CN112619696B - Composite bed hydrocracking catalyst system and preparation method and application thereof - Google Patents
Composite bed hydrocracking catalyst system and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a composite bed hydrocracking catalyst system and a preparation method and application thereof. The composite bed hydrocracking catalyst system comprises an upper catalyst and a lower catalyst; the catalyst comprises the following components in parts by weight: a) 8-80 parts of solid acid zeolite; b) 0.05 to 8 parts of VIII group metal; c) 1.5-25 parts of VIB group metal oxide; d) 15-90 parts of a binder; the space index of the pore channel of the solid acid zeolite is between 6 and 18, and the space index of the zeolite contained in the upper catalyst is larger than that of the zeolite contained in the lower catalyst. The catalyst system is used in the hydrocracking reaction for producing light arene and cracking material from sulfur-nitrogen-containing and high arene material, such as catalytic diesel oil, and has the characteristic of high arene product purity.
Description
Technical Field
The invention relates to the field of petroleum refining catalysts, and further relates to a composite bed hydrocracking catalyst system and a preparation method and application thereof.
Background
Hydrocracking is one of the main processes for deep processing of heavy distillate oil, and refers to a hydrogenation process for reducing 10% or more of molecules in a feedstock oil by hydrogenation reaction. Hydrocracking technology is one of the important means for secondary processing of crude oil and heavy oil lightening, and has become an important way for producing high-quality light oil products and solving the problem of chemical raw material sources due to the characteristics of strong adaptability to raw materials, very flexible operation and product scheme, good product quality and the like. In the existing process, the light oil type hydrocracking process takes gasoline or naphtha as a target product, the naphtha is used for producing light aromatic hydrocarbon through a catalytic reforming process, and olefin products can also be produced through a steam cracking process.
With the stagnation of the increase of the diesel oil demand, the national VI standard is implemented in 2019, and a great amount of excessive inferior oil products, such as catalytic diesel oil and ethylene tar, appear in refining enterprises. Although they have a boiling point in the diesel fraction, they are economically disadvantageous in that they contain a large amount of polycyclic aromatic hydrocarbons and are only used as fuel oils in some enterprises.
On the basis of the existing oil refining type hydrocracking catalyst and process technology, relevant research institutions develop technologies capable of converting catalytic diesel into high-octane gasoline blending components, such as the technologies disclosed in patents CN101724454A and CN 102839018A. The obtained heavy naphtha fraction has aromatic hydrocarbon content between 50-65% and can be used as a high-octane gasoline blending component, and the adopted catalyst contains 20-75wt% of Y-type molecular sieve. However, the Y-type molecular sieve has wide pore channels, the space index is close to 20 (see the literature of Catalytic hydrogenation-catalysis and conservation of the process, chemCatchem 2012,4,292-306), the shape selective effect of cracking non-aromatic hydrocarbon is not realized, and the obtained product C has wide pore channels, and has no shape selective effect of cracking non-aromatic hydrocarbon 8 、C 9 And C 10 The aromatic hydrocarbon content of the fraction is low, the non-aromatic hydrocarbon content is high, the index of reforming oil can not be reached, and the fraction enters an aromatic hydrocarbon combination unit to be used as a raw material for producing benzene and paraxylene, so that the method has obvious difficulty. The document CN1955262a discloses a two-stage hydrocracking method, the hydrocracking catalyst contains Pt-Pd noble metal and non-noble metal, Y zeolite with high pore space index and alumina, the raw material is catalytic diesel oil, the maximum aromatic potential value of naphtha product is only 76.8%, the purity of aromatic hydrocarbon is not high, and the requirement of aromatic hydrocarbon combined equipment can not be met.
Chinese patent CN110180581A describes a catalyst and its use in C 11 + Application of the heavy aromatics in conversion reaction for treating catalytic diesel oil after hydrofining, wherein the purity of xylene products in conversion products reaches 96 percent, and C 9 A and C 10 The purity of A aromatic hydrocarbon is more than 98 percent, and the purity of light aromatic hydrocarbon products is close to that of aromatic hydrocarbon produced in the catalytic reforming process. But the xylene isomerization unit, the toluene disproportionation unit and the adsorption separation unit in the aromatics complex are opposite to the lightThe purity requirement of the aromatic hydrocarbon raw material is high, and the non-aromatic hydrocarbon content of the aromatic hydrocarbon raw material is definitely limited; the purity of the light aromatic hydrocarbon obtained by the technical scheme provided by the patent cannot meet the requirement of an aromatic hydrocarbon combined device.
The method has the advantages that the inferior oil is converted into the light aromatic hydrocarbon which meets the quality index of an aromatic hydrocarbon combination device to the maximum extent, the byproduct can be used as high-quality light hydrocarbon of olefin raw materials, raw materials are provided for chemical devices such as aromatic hydrocarbon and olefin, the utilization of inferior heavy aromatic hydrocarbon resources and the cost reduction and efficiency improvement of the aromatic hydrocarbon industry are realized through the refining and chemical integration, and the method has important technical significance and industrial value. Therefore, a more efficient catalyst system is developed, the purity of light aromatic hydrocarbon obtained by catalyzing diesel oil conversion is further improved, and a higher-quality light aromatic hydrocarbon raw material is provided for an aromatic hydrocarbon combination device, so that the method has important significance.
