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WO1998000384A1 - Procede d'hydrocraquage d'une huile de distillat lourde a des pressions moyennes - Google Patents

Procede d'hydrocraquage d'une huile de distillat lourde a des pressions moyennes Download PDF

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Publication number
WO1998000384A1
WO1998000384A1 PCT/CN1997/000064 CN9700064W WO9800384A1 WO 1998000384 A1 WO1998000384 A1 WO 1998000384A1 CN 9700064 W CN9700064 W CN 9700064W WO 9800384 A1 WO9800384 A1 WO 9800384A1
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WIPO (PCT)
Prior art keywords
weight
alumina
catalyst
pore
zeolite
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.)
Ceased
Application number
PCT/CN1997/000064
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English (en)
French (fr)
Inventor
Yanping Zhang
Yulin Shi
Zhenlin Xiong
Jianwen Shi
Hong Nie
Yahua Shi
Zhihai Hu
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 Research Institute of Petroleum Processing
China Petrochemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Filing date
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Application filed by Sinopec Research Institute of Petroleum Processing , China Petrochemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to JP50370098A priority Critical patent/JP2001503451A/ja
Priority to AU32527/97A priority patent/AU3252797A/en
Priority to EP97928101A priority patent/EP0947575B1/en
Priority to CA002258591A priority patent/CA2258591C/en
Publication of WO1998000384A1 publication Critical patent/WO1998000384A1/zh
Priority to NO19986095A priority patent/NO316647B1/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof

Definitions

  • the invention relates to a catalytic conversion method for heavy distillate oil. More specifically, the present invention relates to a method for producing middle distillates by subjecting heavy distillates to intermediate pressure and argon cracking in the presence of argon.
  • Argon cracking is a petroleum refining method in which molecules of a hydrocarbonaceous feedstock are decomposed in the presence of argon to obtain a more desirable low molecular weight hydrocarbon product.
  • middle distillates such as jet fuel and emu oil
  • Much development has been done in discovering new catalysts and improving cracking conditions.
  • EP-A2 0093552 discloses a single-stage atmosphere cracking method.
  • the aerated treatment catalyst and the argon-cracking catalyst are arranged in the same reactor with the hydroprocessing catalyst in front.
  • the conditions of this method are a pressure of 5.25-7.0 MPa, a temperature of 360 440 'C and an LHSV of (U-10hi' -1 .)
  • the conversion rate of products with a boiling point below 345 'C is 30 40% (volume).
  • Feedstock oil used It is a heavy component oil with an initial boiling point of 200 ° C, usually 340 "C or higher, such as coking heavy gas oil.
  • the catalyst for hydrazone treatment is supported on an amorphous porous support such as silicon dioxide, aluminum vaporized, or silicon aluminum.
  • the hydrocracking catalyst is a Periodic Table VIA or VIII Group A metal supported on a macroporous zeolite such as X or fluorenite or mordenite.
  • the disadvantage of this method is In order to achieve a good distribution of argon-cracking products, argon-cracking must be carried out under the condition that the volume conversion rate of the fraction below 345 ° C is less than 50%.
  • U.S. Patent 4,686,030 discloses a scale containing nitrogen, sparse and boiling points greater than 700.
  • F (371 ′) hydrocarbon feedstock is moderately argon-cracked.
  • Typical mild argon cracking conditions for this process are temperatures of 500 900 ° F, 200 1500 psig hydrogen partial pressure, and LHSV of 0.05-S.Ohr 1 .
  • This method converts 10-50% (bulk) of raw material components with a boiling point above 700 ° F into product components with a boiling point below 700 ° F.
  • the catalyst used is Mo-Ni-P supported on an amorphous porous heat-resistant gaseous carrier. At least 75% of the pores in the catalyst have a diameter of 50 130 Angstroms and a pore diameter of less than 10% by volume of the pore volume. More than 1 10 Angstroms.
  • U.S. Patent No. 4,859,312 and EP-A2-0019959 disclose argon cracking of heavy hydrocarbons Method for producing middle distillate oil. However, these two methods require the organic nitrogen content of the raw material to be less than 50, preferably less than 10 ppmw.
  • the third aspect of the present invention is to provide a method for cracking heavy radon oil by argon cracking using a novel hydrorefining catalyst and an argon cracking catalyst in series to produce intermediate radon oil.
  • the method can be operated under medium pressure conditions and can achieve a single-pass conversion rate of up to 80% by volume. It can directly handle inferior feedstocks with nitrogen contents up to 1500ppm and the feedstock in the hydrocracking section can have nitrogen contents up to ISOppmw.
  • the present invention provides a method for producing middle distillate oil by cracking heavy tritium oil and adding argon.
  • the method includes the following steps:
  • the argon-added refining catalyst used has the following composition: nickel oxide 1-5 wt%, tungsten gasification 12-35 wt%, fluorine 1-9 wt%, and the rest are composite aluminum vaporized aluminum as a carrier, the composite hafnium Aluminized aluminum is composed of one or more small-pore gasified aluminum and one or more large-pore alumina in a weight ratio of 75:25-50:50.
  • the pore volume of 80 Angstroms accounts for more than 95% of the total pore volume of gasified aluminum, and the large pores are aluminum oxides with a pore diameter of 60-600 Angstroms and 70% of the total pore volume.
  • the argon-added cracking catalyst used has the following composition: 0.5-5.0% by weight of fluorine, 2.5-6.0% by weight of nickel gas, 10-38% by weight of tungsten gas, and the rest are carriers.
  • the carrier is composed of 20-90% by weight of aluminum vaporized gas and 1 ()-80% by weight of zeolite, wherein the zeolite is a mesoporous or macroporous zeolite having an acidity value of 1.0-2.0mmol / g as determined by the NH 3 -TPD method.
  • Alumina is an aluminized aluminum having an acidity value of 0.5-0.8 mmol / g as determined by the NH 3 TPD method.
  • Figure 1 shows a simple flow diagram of the method of the invention.
  • the method of the present invention can be implemented with the system shown in FIG. 1.
  • heavy distillate enters the system through line 1 and is mixed with argon from line 2 and recirculated hydrogen from line 3.
  • the mixture then flows through the heat exchanger 4 to a heater 5 where it rises to a temperature suitable for the reaction.
  • the heated material first enters the hydrorefining reactor 6 where it comes into contact with the argon-refined catalyst.
  • the catalyst in the hydrorefining reactor is divided into two or more catalytic beds. Cold argon to control the inlet temperature of the bed.
  • the effluent from the argon-finished reactor enters the hydrocracking reactor 9 via line 7.
  • the oil and hydrogen are further contacted with the hydrocracking catalyst to form the desired product.
  • the hydrocracking catalyst placed in the argon cracking reactor is divided into two or more beds, and cold hydrogen from line 8 is introduced between the beds to control the inlet temperature of the beds.
  • the effluent of the hydrocracking reactor then passes through a heat exchanger 4 to transfer heat to the feed. After the heat exchange, the effluent was mixed with water from line 10 to wash out the ammonia gas formed in the reactor and partially decomposed plutonium. The mixture then enters a high-pressure gas / liquid separator 11 where hydrogen, acidic water and liquid products are recycled for separation.
  • the recycled hydrogen from the separator 1 1 enters the amine scrubber 12 where the desorbed hydrogen is separated in a conventional manner.
  • the purified hydrogen is compressed in the compressor 13 to the operating pressure, thereby entering the high-pressure hydrogen system.
  • the argon-cracked reactor product leaves the separator 11 and enters the low-pressure gas / liquid separator 15 through a line 14.
  • a gas (C 4) from the low pressure separator separating out liquid product the liquid product is fractionated into the column 17 in the naphtha, kerosene, oil and a bottoms qi.
  • the hydrorefining catalyst and the argon cracking catalyst are arranged in the same reactor with the hydrorefining catalyst first.
  • the hydrorefining catalyst used in the method of the present invention has the following composition: based on the total weight of the catalyst composition, nickel ammonium 1 to 5 wt%, tungsten hafnium 12 to 35 wt%, gas 1 to 9 wt%, and the rest It is a composite vaporized aluminum as a carrier.
  • the composite aluminum halide is composed of one or more small-pore alumina and one or more large-pore gasified aluminum.
