CN110508285A - The preparation method of Fe base hydrocracking catalyst for suspension bed - Google Patents
The preparation method of Fe base hydrocracking catalyst for suspension bed Download PDFInfo
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- CN110508285A CN110508285A CN201910908870.1A CN201910908870A CN110508285A CN 110508285 A CN110508285 A CN 110508285A CN 201910908870 A CN201910908870 A CN 201910908870A CN 110508285 A CN110508285 A CN 110508285A
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- suspension bed
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 27
- 239000000725 suspension Substances 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 4
- 229910009112 xH2O Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 241000219782 Sesbania Species 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000005336 cracking Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 239000012053 oil suspension Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 229910001566 austenite Inorganic materials 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 2
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000000571 coke Substances 0.000 description 8
- 241000772415 Neovison vison Species 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 organic acid salt Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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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)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to Petroleum Processing Technology fields, and in particular to a kind of preparation method of Fe hydrocracking catalyst for suspension bed.With FeCl3·6H2O、Fe2(SO4)3·xH2O, using sol-gel method, hydro-thermal method, prepares the high specific surface area and mesoporous γ-Fe for being suitable for poor residuum slurry-bed hydrocracking using cheap sesbania powder as template for inorganic source of iron2O3Catalyst.Synthesis technology of the present invention is simple, synthesis cycle is short, environment friendly and pollution-free, at low cost.Obtained mesoporous γ-Fe2O3Catalyst is with good performance in dreg-oil suspension bed hydrogenation cracking reaction.
Description
Technical field
The present invention relates to the preparations of Fe base hydrocracking catalyst for suspension bed, and in particular to a kind of mesoporous γ-Fe2O3Catalysis
The preparation method of agent.
Background technique
With the continuous development of national economy, demand of the country to light-weight fuel oils such as gasoline, diesel oil and aviation kerosines is not
It is disconnected to increase, and the heaviness of crude oil, in poor quality trend are constantly aggravated, and environmental regulation is increasingly tight to the quality requirement of product oil
Lattice, the lighting of the heaviness, in poor quality and product of crude oil, the contradiction cleaned are constantly aggravated, this holds to petroleum refining industry
Supervention exhibition proposes stern challenge.Mink cell focus Efficient Conversion be improve crude oil utilize and ensure energy supply main means it
One.Mink cell focus feature are as follows: molecular weight is big, the content of complicated composition, hetero atom (S and N), metal (V and Ni) and asphalitine is high,
Its Efficient Conversion and the difficulty of comprehensive utilization are very big.
Hydrotreating/cracking is the conventional means that heavy oil conversion is light fraction oil, but what is be widely used at present consolidates
The disadvantages such as fixed bed hydrogen addition technology there are purification capacities poor, the easy coking and deactivation of catalyst, conversion ratio be low, are not suitable for inferior feedstock oil
Processing and conversion therefore need to develop new mink cell focus hydrogen addition technology.In existing heavy oil conversion technology, suspension bed
Hydrocracking technology adaptability to raw material is strong, high conversion rate, technical process are relatively easy, it is considered to be most promising heavy
Matter oil Efficient Conversion technology.
Catalyst is the core of floating bed hydrogenation technology, is not only played to reactivity worth and distillate Mass Distribution leading
Effect, and influence the running of suspended-bed reactor long period.Currently, the hydrocracking catalyst for suspension bed having been developed that mainly wraps
Include oil-soluble catalyst, water-soluble catalyst and solid powder th-1 catalyst.Oil-soluble catalyst is transition metal (Mo, Ni etc.)
Organic compound, such catalyst and feedstock oil dissolve each other so that active material high degree of dispersion.Oil-soluble catalyst is usual
For metal organic acid salt or organo-metallic compound or complex, such catalyst activity is high, dosage is few but metallorganic
It is at high price.Water-soluble catalyst is the inorganic salts of transition metal M o, Ni, Co etc., after dissolution, emulsification, dehydration, vulcanization i.e.
It can be used.And the major obstacle that complicated cumbersome preparation process early period is the application of such Catalyst such as emulsify, be dehydrated.Solid
Fine catalyst is mainly with loaded catalyst that aluminium oxide, coke etc. are carrier loaded transition metal M o, Ni, Co etc. and micro-
Meter level iron content natural minerals fine powder catalyst.There is coke yield height, catalyst amounts for loaded catalyst greatly, transition metal
The disadvantages of use of Mo, Ni cause catalyst at high cost.