Disclosure of Invention
Aiming at the problem that the purity of aromatic hydrocarbon products is not high enough in the existing hydrocracking reaction technology for producing light aromatic hydrocarbon and cracking materials from catalytic diesel oil, the invention provides a composite bed hydrocracking catalyst system. The catalyst system can be used for producing light aromatic hydrocarbon and cracking material from raw materials containing sulfur, nitrogen and high aromatic hydrocarbon such as catalytic diesel oil, and the product purity of the obtained light aromatic hydrocarbon is higher.
It is an object of the present invention to provide a composite bed hydrocracking catalyst system.
The composite bed hydrocracking catalyst system comprises an upper catalyst and a lower catalyst, wherein the catalysts comprise the following components in parts by weight:
a) 8-80 parts of solid acid zeolite;
b) 0.05 to 8 parts of VIII group metal;
c) 1.5-25 parts of VIB group metal oxide;
d) 15-90 parts of a binder;
the weight parts of the components are 100 parts based on the total weight parts of the components.
According to the composite bed hydrocracking catalyst system, the space index of the pore channels of the solid acid zeolite in the catalyst is between 6 and 18, and the space index of the solid acid zeolite contained in the upper catalyst is larger than that of the solid acid zeolite contained in the lower catalyst.
The above-mentioned solid acid zeolite pore Space Index (SI) is an Index representing the pore width of zeolite and is between 3 and 21. After a specific zeolite is loaded with 0.1-0.5wt% of platinum or palladium noble metal, the zeolite is used for hydrocracking reaction of butylcyclohexane, and the molar ratio of isobutane to n-butane in a product is analyzed, namely the pore space index of the zeolite. The spaciousness of the pore channels of different zeolites can be characterized by the spatial index.
According to the composite bed hydrocracking catalyst system of the present invention, the solid acid zeolite in the catalyst is preferably at least one of zeolite having a space index of 6 to 18, more preferably at least one of beta zeolite, mordenite and MCM-22 zeolite having a space index of 6 to 18. The solid acid zeolite contained in the upper catalyst and the solid acid zeolite contained in the lower catalyst of the catalyst system can be of one type or different types, and the space index of the solid acid zeolite contained in the upper catalyst is larger than that of the solid acid zeolite contained in the lower catalyst.
The solid acid zeolites have a silicon to aluminum molecular ratio of 20 to 200, for example 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200. In a preferred range, the silicon to aluminum molecular ratio is between 30 and 160, e.g., 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160. In the hydrothermal synthesis method of the zeolite, the feeding silicon-aluminum ratio can be regulated and controlled by controlling the ratio of the silicon source to the aluminum source.
The solid acid zeolite of the catalyst is contained in the catalyst composition containing the above-mentioned components in an amount of 8 to 80 parts by weight, preferably 15 to 75 parts by weight, more preferably 30 to 70 parts by weight, specifically, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 79, 80 parts by weight.
According to the composite bed hydrocracking catalyst system of the present invention, the group VIII metal in the catalyst comprises at least one of platinum, palladium, ruthenium, cobalt, nickel and iridium. The group VIII metal component described above may be present in the final catalyst composition as a compound, such as an oxide, chemically combined with one or more other components in the composition, or as a metallic element. This component may be present in the final catalyst composition in any catalytically effective amount. From 0.05 to 8 parts, preferably from 0.1 to 7 parts, more preferably from 0.2 to 5 parts, by weight, calculated on an elemental basis, in the final catalyst composition comprising the components, specific examples thereof include 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8 parts.
The group VIII metal component described above may be incorporated into the catalyst in any suitable manner, for example by co-precipitation with the catalyst support, co-gelling, ion exchange or impregnation, preferably impregnation with a water soluble compound of the metal. Typical platinum group compounds which may be used are chloroplatinic acid, ammonium chloroplatinate, bromoplatinic acid, platinum dichloride, platinum tetrachloride hydrate, tetraamineplatinum chloride, tetraamineplatinum nitrate, dichlorocarbonylplatinum dichloride, dinitrodiaminoplatinum, platinum chloride dihydrate, platinum nitrate, with chloroplatinic acid being preferred as the source of the particularly preferred platinum component. Typical palladium group compounds which may be used are palladium chloride, palladium chloride dihydrate, palladium nitrate dihydrate, tetraamminepalladium chloride, preferably palladium chloride as a source of the particularly preferred palladium component. Typical ruthenium family compounds that can be used are ruthenium nitrate, ruthenium trichloride, preferably ruthenium trichloride as the source of the preferred ruthenium component. Typical cobalt group compounds that may be used are cobalt nitrate, cobalt chloride, cobalt oxalate, with cobalt nitrate being preferred as the source of the particularly preferred cobalt component. Typical nickel group compounds that may be used are nickel nitrate, nickel sulphate, nickel halides, nickel oxalate, nickel acetate, with nickel nitrate being preferred as a source of the particularly preferred nickel component. Typical iridium compounds which may be used are chloroiridate, iridium trichloride, preferably chloroiridate as a source of the particularly preferred iridium component.