  • the composite aluminized aluminum is preferably formed by compounding a small-pore alumina and a large-pore aluminized aluminum. The composite ratio of vaporized aluminum is adjusted according to the weight of the feedstock oil processed by the catalyst.
  • the composite aluminized aluminum support preferably has the following pore distribution: A pore volume with a diameter of 40 to 100 angstroms accounts for more than 75% of the total pore volume.
  • the composite alumina has the conventional specific surface and pore volume of a general aerated refining catalyst carrier, and the specific surface is preferably 200 m 2 / g or more, and more preferably 220 m 2 / g or more.
  • the pore volume It is preferably 0.3 ml / g or more, and more preferably 0.4 ml / g or more.
  • Preparation of the carrier The precursors of small-hole aluminized aluminum and the precursors of large-hole alumina are mixed uniformly according to the required ratio, and then shaped according to the conventional hydrorefining catalyst molding method, and then 550-650. C roasting; 3 to 5 hours to obtain composite gasified aluminum as a carrier;
  • Impregnation of fluorine impregnate the above composite aluminum halide with a fluorine-containing aqueous solution, and bake at 400-600 "for 3-5 hours after drying at 100-130 ° C;
  • Nickel-tungsten impregnation impregnate the above fluorine-containing composite aluminum halide with an aqueous solution containing nickel and tungsten, and dry it at 100 130 ° C and bake at 400-600 'C for 3-5 hours.
  • the precursor of the small-pore aluminized aluminum is preferably hydrated gasified aluminum having a boehmite content of more than 60% by weight, which is preferably prepared by a sodium metaaluminate-digasified carbon method;
  • the product is preferably a hydrated aluminum halide having a boehmite content of more than 50% by weight, which is preferably prepared by a sodium metaaluminate-aluminum sulphate method.
  • the conventional molding methods mentioned herein include methods such as tabletting, ball forming, and extrusion, and preferably extrusion molding.
  • the fluorine-containing aqueous solution refers to an aqueous solution of an inorganic compound containing fluorine, such as an aqueous solution of ammonium fluoride and / or rhenium fluoride.
  • the aqueous solution containing tungsten and nickel is generally composed of ammonium metatungstate, ammonium tungstate, ethyl ammonium metatungstate, or a mixed aqueous solution of nickel metatungstate and nickel nitrate or nickel acetate.
  • the argon-refined catalyst Before use, the argon-refined catalyst can be pre-dried out according to a conventional method.
  • the composition of the hydrocracking halide used in the method of the present invention is: based on the weight of the whole halide, the gas is 0.5-5.0 wt%, the nickel halide is 2.5-6.0 wt%, and the tungsten gas is 10-38. % By weight, the rest is the catalyst support.
  • the halogenating agent carrier is composed of 20 to 90% by weight of aluminum halide and 10 to 80% by weight of zeolite. Wherein zeolite is 1.0-2.0mmol / g with acidity value determined by NH 3 -TPD method.
  • Mesoporous or macroporous zeolite, alumina is an alumina having an acidity value of 0.5-0.8 mmol / g as determined by the NH 3 -TPD method.
  • fluorine is preferably 1.0-4.0% by weight
  • gasified nickel is preferably 2.6-5.0% by weight
  • gaseous rhenium is preferably 19-25% by weight.
  • the aluminum tritide is preferably 50 to 80% by weight
  • the zeolite is preferably 20 to 50% by weight.
  • the preparation method of the argon-added cracking catalyst used in the method of the present invention is as follows:
  • the support of the catalyst is made from hydrated aluminum and zeolite.
  • the hydrated aluminide used is a hydrated and aerated aluminum that can form a vaporized aluminum having an acidity value of 0.5-0.8 mmol / g after calcination under certain conditions.
  • the firing temperature is 500-650 ° C, and the firing time is 2-8 hours or longer.
  • the pore volume of the vaporized aluminum obtained by firing the hydrated aluminum halide is preferably greater than 0.3 ml / g, and the specific surface area is preferably greater than 200 m 2 / g.
  • the hydrated gasified aluminum can be prepared by a sodium metaaluminate-carbonized gas method, an alkyl aluminum or alkane aluminum hydrolyzed method, and a sodium metaaluminate-aluminum sulfate method.
  • the hydrated aluminide can be prepared by the low-carbon alkylaluminum aluminum hydrolysis method described in Chinese patent CN 85100218B: Ci ⁇ C 4 alkylaluminum aluminum, preferably triisooxyaluminum and water content less than 20 5 to 120% by weight, preferably 4 to 15% by weight of low-carbon alcohols (such as water-containing isopropanol) under the conditions of controlling the amount of water close to but not as large as the stoichiometric amount of water required for the hydrolysis reaction of the low-carbon alkylaluminum .
  • the C reaction is 1 to 96 hours, preferably 1 to 16 hours.
  • a preferred hydrated alumina is a hydrated alumina that has a boehmite content of more than 60% by weight.
  • the zeolite is a mesoporous or macroporous zeolite having an acidity value of 1.0-2.0 mmol / g as measured by the NH 3 TPD method.
  • a zeolite may be selected from faujasite, mordenite, ZSM-5 zeolite, Beta zeolite, or omega zeolite.
  • the zeolite can be modified by various methods, such as ion exchange method, impregnation method, and the like.
  • Preferred zeolites are argon or rare earth Y-type zeolites or mordenites.
  • the term "acidity value” used in the present application refers to an acidity value measured by an ammonia programmed temperature desorption method (NH 3 -TPD).
  • the specific measurement steps are as follows: Take a small amount of sample and place it in a thermogravimetric analyzer, and pass in a high-purity argon stream. Heat up to 500 ° C. C constant weight, record the sample weight ⁇ ⁇ Cool down to 150 'C and pass in high-purity atmosphere, stop the atmosphere after adsorption equilibrium. Constant temperature for 1 hour to remove the physically adsorbed atmosphere. Record the sample weight W 2 after ammonia absorption. Program the temperature to 500 ° C at a heating rate of 10 ° C / min, record the weight loss curve, and record the sample weight W 3 after deamination, and calculate the acidity value of the sample by the following formula:
  • thermogravimetric decanter can be, for example, the 951 thermogravimetric decanter in the 9900 thermogravimetric system from DuPont.
  • the argon-cracking catalyst carrier used in the method of the present invention is obtained.
  • a hydrated aluminum halide selected according to the above standards may be mixed with a zeolite selected according to the above standards, or a scale or several types of hydrated rhenium selected according to the above standards may be mixed Aluminium is mixed with one or more zeolites selected according to the above criteria.
  • the mixing ratio of hydrated aluminum halide and zeolite should satisfy the following conditions: After mixing, forming, drying and firing the hydrated aluminum halide and zeolite, the aluminum halide accounts for 20 to 90% by weight, preferably 50 to 80% by weight of the entire catalyst support. .
  • the molding method is a conventional method in the art, such as a method of tabletting, ball forming, or extrusion, and the present invention is preferably an extrusion molding method.
  • the baking temperature is 500-650 -C, and the baking time is 3-5 hours or more.
  • the carrier prepared as described above was supported with gas, nickel halide and tungsten gas as active ingredients.
  • the fluorine can be loaded by a conventional impregnation method, that is, the carrier obtained by the above method is impregnated with a predetermined amount of a fluorine-containing aqueous solution, and then dried and fired.
  • the fluorine-containing aqueous solution refers to an aqueous solution of a fluorine-containing inorganic compound, such as an aqueous solution of ammonium fluoride and / or argon fluoride. Generally, it is dried at 100-130 ° C, and then baked at 400-500 for 3-5 hours.
  • the loading of fluorine generally accounts for 0.5-5.0% by weight of the entire catalyst, preferably 1.0-4.0% by weight.
  • the support of nickel-tungsten can also be performed by conventional impregnation methods, that is, impregnation of the above-mentioned fluorine-containing support with an aqueous solution containing nickel-tungsten Then, it is dried and roasted.
  • the nickel-tungsten-containing aqueous solution is generally composed of ammonium metaborate, ammonium tungstate, ethyl ammonium metatungstate or nickel metatungstate, and nickel nitrate or nickel acetate according to the predetermined nickel in the catalyst.
