CN115888812A - Hydrotreating oil-soluble bimetallic catalyst and preparation method thereof - Google Patents
Hydrotreating oil-soluble bimetallic catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 39
- 239000011733 molybdenum Substances 0.000 claims abstract description 38
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 36
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000002524 organometallic group Chemical group 0.000 claims description 17
- 239000002283 diesel fuel Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 6
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 32
- 239000003245 coal Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 238000004517 catalytic hydrocracking Methods 0.000 description 11
- 238000005336 cracking Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000004939 coking Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000005078 molybdenum compound Substances 0.000 description 5
- 150000002752 molybdenum compounds Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- -1 polycarbonyl Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005261 decarburization Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a hydrotreating oil-soluble bimetallic catalyst and a preparation method thereof, wherein the catalyst comprises organic metal aluminum and organic metal molybdenum; the organic metal aluminum is one of aluminum isopropoxide, aluminum naphthenate and aluminum isooctanoate, and the organic metal molybdenum is one of molybdenum isooctanoate, molybdenum naphthenate and molybdenum hexacarbonyl. The catalyst of the invention is obtained by mixing organic metal and nonpolar solvent. The catalyst can be applied to slurry bed hydrogenation process, direct coal liquefaction and oil-coal mixing, has low cost and simple preparation method, is easy to store and transport, improves the conversion rate of residual oil, and brings more profits for slurry bed residual oil hydrogenation.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a hydrotreating oil-soluble bimetallic catalyst and a preparation method thereof.
Background
With the deterioration of crude oil and the stricter environmental regulations, the deep processing of heavy oil and residual oil becomes more and more important, and therefore, how to extract more light fuel oil from heavier and heavier raw oil becomes one of the important points in the field of petroleum refining. Hydrocracking is a rapidly developing way for lightening heavy raw materials, wherein, the suspension bed (slurry bed) hydrocracking process of residual oil mainly aims to solve the problem of processing poor heavy oil, combines the flexibility of a decarburization process and the improvement of the product quality of a hydrogenation process, and has great potential and broad prospect.
The slurry bed residual oil hydrogenation process is an important process for processing residual oil with large density, high distillation range and high nitrogen and vanadium content, and the process can simultaneously have multiple processes of residual oil cracking, desulfurization, denitrification and the like. The catalyst is the core of slurry bed hydrogenation technology, and the prior slurry bed hydrogenation catalyst has oil-soluble and water-soluble catalysts. The water-soluble catalyst has poor dispersibility in residual oil and is not uniform enough to react. The oil-soluble catalyst containing the same metal element has higher hydrogenation coke-inhibiting activity compared with the water-soluble catalyst, and the adding amount (calculated by metal) of the catalyst can be as low as 10 -6 And (4) stages. Under the condition of the same metal content, the catalytic effect of the oil-soluble catalyst is better than that of the water-soluble catalyst, and an emulsifier is not required to be added, so that the oil-soluble catalyst is an ideal catalyst. Therefore, the use of oil soluble homogeneous catalysts to increase the conversion of the residuum and suppress coke formation is a preferred option for slurry bed hydroprocessing.
The oil-soluble residual oil hydrotreating catalyst has the characteristics of excellent dispersibility, high atom utilization rate, high hydrogenation activity, small subsequent blockage to a reaction pipeline and the like, and is a preferred catalyst for residual oil hydrogenation in a slurry bed. The prior industrial oil-soluble residual oil hydrotreating catalyst has the following problems:
(1) The oil soluble residual oil hydrogenating catalyst is mainly polycarbonyl salt or naphthenate of Ni, mo, co, W, etc. but the oil soluble organic molybdenum compound is used most widely. The oil-soluble organic molybdenum compound can react with S in the reaction process to produce nano MoS 2 Nano MoS 2 Can be used for H due to its unique structural properties 2 After adsorption, a complex is formed and H-H cracking is promoted, and N and S in the raw material are favorably removed under the hydrogenation condition. The oil soluble organic molybdenum compound has good cracking, desulfurizing and denitrifying functions, but the cracking activity of the oil soluble organic molybdenum compound for residual oil with particularly high distillation range is still insufficient, the conversion rate of cracking is not high enough, and the content of heavy components in cracked products is still high.