According to the composite bed catalyst system of the invention, after the VIB group metal oxide and the VIII group metal in the catalyst are combined, the hydrogenation degree can be controlled. The group VIB metal oxide in the catalyst of the present invention is preferably at least one selected from molybdenum oxide (molybdenum dioxide, molybdenum trioxide, etc.) and tungsten oxide (tungsten dioxide, tungsten trioxide, etc.). The group VIB metal oxide component described above may be present in the final catalyst composition in any catalytically effective amount, in parts by weight, from 1.5 to 25 parts, preferably from 3 to 20 parts, more preferably from 4 to 15 parts, specifically for example 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 parts, in the final catalyst composition comprising said component.
The group VIB metal oxide component described above may be incorporated into the catalyst in any suitable manner, for example by co-precipitation with the catalyst support, co-gelling, kneading, ion exchange or impregnation, preferably impregnation with a water-soluble compound of the metal, oven drying and calcination. Typical molybdenum family compounds that can be used are ammonium molybdate, molybdenum trioxide. Ammonium molybdate is preferred as a particularly preferred source of molybdenum oxide. Typical tungsten group compounds that may be used are ammonium tungstate, sodium tungstate, with ammonium tungstate being preferred as a particularly preferred source of tungsten oxide.
According to the composite bed catalyst system of the present invention, at least one of alumina, silica-alumina composite and magnesia-alumina composite is used as a binder in the catalyst of the present invention. The alumina, silica-alumina composite, and magnesia-alumina composite are well established commercial materials, such as various types of pseudo-boehmite products (alumina hydrates) of the Chinese petrochemical catalyst division, silica-alumina composite with the trade designation SIRAL2-SIRAL40, and sepiolite-based magnesia-alumina composites. The binder may be incorporated into the catalyst in any suitable manner, for example by kneading with the solid acid zeolite, extruding, curing, oven drying and calcining to provide the catalyst support.
The binder is 15 to 90 parts by weight, preferably 20 to 70 parts by weight, and more preferably 30 to 60 parts by weight in the catalyst composition containing the component.
According to the composite bed catalyst system of the present invention, conventional components of catalysts in the art, such as diatomaceous earth, activated clay, and the like, may also be included in the catalyst of the present invention. The amount may be a usual amount.
According to the composite bed catalyst system of the present invention, the Space Index (SI) of the solid acid zeolite in the upper catalyst is greater than the SI of the solid acid zeolite in the lower catalyst, preferably by a difference of greater than 0.50, more preferably by a difference of greater than 3.0.
According to the composite bed catalyst system of the invention, the weight ratio of the upper catalyst to the lower catalyst is preferably 1:9 to 9:1, preferably 1:6 to 6:1, more preferably 1:5 to 5:1.
The above-mentioned composite bed catalyst system of the present invention comprises a catalyst packed in the upper part of the reactor and a catalyst packed in the lower part, wherein the order of the upper part and the lower part is the same as the order of the raw materials fed to the reactor. I.e., the order in which the reaction feed contacts the upper catalyst before the lower catalyst during the reaction.
In addition, the upper catalyst and the lower catalyst are preferably arranged in different beds, and the middle is usually divided by a cold hydrogen box and can be conveniently and respectively filled.
It is another object of the present invention to provide a process for the preparation of the composite bed catalyst system of the present invention.
The preparation method of the composite bed catalyst system comprises the steps of filling the catalyst into an upper catalyst and a lower catalyst, wherein the upper catalyst and the lower catalyst can be respectively filled into different beds above and below a reactor, and the middle of the bed is usually divided by a cold hydrogen box and can be conveniently and respectively filled; the weight ratio of the upper catalyst to the lower catalyst is preferably 1:9 to 9:1, preferably 1:6 to 6:1, and more preferably 1:5 to 5:1.
The catalyst in the above-mentioned composite bed catalyst system of the present invention can be prepared by any method known in the art for preparing catalysts, and is not particularly limited. For example, the preparation of the catalyst may include a step of shaping a catalyst support containing the solid acid zeolite and supporting the metal component to obtain a catalyst precursor, followed by reduction of the catalyst precursor. Wherein the carrier can be formed by using the solid acid zeolite and the binder together by a method of extrusion, rolling ball or oil column forming and the like which are common in the field; the supported metal component may be prepared by co-precipitating, co-gelling, kneading, ion-exchanging or impregnating the metal and/or metal compound with the catalyst support as is conventional in the art.
In the above preparation method of the composite bed catalyst system of the present invention, the preparation of the catalyst may specifically comprise the following steps:
mixing the solid acid zeolite with an adhesive, kneading, extruding into strips, drying at 60-150 ℃, and roasting in an air atmosphere at 500-600 ℃ for 3-6 hours to obtain the required catalyst carrier. Preparing a composite metal solution (the solvent can be an organic solvent and water, preferably water) from a VIII group metal compound and a VIB group metal compound, impregnating a catalyst carrier by an isovolumetric impregnation method, drying at 60-150 ℃, and roasting at 400-560 ℃ for 1-4 hours in an air atmosphere to obtain a catalyst precursor. The catalyst precursor is reduced to 400-500 ℃ under the condition of hydrogen and kept for 2-24 hours, and the required hydrocracking catalyst can be obtained.
