CN113908838B - Preparation method of oleophylic Fe-based suspension bed hydrocracking catalyst - Google Patents
Preparation method of oleophylic Fe-based suspension bed hydrocracking catalyst Download PDFInfo
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- CN113908838B CN113908838B CN202111344021.1A CN202111344021A CN113908838B CN 113908838 B CN113908838 B CN 113908838B CN 202111344021 A CN202111344021 A CN 202111344021A CN 113908838 B CN113908838 B CN 113908838B
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- mesoporous
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000000725 suspension Substances 0.000 title claims abstract description 32
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008117 stearic acid Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000000428 dust Substances 0.000 claims abstract description 3
- 239000002023 wood Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 238000001556 precipitation Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 7
- 239000000571 coke Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkane carboxylic acid Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a lipophilic Fe-based suspension bed hydrocracking catalyst, which comprises the steps of preparing ferric oxide with a mesoporous structure by taking waste wood dust as a template agent through a hydrothermal-precipitation method, and carrying out surface modification on the ferric oxide by using macromolecular organic matters (such as stearic acid and the like) to obtain the lipophilic ferric oxide catalyst. The prepared catalyst has lipophilicity, is used for hydrocracking reaction of inferior heavy oil suspension bed, shows good reaction performance, effectively inhibits coke and gas generation, and improves the yield of liquid distillate.
Description
Technical Field
The invention belongs to the technical field of hydrocracking in petrochemical industry, and particularly relates to a preparation method of an oleophylic Fe-based suspension bed hydrocracking catalyst.
Background
In recent years, the reserves of conventional crude oil are rapidly reduced, the trend of heavy and poor quality is increased, and the market demand for light fuel oil such as gasoline, diesel oil and aviation kerosene is continuously increased. Thus, efficient conversion of heavy oils is of great importance for satisfying energy supplies. The heavy oil molecules have complex composition, high viscosity, high density, high content of sulfur, nitrogen and metal impurities, and great difficulty in efficient conversion. Currently, hydrotreating and hydrocracking are the most effective means for removing impurities and upgrading heavy oil. In the existing hydrogenation process, the suspension bed hydrogenation technology has the advantages of strong raw material adaptability, high light product yield and the like, becomes a hot spot and a key point of research in the oil refining industry, and has good application prospect. The core of the suspension bed hydrocracking technology is a catalyst, which mainly comprises: homogeneous catalysts and heterogeneous catalysts, wherein the homogeneous catalysts include water-soluble and oil-soluble catalysts, the heterogeneous catalysts are typically solid powder catalysts. The water-soluble catalyst is mainly an emulsion formed by mixing molybdate solution and organic matters. The catalyst needs to be dispersed, emulsified, dehydrated and other steps before use, and the pretreatment is quite complex. The oil-soluble catalyst is prepared by reacting metal salt with organic solvent to form organic metal salt, such as molybdenum naphthenate, molybdenum isooctanoate, etc., and has high hydrogenation activity and less coke formation, but the catalyst has high production cost due to the inclusion of metal Mo and organic matters. Solid powder catalysts are generally classified into natural mineral powder catalysts and supported catalysts of metals Mo, ni, co, etc. The natural mineral powder catalyst is mainly natural ore rich in Fe, the price of the catalyst is extremely low, but the catalyst has poor catalytic activity and is not suitable for being independently used as a suspension bed hydrocracking catalyst; the catalyst of transition metal loaded on alumina, amorphous silicon aluminum, molecular sieve, coke and the like has higher catalytic activity, but the production cost is high due to the use of transition metal Mo, co and the like. For this reason, a new generation of catalysts needs to be developed to meet the needs of the suspension hydrocracking industry application.
The Fe oxide has low price and hydrogenation activity, and has been widely used in the Fischer-Tropsch synthesis industry. However, the density of the iron oxide is large, the porosity is small, and the requirement of the suspension bed hydrocracking reaction is difficult to meet. Therefore, the invention designs and develops the lipophilic mesoporous ferric oxide for the suspension bed hydrocracking reaction, and the catalyst has high dispersibility in heavy oil, so that the catalyst is maximally utilized. Meanwhile, the abundant pore structure is beneficial to the diffusion mass transfer of macromolecules.
