CN101490215A - Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make distillate - Google Patents

Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make distillate Download PDF

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CN101490215A
CN101490215A CNA2007800273469A CN200780027346A CN101490215A CN 101490215 A CN101490215 A CN 101490215A CN A2007800273469 A CNA2007800273469 A CN A2007800273469A CN 200780027346 A CN200780027346 A CN 200780027346A CN 101490215 A CN101490215 A CN 101490215A
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zeolite
composition
catalyzer
weight
unit cell
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王理
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • 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
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • 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
    • 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
    • B01J29/084—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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

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

Abstract

Increased selectivity of middle distillate and/or increased catalyst activity are obtained in a hydrocracking process by the use of a catalyst containing a beta zeolite and a Y zeolite having a unit cell size of 24.33 to 24.38 angstrom. The catalyst may also contain an additional Y zeolite having a unit cell size of from 24.25 to 24.32 angstrom.

Description

Contain the hydrocracking catalyst of β zeolite and Y zeolite and in the process that is used to make overhead product
Invention field
[0001] the present invention relates to catalyst composition and the application in hydrocarbon conversion process, particularly hydrocracking process.The present invention relates more specifically to contain Y zeolite and the β zeolite catalyst composition as active cracking component.The present invention be more particularly directed to make the hydrocracking process of middle distillate.
Background technology
[0002] by crude oil derived raw material is carried out hydrocracking, the petroleum refining industry is made required product usually, for example turbine fuel, diesel-fuel and be known as other liquid hydrocarbons of middle distillate, and low-boiling point liquid for example petroleum naphtha and gasoline.Hydrocracking also has other useful results, has for example removed sulphur and nitrogen by hydrogen treatment from raw material.The raw material through being usually used in hydrocracking is gas oil and the heavy gas oil that is obtained by crude oil by distillation.
[0003] hydrocracking is usually in suitable reactor vessel, by under appropriate condition, comprise the temperature of rising and the existence of elevated pressure and hydrogen, gas oil or other hydrocarbon feeds are contacted with suitable hydrocracking catalyst, to obtain the lower product of ensemble average boiling point, it contains the distribution of the required hydrocarbon product of refining.Though the operational condition in the hydrocracking reactor has some influences to the productive rate of product, hydrocracking catalyst is a principal element of the above-mentioned productive rate of decision.
[0004] based on the person's character of the main cracking component of catalyzer, hydrocracking catalyst can carry out preliminary classification.This classification with hydrocracking catalyst be divided into based on amorphous cracking component a class (for example silica-alumina) and based on the class (for example β or Y zeolite) of zeolite as cracking component.Based on the primary product of its expectation, hydrocracking catalyst can also be classified, and wherein two kinds of primary products are petroleum naphtha and " overhead product ", and this term has the retortable petroleum derived fraction that boiling spread is higher than petroleum naphtha at hydrocracking refining field middle finger.Overhead product is usually included in the refinery product that reclaims as kerosene and diesel-fuel.At present, overhead product has very high demand.For this reason, refining has concentrated on and can optionally make on the hydrocracking catalyst of overhead product cut.
[0005] three kinds of main catalyst performances estimating the hydrocracking catalyst performance be used to make overhead product are active, selectivity and stability.Active can mensuration by such method, promptly keeping under other hydrocracking conditions and the same materials, relatively using different catalysts to produce the required temperature of ebullient product that in required scope, (for example is lower than 371 ℃ (700 ℉)) of particular percentile (normally 65%) for distillment.The required temperature of special catalyst is low more, and this activity of such catalysts is high more with respect to the catalyzer that needs higher temperature.The selectivity of hydrocracking catalyst can be measured in aforementioned required active testing process, and measure by such method, promptly conduct is by in required overhead product scope, and for example 149 ℃ (300 ℉) is to 371 ℃ (700 ℉), the per-cent cut of ebullient product.Stability be under the condition of active testing during the processing hydrocarbons raw material in the time period that prolongs, catalyzer continues its active criterion on which kind of degree.Stability usually according in order to keep 65% or temperature required variation every day of other given conversion measure.
[0006] though be used for making the cracking catalyst of overhead product and be known and used in commercial environment, need under given activity, have more highly selective always and/or under specific selectivity, have more highly active novel hydrogenation cracking catalyst and be used to make overhead product.
Summary of the invention