It is a further object of the present invention to provide the use of the composite bed catalyst system of the present invention.
The composite bed catalyst system can be applied to the reaction of producing light aromatic hydrocarbon and cracking material from raw materials containing sulfur, nitrogen and high aromatic hydrocarbon such as catalytic diesel oil, and the like, and comprises the step of contacting the catalytic diesel oil after hydrofining with the composite bed catalyst system under the hydrogen condition.
The hydrofined catalytic diesel oil is hydrogenatedUnder the condition of contacting with the composite bed catalyst system, the light aromatic hydrocarbon product is obtained through cracking, ring opening and dealkylation. The light aromatic hydrocarbon product refers to aromatic hydrocarbon with carbon number less than 11, including C 6 Aromatic hydrocarbons such as benzene; c 7 Aromatic hydrocarbons such as toluene; c 8 Aromatic hydrocarbons such as ethylbenzene, xylene; c 9 Aromatic hydrocarbons such as methylethylbenzene, propylbenzene, trimethylbenzene; c 10 Aromatic hydrocarbons, such as tetramethylbenzene, dimethylethylbenzene, diethylbenzene.
The composite bed catalyst system of the invention can be suitable for treating the catalytic diesel oil after hydrofining, and the catalytic diesel oil and other raw materials need to be subjected to hydrofining treatment.
The nitrogen content of the hydrofined catalytic diesel oil is greatly reduced to less than 20ppm, more preferably less than 15ppm, wherein the nitrogen-containing species comprise high-boiling carbazoles, indole substances and the like.
The content of the aromatic hydrocarbon of the hydrogenated and refined catalytic diesel oil is more than 60wt%, more preferably more than 65wt%, and the catalytic diesel oil comprises non-aromatic hydrocarbon, monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon, tricyclic aromatic hydrocarbon and other components. The bicyclic aromatic hydrocarbon comprises naphthalene series, indene series, acenaphthene and the like, and the tricyclic aromatic hydrocarbon comprises anthracene, phenanthrene and the like. For example 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%.
The composite bed catalyst system of the invention is applied to the reaction for producing light aromatic hydrocarbon and cracking material from sulfur-nitrogen-containing and high aromatic hydrocarbon raw materials such as catalytic diesel oil, and the like, and the reaction conditions comprise: the temperature is 300-450 ℃, the hydrogen partial pressure is 2.0-10.0 MPa, and the liquid phase space velocity is 0.2-4.0 hours -1 The volume ratio of hydrogen to hydrocarbon is 500-4000.
The solid acid zeolite with higher SI contained in the catalyst on the upper part of the composite bed catalyst system has good nitrogen resistance; the lower catalyst contains lower SI solid acid zeolite with stronger shape-selective cracking capability, stronger cracking capability for catalyzing non-aromatic hydrocarbon in diesel oil raw material after hydrofining and non-aromatic hydrocarbon secondarily generated in 65-210 ℃ fraction, and more tendency to deep cracking to C 3 -C 5 Light hydrocarbon reaction, thereby being beneficial to obtaining light aromatic hydrocarbon with higher purity. The composite bed catalyst system of the invention is used for catalyzing diesel fuelThe hydrocracking reaction for producing light aromatic hydrocarbon and cracking material with oil, sulfur, nitrogen and high aromatic hydrocarbon material has the feature of high purity of aromatic hydrocarbon product. The aromatic hydrocarbon content in the heavy naphtha product at 65-210 ℃ is more than 85wt%, and the requirement of an aromatic hydrocarbon combination device on the purity of the light aromatic hydrocarbon product can be directly met.
Detailed Description
The following describes in detail specific embodiments of the present invention. It is to be noted, however, that the scope of the present invention is not limited thereto, but is defined by the appended claims. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, and these simple modifications all belong to the protection scope of the invention.
It is to be noted that the various features described in the following detailed description may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the present invention may be made without departing from the spirit of the present invention, and the technical solutions formed thereby are part of the original disclosure of the present specification and also fall within the scope of the present invention, and should not be considered as new matters which are not disclosed or contemplated herein, unless such combination is considered obvious and unreasonable by those skilled in the art.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, 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 invention belongs. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
Unless explicitly stated otherwise, all percentages, parts, ratios, etc. referred to in this specification are by weight unless not otherwise generally recognized by those of skill in the art; the temperature is given in units of degrees Celsius, the pressure is in gauge pressure, and the space velocity mentioned is the liquid hourly space velocity LHSV.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, the various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
In the present invention, the composition of the catalyst was analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods. The ICP test conditions were: agilent Optima 8000 type inductively coupled plasma emission instrument (ICP-AES). XRF test conditions were: rigaku ZSX 100e model XRF instrument.
