CN111135819A - Hydrocracking supported catalyst for inferior residual oil suspension bed and preparation method thereof - Google Patents
Hydrocracking supported catalyst for inferior residual oil suspension bed and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012053 oil suspension Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000012876 carrier material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 21
- 238000004939 coking Methods 0.000 abstract description 14
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 42
- 238000004073 vulcanization Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
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- 230000000694 effects Effects 0.000 description 11
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- 238000010521 absorption reaction Methods 0.000 description 10
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- 239000000295 fuel oil Substances 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000000571 coke Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910001570 bauxite Inorganic materials 0.000 description 5
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- 239000000446 fuel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 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 3
- 238000011161 development Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- -1 Mo and Ni Chemical class 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 150000002894 organic compounds Chemical group 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
- B01J23/75—Cobalt
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- 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
- B01J23/755—Nickel
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- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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Abstract
The invention discloses a preparation method of a supported catalyst for poor-quality residual oil suspension bed hydrocracking, belonging to the field of catalyst preparation. The catalyst consists of a metal active component and a carrier material, wherein the metal active component is one or more of Mo, W, Co or Ni elements, the dosage of the metal active component is 1-10 wt% of the total amount of the catalyst, and the carrier material is changed into the carrier materialThe modified rectorite is one of roasting method or hydrothermal treatment method, and the modification temperature is 400-1000%oC. The preparation method of the catalyst is an isometric impregnation method. The invention prepares the high-performance inferior residual oil suspension bed hydrocracking catalyst by controlling the dosage of the hydrogenation active phase and the structural property of the carrier material, and has the characteristics of simple preparation process, low price, no toxicity and the like. The catalyst is applied to the hydrocracking reaction of a suspension bed, and has the advantages of high selectivity of naphtha and middle distillate oil, low yield of gas and coking rate and the like.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to preparation of a supported catalyst for poor-quality residual oil suspension bed hydrocracking.
Background
At present, society and technology are in a more rapid development stage, and the energy gap is gradually expanded. Although renewable new energy sources such as wind energy, solar energy and the like are developed worldwide, the huge energy gap and the larger reserved quantity of petroleum are destined to the wide application of petroleum resources within a certain time. According to the statistics of the Organization of Petroleum Exporting Countries (OPEC), the global crude oil demand is increased by 1.50mb/d (million barrels per day) in 2018 compared with the global crude oil demand in the last year, and the global crude oil demand is predicted to be increased by 1.29mb/d again in 2019 to reach 100.08 mb/d. However, the storage amount of conventional crude oil is decreasing, and the crude oil is getting heavier and worse. With the continuous development of national economy, the market demand for clean fuel oil products is continuously increased, and the requirements of environmental regulations on the quality of finished oil are increasingly strict. This poses a serious challenge to the green sustainable development of the refinery industry. The high-efficiency conversion of heavy oil is one of the important means for improving the utilization of crude oil and guaranteeing the energy supply. The heavy oil is characterized by high density, high viscosity, very complex composition, large molecular weight, high content of heteroatoms (S and N), metals (V and Ni) and asphaltenes, and mainly comprises the following components: residual oil, shale oil, oil sand oil, coal tar, super heavy oil and the like. Currently, hydrocracking/processing is an important process for converting heavy oils into light distillates. However, the widely used fixed bed hydrogenation technology has the disadvantages of poor applicability of raw materials, low conversion rate of heavy oil, easy coking and inactivation of catalysts and the like. Therefore, it is necessary to develop new hydrogenation technology for heavy oil.
The suspension bed hydrogenation process has high heavy oil conversion rate, strong raw material suitability, relatively simple process and wide prospect in industrial application.
In the hydrocracking reaction of the suspension bed, the catalyst plays a crucial role in the conversion of heavy oil and the distribution of products, and simultaneously influences the long-term operation of the suspension bed reactor. The suspension bed hydrocracking catalyst mainly comprises a homogeneous oil-soluble catalyst, a water-soluble catalyst and a solid powder catalyst. The oil-soluble catalyst is an organic compound of transition metals such as Mo and Ni, and the like, has good dispersity, high activity and small dosage, but the price of metal organic matters is high. The water-soluble catalyst is inorganic salt of transition metal Mo, Ni, Co, etc. and can be used after dissolving, emulsifying, dehydrating and vulcanizing. The complex and tedious early preparation processes such as emulsification, dehydration and the like limit the industrial application of the catalyst. The solid powder catalyst is mainly iron-rich natural mineral fine powder and a catalyst which takes alumina, natural minerals, coke and the like as carrier materials to load transition metals Mo, Ni, Co and the like. The natural iron ore fine powder catalyst has the defects of low raw material conversion rate, high gas and coke yield, large catalyst consumption and the like.
