.43ml/g～0.65ml/g, average pore size 8.0nm～12nm, infrared acidity 0.5mmol/g～1.3mmol/g.
The specific embodiment
The Y molecular sieve modification is according to prior art, and the NaY zeolite is carried out the ammonium salt exchange, and hydrothermal treatment consists and acid treatment obtain brilliant bag parameter 2.390nm～2.416nm, and degree of crystallinity is greater than 96%, specific area 780m
2/ g～950m
2/ g, pore volume 0.40ml/g～0.55ml/g, infrared acidity 0.5mmol/g～1.3mmol/g.
Embodiment 1
43 gram modified Y molecular sieves, 17 gram SBA-15,7 gram molybdenum trioxides are mixed, add 4ml red fuming nitric acid (RFNA) and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
20 grams Germany are produced SB aluminium oxide, 5 gram kaolin, 3 gram magnesia mix, be placed in the palladium chloride solution that contains Pd metal 1.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 5.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 6ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 2 gram sesbania powder to mix, and is extruded into Φ 2mm cylindrical bar on banded extruder, is warmed up to 120 ℃ of freeze-day with constant temperature 6 hours with 2 ℃/Min speed.The gained sample is placed in the tubular type kiln roasting, 200 ℃ of roastings after 2 hours again 600 ℃ of roastings 4 hours.After naturally cooling to room temperature, sample is crushed to particle diameter 10 orders～18 orders.Particle diameter 10～18 purpose samples under nitrogen atmosphere, are raised to 180 ℃ with 8 ℃/minute, kept 30 minutes, then be raised to 200 ℃ with 5 ℃/minute and kept 2 hours, gained is catalyst.
Embodiment 2
30 gram modified Y molecular sieves, 20 gram SBA-15,5 gram molybdenum trioxides are mixed, add 6ml concentrated hydrochloric acid and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
30 grams Germany are produced SB aluminium oxide, 4 gram kaolin, 4 gram magnesia mix, be placed in the rhodium chloride solution that contains Rh metal 0.8 gram and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 6.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 9ml concentrated hydrochloric acid and suitable quantity of water, adds 2 gram sesbania powder to mix, and is extruded into Φ 2mm cylindrical bar on banded extruder, is warmed up to 120 ℃ of freeze-day with constant temperature 6 hours with 2 ℃/Min speed.The gained sample is placed in the tubular type kiln roasting, 220 ℃ of roastings after 2 hours again 600 ℃ of roastings 4 hours.After naturally cooling to room temperature, sample is crushed to particle diameter 10 orders～18 orders.Particle diameter 10～18 purpose samples under nitrogen atmosphere, are raised to 180 ℃ with 8 ℃/minute, kept 30 minutes, then be raised to 250 ℃ with 5 ℃/minute and kept 2 hours, gained is catalyst.
Embodiment 3
40 gram modified Y molecular sieves, 15 gram SBA-15,6 gram tungstic acids are mixed, add 5ml red fuming nitric acid (RFNA) and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
25 grams Germany are produced SB aluminium oxide, 4 gram kaolin, 4 gram boric acid mix, be placed in the chloride mixed solution that contains Rh metal 0.7 gram and flood, flood after 12 hours 120 drying 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 5.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 9ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 2 gram sesbania powder to mix, and is extruded into Φ 2mm cylindrical bar on banded extruder, is warmed up to 120 ℃ of freeze-day with constant temperature 6 hours with 2 ℃/Min speed.The gained sample is placed in the tubular type kiln roasting, 250 ℃ of roastings after 2 hours again 550 ℃ of roastings 4 hours.After naturally cooling to room temperature, sample is crushed to particle diameter 10 orders～18 orders.Particle diameter 10～18 purpose samples under nitrogen atmosphere, are raised to 180 ℃ with 8 ℃/minute, kept 30 minutes, then be raised to 250 ℃ with 5 ℃/minute and kept 3 hours, gained is catalyst.