Natural iron ore is because its is from a wealth of sources, cheap, as mink cell focus hydrocracking catalyst for suspension bed by extensive
Concern.Using red mud as hydrocracking catalyst for suspension bed, in 480 DEG C, the condition of 15 MPa, 5 wt% of catalyst amount
Under, the conversion ratio of decompression residuum is about 60%, and petrol and diesel oil yield is about 30%, and coke yield is about 5% [Applied
Catalysis A: General,2012, 447– 448, 186–192 ]；Matsumura etc. adds by suspension bed of limonite
Hydrogen Cracking catalyst, the content of active component Fe are about 57 wt%, are used in 450 DEG C, 14.7 MPa of reaction pressure, catalyst
Amount be 12 wt% under the conditions of, the conversion ratio of decompression residuum is about 70%, green coke amount be about 3 wt% [Fuel, 2005,84,
417-421]；Exxon Mobil Corporation is with Fe2O3Floating bed hydrocracking processing, catalyst are carried out to decompression residuum for catalyst
7 wt% of dosage, 440oC, under 20 MPa of reaction pressure, the carbon residue conversion ratio in decompression residuum is about 40% [1978. US
patent 4067799].Petro-Canada using ferric sulfate and petroleum coke mixed grinding at the particle less than 30 μm as
Catalyst, under the conditions of 440 DEG C of reaction temperature, 14 MPa of reaction pressure, 5 wt% of catalyst amount, the conversion ratio of asphalitine is
70%[1991. US patent 4999328].It can be seen that iron ore has very well as hydrocracking catalyst for suspension bed
Application prospect, but up for solving the problems such as the catalyst activity is low, dosage is big.In nature the oxide of iron with
A variety of crystal habits exist, and the oxide of common iron includes α-Fe2O3、γ-Fe2O3、Fe3O4And FeO.α-Fe2O3And γ-
Fe2O3Has many advantages, such as to prepare relatively simple, relative low price, it is often more important that in dreg-oil suspension bed hydrogenation cracking reaction
With good result, however γ-Fe2O3With more cation vacancies, however the activated centre of catalyst is concentrated mainly on defect
At position.Therefore, theoretically γ-Fe2O3Its catalytic effect is better than α-Fe in dreg-oil suspension bed hydrogenation cracking reaction2O3。
During mink cell focus slurry-bed hydrocracking, conventional Fe2O3Narrow cellular structure is difficult to meet heavy oil big
The diffusion mass transfer requirement of molecule, preparing has the mesoporous Fe for being suitble to heavy oil solid tumor mass transfer2O3It is the master for solving the problems, such as this
Want method.Preparation γ-Fe at present2O3Method mainly have: sol-gal process, hydro-thermal method, coprecipitation, template etc. be made
Fe2O3Presoma is roasted presoma to obtain γ-Fe2O3.About Fe2O3Preparation it has been reported that Zhou Guowei team utilize
Hydro-thermal method is using cetyl trimethylammonium bromide and didodecyldimethylammbromide bromide as template, using FeCl36H2O as nothing
Machine source of iron prepares the mesoporous Fe that aperture is 2-4 nm2O3(105600833 A of CN)；Ma Limeng seminar utilizes collosol and gel
Method is using tetraethyl orthosilicate, sucrose and F127 as template, and with Fe(NO3)39H2O for inorganic source of iron, preparing specific surface area is 89
m20 .43 cm of/g, Kong Rongwei3/ g, aperture are the mesoporous Fe of 21.5 nm2O3(106241884 A of CN)；Chen Pingan etc. will be different
The molysite and ammonium salt of type carry out hydro-thermal to it after mixing according to a certain percentage, prepare the disk that partial size is 0.5-10 μm
Shape Fe2O3(109574086 A of CN)；Jia Dongdong seminar, using urea as template, is inorganic with ferric nitrate using sol-gal process
Spherical nanometer α-Fe is made in source of iron2O3(109999810 A of CN)；Fan Feng, by directly mixing beta molecular sieve with ferric nitrate
Method be made macropore α-Fe2O3(109928428 A of CN).Currently, mesoporous Fe2O3Template price used in materials synthesis is high
Expensive, preparation process is complicated, and has certain pollution to environment in removed template method.