  • a mixed aqueous solution made of tungsten content. It is generally dried at 100-130 and then baked at 400-500 'C for 3-5 hours.
  • the loading amount of nickel should be 2.5-6.0% by weight, preferably 2.6-5.0% by weight, of the tritiated nickel.
  • the loading of tungsten should make the gasification pigeons account for 10-38% by weight of the entire catalyst, preferably 19-25% by weight.
  • the hydrocracking catalyst used in the method of the present invention can be used under conventional argon hydrocracking conditions. Before use, it can be pre-dried out according to conventional methods.
  • the raw materials used in the method of the present invention may be various raw materials suitable for the conventional hydrocracking method. Because the method of the present invention uses a hydrorefining catalyst and a hydrocracking catalyst in series, the hydrorefining catalyst has excellent dephosphazation, denitrification, and aromatic argon addition performance, while the hydrocracking catalyst has excellent anti-thorium resistance (argon cracking).
  • the nitrogen content in the section feed is as high as 150 ppmw), so the present invention is more suitable for processing heavy distillate oils with high nitrogen content.
  • the boiling range dry point is> 500 TC, generally 500-580 'C, and the nitrogen content can be as high as 1500 ppmw, heavy distillates with a high content of tritium, such as atmospheric or vacuum gas oil, coking gas oil and slag-containing catalytic cracking cycle oil.
  • the nitrogen content in heavy peptidium oil is best controlled at not more than 1300 ppmw, and the sparse content is best controlled at not more than 3.0% by weight. This can ensure that the operating time of the catalyst before regeneration is not less than one year.
  • the method of the present invention uses a series of combined hydrorefining catalyst and hydrocracking catalyst.
  • the hydrorefining catalyst and the argon cracking catalyst may be installed in the same reactor or different reactors, and the argon refining and argon cracking reaction conditions may be substantially the same or different.
  • the temperature of argon refining and hydrocracking reactions can be controlled with cold hydrogen.
  • the hydrogen-to-oil ratio of the argon cracking section can be adjusted by recirculating hydrogen from the line 8.
  • Conditions for hydrorefining and hydrocracking include a hydrogen partial pressure of 6.0-10.0 MPa, preferably 6.5-1. 5 MPa, an average reaction temperature of 340-440 "C, preferably 350-420 TC, and the time and space of the raw material liquid.
  • the hydrogen partial pressure should be at least 85% of the total pressure.
  • the loading ratio of the hydrorefining catalyst and the argon cracking catalyst can be adjusted according to the properties of the raw materials used. The worse the quality of the raw materials, the larger the proportion of the aerated refining catalyst.
  • the loading volume ratio of argon-refined catalyst and hydrocracking catalyst can be adjusted in the range of 25: 75-75: 25.
  • the amount of protective agent added is generally 1 -20 "/ « for the volume of hydrorefining catalyst, depending on the nature of the raw materials.
  • the process method provided by the present invention can be implemented on a newly-built medium-pressure argon cracking unit, or it can be implemented on an existing medium-pressure puffer unit with necessary modifications.
  • This group of examples illustrates the preparation method of the argon-added refining catalyst support provided by the present invention.
  • the precursor of the small-pore gasified aluminum used in this example is the hydrated gasified aluminum (the first hydrated aluminum oxide) industrial product prepared by the sodium metaaluminate-carbon dioxide method-dry pseudoboehmite (Shandong, China Aluminum plant), which contains 80% by weight of gibbsite and 5% by weight of gibbsite.
  • the specific surface and pore distribution of the small-hole aluminized aluminum (B) formed after baking at 550 for 4 hours are shown in Table 1.
  • the macroporous aluminide precursor used in this embodiment is a hydrated gasified aluminum produced by the sodium metaaluminate-aluminum sulfate method (the second hydrated aluminide).
  • Catalyst plant where the content of mono-boehmite is 68% by weight and the content of gibbsite is 5% by weight.
  • the specific surface and pore distribution of the macroporous aluminum (C) formed after baking for 4 hours at 550 are listed in Table 1. .
  • Mix the two hydrated aluminum halides according to the required weight ratio (see Table 1), add an appropriate amount of extrusion aid, adhesive and water, and squeeze into an external Trilobal strips with a circle diameter of 1.4 mm were dried at 120 'C and calcined at 550-650 for 4 hours respectively to obtain catalyst carriers D-H.
  • the specific surface and pore distribution measured by the BET low-temperature nitrogen adsorption method (the same below) are shown in Table 1.
  • This group of examples illustrates the preparation method of the argon-added refining catalyst of the present invention.
  • aluminized aluminum support D-H prepared in Examples 1-5 soak it with a certain amount of ammonium fluoride (chemically pure) aqueous solution for 1 hour, dry it at 120, and fire it at different temperatures 4 Hours, a fluoride-containing aluminum halide carrier was obtained.
  • Table 2 shows the amount of each raw material and the temperature and time for firing.
  • a certain amount of a mixed aqueous solution of ammonium metatungstate (chemically pure) and nickel nitrate (chemically pure) was immersed in a gaseous aluminum carrier for 4 hours, dried at 120 X, and calcined at different temperatures for 4 hours to obtain a catalyst I-S. .
  • Table 3 shows the amount of each raw material, the calcination temperature and time, and Table 4 shows the content of the active components of the prepared catalyst.
  • determination method of NiO and W0 3 content please refer to the "Petrochemical Tillering Method” (RIPP test Method), P360-361, Science Press (1990).
  • determination method of fluorine see pages P185-187 of the same book. Examples of impregnation and roasting conditions of carrier fluorine
  • Nickel-tungsten impregnation roasting conditions For nickel nitrate ⁇ Ammonium tungstate Water consumption, temperature, ° c time, hour quantity, gram consumption, gram ml
  • the air carrier was impregnated with an aqueous solution containing 35.5 g of ammonium metatungstate and 12 g of nickel nitrate for 4 hours, dried at 120 ° C, and calcined at 480 ° C for 4 hours to obtain catalyst 17, which became W0: 22.1% by weight and NiO: 2.3% by weight. , F 4.1% by weight.
  • hydrated aluminum ⁇ and hydrated gasified aluminum B were used, respectively.
  • hydrated aluminum A is prepared according to the method disclosed in Chinese patent CIN 85100218B, and the specific preparation method is as follows:
  • Hydrated and gasified aluminum B is an industrial product prepared by 4 methods of sodium aluminate two gasification (product name is dry pseudoboehmite, produced by Shandong Aluminum Plant of China).
  • Table 5 shows the gibbsite content of the above hydrated and gasified aluminum and the acidity value, specific surface area, and porosity of the hydrated aluminum that were formed after calcination at 550 X: 600 "CA 650 ° C for 4 hours.
  • the volume, specific surface area and pore volume were determined by BET low temperature nitrogen adsorption method.
  • argon zeolite (), rare earth Y zeolite (Rf: Y), and argon-type mordenite () were used, respectively.
  • Table 6 shows the silica-to-aluminum ratio, acidity value and rare earth element gas content of the above zeolites.
  • the content of rare-earth element gaseous compounds was determined by X-ray fluorescence photofluorescence (see Analysis Methods for Petrochemicals (Test Methods), P368 370, Science Press, 1990).
  • Table 7 shows the amount of each raw material and the calcination temperature and time during the preparation of the catalyst support.
  • Table 8 shows the amount of support, the amount of ammonium fluoride, and the temperature and time for firing.
  • Table 9 shows the amount of ammonium metatungstate and nickel nitrate and the calcination temperature and time.
  • Table 10 shows the content of each active ingredient in the prepared catalyst.
  • the content of Ni () and Wtb is determined by plasma emission spectrometry (1CP / AES) (see “Analytical Method of Petrochemical Technology (RIPP Test Method)" P360 ⁇ 361, Science Press, 1990).
  • the content of fluorine is Measured by the fluoride ion electrode method (see the same book P 185 ⁇ 187).
  • Example Nickel-tungsten impregnation Roasting conditions No. Nickel nitrate dosage Ammonium metatungstate dosage Water dosage Temperature Time
  • the fluorine-containing support was impregnated with an aqueous solution containing 72 g of nickel nitrate and 145 g of ammonium metatungstate for 4 hours, dried at 120 ° C, and 48 () X: roasted.