Some reports have been made on the preparation of lipophilic solid powder, esmaiel Soleimani and the like, which use palmitic acid to modify CuO nano catalystThe catalyst is prepared by photocatalytic methyl orange degradation [ Esmaiel Soleimani, roghiyeh Taheri, nano-Structure& Nano-Objects,10(2017) 167–175]. The palmitic acid layer adheres to the CuO surface to suspend it in the methyl orange solution. The modified nano CuO has improved hydrophobicity and lipophilicity, and the modification method is simple physical adsorption. CN1657410a discloses a nano SiO 2 Surface modification method, which is to modify SiO 2 Placing the mixture into a solution, and dripping 4-6 times of silane coupling agent under the high temperature condition to obtain lipophilic nano SiO 2 . The preparation process uses a large amount of modifier, has high production cost and is not suitable for large-scale production. CN109370265a discloses a surface oleophylic modification method of nano silicon dioxide, which comprises the following preparation processes: adding silicon dioxide and trimethyl siloxane modifier into alkaline solution to carry out surface grafting reaction, so as to graft long carbon chain alkyl structure on the surface of the silicon dioxide, and obtain the surface oleophylic silicon dioxide. CN1872918A discloses a method for modifying inorganic micro-powder by lipophilicity, which uses inorganic micro-oxide or inorganic nano-powder-oxide intermediate to carry out surface coating treatment under different pH conditions by selecting different organic matters, thereby obtaining the surface lipophilicity modified nano-composite powder. CN107629471a discloses a method for preparing lipophilic type nano titanium dioxide by modifying nano titanium dioxide, which comprises the steps of adding titanium dioxide into an aqueous solution under a certain state, and adding a silane coupling agent into the titanium dioxide solution to synthesize the lipophilic type nano titanium dioxide. The asphalt emulsion has the advantages of long storage time and good dispersibility when being applied to emulsified asphalt. However, the silane coupling agent is easy to generate hydrolysis reaction when being exposed in an aqueous phase system. EP2736052A1 discloses an organic modification of the surface of metal and metal oxide materials and a process for their preparation by coating the surface of an inorganic metal or metal oxide with an organic substance, mainly an organic compound of an amine group or derivative thereof, which forms a strong chemical bond with the inorganic metal or metal oxide. UO20200056049A1 discloses a preparation method of novel hydrophobic and oleophylic alumina, which comprises the following preparation processes: organic composition containing an alkane carboxylic acid having less than 10 carbon atoms and a catalyst comprisingMixing alumina compound slurry, forming acid modified slurry under the condition that the pH value is more than 7, and obtaining the hydrophobic and oleophylic alumina material after hydrothermal treatment.
The preparation method of the hydrophobic oleophilic inorganic powder is more severe in implementation conditions, and no report is published about the preparation of the oil-soluble mesoporous iron oxide catalyst suitable for suspension bed hydrocracking. The invention aims to prepare a lipophilic mesoporous ferric oxide suspension bed hydrocracking catalyst through surface interface modification, which takes self-made mesoporous gamma-ferric oxide as a matrix, adopts a solvothermal method to prepare the lipophilic mesoporous ferric oxide suspension bed hydrocracking catalyst in the presence of organic matters or organic solvents/water, and the lipophilic catalyst prepared in the hydrocracking reaction shows good reaction performance compared with a solid powder catalyst, improves the yield of liquid products, and effectively reduces the yield of gas and coke.
Disclosure of Invention
The invention aims to provide a preparation method of an oleophylic Fe-based suspension bed hydrocracking catalyst, which is used for improving the reactivity of the catalyst in suspension bed hydrocracking processing of inferior heavy oil.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the oleophylic Fe-based suspension bed hydrocracking catalyst adopts a hydrothermal-coprecipitation method to obtain mesoporous ferric oxide powder, the surface of the mesoporous ferric oxide is modified by a solvothermal method, and the oleophylic mesoporous ferric oxide catalyst is obtained by regulating and controlling the types and the use amount of organic matters and changing the reaction temperature and time, and the preparation method comprises the following steps:
(1) Adding ethanol, deionized water solution, isopropanol and acetic acid with the mass ratio of 1:3 into wood dust powder, and stirring for several hours at a certain temperature;
(2) Dropwise adding an alkaline solution into an iron salt solution, vigorously stirring to form a dark red suspension, stirring for 5-10 min, and adding the mixed solution obtained in the step (1) into the suspension to form a gel solution;
(3) Drying the gel obtained in the step (2) in a baking oven at 100-180 ℃ for several hours, and roasting the gel at 300-600 ℃ in an air atmosphere for 2-12 h to obtain an iron oxide sample;
(4) Adding an organic modifier into a solvent to prepare an organic solution with the mass fraction of 0.5-25%;
(5) Adding the ferric oxide material obtained in the step (4) into an organic solution, fully stirring at 30-80 ℃ for 0.5-12 h, and carrying out ultrasonic treatment for 20 min;
(6) Transferring the obtained solution to a crystallization kettle, and reacting for several hours at 100-200 ℃;
(7) And (3) centrifuging or filtering the reaction liquid, and drying at 50-150 ℃ to obtain the surface oleophylic ferric oxide catalyst.