The supported catalyst is composed of a carrier material and a metal active component, so that the catalyst has the advantages of high adjustable property, high raw material conversion rate, low yield of gas and coke and wide industrial application prospect.
Jan Mosio-Mosiewski et Al studied Ni-Mo/Al2O3The hydrocracking activity of the catalyst on the vacuum residue of the Ural crude oil is that the catalyst is used for hydrocracking the vacuum residue of the Ural crude oil in a continuous suspension bed reactor at the reaction temperature of 430 ℃, the reaction pressure of 12-20 MPa and the liquid phase space velocity of 0.25-0.75 h-1The gas phase space velocity is 2500 h-1The activity evaluation is performed under the same conditions, the liquid yield in the hydrogenation process reaches 61.6-88.7 wt%, and the desulfurization rate reaches 70-85 wt% [ Applied Catalysis A: General 283 (2005) ] 147-](ii) a In a continuous ebullated bed reactor, Eduard Manek et Al studied Ni-Mo/Al2O3The hydrocracking activity of the catalyst on the Ural crude oil vacuum residue is evaluated under the conditions that the reaction temperature is 339-419 ℃ and the reaction pressure is 18 MPa, the hydrodesulfurization rate reaches 87.9 wt%, and the coke rate is only 0.24-0.28 wt% [ Fuel Processing Technology 159 (2017) -](ii) a France sco Regali et al load platinum or palladium on amorphous silica-alumina to make a bifunctional supported catalyst, and pass n-hexadecane (n-C)16H34) The hydrocracking reaction of (A) was tested at a reaction temperature of 310 ℃ and a reaction pressure of 30 Bar, H2/n-C16H34The activity evaluation was carried out under the condition that the feed molar ratio was 10/1, the conversion rate of n-hexadecane reached 90%, and the reaction [ Catalysis Today 214 (2013) 12-18 ] proceeded stably within 15h](ii) a Juntao Du and the like take inorganic minerals in coal tar as carriers and Mo and Ni as active components of a hydrogenation active phase, the coal tar of the Shanxi elmlin lignite is subjected to hydrocracking activity evaluation, under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 9 MPa and the dosage of a catalyst is 3.05 wt%, the conversion rate of the coal tar is about 62.8%, and the liquid yield is 84.4% [ Fuel 215 (2018) ] 370-](ii) a P.P. Dik et Al preparation of NiMo/FAU-Al by hydrothermal method2O3The load type catalyst is used for carrying out hydrocracking activity evaluation on vacuum gas oil, and the hydrocracking activity evaluation is carried out at the reaction temperature of 410 ℃, the reaction pressure of 16 MPa and the catalyst area of 20cm3Under the condition of (3 layers), the gas yield of vacuum gas oil is 5%, the naphtha yield is 13.6%, and the diesel oil yield is about 57.8% [ Fuel 237 (2019) & 178- & 190-](ii) a Pengli Niu and the like take natural bauxite as a carrier, modify the natural bauxite carrier through an acid treatment method, and add the natural bauxite carrier by an isometric immersion methodPreparation of suspension bed hydrocracking catalyst from hydrogenation active phase, wherein the content of hydrogenation active phase active component Mo is about 7 wt% (in MoO)3Mass fraction) of the tar, the hydrocracking activity of the tar at high temperature is evaluated, the conversion rate of the vacuum residue is about 85 percent, the coke formation is about 0.7 percent under the conditions of the reaction temperature of 430 ℃, the reaction pressure of 12.5MPa and the catalyst dosage of 3.1 weight percent [ Energy Fuels 2016, 30, 9203-](ii) a Jianweii Li and the like take natural bauxite as a carrier, modify the natural bauxite carrier through a hydrothermal treatment method, and add a hydrogenation active phase to prepare a suspension bed hydrocracking catalyst by an isometric impregnation method, wherein the content of an active component Mo of the hydrogenation active phase is about 3.5 wt% (by MoO)3Mass fraction) of the crude oil, the hydrocracking activity evaluation is carried out on the coal tar at the high temperature of the crane wall, under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 12.5MPa and the dosage of the catalyst is 3 wt%, the conversion rate of the vacuum residue is about 92 percent, and the coke formation is about 0.3 percent [ Fuel Processing Technology 175 (2018) -]。
At present, the developed supported catalyst has the problems of low selectivity of naphtha and middle distillate, coking of the catalyst, high cost of the catalyst and the like.