  • Catalyst 26 was obtained with a composition of W () 3 19.0% by weight, Ni () 4.6% by weight, and F 1.2%.
  • Example 17 the argon-added catalyst 17 prepared in Example 17 is used.
  • Examples 27, 28, and 29 the following three raw materials were used: A-vacuum gas oil of Saudi Arabia's medium crude oil, B-vacuum gas oil of China's intermediate base crude oil, and C-obtained from catalytic cracking of slag-containing heavy oil.
  • Emu oil and straight-run light gas oil are mixed oils obtained at a weight ratio of 69:31. Their properties are listed in Table 11 below.
  • This embodiment uses a raw material A.
  • the method provided by the present invention can convert a heavy distillate with a high sparse and high aromatic content into a light naphtha fraction with a saturated hydrocarbon content of up to 97% by weight under medium pressure; the content is ⁇ ().
  • 5ppmw Heavy naphtha fractions with aromatic potential up to 58% by weight; kerosene fractions with smoke points and aromatics that meet jet fuel specifications; tritium content of only 21 ppm v, freezing point 28 X :, emu oil fractions with cetane number close to 62;
  • characteristic factor> 12 aromatics correlation index ⁇ , sulfur content 23ppmw,
  • the middle distillate oil with a distillation range of 145-350 has a yield of 46% by weight and a selectivity of 65.6% by weight.
  • the raw material B is used.
  • the reactor, the catalyst used, the total volume of the packed catalyst, the packed volume ratio, and the pre-sulfidation of the catalyst were the same as those in Example 27.
  • the operating conditions were as follows: hydrogen partial pressure 6.4 MPa (total pressure 7.5 MPa), and reaction temperature (hydrorefining / aerated cracking) ) 391/384, liquid hourly space velocity 0.5hr 1 and hydrogen / oil volume ratio 1000.
  • the gas content of the feed in the argon cracking section was 46ppimv, and the volume conversion rate of the product in one pass was 350.5%.
  • the distribution and properties of the obtained products are listed in Table 13.
  • the raw material C is used.
  • Example 27 The same reactor as in Example 27 was charged with a total volume of 0.3 liters of argon-added refining catalyst 17 and hydrocracking catalyst 26, and the filling volume ratio of the two was 60:40.
  • the catalyst was pre-dried as in Example 27.
  • the operating conditions are as follows: partial pressure of argon 7.8 MPa (total pressure: 9.2 MPa), reaction temperature (refined with argon / cracking with chlorine) 360/367 ° C, liquid hourly space velocity 0.85hr, argon oil volume ratio (refined with argon / Add argon cracking) 807/1003.
  • the distribution and properties of the product are listed in Table 14.
  • the yield of middle distillate at 145-350 ° C is 67.8% by weight, and the selectivity is 75.4% by weight.

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Description

一种重质馏分油的中压加氢裂化方法 本发明的技术领域
本发明涉及一种重质馏分油的催化转化方法。 更具体地说， 本发明涉 及将重质馏分油在氩气存在下进行中压加氩裂化生产中间馏分油的方法。
本发明的技术背景
加氩裂化是一种石油炼制方法， 其中烃质原料的分子在氬气存在下部 分分解以获得更希求的低分子量烃产品。 近年来， 世界范围内原油重质和 劣质倾向日益明显， 与此同时， 对中间馏分油如喷气燃料和柒油的需求量 却不断增长， 这促使加氬技术迅速发展。 人们在发现新型催化剂和改进裂 化条件方面做了许多开发工作。
EP - A2 0093552公开了一种单段加氛裂化方法。加氣处理催化剂 与加氬裂化催化剂布置在同一个反应器中且加氫处理催化剂位于前面。 该 方法的条件为 5.25-7.0MPa 的压力， 360 440 'C的温度和（U - 10hi'- 1的 LHSV。 沸点为 345 'C以下产品的转化率为 30 40 % (体） 。 所用原料 油是初沸点为 200 °C通常为 340 "C或更高的重质馆分油如焦化重瓦斯油。 加氪处理催化剂为负载在无定型多孔载体如二氣化硅、 氣化铝或硅铝载体 上的一种或多种周期表 VIA或 VII1A族金属。 加氢裂化催化剂为负载在大 孔沸石如 X或 Υ沸石或丝光沸石上的周期表 VIA或 VIII A族金属。 该方 法的缺点在于为达到加氬裂化产品的良好分布， 必须在 345 °C以下熘分的 体积转化率小于 50 %的条件下进行加氬裂化。