(2) The preparation process of the catalyst is complex, the cost is high, and the using addition amount is large.
Therefore, the development of the oil-soluble residual oil hydrotreating catalyst with good hydrogenation activity and high conversion rate has very important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a hydrotreating oil-soluble bimetallic catalyst and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the hydrotreating oil-soluble bimetallic catalyst protected by the invention comprises organometallic aluminum and organometallic molybdenum; the organometallic according to the present invention refers to a compound comprising an organic compound and a metal; in the invention, the organometallic aluminum is one of aluminum isopropoxide, aluminum naphthenate and aluminum isooctanoate, and the organometallic molybdenum is one of molybdenum isooctanoate, molybdenum naphthenate and molybdenum hexacarbonyl.
After the crude oil is usually processed by atmospheric and vacuum distillation, about 50% of high-quality light distillate oil enters subsequent procedures for treatment, the remaining 50% is heavy oil commonly called residual oil, and the residual oil has high contents of impurities, condensed rings and multi-carbon aromatic hydrocarbons and is difficult to process.
In the prior art, molybdenum, tungsten, iron, nickel and other elements are used for preparing a bimetallic catalyst, for example, patent CN106693975B discloses an oil-soluble Fe-Ni bimetallic catalyst, the active ingredients of the catalyst are iron and nickel, the catalyst is used for coal-oil hydrogenation co-refining, and the catalyst have a synergistic effect, so that the hydrogenation activity is high, the coke inhibition effect is good, and the coal conversion rate is high; patent CN106391111A discloses an oil-soluble catalyst, which comprises group VIB metal Mo and/or W, and at least one of group VIII metal Fe, co or Ni, and has excellent catalytic hydrogenation activity and coking inhibition capability on inferior heavy oil; the patent CN104888796B discloses an oil-soluble Mo-Ni bimetallic catalyst suitable for poor-quality residual oil suspension bed hydrocracking, wherein the Mo-Ni (1/1) bimetallic catalyst has a better targeted catalytic effect on heavy components (> 480 ℃) in a residual oil hydrocracking reaction system, and provides sufficient activated hydrogen and macromolecular free radicals and alkyl free radicals generated by a time-closed cracking reaction, so that condensation of the macromolecular free radicals is inhibited.
However, the above patents all utilize the redox action of the subgroup elements for hydrogenation/dehydrogenation reactions, and belong to hydrogenation radical cracking. The slurry bed residual oil hydrogenation catalyst is an oil-soluble Mo and Al bimetallic catalyst, belongs to the catalytic cracking of carbonium ions, additionally introduced Al can additionally introduce acid catalysis in the slurry bed hydrogenation reaction process, al is used as an acid catalytic active site, belongs to the catalytic cracking reaction of carbonium ions, and can further improve the residual oil conversion rate, and in addition, the introduction of Al element can stabilize MoS in the reaction process 2 Nanostructure, enhanced MoS 2 The service life of (2). After the reaction is finished, al generates strong adsorption gel under the action of water or dilute acid/dilute alkali in an absorption stabilizer, and MoS can be converted 2 And solid particles are adsorbed in the water phase, so that the viscosity of oil slurry in the product is reduced, and the recycling of the Mo element is realized.
The hydrogenation protective agent prepared by the prior art mainly takes alumina and/or modified alumina as a carrier, and is different from the prior art in that the non-supported catalyst is prepared by the invention, and aluminum is taken as a catalytic active site of acid, so that the residual oil hydrocracking conversion rate and the gasoline octane number can be improved.
Further, in the catalyst, the weight ppm of aluminum: weight ppm of molybdenum = (0.5 to 4): 1.
When the weight ppm ratio of the aluminum to the molybdenum is in a certain range, the catalyst can be ensured to have higher cracking and hydrogenation activity.
Further, in the catalyst, the weight ppm of aluminum: weight ppm of molybdenum = (0.5-1.5) = (1).
The invention also provides a preparation method of the hydrocracking oil-soluble bimetallic catalyst, which comprises the step of mixing 2 organic metals and a nonpolar solvent according to the mass ratio of 1 (30-80) respectively to obtain the hydrocracking oil-soluble bimetallic catalyst.
