CN108624357B - Catalytic diesel oil conversion process - Google Patents

Catalytic diesel oil conversion process Download PDF

Info

Publication number
CN108624357B
CN108624357B CN201710182289.7A CN201710182289A CN108624357B CN 108624357 B CN108624357 B CN 108624357B CN 201710182289 A CN201710182289 A CN 201710182289A CN 108624357 B CN108624357 B CN 108624357B
Authority
CN
China
Prior art keywords
alumina
carbon
roasting
reaction
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710182289.7A
Other languages
Chinese (zh)
Other versions
CN108624357A (en
Inventor
柳伟
方向晨
杜艳泽
王凤来
秦波
高杭
张晓萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201710182289.7A priority Critical patent/CN108624357B/en
Publication of CN108624357A publication Critical patent/CN108624357A/en
Application granted granted Critical
Publication of CN108624357B publication Critical patent/CN108624357B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a catalytic diesel oil conversion process, which comprises the following steps: (1) the mixture of catalytic cracking diesel oil and hydrogen firstly enters a hydrogenation reactor for hydrofining reaction; (2) the effluent of the hydrorefining reaction directly enters a cracking reactor and is in contact reaction with a hydrocracking catalyst bed layer in the cracking reactor; wherein, an upper hydrocracking catalyst bed layer and a lower hydrocracking catalyst bed layer are arranged in the hydrocracking reactor in a grading way; the upper bed catalyst takes W-Ni and/or Mo-Ni as active metal components and takes modified Y molecular sieve and alkali metal and/or alkaline earth metal modified alumina as carriers; the lower bed layer catalyst takes Mo-Co as an active metal component, and takes a modified Y molecular sieve and carbon-deposited alumina as carriers; (3) and (3) separating and fractionating the hydrocracking reaction effluent obtained in the step (2) to obtain a naphtha component and a diesel component. The process reduces the hydrogenation saturation of the generated gasoline component and improves the octane number of the gasoline component on the premise of better meeting the conversion rate of catalytic diesel.