The hydrothermal temperature of the step (1) is 30-80 ℃, and the stirring time is 1-3 h.
The pH value of the suspension system formed in the step (2) is maintained between 7 and 12.
Drying the gel liquid in the step (3) in an oven at 100-180 ℃ for 1-8 h; the roasting temperature is 300-600 ℃ and the roasting time is 2-12 h.
The organic modifier in the step (4) is one or two of palmitic acid, stearic acid, oleic acid, lauric acid, p-methylbenzoic acid, m-methylbenzoic acid, sodium stearate and caprylic acid;
and (3) preparing the organic solution with the mass fraction of 0.5-25%.
The hydrothermal temperature in the step (5) is 30-80 ℃, and the stirring time is 0.5-6 h.
The reaction temperature in the step (6) is not higher than 200 ℃, and the reaction time is 2-48 and h.
And (3) the separation process in the step (7) is ethanol centrifugation or filtration washing, the drying temperature is not lower than 60 ℃, and the drying time is not lower than 12h.
The specific application of the oleophylic mesoporous ferric oxide suspension bed hydrocracking catalyst obtained by the method is as follows: mixing inferior heavy oil and a lipophilic mesoporous ferric oxide suspension bed hydrocracking catalyst, and placing the mixture into a batch reaction kettle of a simulated suspension bed reactor under the reaction conditions of: the reaction temperature is 400-440 ℃ (preferably 410-430 ℃), the initial hydrogen pressure is 5-11 MPa (preferably 9-11 MPa), the stirring rotation speed is 200-1000 r/min (preferably 500-800 r/min), the vulcanization time is 1-6 h, the catalyst dosage is 0.5-10%, and the reaction performance of the catalyst is evaluated.
The invention has the beneficial effects that:
1) The method screens the organic matters and controls the lipophilicity of the oil-soluble mesoporous iron oxide catalyst by regulating and controlling the concentration of the organic matters, and the catalyst has good dispersion performance and thermal stability in organic solutions such as gasoline, toluene, residual oil and the like.
2) The lipophilic mesoporous ferric oxide prepared by the invention can be effectively dispersed into inferior residuum, has better coking inhibition in the residuum hydrocracking process, and simultaneously improves the liquid distillate oil yield and the crude oil conversion rate.
3) The lipophilic mesoporous ferric oxide prepared by the invention has the advantages of green and simple preparation process of the material, low raw material price, suitability for large-scale production and good application prospect in industry.
Drawings
FIG. 1 is an XRD spectrum of the lipophilic mesoporous iron oxide obtained in example 1 and example 2 and the mesoporous iron oxide obtained in comparative example.
FIG. 2 is a graph showing the examination of dispersibility of the lipophilic mesoporous iron oxides obtained in example 1 and example 2 and the mesoporous iron oxides obtained in comparative examples.
FIG. 3 is a Fourier transform infrared spectrum of the lipophilic mesoporous iron oxide obtained in example 1, example 2 and the mesoporous iron oxide obtained in comparative example.
FIG. 4 shows N of the lipophilic mesoporous iron oxides obtained in example 1 and example 2 and the mesoporous iron oxides obtained in comparative example 2 Adsorption and desorption of the attached drawings.
Detailed Description
In order to further understand the present invention, the following examples will be used to describe the lipophilic mesoporous iron oxide according to the present invention with reference to the accompanying drawings.
Comparative example
4.0 g chip powder and 5.0 g acetic acid were added to 45 mL m Ethanol :m Water and its preparation method =1: 3, adding 2.0. 2.0 g isopropanol, stirring at 80deg.C for 2h formsForming solution A. 0.10 mol FeCl 3 •6H 2 O is dissolved in 40 mL deionized water, and stirred at 80 ℃ for 1 h to prepare 2 mol/L FeCl 3 Solution B; 2.0 mol/L NaOH alkaline solution is prepared and dropwise added into the solution B to form reddish brown precipitate, and the dropwise addition of the alkaline solution is stopped until the pH value is 10 to form solution C. Adding the solution A into the solution C to form reddish brown gel solution, and stirring for 5 min. Standing at normal temperature for 2h, drying, transferring to a muffle furnace, roasting for 3 h at 500 ℃, filtering and washing the roasted sample with deionized water until the pH is 7, and drying for 12h at 120 ℃ to obtain the mesoporous ferric oxide.