The present invention proposes to prepare with cheap raw material, using the synthesis technology of simple green with meso-hole structure, high ratio
γ-the Fe of surface area, Gao Kongrong2O3Material, the catalyst are answered in mink cell focus slurry-bed hydrocracking with less dosage
With working well, there is good commercial and industrial application value.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of Fe base hydrocracking catalyst for suspension bed.With FeCl3·6H2O、
Fe2(SO4)3·xH2O is that inorganic source of iron, using sol-gel method, hydro-thermal method, is prepared using cheap sesbania powder as template
It is suitable for the high specific surface area and mesoporous γ-Fe of poor residuum slurry-bed hydrocracking2O3Catalyst.Wherein template plays
It prevents from aoxidizing the effect that iron skeleton collapses and induce meso-hole structure to be formed in crystallization process.
To achieve the above object, the present invention takes following technical scheme:
The preparation method of Fe base hydrocracking catalyst for suspension bed, the specific steps are as follows:
(1) inorganic source of iron is added into deionized water and is prepared into certain density inorganic source of iron solution, by inorganic source of iron solution into
Row water bath processing；
(2) aqueous slkali is prepared, prepared aqueous slkali is slowly added in the inorganic source of iron solution of step (1) preparation, wait be produced
The pH of raw mixture is 7.0-12.0, stops that alkaline solution is added dropwise；
(3) template is dissolved in deionized water and dehydrated alcohol mixed solution, while organic solvent and alkali is added thereto, it is right
It is spare after its progress stirring in water bath processing；
(4) compounding substances prepared by step (3) are added in the sample of step (2) preparation, quickly stirring forms gelatinous mass；
(5) institute is made in the gel seal for preparing step (4) after being stood, dried, roasted, wash and being dried to it
State catalyst.
The inorganic source of iron that step (1) uses is FeCl3·6H2O or Fe2(SO4)3·xH2O, purity be technical purity with
On, the ferrous solution concentration of preparation is 2-8 mol/L.
Step (1) water bath heating temperature is 50-90 DEG C, revolving speed 400-800 r/min, and the time is 0.5-5 h.
Step (2) neutral and alkali solution is NaOH solution, and concentration is 2-7 mol/L；
The template that step (3) uses is sesbania powder.
Template described in step (3) is dissolved in deionized water and dehydrated alcohol mixed solution, wherein deionized water and mould
The mass ratio of plate agent is 2:1-10:1；The mass ratio of deionized water and dehydrated alcohol is 2:1-6:1.
Step (3) organic solvent is isopropanol, glacial acetic acid, and quality is added in sesbania powder and mass ratio is added in isopropanol
And it is 10:1-10:3 that quality and glacial acetic acid addition mass ratio, which is added, in sesbania powder；Alkali is NaOH, sesbania powder be added quality with
It is 10:3-10:8 that mass ratio, which is added, in NaOH；
The temperature of stirring in water bath described in step (3) is room temperature, and revolving speed is 500-700 r/min, and stirring in water bath temperature is 50-90
DEG C, the time is 1-5 h.
The pH that step (3) prepares mixture is 7.0-12.0.
The mass ratio that the mixture of step (3) preparation and the sample of step (2) preparation are added in step (4) is 1:2-1:
10。。
Dwell temperature is 20-70 DEG C in step (5), and time of repose is 0.5-5 h；Drying temperature is 80-170 DEG C, is done
The dry time is 5-9 h；Maturing temperature is 380-500 DEG C, and calcining time is 2-7 h.
Remarkable advantage of the invention is:
(1) Fe prepared by the present invention2O3Average pore size be 7.0-25.0 nm, Kong Rongwei 0.03-0.45 cm3/g, specific surface
Product is 14-150 m2/g.
(2) the mesoporous Fe of present invention gained2O3Material is γ-Fe2O3, the mesoporous γ-Fe2O3Material is being used for slag inferior
The process of oily slurry-bed hydrocracking has good result.