美国专利 4， 686 , 030公开了一秤含氮、疏和沸点大于 700。F ( 371 ' ) 的烃原料緩和加氬裂化的方法。 该方法的典型緩和加氬裂化条件为 500 900° F 的温度， 200 1500psig的氫分压和 0.05 - S.Ohr 1的 LHSV。 该方法使 10 - 50 % (体） 的沸点在 700°F 以上的原料组分转化成沸点在 700°F 以下的产品组分。 所用的催化剂为负载在无定型多孔耐热氣化物载 体上的 Mo-Ni-P， 该催化剂中至少 75 %的孔的直径为 50 130埃， 小于 10 % (体积） 的所述孔体积的孔径大于 1 10埃。
美国专利 4， 859 , 312和 EP-A2-0019959公开了一种加氩裂化重烃 油生产中间馏分油的方法。 但这两种方法要求原料的有机氮含量小于 50 , 优选小于 lOppmw。
本发明的目的
本发明的 3的是提供一种使用 串联的新型加氫精制催化剂和加氬裂 化催化剂将重质熘分油加氩裂化以生产中间熘分油的方法。 该方法可在中 压条件下操作并可获得高达 80体％的一次通过转化率， 能直接处理氮含量 高达 1500ppm 的劣质原料油而且加氫裂化段的进料的氮含量可高达 ISOppmw。
本发明概述
本发明提供一种将重质镏分油加氩裂化生产中间馏分油的方法， 该方 法包括下列步骤：
( 1 ) 在加氢精制条件下将重质馏分油与一种加氣精制催化剂接触以 加氫精制该重质馅分油； 和
( 2 ) 在加氫裂化条件下将加氣精制后的重质馏分油不经中间分离与 一种加氣裂化催化剂接触以加氫裂化该加氬精制后的重质馏分油，
所用的加氬精制催化剂有下列组成：氧化镍 1 - 5重％，氣化钨 12 - 35 重" /。， 氟 1 - 9 重％， 其余为作为载体的复合氣化铝， 所述复合氡化铝是 由一种或多种小孔氣化铝与一种或多种大孔氧化铝按照 75:25 - 50:50的重 量比复合而成的， 其中小孔氡化铝为孔直径小于 80埃孔的孔体积占总孔体 积 95 %以上的氣化铝， 大孔氡化铝为孔直径 60 - 600埃孔的孔体积占总 孔体积 70 %以上的氣化铝， 所述孔分布是采用 BET低温氮吸附法測得； 所用的加氬裂化催化剂有下列组成： 氟 0.5-5.0 重％、 氣化镍 2.5-6.0 重％、 氣化钨 10 - 38重％、 其余为载体， 该载体是由 20 - 90重％的氣 化铝和 1() - 80重％的沸石组成，其中沸石为 NH3― TPD法测定的酸度值 为 1.0-2.0mmol/g的中孔或大孔沸石， 氧化铝为 NH3 TPD法测定的酸度 值为 0.5-0.8mmol/g的氡化铝。
附图的简单说明
图 1示出本发明方法的一种简单流程示意图。
本发明的方法可用图 1 所示的系统进行实施。 参见图 1 ， 重质馏分油经管线 1进入系统并与管线 2 的氩气和管线 3 的再循环氫气混合。 然后混合物流过热交换器 4， 到加热器 5， 在其中混 合物升到适合反应的温度。 加热后的物料首先进入加氫精制反应器 6 ， 在 此它与加氬精制催化剂接触， 在加氫精制反应器中的催化剂分成两个或多 个催化床层， 床层间引入来自管线 8 的冷氬气以控制床层的入口温度。 加 氬精制反应器的流出物经管线 7进入加氫裂化反应器 9 。 在加氫裂化反应 器中， 油和氢气进一步与加氫裂化催化剂接触以形成所需产物。 类似地， 放在加氩裂化反应器中的加氫裂化催化剂分成两个或多个床层， 床层间引 入来自管线 8 的冷氢气以控制床层的进口温度。 然后加氢裂化反应器的流 出物经过热交换器 4以传热给进料。 在热交换后， 流出物与来自管线 10的 水混合以洗出在反应器中形成的氨气和部分破化氪。 混合物然后进入高压 气 /液分离器 11， 在其中再循环氢气、 酸性水和液体产品进行分离。 来自分 离器 1 1 的再循环氫气进入胺洗涤器 12 ， 在其中疏化氫以常规方式分离。 纯化后的氢气在压缩器 13 中压缩到操作压力， 由此进入高压氫气系统。 加 氬裂化反应器产品离开分离器 11， 经管线 14进到低压气 /液分离器 15。 在 低压分离器 15 中， 气体 （ C4 ) 从液体产品中分离出来， 液体产品在塔 17 中被分馏成石脑油、 煤油、 柒油和塔底馏分。
也可如 EP - A2 0093552 中公开的， 加氢精制催化剂与加氩裂化 催化剂布置在同一个反应器中且加氢精制催化剂在前。
本发明的详述
加氬精制催化剂
用于本发明方法中的加氫精制催化剂，其组成为：基于催化剂组合物的 总重量,氨化镍 1 - 5重％、 氡化钨 12 - 35重％， 氣 1 - 9重％， 其余为 作为载体的复合氣化铝。 该复合氡化铝是由一种或多种小孔氧化铝与一种 或多种大孔氣化铝复合而成。 该复合氡化铝优选是由一种小孔氣化铝与一 种大孔氡化铝复合而成。 氣化铝的复合比例是根据该催化剂所加工的原料 油的轻重进行调整的。 当原料是轻廣馆分油时可以加大小孔氣化铝的用 量， 当原料是重质馏分油时則宜加大大孔氧化铝的用量。 用于 80 550 。C 的石油馏分加氫精制时， 小孔氨化铝和大孔氣化铝的重量比应为 75 ： 25 50 ： 50。 此时， 复合后的氡化铝载体优选具有如下孔分布： 直径 40 - 100埃孔的孔体积占总孔体积的 75 %以上。
在加氫精制催化剂中， 其复合氧化铝具有一般加氣精制催化剂载体的 常规的比表面和孔体积， 其比表面优选 200米 2/克以上， 更为优选 220米 2/ 克以上， 孔体积优选 0.3毫升 /克以上， 更为优选 0.4毫升 /克以上。
上述加氢精制催化剂的具体制备步骤如下：
1.载体的制备： 将小孔氡化铝的前身物和大孔氧化铝的前身物按照所需 的比例混合均勻， 按常规的加氢精制催化剂成型方法成型， 然后于 550 - 650 。C焙烧 ; 3 - 5小时得到了作为载体的复合氣化铝；
2.氟的浸渍： 用含氟水溶液浸渍上述复合氡化铝， 100 - 130 °C烘干后 于 400 600 " 焙烧 3 -— 5小时；
3.镍 -钨的浸渍： 用含镍和钨的水溶液浸渍上述含氟复合氡化铝， 100 130 °C烘干后于 400 - 600 'C焙烧 3 - 5小时。
其中所说小孔氡化铝的前身物优选是一水铝石含量大于 60重％的水合 氣化铝， 它优选用偏铝酸钠 -二氣化碳法制得； 大孔氣化铝的前身物优选 是一水铝石含量大于 50重％的水合氡化铝， 它优选用偏铝酸钠 -疏酸铝法 制得。
其中所说的常规成型方法包括压片、 成球和挤条等方法， 优选采用挤 条成型的方法。
其中所说含氟水溶液指含氟的无机化合物水溶液， 如氟化铵和 /或氟化 氪的水溶液。
其中所说含钨和镍的水溶液一般由偏钨酸铵、 钨酸铵、 乙基偏钨酸铵 或偏钨酸镍和硝酸镍或醋酸镍制成的混合水溶液。
在使用前， 加氬精制催化剂可按常规方法进行预疏化处理。
加氬裂化催化剂
用于本发明方法中的加氫裂化偁化剂的组成为： 基于整个伥化剂的重 量， 氣为 0.5-5.0重％， 氡化镍为 2.5-6.0重％, 氣化钨为 10 ― 38重％， 其 余为催化剂载体。 该伥化剂载体由 20 - 90重％的氡化铝和 10 - 80重％ 的沸石组成。 其中沸石为 NH3 - TPD法测定的酸度值为 1.0-2.0mmol/g的 中孔或大孔沸石， 氡化铝为 NH3 - TPD法测定的酸度值为 0.5-0.8mmol/g 的氧化铝。
在上述催化剂活性组分中， 基于整个催化剂的重量， 氟优选 1.0-4.0重 %， 氣化镍优选 2.6-5.0重％, 氣化鸪优选 19 - 25重％。 在上述催化剂载 体中， 氡化铝优选 50 - 80重％， 沸石优选 20 - 50重％。
用于本发明方法中的加氬裂化催化剂的制备方法如下：
( 1 ) 加氩裂化催化剂载体的制备
催化剂的载体由水合氣化铝和沸石制得。 所用的水合氡化铝为在一定 条件下焙烧后能形成酸度值为 0.5-0.8 mmol/g的氣化铝的水合氣化铝。 焙 烧温度为 500 - 650 °C， 焙烧时间为 2 - 8小时或更长。 在此条件下焙烧 水合氡化铝所得到的氣化铝的孔体积最好大于 0.3ml/g， 比表面积最好大于 200m2/g 。
所述水合氣化铝可由偏铝酸钠 -二氣化碳法、 烷基铝或烷氣基铝水解 法、 偏铝酸钠 -硫酸铝法制得。