Description

Catalytic diesel oil conversion process
Technical Field
The invention belongs to the technical field of hydrotreatment, and particularly relates to a catalytic diesel oil hydroconversion process.
Background
Since the new century, along with the increasing enhancement of people's environmental awareness, the stricter of national environmental regulations and the rapid development of national economy, the demand of various countries in the world for clean motor fuels is increasing. The catalytic cracking (FCC) technology is one of the main technological means for heavy oil conversion, and plays an important role in oil refining enterprises of various countries in the world. The annual processing capacity of a catalytic cracking unit in China currently exceeds 1 hundred million tons, which is second only to the United states. In the gasoline and diesel oil products, the catalytic cracking gasoline accounts for about 80 percent, and the catalytic diesel oil accounts for about 30 percent. In recent years, with the increasing weight of the quality of domestic processed crude oil, the raw materials processed by catalytic cracking are also increasingly heavy and inferior, and in addition, in order to achieve the purpose of improving the quality of gasoline or increasing the yield of propylene, a plurality of enterprises modify a catalytic cracking unit or increase the operation severity of the catalytic cracking unit, so that the quality of catalytic cracking products, particularly catalytic diesel oil, is further deteriorated.
In order to improve the utilization rate of petroleum resources, improve the overall quality level of gasoline and diesel fuel, realize the aims of product blending optimization and product value maximization and meet the continuously increasing demands for clean fuel in China, the hydrocracking process technology for producing high-added-value naphtha component and low-sulfur clean diesel fuel by the hydroconversion of high-aromatic-hydrocarbon diesel has good application prospect. Researchers at home and abroad also carry out a great deal of research work. The hydrocracking technology is adopted to convert the catalytic cracking light cycle oil into ultra-low sulfur diesel oil and a high octane number gasoline blending component.
US2010116712 discloses a catalytic diesel hydro-conversion method, which adopts a conventional process method and a cracking catalyst, raw oil is firstly pretreated and then contacted with the cracking catalyst to produce clean diesel and gasoline with high new-value. However, this method cannot selectively reduce the hydrogenation saturation of gasoline components, and therefore, the octane number loss of gasoline products is large.
EP20110834653 discloses a preparation method of a polycyclic aromatic hydrocarbon hydroconversion catalyst, the catalyst carrier is composed of β molecular sieves and pseudo-boehmite, active metal components of group VIB and group VIII are added by a conventional method, but the catalyst has strong saturation capacity on gasoline components, and is not beneficial to catalyzing the process of producing high octane gasoline by diesel hydroconversion.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalytic diesel oil conversion process, which can reduce the hydrogenation saturation of the generated gasoline component and improve the octane number of the gasoline component on the premise of meeting the conversion rate of the catalytic diesel oil.
The catalytic diesel conversion process comprises the following steps:
(1) the mixture of catalytic cracking diesel oil and hydrogen firstly enters a hydrogenation reactor for hydrofining reaction;
(2) the effluent of the hydrorefining reaction directly enters a cracking reactor and is in contact reaction with a hydrocracking catalyst bed layer in the cracking reactor; wherein, the hydrocracking reactor is internally provided with an upper hydrocracking catalyst bed layer and a lower hydrocracking catalyst bed layer in a grading way, and the mass ratio of the hydrocracking catalysts in the upper hydrocracking catalyst bed layer to the lower hydrocracking catalyst bed layer is 1: 5-5: 1, preferably 1: 2-2: 1; the upper bed catalyst uses W-Ni and/or Mo-Ni as active metal component, uses modified Y molecular sieve and alumina loaded with alkali metal or alkaline earth metal as carrier, and uses WO3And/or MoO38-18 percent of NiO 2-10 percent of modified Y molecular sieve, 40-90 percent of modified Y molecular sieve, preferably 50-80 percent of modified Y molecular sieve, 0.2-5 percent of alkali metal and/or alkaline earth metal oxide, preferably 1-3 percent of modified Y molecular sieve, and the balance of alumina; the lower bed layer catalyst takes Mo-Co as an active metal component, a modified Y molecular sieve and carbon-deposited alumina as carriers, and MoO is calculated by the weight of the catalyst38-18 wt%, 2-10 wt% of CoO, 5-50% of modified Y molecular sieve, preferably 10-40%, 10-50% of alumina, preferably 20-40%, 0.2-12% of carbon, preferably 2-5%; the alkali metal and the alkaline earth metal are selected from one or more of Na, K, Mg and Ca, and Na and/or Mg are preferred;
(3) and (3) separating and fractionating the hydrocracking reaction effluent obtained in the step (2) to obtain a naphtha component and a diesel component, wherein the naphtha component is directly taken out of the device to be used as a high-octane gasoline blending component, and the diesel component can be directly taken out of the device to blend diesel and can also be circulated back to the cracking reactor for further reaction.
In the process of the invention, the selected hydrofining catalyst can be a commercial product or can be prepared according to the conventional knowledge in the field. The hydrorefining catalyst used in the invention can adopt a conventional hydrocracking pretreatment catalyst, generally uses VIB group and/or VIII group metals as active components, and uses alumina or silicon-containing alumina as a carrier. The group VIB metal is typically Mo and/or W and the group VIII metal is typically Co and/or Ni. Based on the weight of the catalyst, the content of the VIB group metal is 8-28 wt% calculated by oxide, and the content of the VIII group metal is 2-15 wt% calculated by oxide.
In the process, the preparation method of the upper bed layer catalyst comprises the following steps: (a) firstly, adopting an alkali metal and/or alkaline earth metal dipping solution to dip alumina powder, and then drying and roasting; (b) and (b) uniformly mixing the alumina obtained in the step (a) with a Y molecular sieve, a VIB group active metal compound and a VIII group active metal compound, adding dilute nitric acid into the mixture to form slurry, extruding the slurry into strips, forming the strips, drying and roasting the strips to obtain the catalytic diesel oil conversion catalyst.
The alkali metal and the alkaline earth metal in the step (a) are selected from one or more of Na, K, Mg and Ca, and Na and/or Mg are preferred; the impregnation method in the step (a) is saturated impregnation, and the liquid-solid mass ratio in the impregnation process is 1.5: 1-3: 1; the dipping solution containing alkali metal and/or alkaline earth metal is aqueous solution of alkali metal and/or alkaline earth metal salt; wherein, the alkali metal and/or alkaline earth metal salt is nitrate of alkali metal or alkaline earth metal. The content of alkali metal and/or alkaline earth metal salt in the impregnation liquid is 2-15 g/100ml according to the corresponding oxide, and the concentration of the alkali metal and/or alkaline earth metal salt in the impregnation liquid can be correspondingly adjusted according to the product requirement. The drying conditions of the step (a) are as follows: drying for 1-5 hours at 80-120 ℃ in an air atmosphere; the roasting conditions are as follows: roasting for 1-5 hours at 400-700 ℃ in an air atmosphere.