The XRD spectrum of the mesoporous ferric oxide obtained in the example is shown in figure 1; the dispersibility of the mesoporous iron oxide in gasoline is shown in FIG. 2, the Fourier transform infrared spectrum of the mesoporous iron oxide is shown in FIG. 3, and the N of the mesoporous iron oxide is shown in the example 2 The adsorption and desorption curves are shown in fig. 4.
Suspension bed hydrocracking reaction evaluation of catalyst Using vacuum residuum as raw material 40.0. 40.0 g vacuum residuum, 30000 ppm catalyst of the comparative example and a certain amount of CS 2 Adding into a high-temperature high-pressure reactor with the volume of 250 mL, H 2 The initial pressure is 11 MPa. First, the catalyst was sulfided at a temperature of 350℃for 5 h, followed by 2h at a temperature of 430℃and a stirring rate of 800 r/min. The hydrocracking reaction results of the catalyst are shown in Table 1.
Example 1
The procedure for the preparation of mesoporous iron oxide was the same as in the comparative example.
Dissolving 1.0 g sodium stearate into 40 mL n-hexane, stirring at normal temperature for 30 min, dispersing 2.0 g mesoporous ferric oxide in organic solution, hydrothermally stirring at 70deg.C for 2h, and performing ultrasonic treatment for 20 min; transferring the mixture to a 100 mL crystallization kettle, and thermally reacting at 100 ℃ for 24 h; naturally cooling to room temperature, centrifugally washing with absolute ethyl alcohol to obtain a reddish brown solid, and drying the solid at 100 ℃ for 12 hours to obtain the lipophilic mesoporous ferric oxide.
The XRD spectrum of the lipophilic mesoporous iron oxide obtained in the example is shown in figure 1, the dispersibility of the lipophilic mesoporous iron oxide obtained in the example in gasoline is shown in figure 2, and the lipophilic mesoporous iron oxide obtained in the exampleThe Fourier transform infrared spectrum of the ferric oxide is shown in figure 3, and the obtained lipophilic mesoporous ferric oxide has N 2 The adsorption and desorption curves are shown in fig. 4.
The experimental conditions of the hydrocracking reaction of the catalyst suspension bed are the same as those of the comparative example, and the reaction results are shown in Table 1.
Example 2
The procedure for the preparation of mesoporous iron oxide was the same as in the comparative example.
Dissolving 1.0 g stearic acid into 40 mL deionized water, stirring at normal temperature for 30 min, dispersing 2.0 g mesoporous ferric oxide into organic solution, hydrothermally stirring at 70deg.C for 2h, and performing ultrasonic treatment for 20 min; transferring the mixture to a 100 mL crystallization kettle, and reacting 24 h in an oven at 120 ℃; naturally cooling to room temperature, centrifugally washing with absolute ethyl alcohol to obtain a reddish brown solid, and drying the solid at 110 ℃ for 12 hours to obtain the lipophilic mesoporous ferric oxide.
The XRD spectrum of the lipophilic mesoporous iron oxide obtained in the example is shown in figure 1, the dispersibility of the lipophilic mesoporous iron oxide obtained in the example in gasoline is shown in figure 2, the Fourier transform infrared spectrum of the lipophilic mesoporous iron oxide obtained in the example is shown in figure 3, and the N of the lipophilic mesoporous iron oxide obtained in the example 2 The adsorption and desorption curves are shown in fig. 4.
The experimental conditions of the hydrocracking reaction of the catalyst suspension bed are the same as those of the comparative example, and the reaction results are shown in Table 1.
Example 3
The procedure for the preparation of mesoporous iron oxide was the same as in the comparative example.
Dissolving 2.0. 2.0 g stearic acid into 40 mL toluene, stirring at normal temperature for 30 min, dispersing 4.0 g mesoporous ferric oxide into organic solution, hydrothermally stirring at 70 ℃ for 2h, and performing ultrasonic treatment for 20 min; transferring the mixture to a 100 mL crystallization kettle, and reacting 24 h in an oven at 120 ℃; naturally cooling to room temperature, centrifugally washing with absolute ethyl alcohol to obtain a reddish brown solid, drying the solid at 110 ℃ for 12 hours, sampling and packaging.