In the present invention, the organometallic: the mass ratio of the nonpolar solvent is 1 (40-60).
Further, the non-polar solvent includes, but is not limited to, diesel, gasoline, light diesel, petroleum ether, n-pentane, n-hexane, etc.; in the present invention, the nonpolar solvent is diesel oil.
Further, the components of the diesel oil include but are not limited to one or more of common two-line oil, common three-line oil, catalytic diesel oil and hydrogenated diesel oil.
"hydroprocessing" as referred to herein includes all processes wherein a hydrocarbon feedstock is reacted with hydrogen at effective temperatures and pressures, including but not limited to hydrogenation, hydrotreating, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodewaxing, and hydrocracking, including selective hydrocracking, and the like. In the present invention, hydrocracking is preferred.
The invention also provides an application of the hydrotreating oil-soluble bimetallic catalyst in a slurry bed residual oil hydrogenation process.
The application of the invention comprises: preparing an organometallic aluminum and organometallic molybdenum catalyst;
(2) Mixing organic metal catalyst, sulfur powder and residual oil, reacting at 380-500 deg.c and 10-30 MPa, cooling and vacuum distilling.
In the invention, (2), hydrogen is adopted to replace the air in the reaction kettle, so that the gas pressure in the reaction kettle reaches 10-30 MPa, and the reaction is carried out for 2-4 hours at the temperature of 380-500 ℃;
further, the mass of aluminum in the organometallic catalyst is 150 to 800ppm and the mass of molybdenum is 300 to 500ppm per 100g of the residual oil.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, between the upper and lower limit of that range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.
The invention has the following beneficial effects:
(1) Al additionally introduced by the oil-soluble bimetallic catalyst provided by the invention exists in an atomic or nano-particle form in the slurry bed hydrogenation reaction process, and acid catalysis is additionally introduced, so that the cracking of heavy components in residual oil can be assisted, and the residual oil hydrocracking conversion rate and the gasoline octane number are improved; the introduction of Al element can also stabilize MoS in the reaction process 2 Nanostructure, enhanced MoS 2 The service life of (2). After the reaction is finished, al generates strong adsorption gel under the action of water or dilute acid/dilute alkali in an absorption stabilizer, and MoS can be converted 2 And the solid particles are adsorbed in the water phase, so that the viscosity of the oil slurry in the product is reduced, and the recovery and utilization of the Mo element are realized; the oil soluble molybdenum compound exists in the form of atoms or nano particles and has the functions of cracking, desulfurization and denitrification.
(2) The hydrotreating oil-soluble Mo-Al bimetallic catalyst provided by the invention can improve the residual oil conversion rate when being used in the slurry bed hydrogenation reaction, effectively improves the content of light components such as C1-C4, C5-200 ℃, 200-360 ℃ and the like in a residual oil cracking product, improves the octane number of cracked gasoline, and generates more economic benefits and social benefits for the slurry bed residual oil hydrogenation.
(3) The hydrotreating oil-soluble Mo-Al bimetallic catalyst provided by the invention can obtain more MoO from ash 3 Further recovering and reusing molybdenum element.
(4) The preparation process of the catalyst is simple, the production cost and the production period of the catalyst are greatly reduced, and the catalyst is suitable for industrial production.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below, and of course, the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments which can be obtained by a person skilled in the art based on the embodiments of the present invention without any inventive step belong to the protection scope of the present invention. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents and solvents used in the present invention are not specifically treated, except as otherwise specified.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.
Comparative example 1
18.5 g of molybdic acid and 100g of isooctanoic acid were added to the flask, then in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. Obtaining a product containing 15.2% MoO 3 Molybdenum isooctanoate.
200g of vacuum residue is weighed and added into a high-pressure reaction kettle with the volume of 1L, 400ppm of Mo molybdenum isooctanoate catalyst and 0.3 g of sulphur powder are sequentially added, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, carrying out reduced pressure distillation, and respectively calculating the conversion rate, the C1-C4 gas, the C5-200 ℃ fraction yield, the 200-360 ℃ fraction yield, the 360-520 ℃ fraction yield and the >520 ℃ fraction yield. Washing the residue with toluene, centrifuging, drying, weighing and calculating the coking rate. The hydrogenation effect of the residue is shown in Table 1.