Detailed description of the invention
Fig. 1 is mesoporous Fe prepared by the present invention2O3The wide-angle XRD diagram of nano material；
Fig. 2 is mesoporous Fe prepared by the present invention2O3The nitrogen adsorption desorption figure of catalyst；
Fig. 3 is mesoporous Fe prepared by the present invention2O3The graph of pore diameter distribution of catalyst.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, but protection scope of the present invention is not
It is limited to this.
It is first that the raw materials used Unify legislation of specific embodiment is as follows to avoid repeating, it is repeated no more in example.
The purity of the molysite is technical pure or more.
The purity of the NaOH is technical pure or more.
Embodiment 1
(1) at room temperature by 27.05 gFeCl3·6H2The FeCl for being prepared into 2 mol/L is added into 39.2 ml deionized waters in O3It is molten
Liquid, 1 h of water-bath heating stirring at 80 DEG C；
(2) prepared NaOH solution, is added dropwise the FeCl of step (1) preparation by the NaOH solution for preparing 6 mol/L3Solution
In, rufous floccule will be then generated, after the pH value of solvent in rufous floccule is 11.2 or more, stops that NaOH is added dropwise
Solution；
(3) by the powdered sesbania powder of 5 g, 2 g isopropanols, 5g glacial acetic acid and 5 gNaOH be added to 40 ml deionized waters with it is anhydrous
Ethyl alcohol (is counted, deionized water: dehydrated alcohol=3:1) in mass ratio in mixed solution, and 3 h, then 1 h of ultrasound is stirred at room temperature, finally exists
1.5 h of stirring in water bath at a temperature of 80 DEG C；
(4) the final resulting mixture of step (3) is added in the rufous floccule of step (2) preparation, quickly stirs 1
Min forms gel, stops stirring；
(5) after the final obtained compounding substances of step (4) being sealed in reactor, it stands to 2 h at room temperature, 150
DEG C dry 5 h, then 450 DEG C of 3 h of roasting, are down to room temperature to furnace temperature naturally, take out sample deionized water and alcohol mix it is molten
Liquid washing, then obtained material is put into 60 DEG C of baking ovens and is dried, drying object matter is finally sealed preservation.
Prepared iron oxide is γ-Fe2O3, specific surface area is 135.4 m2/g, 0.28 cm3/g of Kong Rongwei, is averaged
Aperture is 13.9 nm.In dreg-oil suspension bed hydrogenation cracking reaction, the catalyst is at 420 DEG C of temperature, initial H2Pressure 13
Under Mpa, bottoms conversion is 88.7 wt%, and the yield of naphtha and intermediate oil is about 57.0 wt%, and coke yield is
1.3 wt%。
Embodiment 2
(1) at room temperature by 27.05 gFeCl3·6H2The FeCl for being prepared into 2 mol/L is added into 39.2 ml deionized waters in O3It is molten
Liquid, 1 h of water-bath heating stirring at 80 DEG C；
(2) prepared NaOH solution, is added dropwise the FeCl of step (1) preparation by the NaOH solution for preparing 6 mol/L3Solution
In, rufous floccule will be then generated, after the pH value of solvent in rufous floccule is 11.2 or more, stops that NaOH is added dropwise
Solution；
(3) the powdered sesbania powder of 10 g, 2 g isopropanols, 5g glacial acetic acid and 5 gNaOH are added to 40 ml deionized waters and nothing
Water-ethanol (is counted, deionized water: dehydrated alcohol=3:1) in mass ratio in mixed solution, 3 h, then 1 h of ultrasound is stirred at room temperature, finally
In 80 DEG C of at a temperature of stirring in water bath 1.5 h；
(4) the final resulting mixture of step (3) is added in the rufous floccule of step (2) preparation, quickly stirs 1
Min forms gel, stops stirring；
(5) after the final obtained compounding substances of step (4) being sealed in reactor, it stands to 2 h at room temperature, 150
DEG C dry 5 h, then 450 DEG C of 3 h of roasting, are down to room temperature to furnace temperature naturally, take out sample deionized water and alcohol mix it is molten
Liquid washing, then obtained material is put into 60 DEG C of baking ovens and is dried, drying object matter is finally sealed preservation.