The VIB group active metal in the step (b) is selected from W and/or Mo, the VIII group active metal is selected from Ni, the content of VIB group metal compounds in the mixture is 8wt% -18 wt% in terms of corresponding oxides, and the content of VIII group metal compounds in the mixture is 2wt% -10 wt% in terms of corresponding oxides. The concentration of the dilute nitric acid is 3-30 wt%.
The drying conditions in the step (b) are as follows: drying for 1-5 hours at 80-120 ℃ in an air atmosphere; the roasting conditions are as follows: roasting for 1-5 hours at 400-700 ℃ in an air atmosphere;
the method of the present invention may also be carried out by a saturation impregnation method. Firstly, mixing alumina powder loaded with alkali metal and/or alkaline earth metal with a Y molecular sieve to prepare a carrier, and then, carrying out saturated impregnation on the carrier by using an aqueous solution containing VIII group and VIB group salts; the active metal of the VIB group is selected from W and/or Mo, the active metal of the VIII group is selected from Ni, the content of the VIB group metal compound in the impregnating solution is 10-40 g/100ml calculated according to corresponding oxides, the content of the VIII group metal compound is 3-20 g/100ml calculated according to corresponding oxides, and the concentration of the metal compound in the impregnating solution can be correspondingly adjusted according to the needs of products.
In the process of the invention, the upper bed layer catalyst is preferably prepared by the following method: (I) uniformly mixing the modified Y molecular sieve and alumina loaded with alkali metal and/or alkaline earth metal, adding dilute nitric acid into the mixture to form slurry, extruding the slurry into strips, forming the strips, drying and roasting the strips to obtain a silicon-aluminum carrier containing the modified Y molecular sieve; (II) contacting the carrier with a carbon source, and then carrying out carbon deposition reaction to obtain a carbon deposition carrier; (III) roasting the carbon-deposited carrier in oxygen-containing gas to obtain a decarburized carrier; the carbon content of the decarbonization carrier is 20-80%, preferably 30-70% of that of the carbon deposition carrier; wherein the oxygen content of the oxygen-containing gas is 0.5-8 v%; the roasting temperature is 250-390 ℃, preferably 300-390 ℃, and the roasting time is 3.5-20 hours, preferably 4-12 hours; (IV) introducing an active metal component precursor into the decarburized carrier and drying; and (V) carrying out heat treatment on the product obtained in the step (IV), converting the active metal component precursor into an active metal oxide, and retaining the carbon on the decarburizing carrier.
The carbon source is selected from various gaseous or liquid carbonaceous substances, and can be liquid or gaseous unsaturated olefins, such as normal or isomeric olefins and diolefins of C2-C10. In order to increase the coking efficiency, the carbon source may be selected from at least one of petroleum ether, benzene, toluene, xylene, catalytic gasoline, coker gasoline, butadiene, pentadiene, hexadiene, butene, pentene, heptene, and nonene.
The conditions for contacting the carrier and the carbon source comprise: the pressure is 0.1-1 MPa, and the time is 0.1-6 h. When the carbon source is in a gaseous state, the pressure is 0.1-1 MPa, and the time is 0.1-2 h; when the carbon source is in a liquid state, the pressure is 0.1-1 MPa, and the time is 0.5-6 h. The carrier is in full contact with the carbon source, and is generally carried out at normal temperature, wherein the normal temperature is generally 25-40 ℃.
The carbon deposition reaction may convert the carbon source to carbon at the surface of the support. Preferably, the carbon deposition reaction is carried out in the presence of an oxygen-containing atmosphere, and the carbon deposition reaction temperature is 100-500 ℃, preferably 180-300 ℃; the carbon deposition reaction time is 20-200 h, preferably 50-100 h.
In the carbon deposition reaction, the oxygen content of oxygen-containing atmosphere is 10-100 v%, and the oxygen-containing atmosphere is selected from air or a mixture of oxygen and inert gas, preferably air.
In the step (III) of the method for preparing a hydrocracking catalyst, the calcination temperature is preferably 300 to 390 ℃; the roasting time is 4-20 h.
Putting the carbon deposit carrier into a roasting furnace, heating from room temperature to the roasting temperature at a heating rate of 20-40 ℃/h, and keeping the temperature at the roasting temperature for the roasting time; the volume ratio of the oxygen-containing gas to the carbon-deposited carrier is (500-5000): 1.
in order to realize proper decarbonization, the atmosphere during roasting, the heating rate during roasting, the heating end temperature and the roasting time are controlled, specifically, the carbon-deposited carrier is placed in the low-oxygen-content atmosphere, the temperature is increased to the roasting temperature from room temperature in a roasting furnace at a specific heating rate, the roasting temperature is lower than the general high-temperature roasting, and the long roasting time is kept, namely, the slow roasting is carried out at the low roasting temperature for a long time. In the invention, the room temperature is 25-40 ℃.
And converting the active metal component precursor into an active metal oxide, and reserving the carbon on the decarburized carrier. In a preferred embodiment, the heat treatment comprises: and (3) roasting the product obtained in the step (IV) for 2-10 hours at the temperature of 400-700 ℃ in inert gas to obtain the hydrocracking catalyst. The specific process can be as follows: and (2) roasting in a roasting furnace, namely introducing inert gas into the roasting furnace for replacement, wherein the inert gas introduction speed controls the volume ratio of gas/agent (inert gas to impregnated and dried decarburized carrier) to be (500-5000): 1, replacing inert gas into the atmosphere of the roasting furnace, and after the purity of oxygen is lower than 0.1 volume percent, adding 20E to EAnd heating the roasting furnace to the roasting temperature at the heating rate of 40 ℃/h, and keeping the temperature to finish roasting within the roasting time. The inert gas used for the calcination may be N2Helium, neon and argon.
According to the method, firstly, a carrier in contact with a carbon source is subjected to carbon deposition reaction in an oxygen-containing atmosphere, so that the carbon source covers acid centers on the carrier; and then, selectively burning off the deposited carbon deposited on the non-strong acid by slowly roasting the carbon-deposited carrier in oxygen-containing gas with low oxygen content at low temperature, so that the obtained decarburized carrier has a proper infrared acid distribution structure. Then, the active metal is impregnated to obtain the hydrocracking catalyst. And finally, carrying out inert high-temperature long-time roasting or low-temperature aerobic long-time roasting to obtain the hydrocracking catalyst with certain carbon content. The hydrocracking catalyst provided by the invention has reasonable infrared acid strength distribution and proper dispersion of active metal components, can obviously improve the reaction effect of the hydrocracking catalyst at the initial running stage when used for catalyzing the hydrocracking reaction of diesel oil, and obviously improves the yield, total liquid yield and octane number of gasoline products; and the catalyst can maintain good catalytic stability during operation.