In the present invention, the hydrocracking product composition is determined by gas chromatography. The chromatography model is Agilent7890A, and is prepared by providing FID detector and PONA capillary chromatography column, wherein the chromatography column is heated by program, the initial temperature is 90 deg.C, the temperature is maintained for 15 min, and then the temperature is raised to 220 deg.C at the rate of 15 deg.C/min, and the temperature is maintained for 45 min.
The data of the main results of the examples and comparative examples of the present invention were calculated based on:
1. the solid acid zeolite Space Index (SI) is characterized as follows (ChemCatChem 2012,4,292-306):
SI＝Y iso-butane /Y n-butane
SI is an index representing the channel width of the zeolite and is between 3 and 21. After a specific zeolite is loaded with 0.1-0.5wt% of platinum or palladium noble metal, the zeolite is used for hydrocracking reaction of butylcyclohexane, and the molar ratio of isobutane to n-butane in a product is analyzed, namely the pore space index of the zeolite. The spaciousness of the pore channels of different zeolites can be characterized by the spatial index.
2、C 11 + The conversion of aromatics is calculated by the formula:
3. the calculation formula of the aromatic hydrocarbon content in the heavy naphtha is as follows:
to illustrate the effectiveness of the present invention, two representative hydrorefined catalyzed diesel feedstocks are provided, the compositions of which are shown in Table 1. The catalyst raw materials of the embodiment and the comparative example of the invention can be obtained from the market, all the solid acid zeolite molecular sieves and the pseudoboehmite are from China petrochemical catalyst division, and the amorphous silicon aluminum is purchased from Sasol company.
TABLE 1
| Raw oil 1 | Raw oil 2 | |
| Density (4 ℃ C.) | 0.91 | 0.92 |
| Sulfur (wtppm) | 93 | 56 |
| Nitrogen (wtppm) | 14.3 | 7.4 |
| Non-aromatic hydrocarbons (wt) | 25.60 | 17.60 |
| Monocyclic aromatic hydrocarbon (wt%) | 50.08 | 70.27 |
| Polycyclic aromatic hydrocarbons (% by weight) | 24.32 | 12.13 |
| Initial boiling point | 195 | 157 |
| 5％ | 206 | 179 |
| 10％ | 216 | 188 |
| 30％ | 245 | 223 |
| 50％ | 266 | 242 |
| 70％ | 336 | 263 |
| 90％ | 351 | 285 |
| End point of distillation | 365 | 325 |
| Amount (wt%) of > 200 DEG C | 97 | 80 |
The present invention is further illustrated by the following examples.
Comparative example 1
The catalyst filling mode is as follows: only one hydrocracking catalyst C0 is filled in the reactor.
Preparation of catalyst C0: 67g of beta zeolite having a dry content of 90% (SI value 16.48, si/Al molecular ratio = 120), 59.5g of pseudoboehmite having a dry content of 70%, 20g of amorphous Si/Al (SiO) 2 6 percent of dry basis and 80 percent of dry basis) and 4g of sesbania powder are evenly mixed, 8ml of concentrated nitric acid and a proper amount of water are added, and the mixture is kneaded, extruded and formed into strips. Preserving the mixture at room temperature for 24 hours, drying the mixture at 90 ℃ for 12 hours, and roasting the mixture in air atmosphere at 550 ℃ for 4 hours to obtain the hydrocracking catalyst carrier. Preparing a clear solution from a proper amount of nickel nitrate and ammonium tungstate, soaking in the clear solution in the same volume, drying at 100 ℃, and roasting in air at 560 ℃ for 2.5 hours to obtain the nickel nitrate/ammonium tungstate composite materialA catalyst precursor. 20g of the catalyst precursor was reduced to 450 ℃ under hydrogen conditions and held for 4 hours to give catalyst C0. The catalyst C0 had the composition (see table 2) in parts by weight: 1.5 parts of Ni-5.3 parts of WO x 54.6 parts of beta zeolite (SI = 16.48) -37.7 parts of Al 2 O 3 -0.90 parts of SiO 2 . In which WO x X of (2) is between 2 and 3, indicating that it is WO 2 And WO 3 The composite phase of (1).
Raw material 1, having a nitrogen content of 14.3ppm, was continuously fed into a fixed bed reactor packed with catalyst C0. The reaction conditions are as follows: the inlet temperature is 380 ℃, the hydrogen partial pressure is 7.0MPa, and the LHSV airspeed is 1.0 hour -1 Hydrogen to oil volume ratio 2000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion of aromatics was 73.25 wt.%, and the aromatics content in the resulting 65-210 ℃ heavy naphtha fraction was 76.19 wt.%.
Comparative example 2
The same C0 catalyst, loading and reaction conditions as in comparative example 1 were used.
Raw material 2, having a nitrogen content of 7.4ppm, was continuously fed into a fixed bed reactor packed with catalyst C0. The reaction conditions are as follows: the inlet temperature is 420 ℃, the hydrogen partial pressure is 4.0Mpa, and the LHSV space velocity is 2 hours -1 Hydrogen to oil volume ratio 3000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion rate of aromatic hydrocarbon is 75.27wt%, and the aromatic hydrocarbon content in the obtained heavy naphtha fraction at 65-210 ℃ is 79.36wt%.