Embodiment 4
38 gram modified Y molecular sieves, 17 gram SBA-15,3 gram tungstic acids are mixed, add 5ml red fuming nitric acid (RFNA) and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
26 grams Germany are produced SB aluminium oxide, 5 gram kaolin, 5 gram boric acid mix, be placed in the chloride mixed solution that contains Rh metal 0.3 gram and contain Pd metal 0.7 gram and flood, flood after 12 hours 120 drying 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 5.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 9ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 2 gram sesbania powder to mix, and is extruded into Φ 2mm cylindrical bar on banded extruder, is warmed up to 120 ℃ of freeze-day with constant temperature 6 hours with 2 ℃/Min speed.The gained sample is placed in the tubular type kiln roasting, 250 ℃ of roastings after 3 hours again 550 ℃ of roastings 4 hours.After naturally cooling to room temperature, sample is crushed to particle diameter 10 orders～18 orders.Particle diameter 10～18 purpose samples under nitrogen atmosphere, are raised to 180 ℃ with 8 ℃/minute, kept 30 minutes, then be raised to 230 ℃ with 5 ℃/minute and kept 4 hours, gained is catalyst.
Embodiment 5
33 gram modified Y molecular sieves, 16 gram SBA-15,6 gram tungstic acids are mixed, add 5ml concentrated hydrochloric acid and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
27 grams Germany are produced SB aluminium oxide, 5 gram kaolin, 6 gram boric acid mix, be placed in the chloride mixed solution that contains Rh metal 0.5 gram and contain Pd metal 1.0 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 5.5 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 9ml concentrated hydrochloric acid and suitable quantity of water, adds 3 gram citric acids to mix, and is extruded into Φ 2mm cylindrical bar on banded extruder, is warmed up to 120 ℃ of freeze-day with constant temperature 6 hours with 2 ℃/Min speed.The gained sample is placed in the tubular type kiln roasting, 250 ℃ of roastings after 2 hours again 500 ℃ of roastings 3 hours.After naturally cooling to room temperature, sample is crushed to particle diameter 10 orders～18 orders.Particle diameter 10～18 purpose samples under nitrogen atmosphere, are raised to 180 ℃ with 8 ℃/minute, kept 30 minutes, then be raised to 250 ℃ with 5 ℃/minute and kept 2 hours, gained is catalyst.
Embodiment 6
35 gram modified Y molecular sieves, 17 gram SBA-15,5 gram molybdenum trioxides are mixed, add 5ml red fuming nitric acid (RFNA) and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
26 grams Germany are produced SB aluminium oxide, 4 gram kaolin, 5 gram boric acid mix, be placed in the chloride mixed solution that contains Rh metal 0.4 gram and contain Pd metal 0.9 gram and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 6.5 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 9ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 3 gram citric acids, mixes, and below operation is identical with corresponding steps operation in example 5.
Embodiment 7
30 gram modified Y molecular sieves, 20 gram SBA-15,9 gram molybdenum trioxides are mixed, add 7ml concentrated hydrochloric acid and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
28 grams Germany are produced SB aluminium oxide, 7 gram kaolin, 2 gram magnesia mix, be placed in the chloride mixed solution that contains Rh metal 0.4 gram and contain Pd metal 0.9 gram and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 3 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 15ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 3 gram citric acids, mixes, and below operation is identical with corresponding steps operation in example 5.
Embodiment 8
42 gram modified Y molecular sieves, 15 gram SBA-15,6 gram molybdenum trioxides are mixed, add 7ml concentrated hydrochloric acid and suitable quantity of water, stir and place after 2 hours 120 ℃ of dryings 12 hours, grind to form powdery.
22 grams Germany are produced SB aluminium oxide, 6 gram kaolin, 4 gram magnesia mix, be placed in the chloride mixed solution that contains Rh metal 0.2 gram and contain Pd metal 0.5 gram and flood, flood after 12 hours 120 ℃ of dryings 12 hours; And then be placed in the nickel acetate solution that contains Ni metal 5 grams and flood, flood after 12 hours 120 ℃ of dryings 12 hours, grind to form at last powdery.