In parallel with the above experiment, after the reaction was completed, 40 g of water was added to the reaction vessel after the reaction vessel was cooled to room temperature, the temperature was raised to 95 ℃, the mixture was stirred for 4 hours, and the upper oil phase and the lower water phase were separated. The lower aqueous phase was evaporated to dryness at 120 ℃ and calcined at 600 ℃ for 2 hours, and the weight and elemental composition of the participating ash was measured, see table 2.
Comparative example 2
18.5 g molybdic acid and 100g isooctanoic acid were added to the flask, followed by reaction in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. Obtaining a product containing 15.2% MoO 3 Molybdenum isooctanoate.
Adding 1g of nickel naphthenate into 50 g of diesel oil, fully stirring, and obtaining the nickel naphthenate catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a 1L high-pressure reaction kettle, 400ppm of Ni naphthenate catalyst, 400ppm of Mo isooctanoate catalyst and 0.3 gram liter of sulfur powder are sequentially added, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, carrying out reduced pressure distillation, and respectively calculating the conversion rate, the C1-C4 gas, the C5-200 ℃ fraction yield, the 200-360 ℃ fraction yield, the 360-520 ℃ fraction yield and the >520 ℃ fraction yield. Washing the residue with toluene, centrifuging, drying, weighing and calculating the coking rate. The hydrogenation effect of the residue is shown in Table 1.
In parallel with the above experiment, after the reaction was completed, 40 g of dilute hydrochloric acid having a pH of 1 was added to the reaction vessel after the reaction vessel was cooled to room temperature, the temperature was raised to 95 ℃, the mixture was stirred for 4 hours, and the upper oil phase and the lower water phase were separated. The lower aqueous phase was evaporated to dryness at 120 ℃ and calcined at 600 ℃ for 2 hours, and the weight and elemental composition of the participating ash was measured, see table 2.
Example 1
18.5 g of molybdic acid and 100g of isooctanoic acid were added to the flask, then in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. The obtained product contains 15.2% of MoO 3 Molybdenum isooctanoate.
Adding 1g of aluminum isopropoxide into 50 g of diesel oil, fully stirring, and obtaining the aluminum isopropoxide catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a 1L high-pressure reaction kettle, 200ppm of Al aluminum isopropoxide catalyst, 400ppm of Mo molybdenum isooctanoate catalyst and 0.3 gram of sulfur powder are sequentially added, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, carrying out reduced pressure distillation, and respectively calculating the conversion rate, the C1-C4 gas, the C5-200 ℃ fraction yield, the 200-360 ℃ fraction yield, the 360-520 ℃ fraction yield and the >520 ℃ fraction yield. Washing the residue with toluene, centrifuging, drying, weighing and calculating the coking rate. The hydrogenation effect of the residue is shown in Table 1.
In parallel with the above experiment, after the reaction was completed, the reaction kettle was cooled to room temperature, 40 g of dilute hydrochloric acid having a pH of 1 was added to the reaction kettle, the temperature was raised to 95 ℃, stirred for 4 hours, and the upper oil phase and the lower water phase were separated. The lower aqueous phase was evaporated to dryness at 120 ℃ and calcined at 600 ℃ for 2 hours and the weight and elemental composition of the participating ash was measured as shown in table 2.
Example 2
18.5 g molybdic acid and 100g isooctanoic acid were added to the flask, followed by reaction in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. Obtaining a product containing 15.2% MoO 3 Molybdenum isooctanoate.
Adding 1g of aluminum isopropoxide into 50 g of diesel oil, fully stirring, and obtaining the aluminum isopropoxide catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a high-pressure reaction kettle with the volume of 1L, then 400ppm of Al aluminum isopropoxide catalyst, 400ppm of molybdenum isooctanoate catalyst and 0.3 g of sulphur powder are added in sequence, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, distilling under reduced pressure, and respectively calculating the conversion rate, the C1-C4 gas, the fraction yield of C5-200 ℃, the fraction yield of 200-360 ℃, the fraction yield of 360-520 ℃ and the fraction yield of more than 520 ℃. Washing the residue with toluene, centrifuging, drying, and weighing to calculate the coking rate. The hydrogenation effect of the residue is shown in Table 1.