[ example 1 ]
Catalyst C1-T precursor preparation: as in comparative example 1 for catalyst C0 precursor.
Catalyst C1-B precursor preparation: 67g of beta zeolite with a dry basis content of 90% (SI value of 13.01, si/Al molecular ratio = 45), 60.9g of pseudo-boehmite with a dry basis content of 70%, and 4g of sesbania powder were uniformly mixed, 8ml of concentrated nitric acid and a proper amount of water were added, and the mixture was kneaded, extruded and molded. Preserving the mixture at room temperature for 24 hours, drying the mixture at 90 ℃ for 12 hours, and roasting the mixture in air atmosphere at 550 ℃ for 4 hours to obtain the hydrocracking catalyst carrier. Preparing a clear solution from a proper amount of nickel nitrate and ammonium tungstate, soaking in the same volume, drying at 100 ℃, and roasting in air at 560 ℃ for 2.5 hours to obtain the catalyst C1-B precursor.
The filling mode is as follows: the reactor was divided into an upper bed and a lower bed, and 8g of the catalyst C1-T precursor (same as the catalyst C0 precursor) was packed in the upper part and 12g of the catalyst C1-B precursor was packed in the lower part, and 20g in total.
The catalyst precursor is reduced to 450 ℃ under the condition of hydrogen and kept for 4 hours to obtain a composite bed hydrocracking catalyst system C1 containing catalysts C1-T and catalysts C1-B. Wherein the composition of catalysts C1-T is the same as that of catalyst C0 of comparative example 1; the compositions of the catalysts C1-B are shown in a table 2, and the catalysts C1-B are calculated according to the parts by weight: 1.5 parts of Ni-5.3 parts of WO x 54.6 parts of beta zeolite (SI = 13.01) -38.6 parts of Al 2 O 3 . In which WO x X of (a) is between 2 and 3, indicating that it is WO 2 And WO 3 The composite phase of (2).
Raw material 1, nitrogen content 14.3ppm, was continuously injected into a fixed bed reactor packed with a composite bed catalyst system C1. The reaction conditions are as follows: the inlet temperature is 380 ℃, the hydrogen partial pressure is 7.0MPa, and the LHSV space velocity is 1.0 hour -1 Hydrogen to oil volume ratio 2000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion rate of aromatic hydrocarbon is 85.63wt%, and the aromatic hydrocarbon content in the obtained heavy naphtha fraction at 65-210 ℃ is 87.24wt%.
[ example 2 ]
Catalyst C2-T precursor preparation: as in comparative example 1 catalyst C0 precursor was prepared.
Catalyst C2-B precursor preparation: 55.6g of mordenite with the dry content of 90 percent (SI value of 10.21, silicon-aluminum molecular ratio = 28), 71.4g of pseudo-boehmite with the dry content of 70 percent and 4g of sesbania powder are mixed evenly, 8ml of concentrated nitric acid and a proper amount of water are added, and the mixture is kneaded and extruded to form strips. Preserving the mixture for 24 hours at room temperature, drying the mixture for 12 hours at the temperature of 90 ℃, and roasting the mixture for 6 hours at the temperature of 500 ℃ in an air atmosphere to obtain the hydrocracking catalyst carrier. Appropriate amount of cobalt nitrate and ammonium molybdate are prepared into clear solution, after equal volume impregnation, drying is carried out at 100 ℃, and roasting is carried out in air at 400 ℃ for 4 hours, thus obtaining the precursor of the catalyst C2-B.
The filling mode is as follows: filling the reactor with an upper bed layer and a lower bed layer in a divided manner; the catalyst precursor C2-T (same catalyst C0 precursor) 16g was packed in the upper part, and the catalyst precursor C2-B4 g was packed in the lower part, and 20g in total was packed.
The catalyst precursor is reduced to 400 ℃ under the hydrogen condition and kept for 10 hours to obtain a composite bed hydrocracking catalyst system C2 containing a catalyst C2-T and a catalyst C2-B. Wherein the composition of catalysts C2-T is the same as that of catalyst C0 of comparative example 1; the compositions of the catalysts C2-B are shown in Table 2, and the catalysts C2-B are calculated according to the parts by weight: 6.6 parts of Co-10.8 parts of MoO x 41.3 parts of mordenite (SI = 10.21) -41.3 parts of Al 2 O 3 . Wherein MoO x X of (2) is between 2 and 3, indicating that it is MoO 2 And MoO 3 The composite phase of (1).
Raw material 1, nitrogen content 14.3ppm, was continuously injected into a fixed bed reactor packed with a composite bed catalyst system C2. The reaction conditions are as follows: the inlet temperature is 380 ℃, the hydrogen partial pressure is 7.0MPa, and the LHSV airspeed is 1.0 hour -1 Hydrogen to oil volume ratio 2000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion of aromatics was 79.17 wt.%, and the aromatics content in the heavy naphtha fraction at 65-210 ℃ was 85.84 wt.%.
[ example 3 ]
Catalyst C3-T precursor preparation: as in comparative example 1 catalyst C0 precursor was prepared.