The invention provides a heavy oil suspension bed hydrogenation catalyst which takes low-cost rectorite as a carrier material, adopts simple-process, green and environment-friendly roasting and hydrothermal modification, has high conversion rate of raw materials, high selectivity of naphtha and middle distillate oil, low gas and coke yield and low price, and has good industrial application value.
Disclosure of Invention
The invention aims to optimize a carrier material of a catalyst and a modification method of the carrier material, and provides a preparation method of an inferior residual oil suspension bed hydrocracking supported catalyst. The invention takes rectorite as a carrier material, adopts a roasting or hydrothermal method to modify the rectorite, wherein a lamellar structure of the rectorite provides more active sites, and prepares the high-activity low-cost poor residual oil suspension bed hydrocracking catalyst by isovolumetric impregnation. The roasting or hydrothermal modification technology has simple process and is green and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a supported catalyst for poor-quality residual oil suspension bed hydrocracking reaction comprises a metal active component and a carrier material, wherein the metal active component is one or more of Mo, W, Co or Ni elements, and the dosage of the metal active component is 1-10 wt% of the total amount of the catalyst; wherein the carrier material is modified rectorite.
Further, the modified rectorite is specifically: roasting or hydro-thermal modifying natural mineral rectorite, wherein the modifying temperature is 400-1000 ℃, the modifying time is 1-8 h, and the modified rectorite is used as a carrier material.
Further, in the metal component, the precursor of Mo comprises H3[P(Mo3O10)4]Or (NH)4)6Mo7O24·4H2One of O; the precursor of W is (NH)4)6H2W12O40·2H2O; the precursor of Co is CoSO4·7H2O; the precursor of Ni is Ni (NO)3)2·6H2O。
The preparation method of the supported catalyst for the poor-quality residual oil suspension bed hydrocracking reaction comprises the following steps: and loading the metal active component on the surface of the modified rectorite by adopting an isometric impregnation method, and standing, drying and roasting to prepare the supported catalyst.
The application of the supported catalyst in the poor-quality residual oil suspension bed hydrocracking reaction is characterized in that the vacuum residual oil is used as a raw material, the hydrogenation reaction evaluation is carried out in a suspension bed reactor, the reaction temperature is 400-440 ℃, the reaction time is 1-3H, and H is2The volume ratio of the raw oil to the raw oil is 800:1, and the initial reaction H is2The pressure is 11-13 MPa.
The poor-quality residual oil suspension bed hydrocracking catalyst provided by the invention has the advantages of high raw material conversion rate, high selectivity of naphtha and middle distillate oil, low gas and coke yield, simple and green preparation process and low cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst is prepared by adopting lamellar rectorite as a carrier material and impregnating metal active components after simple and green roasting or hydrothermal modification.
(2) The catalyst with modified rectorite as carrier has excellent performance in hydrocracking reaction of inferior residual oil in suspension bed.
(3) The raw material rectorite is low in price and is non-toxic and harmless, so that the prepared catalyst is low in cost and is green and environment-friendly.
Drawings
FIG. 1 XRD spectrum of rectorite.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Taking 4g of natural rectorite, measuring the water absorption rate by the isovolumetric adsorption of deionized water, and configuring (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 2 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and at 325 deg.C for 1 hr, reacting at 400 deg.C for 1.5 hr and under 12.5MPa to obtain gasoline and diesel oil with selectivity of 40.2%, conversion rate of 82.2% and coking rate of 1.3%.
Example 2
Roasting natural rectorite at 450 deg.c for 4 hr, and adding 4g of roasted rectorite into deionized water in the same volumeThe water absorption is measured by adsorption and is configured with (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 7 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: the gasoline and diesel oil are vulcanized for 2 hours at 225 ℃, vulcanized for 1 hour at 325 ℃, the gasoline and diesel oil selectivity is 54.9 percent, the conversion rate is 87.5 percent and the coking rate is 1.4 percent under the conditions that the reaction temperature is 420 ℃, the reaction time is 1.5 hours and the reaction pressure is 13 Mpa.