[0007] has been found that with respect to other at present commercially available preferably have overall silica and aluminum oxide (SiO for making the hydrocracking catalyst that overhead product is used for hydrocracking process, containing Y zeolite (following Y zeolite II) and contain with unit cell dimension or size ao from 24.33 to 24.38 dusts 2/ Al 2O 3) mol ratio less than 30 and SF 6The hydrocracking catalyst of the β zeolite of absorptivity at least 28 weight % (following weight %) has quite improved selectivity or have quite improved activity under specific selectivity under given activity.Catalyzer also contains metallic hydrogenation component, for example nickel, cobalt, tungsten, molybdenum or its combination.Based on the gross weight of β zeolite, Y zeolite II and the carrier of dry substance, catalyzer contains the β zeolite of 0.5 to 5 weight %, and has the weight ratio from 0.5 to 5 of Y zeolite II and β zeolite based on the dry substance catalyzer.The mol ratio that Y zeolite II has overall silica and aluminum oxide is 5.0 to 11.0.In one embodiment, catalyzer contains extra Y zeolite, and Y zeolite II has higher unit cell dimension than extra zeolite.
[0008] believes that the hydrocracking catalyst that contains this Y zeolite and this β zeolite is novel in this area.
[0009] under the hydrocracking condition of routine, comprise the temperature of rising and the existence of elevated pressure and hydrogen, for gas oil and other hydrocarbon feeds being converted into than the harmonic(-)mean boiling point with than the product of low average molecular weight, this catalyzer has very high efficient.In one embodiment, the component that product contains relative vast scale is seethed with excitement in the overhead product scope, is defined herein as 149 ℃ (300 ℉) to 371 ℃ (700 ℉).
Description of drawings
[0010] Fig. 1 is for several hydrocracking catalysts, and the overhead product selectivity is for the active figure of corresponding catalyst.
[0011] Fig. 2 is for several hydrocracking catalysts, heavy overhead product selectivity and light distillate selectivity be compared to the active figure of corresponding catalyst.
Summary of the invention
[0012] β and Y zeolite have been proposed to be used in conjunction with as several different catalysts components, wrap Draw together the catalyst for hydrocracking. For example, US-A-5,275,720, US-A-5,279,726 Hes US-A-5 has described in 350,501 and has used the hydrocracking process that comprises β zeolite and Y zeolite. US-A-5,350,501 described use comprise structure cell size with 24.25 to 24.35 dusts and 4.6mm steam partial pressure and 25 ℃ of lower water vapour absorption abilities are lower than the β of 8.0 % by weight of zeolite The catalyst hydrogenation cracking process of zeolite and Y zeolite and other components. US-A1-2004/0152587 A kind of hydrocracking catalyst has been described, comprise contain have the structure cell size 24.10 to 24.40 dusts, The volume of silica and aluminium oxide than greater than 12 and surface area less than 850m2The faujasite of/g The carrier of the zeolite of structure, and the second zeolite that catalyst can contain different structure cell sizes is for example β zeolite, ZSM-5 zeolite or Y zeolite. Two kinds of different Y zeolites have been proposed to be used in combination As the component of several different catalysts, comprise the catalyst for hydrocracking, as US-A-4,661,239 and US-A-4,925,546 is described.
Detailed Description Of The Invention
[0013] process disclosed herein and composition can turn to for the raw material that will contain organic compound Turn to product, particularly by acid catalysis, for example the hydrocracking organic compound particularly transforms hydrocarbon For than the harmonic(-)mean boiling point with than the product of low average molecular weight. Can be catalyst and/or catalyst carrier Composition comprise β zeolite and Y zeolite II. Composition can also comprise refractory inorganic oxide. When as the catalyst of hydrocracking, it is inorganic that composition contains β zeolite, Y zeolite II, high-melting-point Oxide, and hydrogenation component.
[0014] hydrocracking process and composition disclosed herein relate to the catalyzer that use contains special β zeolite and special Y zeolite.Composition can randomly contain extra Y zeolite.The β zeolite preferably has the mol ratio of relatively low silicon-dioxide and aluminum oxide, and higher relatively SF 6Absorptivity.The unit cell dimension that Y zeolite II has from 24.33 to 24.38 dusts.When having extra zeolite, Y zeolite II has the unit cell dimension higher than Y zeolite I.When this β zeolite and this Y zeolite add in the hydrocracking catalyst in this way, have been found that different results of property.With respect to the catalyzer that contains one or both Y zeolite, higher in overhead product scope ebullient selectivity of product under specific activity, perhaps higher in specific product activity under distillation range ebullient selectivity.
[0015] β zeolite known in this field can be used as the component of hydrocracking catalyst.At US-A-3,308,069 and US issue again and described the β zeolite in 28341, its full content is quoted in the lump at this.The mol ratio that is used for silicon-dioxide that the β zeolite of process disclosed herein and composition has and aluminum oxide is in one embodiment less than 30, in another embodiment less than 25, still in another embodiment greater than 9 and less than 30, in further embodiment greater than 9 and less than 25, in another embodiment greater than 20 and less than 30, perhaps still in another embodiment greater than 15 and less than 25.As what use herein, unless specialize silicon-dioxide and aluminum oxide (SiO in the zeolite 2/ Al 2O 3) mol ratio be based on the mol ratio that is present in the amount of total or whole aluminum oxide and silicon-dioxide (skeleton or non-skeleton) in the zeolite, and be to be called silicon-dioxide and aluminum oxide (SiO sometimes 2/ Al 2O 3) mol ratio.