Catalyst C3-B precursor preparation: 67g of MCM-22 zeolite (SI value 6.85, si/Al molecular ratio = 32) with a dry content of 90%, 86g of pseudo-boehmite with a dry content of 70% and 4g of sesbania powder were mixed uniformly, 8ml of concentrated nitric acid and a proper amount of water were added, and the mixture was kneaded, extruded and molded. Preserving the mixture at room temperature for 24 hours, drying the mixture at 90 ℃ for 12 hours, and roasting the mixture in air atmosphere at 580 ℃ for 3 hours to obtain the hydrocracking catalyst carrier. Appropriate amount of platinic chloride, nickel nitrate and ammonium tungstate are prepared into clear solution, and after equal volume impregnation, the clear solution is dried at 100 ℃ and roasted for 3 hours in air at 500 ℃ to obtain the catalyst C3-B precursor.
The filling mode is as follows: the reactor was divided into an upper bed and a lower bed, and 12g of a catalyst precursor C3-T (same catalyst C0 precursor) was packed in the upper part and 8g of a catalyst precursor C3-B was packed in the lower part, and 20g in total was packed.
The catalyst precursor is reduced to 500 ℃ under the hydrogen condition and kept for 2 hours to obtain a composite bed hydrocracking catalyst system C3 containing a catalyst C3-T and a catalyst C3-B. Wherein the composition of catalyst C3-T is the same as that of catalyst C0 of comparative example 1; the compositions of the catalysts C3-B are shown in Table 2, and the catalysts C3-B are calculated according to the parts by weight: 0.1 part of Pt-1.5 parts of Ni-14.8 parts of WO x 41.8 parts MCM-22 zeolite (SI = 6.85) -41.8 parts Al 2 O 3 。WO x X of (a) is between 2 and 3, indicating that it is WO 2 And WO 3 The composite phase of (1).
Raw material 1, nitrogen content 14.3ppm, was continuously injected into a fixed bed reactor packed with a composite bed catalyst system C3. The reaction conditions are as follows: the inlet temperature is 380 ℃, the hydrogen partial pressure is 7.0MPa, and the LHSV space velocity is 1.0 hour -1 Hydrogen to oil volume ratio 2000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion rate of aromatic hydrocarbon 81.63wt% and the aromatic hydrocarbon content in the obtained heavy naphtha fraction at 65-210 ℃ is 88.65wt%.
[ example 4 ]
Catalyst C4-T precursor preparation: as in comparative example 1 for catalyst C0 precursor.
Catalyst C4-B precursor preparation: the same as in example 2 for the preparation of the precursor of catalyst C2-B.
The filling mode is as follows: the reactor was divided into an upper bed and a lower bed, and the upper bed was filled with 10g of a catalyst precursor C4-T (same catalyst C0 precursor) and the lower bed was filled with 10g of a catalyst precursor C4-B (same catalyst C2-B precursor) in total of 20g.
The catalyst precursor is reduced to 450 ℃ under the hydrogen condition and kept for 4 hours to obtain a composite bed hydrocracking catalyst system C4 containing a catalyst C4-T and a catalyst C4-B. Wherein the composition of catalysts C4-T was the same as that of catalyst C0 of comparative example 1 (see Table 2); catalyst C4-B has the same composition as catalyst C2-B of example 2 (see Table 2).
Raw material 2, nitrogen content 7.4ppm, was continuously injected into a fixed bed reactor packed with a composite bed catalyst system C4. The reaction conditions are as follows: the inlet temperature is 420 ℃, the hydrogen partial pressure is 4.0Mpa, and the LHSV space velocity is 2 hours -1 Hydrogen to oil volume ratio 3000.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion of aromatics is 88.71wt%, the aromatics content in the heavy naphtha fraction at 65-210 ℃ is 95.66wt%.
[ example 5 ]
Catalyst C5-T precursor preparation: as in comparative example 1 for catalyst C0 precursor.
Catalyst C5-B precursor preparation: preparation of catalyst C3-B precursor as described in example 3
The filling mode is as follows: the reactor was divided into an upper bed and a lower bed, and the upper part was filled with 3g of a catalyst precursor C5-T (same catalyst C0 precursor) and the lower part with 17g of a catalyst precursor C5-B (same catalyst C3-B precursor), which was 20g in total.
The catalyst precursor is reduced to 450 ℃ under the hydrogen condition and kept for 4 hours to obtain a composite bed hydrocracking catalyst system C5 containing a catalyst C5-T and a catalyst C5-B. Wherein the composition of catalysts C5-T was the same as that of catalyst C0 of comparative example 1 (see Table 2); the composition of catalysts C5-B was the same as that of catalyst C3-B of example 3 (see Table 2).
Raw material 2, nitrogen content 7.4ppm, was continuously injected into a fixed bed reactor packed with a composite bed catalyst system C5. The reaction conditions are as follows: the inlet temperature is 390 ℃, the hydrogen partial pressure is 6.0MPa, and the LHSV space velocity is 2 hours -1 Hydrogen to oil volume ratio 2500.
After stable operation for 120 hours, sampling and analyzing, and calculating to obtain C 11 + The conversion rate of aromatic hydrocarbon is 92.58wt%, and the aromatic hydrocarbon content in heavy naphtha fraction at 65-210 deg.C is 94.65wt%.