In the process, the preparation method of the lower bed layer catalyst comprises the following steps: (1) fully contacting alumina with liquid or gaseous unsaturated olefin, and then carrying out carbon deposition reaction in an oxygen-containing atmosphere to obtain carbon-deposited alumina; (2) the carbon-deposited alumina, the modified Y molecular sieve, the Mo-containing active metal compound and the Co-containing active metal compound are uniformly mixed, and then the mixture is added with dilute nitric acid to form slurry, extruded into strips, formed, dried and roasted to obtain the catalyst.
Wherein the unsaturated olefin is normal or isomeric olefin and diene with 2-10 carbon atoms; wherein the olefin is in sufficient contact with the molecular sieve, which means that unsaturated olefin diffuses into the molecular sieve; when a gaseous unsaturated olefin is used, the gaseous unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, and the contact time is 0.1-2 hours; when a liquid unsaturated hydrocarbon is used, the liquid unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, the contact time is 0.5-4 hours, and the molecular sieve is completely immersed in the liquid olefin. The olefin is fully contacted with the molecular sieve at normal temperature, and the unsaturated hydrocarbon state is a normal-temperature phase state.
The oxygen-containing atmosphere is one of air, a mixture of oxygen and nitrogen or a mixture of oxygen and inert gas, the volume fraction of oxygen in a gas phase is 10-100%, and air is preferred; the carbon deposition reaction conditions are as follows: the reaction temperature is 50-500 ℃, preferably 100-400 ℃, and the reaction time is 1-200 hours, preferably 10-100 hours.
The carbon content of the carbon-deposited alumina is 0.5-20 wt%, preferably 2-15 wt% based on the weight of the carbon-deposited alumina, and the pore volume ratio of the carbon-deposited alumina to the alumina before carbon deposition is 1: 10-1: 1.5.
The content of the Mo-containing active metal compound is 4-20 wt% in terms of corresponding oxides, and the content of the Co-containing active metal compound is 2-15 wt% in terms of corresponding oxides. The concentration of the dilute nitric acid is 3-30 wt%.
The drying conditions are as follows: drying for 2-8 hours at 90-150 ℃; after the drying process is finished, carbon deposit in the alumina can be removed by roasting in an oxygen-containing atmosphere, and can also be remained in the catalyst by roasting in an inert atmosphere; the roasting conditions are as follows: roasting at 300-600 ℃ for 1-5 hours. The inert atmosphere is selected from N2Helium, neon or argon. The oxygen-containing atmosphere is one of air, a mixture of oxygen and nitrogen or a mixture of oxygen and inert gas, the volume fraction of oxygen in a gas phase is 10% -100%, and air is preferred.
Wherein the Mo-Co active metal can be loaded by adopting a saturated impregnation method. The method comprises the steps of firstly mixing the alumina powder subjected to carbon deposition treatment with a modified Y molecular sieve to prepare a carrier, then carrying out saturated impregnation on the carrier by using an aqueous solution containing Mo and Co, and correspondingly adjusting the concentration of metal compounds in an impregnation solution according to the product requirement.
The modified Y molecular sieve used in the invention can be a molecular sieve modified by a conventional method,the modified Y molecular sieve has the following properties: SiO 22/Al2O3The molar ratio is 8-50, preferably 10-30; the specific surface area is 500-900 m2Per g, preferably 600 to 800 m2(ii)/g; the pore volume is 0.30-0.60 ml/g, preferably 0.35-0.50 ml/g; the relative crystallinity is 80-130%, preferably 90-110%, and the unit cell parameter is 2.432-2.460 nm, preferably 2.435-2.450; the infrared acid amount is 0.4-1.5 mmol/g, preferably 0.5-1.3 mmol/g;
in the process, the process conditions of the hydrofining reaction are as follows: the reaction temperature is 320-440 ℃, and preferably 340-420 ℃; the reaction pressure is 4.0-15.0 MPa, preferably 6.0-12.0 MPa; the liquid hourly space velocity is 0.2-6.0 h-1Preferably 0.5 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100-2000, preferably 500-1500.
In the process, the hydrocracking reaction process conditions are as follows: the reaction temperature is 340-440 ℃, and preferably 360-430 ℃; the reaction pressure is 4.0-15.0 MPa, preferably 6.0-12.0 MPa; the liquid hourly space velocity is 0.2-6.0 h-1Preferably 0.5 to 3.0 hours-1(ii) a The volume ratio of hydrogen to oil is 100-2000, preferably 500-1500.
In the process of the invention, the properties of the catalytic cracking diesel oil are generally as follows: the density is 0.88 to 0.99g/cm3The dry point is 360-400 ℃ and the aromatic hydrocarbon content is 50-95 wt%. The sulfur content of the catalytic cracking diesel oil is generally 0.2wt% -2 wt%, and the nitrogen content is 500-2000 ppm.
Compared with the prior art, the invention has the advantages that: the catalytic diesel oil hydrogenation conversion reaction process is along with the progress of the cracking reaction, the diesel oil fraction ratio in the material flow from top to bottom along the bed layer of the cracking reactor is gradually reduced, the gasoline component ratio is gradually increased, when the hydrogenation capacity of the catalyst is overhigh in the case of a single catalyst system of diesel oil, the diesel oil conversion in the bed layer of the upper reactor is met, and simultaneously, the gasoline component of the lower bed layer is over-saturated, so that the gasoline octane number loss is overlarge; when the hydrogenation activity of the catalyst is insufficient, the cracking ability of the catalyst is affected and the ability of the catalyst to crack diesel oil is reduced. For this reason, a reasonable system should be that the high hydrogenation activity and the high cracking activity at the upper part are used for producing gasoline components by the high-efficiency conversion of catalytic diesel oil, the low hydrogenation activity and the low cracking activity at the lower part are used for reducing the excessive cracking and saturation of the generated gasoline components, and the gasoline yield and the octane number are improved. In addition, the reaction process for producing high-octane gasoline by catalytic diesel oil hydroconversion generally comprises the steps of hydrodenitrogenation of a catalytic diesel oil raw material, and hydrocracking of the denitrification reaction product oil to produce a high-octane gasoline component. The hydrocracking catalyst for hydrocracking reaction usually uses Y molecular sieve and alumina as carrier, and W-Ni or Mo-Ni as active metal component. Alumina in the hydrocracking catalyst in the conventional hydrocracking reaction process is used as a matrix for dispersing the Y molecular sieve and dispersing a cracking center, and meanwhile, the alumina has better hydrogenation activity metal dispersing performance, is favorable for further hydrogenation saturation of a cracked product, and improves the properties of the cracked product. However, for the technology of producing high-octane gasoline by catalytic diesel oil hydroconversion, a cracking catalyst is required to have a certain hydrogenation capacity to terminate carbocation, inhibit excessive cracking and improve the stability of the catalyst, the