In parallel with the above experiment, after the reaction was completed, the reaction kettle was cooled to room temperature, 40 g of dilute hydrochloric acid having a pH of 1 was added to the reaction kettle, the temperature was raised to 95 ℃, stirred for 4 hours, and the upper oil phase and the lower water phase were separated. The lower aqueous phase was evaporated to dryness at 120 ℃ and calcined at 600 ℃ for 2 hours, and the weight and elemental composition of the participating ash was measured, see table 2.
Example 3
18.5 g molybdic acid and 100g isooctanoic acid were added to the flask, followed by reaction in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. The obtained product contains 15.2% of MoO 3 Molybdenum isooctanoate.
Adding 1g of aluminum isopropoxide into 50 g of diesel oil, fully stirring, and obtaining the aluminum isopropoxide catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a 1L high-pressure reaction kettle, then 600ppm of Al aluminum isopropoxide catalyst, 400ppm of Mo molybdenum isooctanoate catalyst and 0.3 gram liter of sulfur powder are added in sequence, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, carrying out reduced pressure distillation, and respectively calculating the conversion rate, the C1-C4 gas, the C5-200 ℃ fraction yield, the 200-360 ℃ fraction yield, the 360-520 ℃ fraction yield and the >520 ℃ fraction yield. Washing the residue with toluene, centrifuging, drying, weighing and calculating the coking rate. The hydrogenation effect of the residue is shown in Table 1.
In parallel with the above experiment, after the reaction was completed, the reaction kettle was cooled to room temperature, 40 g of dilute hydrochloric acid having a pH of 1 was added to the reaction kettle, the temperature was raised to 95 ℃, stirred for 4 hours, and the upper oil phase and the lower water phase were separated. The lower aqueous phase was evaporated to dryness at 120 ℃ and calcined at 600 ℃ for 2 hours and the weight and elemental composition of the participating ash was measured as shown in table 2.
Example 4
18.5 g of molybdic acid and 100g of isooctanoic acid were added to the flask, then in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. Obtaining a product containing 15.2% MoO 3 Molybdenum isooctanoate.
Adding 1g of aluminum isopropoxide into 50 g of diesel oil, fully stirring, and obtaining the aluminum isopropoxide catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a 1L high-pressure reaction kettle, then 400ppm of Al aluminum ethoxide catalyst, 400ppm of Mo molybdenum isooctanoate catalyst and 0.3 g L of sulphur powder are added in sequence, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. Reacting for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, carrying out reduced pressure distillation, and respectively calculating the conversion rate, the C1-C4 gas, the C5-200 ℃ fraction yield, the 200-360 ℃ fraction yield, the 360-520 ℃ fraction yield and the >520 ℃ fraction yield. Washing the residue with toluene, centrifuging, drying, and weighing to calculate the coking rate. The hydrogenation effect of the residue is shown in Table 1.
Example 5
18.5 g molybdic acid and 100g isooctanoic acid were added to the flask, followed by reaction in H 2 The temperature was heated to 190 ℃ under an atmosphere and held for 12 hours. The obtained product contains 15.2% of MoO 3 Molybdenum isooctanoate.
Adding 1g of aluminum isopropoxide into 50 g of diesel oil, fully stirring, and obtaining the aluminum isopropoxide catalyst after the solution is transparent.
200g of vacuum residue is weighed and added into a high-pressure reaction kettle with the volume of 1L, then 400ppm of Al aluminum iso-butoxide catalyst, 400ppm of Mo molybdenum iso-octoate catalyst and 0.3 gram liter of sulphur powder are added in sequence, and stirring is started to fully mix the raw materials. The air in the reaction kettle is replaced by hydrogen, and the hydrogen is filled to a certain pressure. The reaction is carried out for 3h at 430 ℃ and 20 MPa. After the reaction is finished, cooling the reaction kettle to room temperature, collecting the product, distilling under reduced pressure, and respectively calculating the conversion rate, the C1-C4 gas, the fraction yield of C5-200 ℃, the fraction yield of 200-360 ℃, the fraction yield of 360-520 ℃ and the fraction yield of more than 520 ℃. Washing the residue with toluene, centrifuging, drying, and weighing to calculate the coking rate. The hydrogenation effect of the residue is shown in Table 1.