The experimental conditions of the hydrocracking reaction of the catalyst suspension bed are the same as those of the comparative example, and the reaction results are shown in Table 1.
Example 4
The procedure for the preparation of mesoporous iron oxide was the same as in the comparative example.
Dissolving 0.8 g stearic acid into 40 mL deionized water, stirring at normal temperature for 30 min, dispersing 2.0 g mesoporous ferric oxide into organic solution, hydrothermally stirring at 70deg.C for 2h, and performing ultrasonic treatment for 20 min; transferring the mixture to a 100 mL crystallization kettle, and reacting 36 h in an oven at 160 ℃; naturally cooling to room temperature, centrifugally washing with absolute ethyl alcohol to obtain a reddish brown solid, drying the solid at 110 ℃ for 12 hours, sampling and packaging.
The experimental conditions of the hydrocracking reaction of the catalyst suspension bed are the same as those of the comparative example, and the reaction results are shown in Table 1.
Example 5
The procedure for the preparation of mesoporous iron oxide was the same as in the comparative example.
Dissolving 0.8 g p-methylbenzoic acid into 40 mL deionized water, stirring at normal temperature for 30 min, dispersing 2.0 g mesoporous ferric oxide into an organic solution, hydrothermally stirring at 70 ℃ for 2h, and performing ultrasonic treatment for 20 min; transferring the mixture to a 100 mL crystallization kettle, and reacting 24 h in an oven at 120 ℃; naturally cooling to room temperature, centrifugally washing with absolute ethyl alcohol to obtain a reddish brown solid, drying the solid at 110 ℃ for 12 hours, sampling and packaging.
The experimental conditions of the hydrocracking reaction of the catalyst suspension bed are the same as those of the comparative example, and the reaction results are shown in Table 1.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of a lipophilic ferric oxide catalyst is characterized in that: firstly, preparing ferric oxide with a mesoporous structure by using sawdust as a template agent by adopting a hydrothermal-precipitation method, and then carrying out surface modification on the ferric oxide by using macromolecular organic matters to obtain lipophilic ferric oxide; the macromolecular organic matter is at least one of palmitic acid, stearic acid, oleic acid, lauric acid, p-methylbenzoic acid, m-methylbenzoic acid, sodium stearate and caprylic acid;
the method comprises the following steps:
(1) Mixing ethanol, deionized water, isopropanol, acetic acid and wood dust powder, heating in water bath, and stirring;
(2) Dropwise adding an alkaline solution into an iron salt solution, vigorously stirring to form a suspension, and adding the mixture obtained in the step (1) to form a gel solution;
(3) Drying the gel solution, and roasting in an air atmosphere to obtain mesoporous ferric oxide;
(4) Adding macromolecular organic matters into a solvent to prepare an organic solution;
(5) Adding mesoporous ferric oxide into an organic solution, heating in a water bath, stirring, and performing ultrasonic treatment;
(6) And carrying out hydrothermal reaction at 100-200 ℃ for 2-48 h, centrifuging or filtering, washing and drying to obtain the lipophilic ferric oxide.
2. The method according to claim 1, characterized in that: in the step (1), the mass ratio of the ethanol to the deionized water is 1:3, the water bath temperature is 30-80 ℃, and the stirring time is 1-3 h.
3. The method according to claim 1, characterized in that: the pH value of the suspension system in the step (2) is 7-12.
4. The method according to claim 1, characterized in that: the drying temperature in the step (3) is 100-180 ℃ and the time is 1-8 h; the roasting temperature is 300-600 ℃ and the roasting time is 2-12 h.
5. The method according to claim 1, characterized in that: and (3) the mass fraction of the organic solution in the step (4) is 0.5-25%.
6. The method according to claim 1, characterized in that: the water bath temperature in the step (5) is 30-80 ℃, the stirring time is 0.5-6 h, and the ultrasonic treatment is carried out for 20 min.
7. The method according to claim 1, characterized in that: the washing solvent in the step (6) is ethanol; drying at 60 deg.C for 12 hr or more.
8. A lipophilic iron oxide catalyst made by the method of claim 1.
9. A lipophilic iron oxide catalyst prepared according to the method of claim 1 for use in a suspension hydrocracking reaction.
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