hydrogenation active metal loaded on a molecular sieve is beneficial to improving the matching of hydrogenation and an acid center and reducing excessive cracking, the hydrogenation activity belongs to effective hydrogenation activity, and the excessive hydrogenation activity of the active metal on alumina is easy to cause the saturation of aromatic hydrocarbon in a gasoline product, so that the octane number of the gasoline product is reduced, and the octane number of the gasoline product is not beneficial to improving the octane number of the gasoline product, which is undesirable for the technology of producing high-octane gasoline by catalytic diesel oil hydroconversion. The conventional preparation method is generally to directly prepare the alumina and molecular sieve composite carrier, then to impregnate the active components by an impregnation method, the increase or decrease of the active components on the two are synchronous, if the hydrogenation activity on the molecular sieve is increased, the over-high hydrogenation activity on the alumina is easily caused to cause over-hydrogenation saturation, and if the hydrogenation activity on the alumina is decreased and the hydrogenation saturation is reduced, the normal hydrogenation activity of the Y molecular sieve is influenced, and the over-cracking is caused. Therefore, the contradiction which is difficult to solve exists between the hydrogenation capacities of the active components on alumina and molecular sieves in the balance catalyst, and the two are difficult to be considered simultaneously.
The process adopts a grading mode to take W-Ni and/or Mo-Ni metal components with high hydrogenation activity as hydrogenation active metals of the upper-layer catalyst, and the upper-layer catalyst is matched with alumina modified by high molecular sieve content and alkali metal or alkaline earth metal, so that the hydrogenation activity of the active metals loaded on the alumina is inhibited to a certain extent while the hydrogenation activity of the active metals on the Y molecular sieve is not influenced, and the catalyst has moderate hydrogenation activity. The matching of high cracking activity and moderate hydrogenation activity is realized; the lower catalyst adopts the combination of low molecular sieve content and Mo-Co active metal components to realize the matching of low hydrogenation activity and low cracking activity. Meanwhile, in the preparation process of the lower-layer catalyst, the alumina powder is subjected to carbon deposition treatment in advance to form carbon deposition which fills part of pore passages and surfaces of the alumina, so that in the subsequent process of dipping the hydrogenation active components, the loading capacity of the active components on the alumina is reduced, the hydrogenation activity of the active metals loaded on the alumina is inhibited while the hydrogenation activity of the active metals on the Y molecular sieve is not influenced, therefore, the lower-layer catalyst has better hydrogenation reaction selectivity, the excessive hydrogenation of gasoline components generated by cracking on the alumina can be reduced, the octane number of gasoline products is improved, the effective hydrogenation capacity of the catalyst is improved, meanwhile, the active components are more easily loaded on the surface of the molecular sieve in the dipping process, and the usage amount of an active component dipping solution is reduced.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples, but is not limited thereto. The percentages referred to in the examples are mass percentages (except for relative crystallinity), and the liquid-solid ratios are liquid-solid mass ratios. The examples and comparative examples used the same commercial modified Y molecular sieve and macroporous alumina as the support components, both of which were of uniform commercial size.
Example 1
(1) Configuration of NaNO3Aqueous solution, NaNO3In a concentration of Na2O is calculated as 8g/100 ml;
(2) NaNO obtained in step 13Soaking the industrial production macroporous alumina powder in the aqueous solution according to the liquid/solid ratio of 3:1 for 2h, filtering, roasting at 120 ℃ for 2h, and roasting at 550 ℃ for 3 h;
(3) taking the product obtained in the step (2)40g of alumina, 80g of modified Y molecular sieve and MoO in industrial production320g and 20g of nickel nitrate are mixed, 4g/100ml of dilute nitric acid is added to be mixed and rolled in a mixer to be extrudable, and then the catalyst C1 is obtained by extruding, forming, drying and roasting on an extruding machine.
Example 2
(1) Configuration of Mg (NO)3)2Aqueous solution, Mg (NO)3)2The concentration is 4g/100ml calculated by MgO;
(2) mg (NO) obtained in step 13)2Soaking the industrial production macroporous alumina powder in the aqueous solution according to the liquid/solid ratio of 2:1 for 2 hours, filtering, roasting at 110 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours;
(3) mixing 30g of the alumina obtained in the step (2) and 90g of the industrial production modified Y molecular sieve, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer to be extrudable, and extruding on a strip extruding machine to obtain a carrier;
(4) preparing Mo-Ni dipping solution and adding MoO3Adding basic nickel carbonate into distilled water to prepare a partial Mo-Ni impregnation solution, and adjusting MoO in the mixed solution according to the oxide of the metal salt323g/100ml and 8g/100ml of nickel oxide;
(5) and (3) taking the Mo-Ni impregnation solution obtained in the step (4), impregnating the catalyst carrier obtained in the step (3) for 2 hours according to the liquid-solid ratio of 3:1, then drying for 3 hours at 120 ℃, and roasting for 3 hours at 500 ℃ to obtain the catalyst C2.
Example 3
(1) Configuring KNO3Aqueous solution, KNO3In a concentration of Na2O is 10g/100 ml;
(2) NaNO obtained in step 13Soaking the industrial production macroporous alumina powder in the aqueous solution according to the liquid/solid ratio of 2:1 for 2 hours, filtering, roasting at 110 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours;
(3) and (3) mixing 50g of the alumina obtained in the step (2), 100g of the modified Y molecular sieve for industrial production, 25g of metatungstic acid and 20g of nickel nitrate, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer until the mixture can be extruded, extruding the mixture on a strip extruder, forming, drying and roasting to obtain the catalyst C3.
Example 4
(1) Putting 200g of industrially produced macroporous alumina into a closed container filled with butadiene atmosphere, controlling the pressure to be 0.3MPa, fully contacting for 20 minutes, and then heating for 70 hours at 180 ℃ in air atmosphere;
(2) taking 80g of alumina obtained in the step (1), 50g of industrial modified Y molecular sieve and MoO315g and 20g of cobalt nitrate are mixed, 4g/100ml of dilute nitric acid is added into the mixture, the mixture is mixed and rolled in a mixer to be extrudable, and then strip extrusion molding is carried out;
(3) and (3) drying the sample in the step (2) at 120 ℃ for 4h in the air atmosphere, and then transferring the sample into the nitrogen atmosphere to roast the sample for 3h at 500 ℃ to obtain the catalyst C4.
Example 5
(1) Soaking 200g of macroporous alumina industrially produced in heptene for 4 hours, and then heating at 160 ℃ for 120 hours in an air atmosphere;
(2) mixing 100g of alumina obtained in the step (1) and 60g of industrial modified Y molecular sieve, adding 4g/100ml of dilute nitric acid, mixing, rolling, extruding into strips, molding, and drying at 120 ℃ for 4h to obtain a carrier of the embodiment 3;