TABLE 2
Claims (20)
1. A composite bed hydrocracking catalyst system comprises an upper catalyst and a lower catalyst; the catalyst comprises the following components in parts by weight: a) 8-80 parts of solid acid zeolite; b) 0.05 to 8 parts of VIII group metal; c) 1.5-25 parts of VIB group metal oxide; d) 15-90 parts of a binder; the space index of the pore channels of the solid acid zeolite in the catalyst is between 6 and 18, and the space index of the solid acid zeolite contained in the upper catalyst is larger than that of the solid acid zeolite contained in the lower catalyst; the difference between the space index of the solid acid zeolite in the upper catalyst and the space index of the solid acid zeolite in the lower catalyst is 0.50 or more.
2. The catalyst system of claim 1 wherein the solid acid zeolite comprises at least one zeolite having a pore space index between 6 and 18.
3. The catalyst system of claim 2, wherein the solid acid zeolite comprises at least one of beta zeolite, MCM-22, and mordenite.
4. The catalyst system of claim 1, wherein the group VIII metal comprises at least one of platinum, palladium, ruthenium, cobalt, nickel, and iridium.
5. The catalyst system of claim 1, wherein the group VIB metal oxide comprises at least one of molybdenum oxide and tungsten oxide.
6. The catalyst system of claim 5, wherein the group VIB metal oxide comprises at least one of molybdenum dioxide, molybdenum trioxide, tungsten dioxide, and tungsten trioxide.
7. The catalyst system of claim 1, wherein the binder is selected from at least one of alumina, silica-alumina composite, and magnesia-alumina composite.
8. The catalyst system of claim 1, wherein the weight ratio of the upper catalyst to the lower catalyst is 1:9 to 9:1.
9. The catalyst system of claim 1, wherein the weight ratio of the upper catalyst to the lower catalyst is 1:6 to 6:1.
10. The catalyst system of claim 1 wherein the difference between the space index of the solid acid zeolite in the upper catalyst and the space index of the solid acid zeolite in the lower catalyst is 3.0 or greater.
11. The catalyst system according to any one of claims 1 to 10, characterized in that in the catalyst:
15-75 parts of solid acid zeolite; and/or the presence of a gas in the gas,
0.1-7 parts of VIII group metal; and/or the presence of a gas in the gas,
3-20 parts of VIB group metal oxide; and/or the presence of a gas in the gas,
20-70 parts of binder.
12. The method for preparing a composite bed hydrocracking catalyst system according to any one of claims 1 to 11, comprising packing the catalyst as an upper catalyst and a lower catalyst; wherein the preparation of the catalyst comprises a step of forming a catalyst support containing the solid acid zeolite and supporting the metal component to obtain a catalyst precursor, followed by reduction of the catalyst precursor.
13. The method of claim 12, wherein the preparation of the catalyst comprises the steps of:
1) Mixing and drying the components including the solid acid zeolite and the binder, and roasting the mixture in an air atmosphere at 500-600 ℃ to obtain a required catalyst carrier;
2) Preparing metal solution from metal components including VIII group metal compounds and VIB group metal compounds, impregnating the obtained catalyst carrier by an isovolumetric impregnation method, drying, and roasting in an air atmosphere at 400-560 ℃ to obtain a catalyst precursor;
3) Reducing the obtained catalyst precursor to 400-500 ℃ under the condition of hydrogen to obtain the catalyst.
14. The method according to claim 12, wherein the weight ratio of the upper catalyst to the lower catalyst is 1:9 to 9:1.
15. The method of claim 14, wherein the weight ratio of the upper catalyst to the lower catalyst is 1:6 to 6:1.
16. Use of a composite bed hydrocracking catalyst system according to any one of claims 1 to 11, or prepared by a process according to any one of claims 12 to 15, for the production of light aromatics and cracked stocks from catalytic diesel.
17. The use of claim 16, comprising the step of contacting the composite bed hydrocracking catalyst system with catalytic diesel under hydrogen conditions.
18. The use of claim 16 or 17, wherein the catalytic diesel oil is subjected to a hydrofinishing reaction and then contacted with the composite bed hydrocracking catalyst system, and the nitrogen content of the catalytic diesel oil is less than or equal to 20ppm.
19. The use of claim 17, wherein the hydrogen-contacting conditions include: the temperature is 300-450 ℃, the hydrogen partial pressure is 2.0-10.0 MPa, and the liquid hourly space velocity is 0.2-4.0 hours -1 The volume ratio of hydrogen to hydrocarbon is 500-4000.
20. Use according to claim 16 or 17, characterized in that the aromatics content in the resulting heavy naphtha product at 65-210 ℃ is greater than 85 wt.%.
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| US3692696A (en) * | 1970-06-25 | 1972-09-19 | Texaco Inc | Catalyst for hydrocarbon conversion |
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| US3692696A (en) * | 1970-06-25 | 1972-09-19 | Texaco Inc | Catalyst for hydrocarbon conversion |
| CN103664488A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Arene methanol alkylation method for removing oxygen-containing compound impurities |
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