Prepared iron oxide is γ-Fe2O3, specific surface area is 119.1 m2/g, 0.41 cm3/g of Kong Rongwei, is averaged
Aperture is 15.0 nm.In dreg-oil suspension bed hydrogenation cracking reaction, the catalyst is at 420 DEG C of temperature, initial H2Pressure 13
Under Mpa, bottoms conversion is 89.7 wt%, and the yield of naphtha and intermediate oil is about 56.6 wt%, and coke yield is
1.2 wt%。
Embodiment 3
(1) at room temperature by 27.05 gFeCl3·6H2The FeCl for being prepared into 2 mol/L is added into 39.2 ml deionized waters in O3It is molten
Liquid, 1 h of water-bath heating stirring at 80 DEG C；
(2) prepared NaOH solution, is added dropwise the FeCl of step (1) preparation by the NaOH solution for preparing 6 mol/L3Solution
In, rufous floccule will be then generated, after the pH value of solvent in rufous floccule is 11.2 or more, stops that NaOH is added dropwise
Solution；
(3) the powdered sesbania powder of 10 g, 2 g isopropanols, 5g glacial acetic acid and 5 gNaOH are added to 40 ml deionized waters and nothing
Water-ethanol (is counted, deionized water: dehydrated alcohol=3:1) in mass ratio in mixed solution, 3 h, then 1 h of ultrasound is stirred at room temperature, finally
In 80 DEG C of at a temperature of stirring in water bath 1.5 h；
(4) the final resulting mixture of step (3) is added in the rufous floccule of step (2) preparation, quickly stirs 1
Min forms gel, stops stirring；
(5) by the final obtained gel seal of step (4) in high-pressure hydrothermal reaction kettle, after 6 h are handled at 150 DEG C,
150 DEG C of 5 h of drying, then 450 DEG C of 3 h of roasting, are down to room temperature to furnace temperature naturally, take out sample deionized water and alcohol is mixed
Solution washing is closed, then obtained material is put into 60 DEG C of baking ovens and is dried, drying object matter is finally sealed preservation.
Prepared iron oxide is γ-Fe2O3, specific surface area is 136.8 m2/g, 0.26 cm3/g of Kong Rongwei, is averaged
Aperture is 13.6 nm.In dreg-oil suspension bed hydrogenation cracking reaction, the catalyst is at 420 DEG C of temperature, initial H2Pressure 13
Under Mpa, bottoms conversion is 86.6 wt%, and the yield of naphtha and intermediate oil is about 61.2 wt%, and coke yield is
1.1 wt%。
Embodiment 4
(1) at room temperature by 27.05 gFeCl3·6H2The FeCl for being prepared into 2 mol/L is added into 39.2 ml deionized waters in O3It is molten
Liquid, 1 h of water-bath heating stirring at 80 DEG C；
(2) prepared NaOH solution, is added dropwise the FeCl of step (1) preparation by the NaOH solution for preparing 6 mol/L3Solution
In, rufous floccule will be then generated, after the pH value of solvent in rufous floccule is 11.2 or more, stops that NaOH is added dropwise
Solution；
(3) the powdered sesbania powder of 10 g, 2 g isopropanols, 5g glacial acetic acid and 5 gNaOH are added to 40 ml deionized waters and nothing
Water-ethanol (is counted, deionized water: dehydrated alcohol=3:1) in mass ratio in mixed solution, 3 h, then 1 h of ultrasound is stirred at room temperature, finally
In 80 DEG C of at a temperature of stirring in water bath 1.5 h；
(4) the final resulting mixture of step (3) is added in the rufous floccule of step (2) preparation, quickly stirs 1
Min forms gel, stops stirring；
(5) after the final obtained compounding substances of step (4) being sealed in reactor, it stands to 2 h at room temperature, 150
DEG C dry 5 h, then 500 DEG C of 3 h of roasting, are down to room temperature to furnace temperature naturally, take out sample deionized water and alcohol mix it is molten
Liquid washing, then obtained material is put into 60 DEG C of baking ovens and is dried, drying object matter is finally sealed preservation.