TABLE 1 post-reaction product distribution and product Properties
As is clear from Table 1, in examples 1 to 3, the conversion of the residue was slightly improved and the contents of light components such as C1 to C4, C5 to 200 ℃ and 200 to 360 ℃ were significantly increased by adding the aluminum isopropoxide catalyst, as compared with comparative example 1. More light hydrocarbon yield and better gasoline octane number can bring more profits for the residual oil hydrogenation of the slurry bed.
TABLE 2 weight of residual Ash and elemental composition
As is clear from Table 2, in examples 1 to 3, the addition of the aluminum isopropoxide catalyst resulted in more ash being finally removed from the oil and more MoO being obtained from the ash than in comparative examples 1 and 2 3 Further, mo is recovered and reused.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A hydroprocessing oil-soluble bimetallic catalyst, characterized in that the catalyst comprises organometallic aluminum, organometallic molybdenum; the organometallic aluminum is one of aluminum isopropoxide, aluminum naphthenate and aluminum isooctanoate, and the organometallic molybdenum is one of molybdenum isooctanoate, molybdenum naphthenate and molybdenum hexacarbonyl.
2. The hydroprocessing oil-soluble bimetallic catalyst of claim 1, wherein the weight ppm of aluminum in the catalyst is: weight ppm of molybdenum = (0.5 to 4): 1.
3. The hydroprocessing oil-soluble bimetallic catalyst of claim 2, wherein the weight ppm of aluminum in the catalyst is: weight ppm of molybdenum = (0.5 to 1.5): 1.
4. The method for preparing a hydroprocessing oil-soluble bimetallic catalyst as described in any one of claims 1 to 3, characterized in that 2 kinds of organic metal are mixed with the nonpolar solvent respectively in a mass ratio of 1 (30-80).
5. The production method according to claim 4, wherein the organometallic: the mass ratio of the nonpolar solvent is 1 (40-60).
6. The method according to claim 4, wherein the nonpolar solvent is at least one selected from diesel oil, gasoline, light diesel oil, petroleum ether, n-pentane and n-hexane.
7. Use of a hydroprocessing oil soluble bimetallic catalyst as described in any one of claims 1 to 3 in a slurry bed residuum hydroprocessing process.
8. The use according to claim 7, comprising:
(1) Preparing organometallic aluminum and organometallic molybdenum catalysts;
(2) Mixing organic metal catalyst, sulfur powder and residual oil, reacting at 380-500 deg.c and 10-30 MPa, cooling and vacuum distilling.
9. The use according to claim 8, wherein in (2), the air in the reaction kettle is replaced by hydrogen to ensure that the gas pressure in the reaction kettle reaches 10-30 MPa, and the reaction is carried out for 2-4 hours at the temperature of 380-500 ℃.
10. Use according to claim 9, characterized in that the mass of aluminium and the mass of molybdenum in the organometallic catalyst are 150 to 800ppm and 300 to 500ppm, respectively, per 100g of residual oil.
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| CN112934245A (en) * | 2021-01-29 | 2021-06-11 | 福州大学 | Oil-soluble molybdenum-based composite hydrogenation catalyst, and preparation method and application thereof |
| CN114870902A (en) * | 2022-06-15 | 2022-08-09 | 中国石油大学(华东) | Preparation method of organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation |
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| CN112934245A (en) * | 2021-01-29 | 2021-06-11 | 福州大学 | Oil-soluble molybdenum-based composite hydrogenation catalyst, and preparation method and application thereof |
| CN114870902A (en) * | 2022-06-15 | 2022-08-09 | 中国石油大学(华东) | Preparation method of organic acid molybdenum oil-soluble catalyst for slurry bed hydrogenation |
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