(3) preparing Mo-Co impregnating solution, and adding MoO3Adding basic cobaltous carbonate into distilled water to prepare a meta-Mo-Co impregnation solution, and adjusting MoO in the mixed solution according to the oxide of the metal salt330g/100ml、CoO 10g/100ml；
(4) And (3) soaking the catalyst carrier obtained in the step (2) for 2h by taking the Mo-Co soaking solution obtained in the step (3) according to the liquid-solid ratio of 3:1, drying the catalyst carrier for 2h at 150 ℃ in an air atmosphere, and then transferring the dried catalyst carrier to a helium atmosphere for roasting for 4h at 400 ℃ to obtain the catalyst C5.
Example 6
The same procedure as in example 2, except that the calcination atmosphere in the step (3) was changed to air, was conducted to obtain catalyst C6
Example 7
(1) Soaking 200g of macroporous alumina industrially produced in heptene for 2 hours, and then heating at 280 ℃ for 80 hours in an air atmosphere;
(2) mixing 80g of alumina obtained in the step (1), 80g of industrial modified Y molecular sieve, 22g of ammonium metatungstate and 20g of cobalt nitrate, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer until the mixture is extrudable, and extruding and forming;
(3) and (3) drying the sample in the step (2) at 120 ℃ for 4h in the air atmosphere, and then transferring the dried sample into the nitrogen atmosphere to roast the sample for 3h at 550 ℃ to obtain the catalyst C7.
Example 8
(1) Soaking 200g of industrially produced macroporous alumina for 2 hours in hexadiene, and then heating for 50 hours at 360 ℃ in an air atmosphere;
(2) mixing 100g of alumina obtained in the step (1), 50g of modified Y molecular sieve, 30g of ammonium metatungstate and 60g of cobalt nitrate, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer until the mixture is extrudable, and extruding and forming strips;
(3) and (3) drying the sample in the step (2) at 120 ℃ for 4h in the air atmosphere, and then transferring the sample to the nitrogen atmosphere to roast the sample for 3h at 450 ℃ to obtain the catalyst C8.
Example 9
(1) Configuration of NaNO3Aqueous solution, NaNO3In a concentration of Na2O is calculated as 8g/100 ml;
(2) NaNO obtained in step 13Soaking the industrial production macroporous alumina powder in the aqueous solution according to the liquid/solid ratio of 3:1 for 2h, filtering, roasting at 120 ℃ for 2h, and roasting at 550 ℃ for 3 h;
(3) taking 40g of the alumina obtained in the step (2) and 80g of the industrial production modified Y molecular sieve, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer to be extrudable, extruding strips on a strip extruding machine, and forming to obtain a carrier;
(4) placing the carrier obtained in the step (1) in a closed container filled with butadiene atmosphere, controlling the pressure to be 0.3MPa, fully contacting for 20 minutes, and then heating for 80 hours at 200 ℃ in air atmosphere;
(5) placing the carbon deposit carrier obtained in the step (2) in a roasting furnace, introducing oxygen/nitrogen mixed gas with the oxygen content of 1% into the roasting furnace, heating to 380 ℃ at the heating rate of 25 ℃/h, and roasting at constant temperature for 4 h;
(6) preparing a Mo-Ni dipping solution: fetching MoO3Dissolving basic nickel carbonate in water to prepare Mo-Ni impregnating solution, and adding MoO as active metal in the obtained impregnating solution3And NiThe O content is calculated to be 34g/100ml and 11g/100ml respectively;
(7) drying the sample in the step (4) at 120 ℃ for 4 hours;
(8) placing the dried sample obtained in the step (5) in a roasting furnace, and introducing N2Gas is replaced, and the gas/agent ratio is controlled to be 2000;
(9) after the inert gas is replaced to the oxygen purity of 0.08v%, the temperature is raised to 550 ℃ at the heating rate of 40 ℃/h, and the constant temperature treatment is carried out for 6h, thus obtaining the catalyst C9.
Example 10
Configuration of Mg (NO)3)2Aqueous solution, Mg (NO)3)2The concentration is 4g/100ml calculated by MgO;
(2) mg (NO) obtained in step 13)2Soaking the industrial production macroporous alumina powder in the aqueous solution according to the liquid/solid ratio of 2:1 for 2 hours, filtering, roasting at 110 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours;
(3) mixing 30g of the alumina obtained in the step (2) and 90g of the industrial production modified Y molecular sieve, adding 4g/100ml of dilute nitric acid, mixing and rolling in a mixer to be extrudable, and extruding on a strip extruding machine to obtain a carrier;
(4) soaking the carrier obtained in the step (1) in heptene for 4 hours, and then heating at 180 ℃ for 150 hours in an air atmosphere;
(5) placing the carbon deposit carrier obtained in the step (2) in a roasting furnace, introducing oxygen/nitrogen mixed gas with the oxygen content of 3% into the roasting furnace, heating to 350 ℃ at the heating rate of 25 ℃/h, and roasting at constant temperature for 10 h;
(6) preparing a Mo-Ni dipping solution: get MoO3Dissolving basic nickel carbonate in water to prepare Mo-Ni impregnating solution, and adding MoO as active metal in the obtained impregnating solution3And the NiO content was calculated to be 30g/100ml and 11g/100ml, respectively;
(7) drying the sample in the step (4) at 120 ℃ for 4 hours;
(8) placing the dried sample obtained in the step (5) in a roasting furnace, and introducing N2Gas is replaced, and the gas/agent ratio is controlled to be 2000;
(9) after the inert gas is replaced to the oxygen purity of 0.08v%, the temperature is raised to 550 ℃ at the heating rate of 40 ℃/h, and the constant temperature treatment is carried out for 6h, thus obtaining the catalyst C10.
Comparative example 1:
(1) taking 40g of industrially produced alumina, 80g of modified Y molecular sieve and MoO320g and 20g of nickel nitrate are mixed, 4g/100ml of dilute nitric acid is added to be mixed and rolled in a mixer to be extrudable, and then the catalyst B1 is obtained by extruding, forming, drying and roasting on an extruding machine.
Comparative example 2:
(1) taking 80g of industrially produced macroporous alumina, 50g of industrially modified Y molecular sieve and MoO315g and 20g of cobalt nitrate are mixed, 4g/100ml of dilute nitric acid is added into the mixture, the mixture is mixed and rolled in a mixer to be extrudable, and then strip extrusion molding is carried out; (2) and (2) drying the sample in the step (1) at 120 ℃ for 4h, transferring the sample into an air atmosphere, and roasting the sample for 3h at 500 ℃ to obtain the catalyst B2.
Table 1 examples catalyst physicochemical properties.
Figure 641339DEST_PATH_IMAGE001
Example 11
In order to investigate the reaction effect of the grading filling process technology of the catalytic diesel oil hydro-conversion catalyst, an evaluation test is carried out on a small device, the evaluation device adopts single-section series connection and one-time flow to produce gasoline and hydrogenated diesel oil, one reaction is filled with a conventional refined catalyst, the other reaction is respectively filled with catalyst systems with different preparation methods and different grading modes, and the physicochemical properties, the raw oil properties and the evaluation results of the refined catalyst are listed in tables 2-5.
TABLE 2-physical and chemical Properties of the reverse refined catalysts
Figure 982321DEST_PATH_IMAGE002
TABLE 3 Properties of the feed oils
Figure 506844DEST_PATH_IMAGE003
Table 4 shows the loading and operating conditions of the two catalysts.
Figure 431812DEST_PATH_IMAGE004
Table 5 product distribution and property comparison.
Figure 575349DEST_PATH_IMAGE006