Example 3
Roasting natural rectorite at 500 deg.c for 4 hr, taking 4g of roasted rectorite, isovolumic adsorbing with deionized water to measure water absorption rate, and configuring (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 8 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and at 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa to obtain gasoline and diesel oil with selectivity of 62.0%, conversion rate of 84.1% and coking rate of 0.6%.
Example 4
Roasting natural rectorite at 600 deg.C for 4 hr, and removing 4g of roasted rectoriteThe water absorption rate is measured by the isovolumetric adsorption of the ionized water and is configured (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 9 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa, the gasoline-diesel selectivity is 53.6%, conversion rate is 83.3% and coking rate is 1.0%.
Example 5
Calcining natural rectorite at 700 deg.C for 4h, taking 4g calcined rectorite, measuring water absorption by isovolumetric adsorption of deionized water, and configuring (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst which is prepared in the embodiment 10 and has the mass fraction of 3 wt% of reaction oil with sublimed sulfur of the catalyst and the molar ratio of Mo element of the catalyst is 1:20, adding the mixture and raw oil into the reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and at 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa to obtain gasoline and diesel oil with selectivity of 51.1%, conversion rate of 14.5% and coking rate of 0.9%.
Example 6
Hydrothermal activation of natural rectorite at 500 deg.C for 4 hr, and taking 4g of waterThe water absorption of the transformed rectorite is measured by the isovolumetric adsorption of deionized water and is configured (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 13 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa to obtain gasoline and diesel oil with selectivity of 57.1%, conversion rate of 83.5% and coking rate of 0.8%.
Example 7
Performing hydrothermal activation on natural rectorite for 4h at 600 ℃, taking 4g of hydrothermally activated rectorite, measuring the water absorption rate by isovolumetric adsorption of deionized water, and configuring (NH)4)6Mo7O24·4H2O solution, and dipping the hydrogenation active phase on the natural rectorite (the loading is 5wt% MoO) by an equal volume dipping method3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, carrying out hydrocracking reaction by taking medium petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 14 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the mol ratio of Mo element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and at 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa for 57.5% selectivity, 84.0% conversion rate and 0.6% coking rate.
Example 8
Natural rectorite at 5Roasting at 00 deg.C for 4h, taking 4g of roasted rectorite, measuring water absorption by isovolumetric adsorption of deionized water, and configuring (NH)4)6H2W12O40·2H2O solution, and impregnating the hydrogenated active phase onto the natural rectorite by an equal volume impregnation method (the loading is 5wt percent of WO)3) And soaking for 24h, drying, and roasting at 500 ℃ for 4h to obtain the catalyst.
In a suspension bed reactor, hydrocracking reaction is carried out by taking petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the embodiment 15 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the molar ratio of W element of the catalyst being 1:20, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: the gasoline and diesel oil are vulcanized for 2 hours at 225 ℃, vulcanized for 1 hour at 325 ℃, the gasoline and diesel oil selectivity is 50.1 percent, the conversion rate is 82.1 percent and the coking rate is 1.7 percent under the conditions that the reaction temperature is 420 ℃, the reaction time is 1.5 hours and the reaction pressure is 13 Mpa.
Example 9
Roasting natural rectorite at 500 deg.c for 4 hr, measuring water absorption rate of 4g of roasted rectorite by isovolumetric adsorption with deionized water, and configuring CoSO4·7H2And (3) soaking the hydrogenation active phase on the natural rectorite (the load is 5wt% of CoO) by an equal-volume soaking method, drying after soaking for 24 hours, and roasting at 500 ℃ for 4 hours to obtain the catalyst.
In a suspension bed reactor, hydrocracking reaction is carried out by taking petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 16 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the molar ratio of Co element of the catalyst being 1:10, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and at 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa, the gasoline-diesel selectivity is 54.7%, conversion rate is 84.5% and coking rate is 2.0%.