例如， 所述水合氡化铝可采用中国专利 CN 85100218B所述低碳烷氡 基铝水解法制备： 将 Ci~C4烷氡基铝， 最好是三异芮氧基铝和含水量小于 20重％， 最好 4〜15重％的低碳醇 （如含水异丙醇） 在控制水量接近但不大 f低碳烷氡基铝水解反应所需化学计量水的条件下， 在 5~120 。C反应 1~96 小时， 最好 1~16小时。 蒸出含水量小于 0.2重％的低碳醇后， 在固体产物 中加入去离子水。 然后， 在 5~100 C， 最好 78〜； 100 'C老化 120小时， 最 好 6〜40小时， 蒸出含水异丙醇。 将固体产物于 110〜120 烘干， 即可得到 所述水合氣化铝。
优选的水合氡化铝为一水铝石含量大于 60重％的水合氣化铝。
所述的沸石为 NH3 TPD法测得的酸度值为 1.0-2.0 mmol/g的中孔或 大孔沸石。这样的沸石可选自八面沸石、 丝光沸石、 ZSM - 5沸石、 Beta 沸石或 Ω沸石。 该沸石可以用各种方法加以改性， 如离子交换法、 浸渍法 等。 优选的沸石为氩型或稀土型的 Y型沸石或丝光沸石。
在本申请中所用术语 "酸度值" 是指用氨程序升温脱附法 （ NH3 - TPD ) 测定的酸度值。 具体测定步骤如下： 取少量样品置于热重分柝仪中， 通入高纯氬气流。 升温至 500 。C恒重， 记录样品重量 \¥ 降温至 150 'C并通入高纯氛气， 吸附平衡后停止进氛。 恒温 1 小时以脱除物理吸附的氛气。 记录吸氨后的样品重量 W2。 以 10 °C / 分的升温速率程序升温至 500 ， 记录失重曲线， 并记录脱氨后的样品重 量 W3， 由下式计算出样品的酸度值：
W2(mg)-W3(mg)
酸度值 = (mmol/g)
W,(g) χ氨的分子量
其中的热重分柝仪可采用例如杜邦公司出品的 9900热分柝系统中 951 热重分柝仪。
将按上述标准选择的水合氡化铝与按上述标准选择的沸石按一定比例 混合均 后成型、 干燥并焙烧后， 即得到本发明方法所用加氩裂化催化剂 载体。
在加氬裂化催化剂载体的制备过程中可将按上述标准选择的一种水合 氡化铝与一种按上述标准选择的沸石相混合， 也可将一秤或几种按上述标 准选择的水合氡化铝与一种或几种按上述标准选择的沸石相混合。
水合氡化铝与沸石的混合比应满足这样的条件： 水合氣化铝与沸石混 合、 成型、 干燥并焙烧后， 氡化铝占整个催化剂载体的 20 - 90重％， 优 选 50 - 80重％。
所述成型方法为本领域的常规方法， 如压片、 成球或挤条等方法'， 本 发明优选挤条成型的方法。
上述焙烧温度为 500 - 650 -C , 焙烧时间为 3 - 5小时或更长。
( 2 ) 活性成分的负载
在依上述方法制得的载体上负载作为活性成分的氣、 氡化镍和氣化 钨。
氟的 载可采用常规的浸渍的方法， 即将按上述方法得到的载体用预 定量的含氟水溶液浸渍， 然后烘干、 焙烧。 所述含氟水溶液指含氟的无机 化合物的水溶液， 如氟化铵和 /或氟化氩的水溶液。 一般在 100 - 130 °C进 行烘干， 然后于 400 - 500 焙烧 3 - 5小时。 r、 氟的负载量一般占整个催化剂的 0.5 - 5.0重％， 优选 1.0-4.0重％„ 镍-钨的 载也可采用常规的浸渍的方法， 即将上述含氟载体用含镍 -钨的水溶液浸渍， 然后烘干、 焙烧。 所述含镍-钨的水溶液一般是由偏 鸪酸铵、 钨酸铵、 乙基偏钨酸铵或偏钨酸镍和硝酸镍或醋酸镍按催化剂中 预定的镍-钨含量制成的混合水溶液。 一般在 100 - 130 进行烘干， 然 后于 400— 500 'C焙烧 3 - 5小时。
镍的负载量应使氡化镍占整个催化剂的 2.5-6.0重％， 优选 2.6-5.0重 %。 钨的负载量应使氣化鸽占整个催化剂的 10 - 38重％， 优选 19 - 25 重％。
本发明方法所用的加氫裂化催化剂可在常规的加氬裂化条件下使用。 在使用前， 可按常规方法进行预疏化处理。
本发明方法适用的原料
本发明方法所用的原料可以是通常加氫裂化方法所适用的各种原 料。 由于本发明方法串联使用加氫精制催化剂和加氫裂化催化剂， 加氫精 制催化剂具有优良的脱疏、 脱氮和芳烃加氬性能， 而加氫裂化催化剂具冇 优良的抗氪能力 （加氩裂化段进料中的氮含量允许高达 150ppmw ) ， 因而 本发明更适合处理疏、 氮含量高的重质馏分油， 例如沸程干点 >500 TC， 一 般为 500 - 580 'C， 氮含量可高达 1500ppmw， 硤含量可高达 3.5重％的 重质馏分油， 如常压或减压瓦斯油、 焦化瓦斯油和摻渣催化裂化循环油。
重质镏分油中氮含量最好控制在不大于 1300ppmw ,疏含量最好控制 在不大于 3.0重％， 这样可保证催化剂在再生前的运转时间不小于 1年。
本发明方法的工艺条件
如上所述， 本发明的方法使用串联组合的加氫精制催化剂和加氫裂化 催化剂。 加氫精制催化剂和加氩裂化催化剂可装在同一个反应器或不同的 反应器， 加氩精制和加氩裂化反应条件可基本相同或不同。 例如加氩精制 和加氫裂化反应的温度可用冷氫来控制。 加氬裂化段的氫油比可由来自管 线 8的再循环氫气来调节。
加氢精制和加氫裂化的条件包括氫分压为 6.0-10.0MPa ， 优选 6.5- .5MPa， 平均反应温度为 340― 440 "C , 优选 350— 420 TC， 原料液时空 速 （ LHSV ) 0.1-3.0111· ， 优选 0.2-1.0hr_1， 和氫 /油体积比 400 - 1200 , 优选 600― 1000。
氫分压应至少是总压的 85 %。
加氫精制催化剂与加氩裂化催化剂的装填比可根据所采用原料的性 质调整。 原料质量越差， 加氣精制催化剂占的比例也就越大。 加氬精制催 化剂和加氫裂化催化剂的装填体积比可在 25： 75 - 75： 25的范围内调 埜。
若原料中残炭、 沥青质或金属含量较高， 为防止儐化剂床层的压力降 过快地达到限定值， 可在加氫精制催化剂前加入一定量的保护剂以保证装 置长时间地运转， 保护剂的加入量一般为加氫精制催化剂体积的 1 ― 20 "/« , 据原料性质而定。
上述所有工艺条件是在一般情况下使用的， 根据所用原料的种类、 性 质不同， 所希求目的产物的分布不同， 与其它石油加工单元的组合不同， 它可加以调整， 这是本领域技术人员显而易见的。
本发明提供的工艺方法可在一新建的中压加氬裂化装置上实施， 也可 在做些必要的改动的现有中压加氲装置上实施。
本发明的最佳实施方案
下面的实施例将对本发明做进一步说明， 但并不因此而限制本发明。
实施例 1 - 5
这组实例说明本发明提供的加氩精制催化剂载体的制备方法。
本实例采用的小孔氣化铝的前身物为偏铝酸钠 -二氡化碳法制得的水 合氣化铝 (第一种水合氡化铝）工业产品 -干拟薄水铝石（中国山东铝厂）， 其中一水铝石含量 80重％， 三氷铝石含量 5重％。 经 550 焙烧 4小时后 形成的小孔氡化铝 ( B ) 的比表面和孔分布列于表 1 中。 本实施例采用的 大孔氡化铝前身物为偏铝酸钠 -硫酸铝法制得的水合氣化铝 (第二种水合 氡化铝） 工业产品 -长岭干胶粉 （中国长岭炼油厂催化剂厂） ， 其中一水 铝石含量 68重％， 三水铝石含量 5重％， 经 550 焙烧 4小时后形成的大 孔氣化铝 （ C ) 的比表面和孔分布列于表 1 中。 将两种水合氡化铝按所需 的重量比 （见表 1 ) 混合均 ， 加入适量助挤剂、 胶粘剂和水， 挤成外接 圓直径为 1.4毫米的三叶型条， 120 'C烘干， 分別在 550 - 650 焙烧 4 小时， 制得催化剂载体 D - H。 用 BET低温氮吸附法 （下同） 测得其比 表面和孔分布列于表 1 中。
表 1
Figure imgf000011_0001
实例 6 - 16
这组实例说明本发明的加氩精制催化剂的制备方法。
分别称取一定量的实例 1 - 5制备的氡化铝载体 D - H , 用一定量的 氟化铵 （化学纯） 水溶液浸渍 1 小时， 120 烘干， 在不同温度下焙烧 4 小时， 得到含氟氡化铝载体。 表 2给出了各原料用量及焙烧温度和时间。 用一定量偏钨酸铵 （化学纯） 和硝酸镍 （化学纯） 的混合水溶液浸渍 含氣氣化铝载体 4小时， 120 X 烘干， 在不同温度下焙烧 4小时， 制得催 化剂 I - S。 表 3给出了各原料用量， 焙烧温度及时间， 表 4則给出了制 备出的催化剂的活性组分的含量， 其中 NiO、 W03含量測定方法参见《石 油化工分柝方法》 （ RIPP试验法）， P360 - 361， 科学出版社 （ 1990 )， 氟的测定方法参见同书的 P185 - 187页。