Claims (21)

1. A catalytic diesel conversion process, characterized by comprising the following: (1) the mixture of catalytic cracking diesel oil and hydrogen firstly enters a hydrogenation reactor for hydrofining reaction; (2) the effluent of the hydrorefining reaction directly enters a cracking reactor and is in contact reaction with a hydrocracking catalyst bed layer in the cracking reactor; wherein, the hydrocracking reactor is internally provided with an upper hydrocracking catalyst bed layer and a lower hydrocracking catalyst bed layer in a grading way, and the mass ratio of the hydrocracking catalysts in the upper hydrocracking catalyst bed layer to the lower hydrocracking catalyst bed layer is 1: 5-5: 1; the upper bed catalyst uses W-Ni and/or Mo-Ni as active metal component, uses modified Y molecular sieve and alumina loaded with alkali metal or alkaline earth metal as carrier, and uses WO3And/or MoO38-18 percent of NiO 2-10 percent of modified Y molecular sieve, 0.2-5 percent of alkali metal and/or alkaline earth metal oxide and the balance of alumina; the lower bed layer catalyst takes Mo-Co as an active metal component, a modified Y molecular sieve and carbon-deposited alumina as carriers, and MoO is calculated by the weight of the catalyst38-18 wt%, 2-10 wt% of CoO, 5-50% of modified Y molecular sieve, 10-50% of alumina and 0.2-12% of carbon; (3) separating and fractionating the hydrocracking reaction effluent obtained in the step (2) to obtain a naphtha component and a diesel component; the upper bed layer catalyst is prepared by the following method: (I) uniformly mixing the modified Y molecular sieve and alumina loaded with alkali metal and/or alkaline earth metal, adding dilute nitric acid into the mixture to form slurry, extruding the slurry into strips, forming the strips, drying and roasting the strips to obtain a silicon-aluminum carrier containing the modified Y molecular sieve; (II) contacting the carrier with a carbon source, and then carrying out carbon deposition reaction to obtain a carbon deposition carrier; (III) the carbon deposit carrier is in oxygen-containing gasRoasting in the body to obtain a decarburized carrier; the carbon content of the decarburizing carrier is 20-80% of that of the carbon-deposited carrier; wherein the oxygen content of the oxygen-containing gas is 0.5-8 v%; the roasting temperature is 250-390 ℃, and the roasting time is 3.5-20 h; (IV) introducing an active metal component precursor into the decarburized carrier and drying; and (V) carrying out heat treatment on the product obtained in the step (IV), converting the active metal component precursor into an active metal oxide, and retaining the carbon on the decarburizing carrier.
2. The process of claim 1, wherein: the alkali metal and the alkaline earth metal are selected from one or more of Na, K, Mg and Ca.
3. The process of claim 1, wherein: the preparation method of the upper bed catalyst comprises the following steps: (a) firstly, adopting an alkali metal and/or alkaline earth metal dipping solution to dip alumina powder, and then drying and roasting; (b) and (b) uniformly mixing the alumina obtained in the step (a) with the modified Y molecular sieve, the VIB group active metal compound and the VIII group active metal compound, adding dilute nitric acid into the mixture to form slurry, extruding the slurry into strips, forming the strips, drying and roasting the strips to obtain the catalytic diesel oil conversion catalyst.
4. A process according to claim 3, wherein: the alkali metal and the alkaline earth metal in the step (a) are selected from one or more of Na, K, Mg and Ca; the impregnation method is saturated impregnation, and the liquid-solid mass ratio in the impregnation process is 1.5: 1-3: 1; the alkali metal and/or alkaline earth metal dipping solution is an aqueous solution of alkali metal and/or alkaline earth metal salt; the content of alkali metal and/or alkaline earth metal salt in the impregnation liquid is 2-15 g/100mL according to corresponding oxide.
5. A process according to claim 3, wherein: the drying conditions of the step (a) are as follows: drying for 1-5 hours at 80-120 ℃ in an air atmosphere; the roasting conditions are as follows: roasting for 1-5 hours at 400-700 ℃ in an air atmosphere.
6. A process according to claim 3, wherein: the VIB group active metal in the step (b) is selected from W and/or Mo, the VIII group active metal is selected from Ni, the content of VIB group metal compounds in the mixture is 8wt% -18 wt% in terms of corresponding oxides, and the content of VIII group metal compounds in the mixture is 2wt% -10 wt% in terms of corresponding oxides.
7. The process of claim 1, wherein: the carbon source is selected from at least one of petroleum ether, benzene, toluene, xylene, catalytic gasoline, coker gasoline, butadiene, pentadiene, hexadiene, butene, pentene, heptene and nonene.
8. The process of claim 1, wherein: the conditions for contacting the carrier and the carbon source comprise: the pressure is 0.1-1 MPa, and the time is 0.1-6 h.
9. The process of claim 1, wherein: the carbon deposition reaction is carried out in the presence of an oxygen-containing atmosphere, the carbon deposition reaction temperature is 100-500 ℃, and the carbon deposition reaction time is 20-200 h; the oxygen content of the oxygen-containing atmosphere is 10 to 100 v%.
10. The process of claim 1, wherein: in the step (III), the roasting temperature is 300-390 ℃, and the roasting time is 4-20 h.
11. The process of claim 1, wherein: the heat treatment comprises: and (3) roasting the product obtained in the step (IV) for 2-10 hours at the temperature of 400-700 ℃ in inert gas to obtain the hydrocracking catalyst.
12. The process of claim 1, wherein: the preparation method of the lower bed catalyst comprises the following steps: (1) fully contacting alumina with liquid or gaseous unsaturated olefin, and then carrying out carbon deposition reaction in an oxygen-containing atmosphere to obtain carbon-deposited alumina; (2) the carbon-deposited alumina, the modified Y molecular sieve, the Mo-containing active metal compound and the Co-containing active metal compound are uniformly mixed, and then the mixture is added with dilute nitric acid to form slurry, extruded into strips, formed, dried and roasted to obtain the catalyst.
13. The process of claim 12, wherein: the unsaturated olefin is normal or isomeric olefin and diene with 2-10 carbon atoms; wherein said olefin is in intimate contact with the alumina means that the unsaturated olefin diffuses into the alumina interior; when a gaseous unsaturated olefin is used, the gaseous unsaturated olefin is contacted with the alumina under the following conditions: the pressure is 0.1-1.0 MPa, and the contact time is 0.1-2 hours; when a liquid unsaturated hydrocarbon is used, the conditions for contacting the liquid unsaturated olefin with alumina are as follows: the pressure is 0.1-1.0 MPa, the contact time is 0.5-4 hours, and the alumina is completely immersed in the liquid olefin.
14. The process of claim 12, wherein: the oxygen-containing atmosphere is one of air, a mixture of oxygen and nitrogen or a mixture of oxygen and inert gas, and the volume fraction of oxygen in a gas phase is 10% -100%; the carbon deposition reaction conditions are as follows: the reaction temperature is 50-500 ℃, and the reaction time is 1-200 hours.
15. The process of claim 12, wherein: the carbon content of the carbon-deposited alumina is 0.5wt% -20 wt% based on the weight of the carbon-deposited alumina, and the pore volume ratio of the carbon-deposited alumina to the alumina before carbon deposition is 1: 10-1: 1.5.
16. The process of claim 12, wherein: the content of the Mo-containing active metal compound is 4-20 wt% in terms of corresponding oxides, and the content of the Co-containing active metal compound is 2-15 wt% in terms of corresponding oxides.
17. The process of claim 12, wherein: the drying conditions are as follows: drying for 2-8 hours at 90-150 ℃; after the drying process is finished, the carbon deposit in the alumina is roasted and removed in an oxygen-containing atmosphere or roasted and remained in the catalyst in an inert atmosphere; the roasting conditions are as follows: roasting at 300-600 ℃ for 1-5 hours.
18. The process of claim 1, wherein: the modified Y molecular sieve has the following properties: SiO 22/Al2O3The molar ratio is 8-50, and the specific surface area is 500-900 m2The specific surface area of the material is 0.30-0.60 mL/g, the relative crystallinity is 80-130%, the unit cell parameter is 2.432-2.460 nm, and the infrared acid amount is 0.4-1.5 mmol/g.
19. The process of claim 1, wherein: the process conditions of the hydrofining reaction are as follows: the reaction temperature is 320-440 ℃, the reaction pressure is 4.0-15.0 MPa, and the liquid hourly space velocity is 0.2-6.0 h-1The volume ratio of hydrogen to oil is 100-2000.
20. The process of claim 1, wherein: the hydrocracking reaction has the following process conditions: the reaction temperature is 340-440 ℃, the reaction pressure is 4.0-15.0 MPa, and the liquid hourly space velocity is 0.2-6.0 h-1The volume ratio of hydrogen to oil is 100-2000.
21. The process of claim 1, wherein: the properties of the catalytic cracking diesel oil are as follows: the density is 0.88 to 0.99g/cm3The dry point is 360-400 ℃, the aromatic hydrocarbon content is 50-95 wt%, the sulfur content is 0.2-2 wt%, and the nitrogen content is 500-2000 ppm.
CN201710182289.7A 2017-03-24 2017-03-24 Catalytic diesel oil conversion process Active CN108624357B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710182289.7A CN108624357B (en) 2017-03-24 2017-03-24 Catalytic diesel oil conversion process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710182289.7A CN108624357B (en) 2017-03-24 2017-03-24 Catalytic diesel oil conversion process