Example 10
Roasting natural rectorite at 500 deg.C for 4 hr, and taking 4g, measuring the water absorption rate of the calcined rectorite through the isovolumetric adsorption of deionized water, and configuring Ni (NO)3)2·6H2And (3) soaking the hydrogenation active phase onto the natural rectorite (the load is 5wt% of NiO) by using an equal-volume soaking method in the O solution for 24 hours, drying, and roasting at 500 ℃ for 4 hours to obtain the catalyst.
In a suspension bed reactor, hydrocracking reaction is carried out by taking petroleum mixed residual oil as a reactant, mechanically and uniformly mixing the catalyst prepared in the example 17 with the mass fraction of 3 wt% of reaction oil and sublimed sulfur with the molar ratio of Ni element of the catalyst being 1:10, adding the mixture and raw oil into a reactor, and carrying out in-situ vulcanization on the catalyst by adopting a two-stage vulcanization method, wherein the vulcanization conditions are as follows: sulfurizing at 225 deg.C for 2 hr and 325 deg.C for 1 hr, reacting at 420 deg.C for 1.5 hr and under 13MPa, the gasoline-diesel selectivity is 53.6%, conversion rate is 83.6% and coking rate is 1.8%.
In conclusion, in the residue hydrocracking reaction, compared with the unmodified rectorite catalyst, the catalyst taking the calcined or hydrothermally modified rectorite as the carrier obviously improves the selectivity of gasoline and diesel distillate oil by more than 15 percent, slightly increases the residue conversion rate by about 5 percent, and simultaneously keeps lower coking rate.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A hydrocracking supported catalyst for poor-quality residual oil suspension bed is characterized in that: the catalyst consists of a metal active component and a carrier material, wherein the metal active component is one or more of Mo, W, Co or Ni elements, and the dosage of the metal active component is 1-10 wt% of the total amount of the catalyst; wherein the carrier material is modified rectorite.
2. The supported catalyst for slurry bed hydrocracking of inferior residuum according to claim 1, characterized in that: in the metal active component, the precursor of Mo is (NH)4)6Mo7O24·4H2O or H3[P(Mo3O10)4]One of (1); the precursor of W is (NH)4)6H2W12O40·2H2O; the precursor of Co is CoSO4·7H2O; the precursor of Ni is Ni (NO)3)2·6H2O。
3. The supported catalyst for slurry bed hydrocracking of inferior residuum according to claim 1, characterized in that: the carrier material is modified rectorite.
4. The supported catalyst for slurry bed hydrocracking of inferior residuum according to claim 3, characterized in that: the modified rectorite is specifically as follows: roasting or hydro-thermal modifying natural mineral rectorite.
5. The supported catalyst for slurry bed hydrocracking of inferior residuum according to claim 4, characterized in that: the roasting or hydrothermal modification conditions are as follows: the modification temperature is 400-1000 ℃, and the modification time is 1-8 h.
6. The preparation method of the supported catalyst for hydrocracking the inferior residual oil in the suspension bed as claimed in any one of claims 1 to 5, wherein the preparation method comprises the following steps: and loading the metal component on the surface of the carrier material by adopting an isometric impregnation method, and drying and roasting to obtain the supported catalyst.
7. The application of the supported catalyst of any one of claims 1 to 5 in hydrocracking of inferior residual oil in a suspension bed is characterized in that: the poor residual oil is evaluated by adopting a suspension bed reactor to carry out reaction at the reaction temperature of 400 DEGoC-440 ℃, the reaction time is 1-3H, and the initial reaction H2The pressure is 8-15 Mpa.
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Cited By (5)
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| WO2021143710A1 (en) * | 2020-01-17 | 2021-07-22 | 福州大学 | Supported catalyst for suspended bed hydrocracking of inferior residue oil, and preparation method therefor |
| CN113926489A (en) * | 2021-11-14 | 2022-01-14 | 福州大学 | A kind of preparation method of heavy oil suspended bed hydrocracking catalyst |
| CN114437824A (en) * | 2020-10-30 | 2022-05-06 | 中国科学院宁波材料技术与工程研究所 | A kind of method for producing clean fuel from coal tar whole fraction |
| CN114917934A (en) * | 2022-06-15 | 2022-08-19 | 中国石油大学(华东) | Preparation method of tungsten-based catalyst applied to hydrocracking of heavy oil in suspension bed |
| CN119613219A (en) * | 2025-02-13 | 2025-03-14 | 孝义市晋茂化工有限公司 | Coking crude benzene catalytic hydrofining method |
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