Figure imgf000012_0001
实例编 所用载体 氟的浸渍 焙烧条件
Ύ
编号 用量， 克 NH4F用量， 克水用量，毫升温度， "C 时间，
小时
6 D 50 6.0 33 530 4
7 E 200 22.6 132 530 4
8 E 50 6.0 33 450 4
9 E 50 6.0 33 500 4
10 E 50 6.0 33 530 4
11 E 50 6.0 33 530 4
12 E 50 6.0 33 530 4
13 E 50 12.6 33 530 4
14 F 50 6.0 33 530 4
15 G 200 22.6 132 530 4
16 H 200 22.6 132 530 4 实例编号 镍 -钨的浸渍 焙烧条件 硝酸镍用 ^钨酸铵 水用量， 温度, °c 时间， 小时 量 , 克 用量， 克 毫升
6 6.0 17.5 32 500 4
7 24.2 70.0 128 500 4
8 6.0 17.5 32 500 4
9 6.0 17.5 32 500 4
10 6.0 17.5 32 420 4
1 1 6.0 17.5 32 480 4
12 1 1,7 10.8 32 500 4
13 4.3 27.4 32 500 4
14 6.0 17.5 32 420 4
15 24.2 70.0 128 500 4
16 24.2 70.0 128 500 4
Figure imgf000013_0001
实例编号 催化剂编号 催化剂活性纽分含量， 重％
wo3 NiO F
6 I 22.0 2.3 4.0
7 J 21.3 2.3 4.0
8 K 22.0 2.3 3.9
9 L 22.1 2.3 3.9
10 M 22.0 2.3 4.1
1 1 N 21.9 2.3 4,0
12 O 14.0 4.8 2.0
13 V 30.0 1.5 7.6
14 Q 21.8 2.3 3.9
15 R 22.0 2.3 4.0
16 S 22.0 2.3 4.0 实施例 17
称取 140g 小孔氡化铝的前身物 （用偏铝酸钠 -二氣化碳法制得， 山 东铝厂出品） ， 另称馭 60g 大孔氡化铝的前身物 （用偏铝酸钠 硫酸铝法 制得， 长呤炼油厂催化剂厂出品） ， 加入助挤剂， 胶粘剂和水， 挤成外接 圓直径为 1.4mm的三叶型条， 120 'C烘干， 550 'C焙烧 4小时， 得到催化 剂载体 <>该载体用含 12g NH4F的水溶液浸 1 小时， 120 'C烘干， 500 'C焙 烧 4小时， 得到含氟载体。 用含 35.5g偏钨酸铵、 12g硝酸镍的水溶液浸含 氣载体 4小时， 120 'C干燥， 480 'C焙烧 4小时， 得到催化剂 17 , 纽成为 W0 ： 22.1 重％、 NiO:2.3重％、 F 4.1 重％。
在实例 18~26 中， 分別使用 了水合 化铝 Λ和水合氣化铝 B。 其中， 水合 化铝 A是按中国专利 CIN 85100218B公开的方法钊备的， 具体制备 方法如下：
在带搅拌和回流冷凝管的反应釜中加入 5588克含 13.2重％水的异丙 醇， 加热至沸腾， 将 2941 克融化的三异丙氡基 ^滴加到反应釜中， 回流反 应 6小时， 蒸出含水量 0.2重％的异丙醇 3555克， 在反应釜中加入 8.8升 去离子水， 在 80 老化 16小时， 老化的同时,蒸出含水异丙醇， 将固体产 物亍 12() X：烘干得到水合氡化 A 。
水合氣化铝 B是 铝酸钠 二氣化 4法^备的工业产品 （产品名称为 干拟薄水铝石， 中国山东铝厂出品 ) "
表 5給出 了上述水合氣化铝的一水铝石含量及水合氣化铝经 550 X：、 600 "C A 650 °C焙烧 4小时后形成的氣化铝的酸度值、 比表面枳和孔体积,, 比表面积和孔体枳采用 BET低温氮吸附法测定。
在实例 18〜26中， 分別使用了氬 \ 沸石 （ )、稀土 Y沸石 （ Rf:Y ) 和氬型丝光沸石 （ ) 。
表 6给出 了上述沸石的硅铝比、 酸度值和稀土元素氣化物的含量。
其中， 稀土元素氣化物的含量采用 X射线荧光光谙法测定 （参见 《石 油化工分析方法 （ 试验方法）》， P368 370 ,科学出版社， 1990 )。
I 表 5水合氣化铝
水 编号 A B
入口
一水铝石含量 68 62
化 (重％)
铝
焙烧温度 （'C ) 550 600 650 550 600 650 氣 酸度值（mmol/g) 0.7156 0.7028 0.6760 0.6700 0.6565 0.6214 化 比表面积（m2/g) 268 252 240 292 278 265
孔体积（nil/g) 0.61 0.61 0.60 0.41 0.40 0.40
表 6沸石
Figure imgf000015_0001
实例 18 24
这些实施例涉及本发明方法所用加氫裂化催化剂的制备。
( 1 ) 加氬裂化催化剂载体的制备
分别定量称取水合氣化铝 A和水合氧化铝 B , 分别与定量的氬 Y沸石 ( ΙΠ ) 、 稀土 Y沸石 （ REY ) 或氬型丝光沸石 （ HM ) 混合均匀， 加 入适量助挤剂、 胶粘剂和水， 挤成外接圓直径为 1.8毫米的三叶形条， 烘千 后焙烧。
表 7给出 了催化剂载体制备过程中各原料用量及焙烧温度和时间。
( 2 ) 氟的负载 定量称取上述载体， 用氣化铵水溶液浸渍 1 小时， 于 120 °C烘干后焙 烧。
表 8给出了载体的用量、 氟化铵的用量及焙烧温度和时间。
( 3 ) 镍 钨的浸渍
用预定量的偏钨酸铵和硝酸镍混合水溶液浸渍上述含氣载体 4小时， 于 120 'C烘干， 焙烧后即得本发明提供的催化剂,，
表 9给出 了偏钨酸铵和硝酸镍的用量及焙烧温度和时间。
表 10给出了制得的催化剂中各活性成分的含量。 其中 Ni()和 Wtb的 含量是采用等离子体发射光谱法 （ 1CP/AES ) 测定的 （参见 《石油化工分 析方法 （ RIPP试验方法） 》 P360~361 ， 科学出版社， 1990 ) , 氟的含 是采用氟离子电极法测定的 （参见同书 P 185~187 ) 。
实例 18 24所制得的催化剂分别记为催化刖 18 - 24 。 表 7 催化剂载体的制备
Figure imgf000016_0001
* 氷合氡化铝和沸石的量均以干基重量计 (,
I " 表 8 氟的浸溃
Figure imgf000017_0001
表 9镍 -钨的浸渍
实例 镍 钨浸渍 焙烧条件 编号 硝酸镍用量 偏钨酸铵用量 水用量 温度 时间
(克） (克） (毫升） (小时） 实例 18 43.1 72.5 250 450 4 实例 19 65.4 163.0 250 450 4 实例 20 55.8 126.8 250 480 4 实例 21 87.7 220.2 250 420 4 实例 22 71.8 170.2 250 450 4 实例 23 73.4 150.7 250 450 4 实例 24 44.7 180.4 250 450 4 表 10催化剂的活性成分含量
Figure imgf000018_0001
实施例 25
分别称取 185克水合氣化铝 A 与 50克氬 Y沸石 （ HY ) 均勻混合， 加入助挤剂、 胶粘剂和水， 挤成外接圓直径 1.8毫米的三叶形条， 120 X〕干 燥， 焙烧 4小时， 得到催化剂载体。 载体用含 26克氟化铵的水溶液 渍 1 小时， 120 °C烘干， 500 "C焙烧 4小时， 得到含氣载体。 用含 65克 硝酸镍和 150克偏钨酸铵的水溶液浸溃含氟载体 4小时， 120 干燥， 480 C焙烧 4小时， 得到催化剂 25 , 其组成为 W()320.8重％， N ) 4.0 重％， F2. 重0 /
实施例 26