Publications (2)

Publication Number Publication Date
CN108624357A CN108624357A (en) 2018-10-09
CN108624357B true CN108624357B (en) 2020-03-17

Family

ID=63707723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710182289.7A Active CN108624357B (en) 2017-03-24 2017-03-24 Catalytic diesel oil conversion process

Country Status (1)

Country Link
CN (1) CN108624357B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112642395A (en) * 2019-10-11 2021-04-13 中国石油化工股份有限公司 Molecular sieve compound and composite material as well as preparation method and application thereof
CN114686256B (en) * 2020-12-31 2023-07-04 中国石油化工股份有限公司 Grading method of hydrocracking catalyst
CN114686259B (en) * 2020-12-31 2023-07-28 中国石油化工股份有限公司 Catalytic diesel oil hydro-conversion method with catalyst grading
CN114686257B (en) * 2020-12-31 2023-07-04 中国石油化工股份有限公司 Catalyst grading method for two-stage hydrocracking process
CN116020475B (en) * 2021-10-25 2024-07-02 中国石油化工股份有限公司 Hydrocracking post-treatment catalyst and preparation method and application thereof
CN116020476B (en) * 2021-10-25 2024-07-02 中国石油化工股份有限公司 Hydrogenation pretreatment catalyst and preparation method and application thereof
CN116020433B (en) * 2021-10-25 2024-07-02 中国石油化工股份有限公司 Carbonaceous alumina and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104611029A (en) * 2013-11-05 2015-05-13 中国石油化工股份有限公司 Catalytic cracking diesel fuel hydroconversion method
CN105536855A (en) * 2014-11-03 2016-05-04 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst containing Y molecular sieve
CN105618111A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 Preparation of catalyst catalyzing diesel hydro-conversion, and hydrogenation process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104611029A (en) * 2013-11-05 2015-05-13 中国石油化工股份有限公司 Catalytic cracking diesel fuel hydroconversion method
CN105536855A (en) * 2014-11-03 2016-05-04 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst containing Y molecular sieve
CN105618111A (en) * 2014-11-03 2016-06-01 中国石油化工股份有限公司 Preparation of catalyst catalyzing diesel hydro-conversion, and hydrogenation process

Also Published As

Publication number Publication date
CN108624357A (en) 2018-10-09

Similar Documents

Publication Publication Date Title
CN108624357B (en) Catalytic diesel oil conversion process
CN108624356B (en) Catalytic diesel oil hydro-conversion process
EP3168283B1 (en) Hydrocracking catalyst, preparation method and use thereof
CN104673377B (en) A kind of method for upgrading of catalytically cracked gasoline
CN101508912B (en) Deep desulfurization-octane value recovery hydrogenation modification method for low grade gasoline
CN106669787A (en) Hydrocracking catalyst grading method and catalytic diesel oil hydro-conversion process
US10011779B2 (en) Adsorbent for desulfurization of gasoline and method for desulfurization of gasoline
CN106221794A (en) A kind of selective hydrodesulfurization method
CN107304375A (en) A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process
CN103666548A (en) Selective hydrogenation method for gasoline
CN113122311B (en) Hydrofining catalyst grading method
CN102041042B (en) Inferior wax oil hydrotreating method
CN112779050A (en) Processing method of poor-quality catalytic diesel oil
CN105618111B (en) A kind of preparation method and hydrogenation technique of catalytic diesel oil hydrogenation conversion catalyst
CN104673379B (en) A kind of deep desulfurization of gasoline method
CN105709801B (en) A kind of preparation method of chemical industry type hydrocracking catalyst
CN109370645B (en) Catalytic cracking gasoline modification method
CN108620120B (en) Preparation method of catalyst for catalyzing diesel oil hydrogenation conversion
WO2016123861A1 (en) Method for upgrading catalytic cracking gasoline
CN106669788B (en) The preparation method of hydrocracking catalyst
CN106675645A (en) Catalytic diesel oil hydro-conversion process catalyst grading method
CN106669785A (en) preparation method of hydrocracking catalyst
CN115895719B (en) Process method for deep hydrogenation conversion of high aromatic catalytic cracking diesel oil
CN114984970B (en) Grading method and application of catalyst for hydrodesulphurization of catalytic slurry oil
CN114471670B (en) Catalyst for hydrocracking and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20230828

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right