The solid powder that above-mentioned two steps are obtained mixes, and adds 15ml red fuming nitric acid (RFNA) and suitable quantity of water, adds 3 gram citric acids, mixes, and below operation is identical with corresponding steps operation in example 5.
Claims (5)
1. living beings heavy-oil hydrogenation Cracking catalyst, the catalytic hydrogenation activity component is VIII family metal, auxiliary agent is the group vib metal oxide, catalyst carrier is formed by modified Y molecular sieve, SBA-15, aluminium oxide, kaolin, conditioning agent magnesia or boric acid kneading, it is characterized in that: VIII family metal noble metal is selected one or both in Pt, Pd, Rh, Ru, and base metal is selected a kind of in Fe, Co, Ni; Molybdenum trioxide or tungstic acid in selection of auxiliary group vib metal oxide; Take catalyst weight percentage as benchmark, bullion content 0.7%～1.5%, base metal content 2%～7%, auxiliary agent 3%～10%, Y zeolite content 30%～45%, SBA-15 content 11%～20%, alumina content 20%～35%, kaolin content 4%～9%, conditioning agent magnesia or boric acid content 2%～5%.
2. the preparation method of living beings heavy-oil hydrogenation Cracking catalyst according to claim 1, it is characterized in that: modified Y molecular sieve, SBA-15, auxiliary agent are mixed by proportioning, contact drying after adding peptizing agent, grind to form powdery, prepare catalyst precarsor A; Aluminium oxide, kaolin, conditioning agent are mixed by proportioning, be placed in successively and contain VIII family's noble metal and non-noble metal water-soluble salt solution floods, drying grinds to form powdery, prepares catalyst precarsor B; Precursor A and B are mixed, add peptizing agent, the extrusion aid kneading; Extruded moulding, drying, roasting is crushed to 10 orders～18 orders, namely gets catalyst sample after low-temperature reduction.It is characterized in that: the acid carrier of cracking function will be provided in catalyst preparation process and provide the activated centre of hydrogenating function to separate preparation.Be that precursor A is the part carrier that the cracking acid site can be provided, precursor B loads on the hydrogenation activity component on this part carrier in Kaolinite Preparation of Catalyst part carrier, and adds simultaneously the conditioning agent of regulating hydrogenation and cracking function balance.
3. method according to claim 2, it is characterized in that: the catalyst roasting divides the roasting of two temperatures section, respectively 180 ℃～250 ℃ roastings 1～3 hour and 480 ℃～650 ℃ roastings 2～5 hours.
4. method according to claim 2 is characterized in that: catalyst reduction adopts temperature-programmed mode to carry out, and during reduction, temperature programming is 8 ℃/minute and is raised to 180 ℃, keeps 30 minutes, then is raised to 200 ℃～300 ℃ maintenances 2～5 hours with 5 ℃/minute.
5. catalyst according to claim 1, is characterized in that: the specific area 690m of catalyst
2/ g～850m
2/ g, pore volume 0.43ml/g～0.65ml/g, average pore size 8.0nm～12nm, infrared acidity 0.5mmol/g～1.3mmol/g.
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| CN106669782A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method and application thereof |
| CN108067290A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | Carrier and catalyst of a kind of sieve containing bimolecular and its preparation method and application |
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| CN108067287A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of carrier of the molecular sieve containing SBA-15 and its preparation method and application |
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| CN108067287B (en) * | 2016-11-17 | 2021-04-06 | 中国石油化工股份有限公司 | Carrier containing SBA-15 molecular sieve, preparation method and application thereof |
| CN108067290B (en) * | 2016-11-17 | 2021-05-04 | 中国石油化工股份有限公司 | Carrier and catalyst containing bimolecular sieve, and preparation method and application thereof |
| CN109575988A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The method of tar made fuel oil |
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| CN109289903B (en) * | 2018-09-19 | 2020-09-22 | 华南理工大学 | HZSM-5 supported Fe-Pd bimetallic catalyst for lignin depolymerization and preparation method thereof |
| CN116239467A (en) * | 2022-12-13 | 2023-06-09 | 南通宝凯药业有限公司 | Preparation method of high-purity difluoroethyl acetate |
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