Prepared iron oxide is γ-Fe2O3, specific surface area is 83.6 m2/g, 0.13 cm3/g of Kong Rongwei, average hole
Diameter is 7.6 nm.In dreg-oil suspension bed hydrogenation cracking reaction, the catalyst is at 420 DEG C of temperature, initial H213 Mpa of pressure
Under, bottoms conversion is 85.5 wt%, and the yield of naphtha and intermediate oil is about 54.6 wt%, coke yield 2.1
wt%。
Embodiment 5
(1) at room temperature by 27.05 gFeCl3·6H2The FeCl for being prepared into 2 mol/L is added into 39.2 ml deionized waters in O3It is molten
Liquid, 1 h of water-bath heating stirring at 80 DEG C；
(2) prepared NaOH solution, is added dropwise the FeCl of step (1) preparation by the NaOH solution for preparing 6 mol/L3Solution
In, rufous floccule will be then generated, after the pH value of solvent in rufous floccule is 11.2 or more, stops that NaOH is added dropwise
Solution；
(3) the powdered sesbania powder of 10 g, 2 g isopropanols, 5g glacial acetic acid and 5 gNaOH are added to 40 ml deionized waters and nothing
Water-ethanol (is counted, deionized water: dehydrated alcohol=3:1) in mass ratio in mixed solution, 3 h, then 1 h of ultrasound is stirred at room temperature, finally
In 80 DEG C of at a temperature of stirring in water bath 1.5 h；
(4) the final resulting mixture of step (3) is added in the rufous floccule of step (2) preparation, quickly stirs 1
Min forms gel, stops stirring；
(5) after the final obtained compounding substances of step (4) being sealed in reactor, it stands to 2 h at room temperature, 150
DEG C dry 5 h, then 500 DEG C of 6 h of roasting, are down to room temperature to furnace temperature naturally, take out sample deionized water and alcohol mix it is molten
Liquid washing, then obtained material is put into 60 DEG C of baking ovens and is dried, drying object matter is finally sealed preservation.
Prepared iron oxide is γ-Fe2O3, specific surface area is 13.9 m2/g, 0.03 cm3/g of Kong Rongwei, average hole
Diameter is 17.6 nm.In dreg-oil suspension bed hydrogenation cracking reaction, the catalyst is at 420 DEG C of temperature, initial H213 Mpa of pressure
Under, bottoms conversion is 83.5 wt%, and the yield of naphtha and intermediate oil is about 52.9 wt%, coke yield 2.0
wt%。
Fig. 1 illustrates that synthetic sample is γ-Fe2O3；
Fig. 2 illustrates the γ-Fe of synthesis2O3With meso-hole structure；
Fig. 3 illustrates the γ-Fe of synthesis2O3Mesoporous average pore size in 30nm or more.
Above-described embodiment is merely a preferred embodiment of the present invention, and it is not intended to limit the protection scope of the present invention, as long as using
Design principle of the invention, and the non-creative variation worked and made is carried out on this basis, it should belong to of the invention
Within protection scope.
Claims (10)
1. the preparation method of Fe hydrocracking catalyst for suspension bed, it is characterised in that: the following steps are included:
(1) inorganic source of iron is added into deionized water and is prepared into inorganic source of iron solution, inorganic source of iron solution is subjected to water bath processing；
(2) aqueous slkali is prepared, prepared aqueous slkali is slowly added in the inorganic source of iron solution of step (1) preparation, wait be produced
The pH of raw mixture is 7.0-12.0, stops that alkaline solution is added dropwise；
(3) template is dissolved in deionized water and dehydrated alcohol mixed solution, while organic solvent and alkali is added thereto, it is right
It is spare after its progress stirring in water bath processing；
(4) compounding substances prepared by step (3) are added in the sample of step (2) preparation, quickly stirring forms gelatinous mass；
(5) institute is made in the gel seal for preparing step (4) after being stood, dried, roasted, wash and being dried to it
State catalyst.
2. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (1)
The inorganic source of iron used is FeCl3·6H2O or Fe2(SO4)3·xH2O, purity are technical purity or more, and the molysite of preparation is molten
Liquid concentration is 2-8 mol/L.
3. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (1)
Water bath heating temperature is 50-90 DEG C, revolving speed 400-800 r/min, and the time is 0.5-5 h.
4. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (2)
Neutral and alkali solution is NaOH solution, and concentration is 2-7 mol/L.
5. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (3)
The template used is sesbania powder.
6. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (3)
Described in template be dissolved in deionized water and dehydrated alcohol mixed solution, wherein the mass ratio of deionized water and template be 2:
1-10:1；The mass ratio of deionized water and dehydrated alcohol is 2:1-6:1.
7. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (3)
The organic solvent is isopropanol, glacial acetic acid, and quality is added in sesbania powder and quality when sesbania powder addition quality is added in isopropanol
It is 10:1-10:3 that mass ratio, which is added, with glacial acetic acid；Alkali is NaOH, and sesbania powder is added quality with NaOH addition mass ratio and is
10:3-10:8；The temperature of stirring in water bath described in step (3) is room temperature, and revolving speed is 500-700 r/min, stirring in water bath temperature
It is 50-90 DEG C, the time is 1-5 h；The pH that step (3) prepares mixture is 7.0-12.0.
8. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (4)
The mass ratio of the middle mixture that step (3) preparation is added and the sample of step (2) preparation is 1:2-1:10.
9. the preparation method of Fe hydrocracking catalyst for suspension bed according to claim 1, it is characterised in that: step (5)
Middle dwell temperature is 20-70 DEG C, and time of repose is 0.5-5 h；Drying temperature is 80-170 DEG C, and drying time is 5-9 h；Roasting
Burning temperature is 380-500 DEG C, and calcining time is 2-7 h.
10. a kind of Fe hydrocracking catalyst for suspension bed prepared such as any one of claim 1 ~ 9 the method, feature exist
In: gained catalyst is mesoporous Fe2O3Material, crystal form are γ-Fe2O3, average pore size is 7.0-25.0 nm, Kong Rongwei 0.03-
0.45 cm3/g, specific surface area are 14-150 m2/g.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021057188A1 (en) * | 2019-09-25 | 2021-04-01 | 福州大学 | Method for preparing catalyst for suspended-bed-based hydrocracking of poor-quality residual oil |
| CN112808273A (en) * | 2021-02-04 | 2021-05-18 | 福州大学 | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed |
| CN114405508A (en) * | 2022-03-10 | 2022-04-29 | 福州大学 | Ti-doped Fe oxide residual oil suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN114797883A (en) * | 2021-01-29 | 2022-07-29 | 福州大学 | Fe-Si supported suspension bed hydrocracking catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587209A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Method for preparing porous oxide molecular sieve using plant template |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN105600833A (en) * | 2015-10-15 | 2016-05-25 | 齐鲁工业大学 | Spherical mesoporous iron oxide and preparation method thereof |
| CN106830095A (en) * | 2017-02-17 | 2017-06-13 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
-
2019
- 2019-09-25 CN CN201910908870.1A patent/CN110508285B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587209A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Method for preparing porous oxide molecular sieve using plant template |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN105600833A (en) * | 2015-10-15 | 2016-05-25 | 齐鲁工业大学 | Spherical mesoporous iron oxide and preparation method thereof |
| CN106830095A (en) * | 2017-02-17 | 2017-06-13 | 中国市政工程中南设计研究总院有限公司 | A kind of meso-porous hollow iron oxide microballoon and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JING JIN等: "Magnetic studies of mesoporous nanostructured iron oxide materials synthesized by one-step soft-templating", 《DALTON TRANSACTIONS》 * |
| 吴永娟等: "磁性介孔γ-Fe2O3制备及其处理含Cr(VI)废水的应用", 《工业水处理》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021057188A1 (en) * | 2019-09-25 | 2021-04-01 | 福州大学 | Method for preparing catalyst for suspended-bed-based hydrocracking of poor-quality residual oil |
| CN114797883A (en) * | 2021-01-29 | 2022-07-29 | 福州大学 | Fe-Si supported suspension bed hydrocracking catalyst and preparation method thereof |
| CN114797883B (en) * | 2021-01-29 | 2023-06-23 | 福州大学 | Fe-Si supported suspension bed hydrocracking catalyst and preparation method thereof |
| CN112808273A (en) * | 2021-02-04 | 2021-05-18 | 福州大学 | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed |
| CN114405508A (en) * | 2022-03-10 | 2022-04-29 | 福州大学 | Ti-doped Fe oxide residual oil suspension bed hydrocracking catalyst and preparation method and application thereof |
| CN114405508B (en) * | 2022-03-10 | 2023-10-10 | 福州大学 | Ti-doped Fe oxide residual oil suspension bed hydrocracking catalyst and preparation method and application thereof |
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