分别称取 185克水合氡化铝 A 与 150克氬 \'沸石 （ HY ) 均勻混合， 加入助挤剂、 胶粘剂和水， 挤成外接圓直径 1.8毫米的三叶形条， 120 °C:干 燥， 600 'C焙烧 4小时， 得到催化剂载体。 载体用含 10克氟化铵水溶液浸 渍 1 小时， 120 'C干燥， 500 'C焙烧 4小时， 得到含氣载体。 用含 72 克硝 酸镍和 145 克偏钨酸铵的水溶液浸渍含氟载体 4 小时， 120 °C干燥， 48() X：焙烧。 得到催化剂 26 , 其组成为 W()3 19.0重％， Ni() 4.6重％, F 1.2 %。
在以下三个实施例中， 使用实施例 17制得的加氬精钊催化剂 17 , 实 例 25和 26制备的加氬裂化催化剂 25和 26。
在实^例 27 ， 28和 29中分別使用下列三种原料： A ― 沙特阿拉伯 中质原油的减压瓦斯油， B -中国中间基原油的减压瓦斯油， C -摻渣重 油催化裂化所得柒油与直馏轻瓦斯油按 69 ： 31 重量比所得的混合油， 它 们的性质列于下表 11
表 11
Figure imgf000019_0001
*电炉法测得
实施例 27
本实施例使用原料 A 。
在 0.4立升的反应器中装填总体积 0.3立升的加氬精制催化剂 17和加 氬裂化催化剂 25，加氩精制催化剂和加氬裂化催化剂的装填体积比为 50 : 0。 催化剂在氢气气氛下用 2 % (重） 的 CS2煤油溶液在不大于 30(TC下 预疏化 28 小时。 然后原料 A 在下列操作条件下与催化剂接触： 氫分压 .6MPa (总压： 1 1.3MPa ) ， 反应温度 （加氩精制 /加氬裂化） 383/380 。C， 液时空速 0.5hr 和氬 /油体积比 1000 。 加氬精制后的加氫裂化段进料 的氮含量 25.3ppmw，一次通过转化为 350 1： -产品的转化率为 63.7^ %。 所得结果给出在下表 12
表 12
Figure imgf000020_0001
由表 12 数据可知， 本发明提供方法可在中压条件下将高疏、 高芳烃 含量的重质馏分油转化成饱和烃含量高达 97重％的轻石脑油馏分； 含量 <().5ppmw , 芳潜高达 58重％的重石脑油馏分； 烟点和芳烃符合喷气燃料 規格的煤油馏分； 硤含量仅为 21 ppm v 、 凝点 28 X：、 十六烷值近 62的 柒油馏分； 以及特性因数 >12 、 芳烃关联指数 <Π 、 硫含量 23ppmw 、
I X 含量 1.3ppmw的尾油馏分。馏程为 145 - 350 的中间馏份油的收率达 46 重％、 选择性达 65.6重％。
实施例 28
本实施例使用原料 B 。
反应器， 所用催化剂、 装填催化剂总体积、 装填体积比及催化剂的预 硫化同实施例 27， 操作条件如下： 氢分压 6.4MPa (总压 7.5MPa ) ， 反 应温度 （加氫精制 /加氛裂化） 391/384 ， 液时空速 0.5hr 1和氢 /油体积 比 1000 。 经加氩精制后加氩裂化段进料的氣含量 46ppimv , 转化为 350 "( 的产品的一次通过的体积转化率为 55.9体％。 所得产品分布及性质列 于表 13 。
表 13
Figure imgf000021_0001
由表 13 数据可知， 本发明提供方法可在中压条件下将高氮含量的重 质馏分油转化成与实例 27同样高质量的各种产品。 馏程为 145 - 370 " 的 4 中间馏分油的收率达 46.7重％、 选择性达 70.2重％。
实施例 29
本实施例使用原料 C 。
在与实施例 27相同的反应器中装入总体积为 0.3立升的加氬精制催化 剂 17和加氢裂化催化剂 26 , 二者的装填体积比为 60 : 40。 催化剂的预 疏化同实施例 27。 操作条件如下： 氬分压 7.8MPa (总压： 9.2MPa ) , 反应温度 （加氬精制 /加氯裂化） 360/367 °C , 液时空速 0.85hr ，， 氬油体 积比 （加氩精制 /加氩裂化） 807/1003。 转化为 350 °C -的产品的一次通过 转化率为 77.0体％， 产品的分布及性质列于表 14 。
表 14
Figure imgf000022_0001
由表 14数据再次可知，本发明在中压条件下可获得各种高质量产
145-350 °C中间馏分油的收率达 67.8重％， 选择性达 75.4重％。

Claims

权 利 要 求
1.一种将重质馏分油加氢裂化生产中间馏分油的方法， 方法包括下列 步骤：
( 1 )在加氢精制条件下将重质馏分油与一种加氢精制催化剂接触以 加氢精制该重质馏分油； 和
( 2 )在加氢裂化条件下将加氢精制后的重质馏分油不经中间分离与 一种加氢裂化催化剂接触以加氢裂化该加氢精制后的重质馏分油，
所用的加氢精制催化剂有下列组成： 氧化镍 1 - 5重％， 氧化钨 12 - 35重。 /。， 氟 1 - 9重％， 其余为作为载体的复合氧化铝， 所述的复合氧化 铝是由一种或多种小孔氧化铝与一种或多种大孔氧化铝按照 75 : 25 - 50： 50的重量比复合而成的， 其中小孔氧化铝为孔直径小于 80埃孔的孔 体积占总孔体积 95 %以上的氧化铝， 大孔氧化铝为孔直径 60 - 600埃孔 的孔体积占总孔体积 70 %以上的氧化铝， 所述孔分布是采用 BET低温氮 吸附法测得；
所用的加氢裂化催化剂有下列组成： 氟 0.5-5.0重％、 氧化镍 2.5-6.0 重％、 氧化钨 10 - 38重％、 其余为栽体， 该栽体是由 20 - 90重％的氧 化铝和 10 - 80重％的沸石组成， 其中沸石为 NH3 - TPD法测定的酸度 值为 1.0-2.0mmol/g的中孔或大孔沸石，氧化铝为 NH3 - TPD法测定的酸 度值为 0.5-0.8mmol/g的氧化铝。
2.按照权利要求 1的方法， 其中所述的加氢精制和加氢裂化条件包括 氢分压 6.0-10MPa， 温度为 340 - 440 " , 氢 /油体积比为 400 - 1200和 液时空速为 0.1-3.0hr― 1。
3.按照权利要求 1的方法， 其中加氢精制催化剂与加氢裂化催化剂的 装填体积比为 25： 75 - 75： 25 .
4.按照权利要求 1 的方法， 其中所述重质馏分油的沸程干点为 500 - 580 V， 氮含量高达 1500ppmw， 硫含量高达 3.5 % (重） 。
5.按照权利要求 4的方法， 其中所述的重质馏分油为常压瓦斯油、 减 压瓦斯油、 焦化瓦斯油、 掺渣催化裂化循环油. 6根据权利要求 1所述的方法， 其中所述的复合氧化铝由一种小孔氧 化铝与一种大孔氧化铝复合而成.
7根据权利要求 1或 6的方法， 其中所述的小孔氧化铝从一水铝石含 量大于 60重％的水合氧化铝得到， 大孔氧化铝从一水铝石含量大于 50重 %水合氧化铝得到.
8根据权利要求 1或 6述的方法， 其中所述的复合氧化铝中孔直径为 40 - 100埃孔的孔体积占总体积的 75 %以上.
9.根据权利要求 1或 6所述的方法， 其中所述的复合氧化铝的比表面 为 220米 2/克以上， 孔体积为 0.4毫升 /克以上.
10.根据权利要求 1的方法， 其中所述的加氢裂化催化剂含氟 1 - 4重 %、 氧化镍 2.6-5.0重％、 氧化钨 19 - 25重％。
11.根据权利要求 1的方法， 其中所述的加氢裂化催化剂栽体是由 50 - 80重％氧化铝和 20 - 50重％沸石组成.
12.根据权利要求 1、 10、 11之一的方法， 其中所述沸石选自八面沸 石、 丝光沸石、 ZSM - 5沸石、 Beta沸石、 Ω沸石中的一种或几种。
13.根据权利要求 12的方法， 其中所述沸石选自氢型或稀土型的 Y型 沸石和 /或丝光沸石.
14.根据权利要求 1、 10、 11之一的方法， 其中所述氧化铝是由选自 偏铝酸钠-二氧化碳法、 烷基铝或烷氧基铝水解法、 偏铝酸钠-硫酸铝法 制备的一种或几种水合氧化铝经焙烧而得到的。
15.根据权利要求 14的方法， 其中所述水合氧化铝的一水铝石含量大 于 60重％ .
PCT/CN1997/000064 1996-06-28 1997-06-27 Procede d'hydrocraquage d'une huile de distillat lourde a des pressions moyennes Ceased WO1998000384A1 (fr)

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