[0016] the β zeolite is synthetic by the reaction mixture that contains template usually.In the use that is used for the template of synthetic β zeolite known in this field.US-A-3 for example, 308,069 and US issue 28341 again and described the use tetraethyl ammonium hydroxide, and US-A-5,139,759 have described the tetraethyl ammonium ion that uses derived from corresponding tetraethyl-ammonium halide, its full content is quoted in the lump at this.The standard method of other preparation β zeolites is entitled as " Verified Synthesis of Zeolitic Materials " (second edition H.Robson (editor) and K.P.Lillerud's (XRD diffractogram), ISBN0-444-50703-5, Elsevier, 2001) described in the book.Think that the selection of specific template agent is also non-key in order to make process success disclosed herein.In one embodiment the β zeolite in air competent time of temperature lower calcination of 500 to 700 ℃ (932 to 1292 ℉) from the β zeolite, to remove template.Remove template calcining can the β zeolite with carry out before or after carrier and/or hydrogenation component combine.Though thinking can be by the template agent removing that goes down in the temperature that is higher than 700 ℃ (1292 ℉), very high calcining temperature can obviously reduce the SF of β zeolite 6Absorptivity.For this reason, think that the temperature that should avoid being higher than 750 ℃ (1382 ℉) removes template when the employed β zeolite of preparation process disclosed herein.For process disclosed herein, the SF of β zeolite 6It is critical that absorptivity is at least 28 weight %.
[0017] though known steam handle (steaming) for example the zeolite of β type can cause zeolite to change actual crystalline texture, the ability of present analytical technology can't accurately detect and/or characterize these variations with regard to the important structure details of zeolite.The ground that replaces, for example test of surface-area of the various physicalies of zeolite is used as the variation that taken place and the index of intensity of variation.For example, think that zeolite absorbs sulfur hexafluoride (SF after steam treatment 6) minimizing of ability is because the minimizing of zeolite crystallinity or size or zeolite micropore getatability causes.But the non-direct contact of the variation of zeolite may be undesirable, because be used for the SF in the catalyzer of process disclosed herein and composition 6Absorptivity is higher relatively.In the embodiment of disclosed herein process and composition, the SF of β zeolite 6No matter whether absorptivity pass through steam treatment, should be at least 28 weight %.
[0018] therefore, the β zeolite of process disclosed herein and composition can be according to SF 6Absorptivity characterizes.This is for example a kind of recognized technology of zeolite of characterization of microporous materials.With absorptive other absorptivity test class for example seemingly, wherein the operating weight difference is measured the SF that sample absorbs that is not contained absorbate by pre-treatment substantially 6Amount.Because its size and dimension holds it back and enters in the hole of diameter less than 6 dusts, thereby uses SF in this test 6Therefore it can be as the tolerance of available aperture and bore dia contraction.This is again the tolerance of zeolite steam treatment effect.In the explanation that this measuring method is oversimplified, preferred under 300 ℃ (572 ℉) predrying in a vacuum 1 hour earlier of sample under atmospheric pressure was heated to 2 hours under 650 ℃ (1202 ℉) in air then, weighed at last.Be placed on SF then 6In 1 hour, then sample is kept the temperature of 20 ℃ (68 ℉).Keep SF 6Vapour pressure under 400torr (53.3kPa (7.7psi)), to provide liquid SF 6Sample weigh once more to measure the SF that absorbs 6Amount.Sample can be suspended on the balance so that simplify these steps in these steps.
[0019] in comprising any large-scale production process of technology such as steam treatment and heating for example, the level difference that may handle independent particle.For example, the particle along the heap bottom that rotary kiln moves may be under the different atmosphere and temperature with the particle that the heap top covers.Also having in production must this factor of consideration in analysis and test final product process.Therefore, any thermometrically that material carries out is recommended to carry out with the representative composite sample of final product all amts, with the misleading of avoiding causing by the test of on independent particle or nonrepresentative sample, carrying out.For example, the absorptivity test is carried out on the representative composite sample.
[0020] though process disclosed herein and composition can use the β zeolite without steam treatment, but process disclosed herein and composition can also use the β zeolite through steam treatment, if in document the steam treatment of β zeolite this steam treatment relatively gentleer.Under appropriate condition and in suitable time, steam treatment β zeolite can produce can disclosed herein process and composition in the catalyzer that uses
[0021] the hydrothermal treatment consists zeolite that is used for hydrocracking catalyst is blunt relatively instrument.For any specific zeolite, steam treatment has reduced the acidity of zeolite.The zeolite of crossing when steam treatment is during as hydrocracking catalyst, and significantly the result is whole overhead product gain in yield, but catalyst activity reduces.Tangible compromise between this productive rate and the activity means for reaching high reactivity, steam treatment β zeolite not, but be cost with low yield produce rate.Significantly compromise is necessary between this productive rate and the activity considers, and it has limited to it seems it is the improvement that obtains by steam treatment β zeolite.When using the β zeolite of steam treatment in the disclosed catalyzer herein, active improvement is restricted on the catalyzer that only contains Y zeolite, and strengthening more appears in the improvement of productive rate on this catalyzer.
[0022] if the β zeolite will carry out steam treatment, this steam treatment can be by different way with being subjected to the type of available devices usually and ability has a strong impact on even successfully carried out by the method for the commercial practical application of its decision.Steam treatment can be used as β zeolite that fixed part keeps or be limited in the container the β zeolite or in being limited in rotary kiln in rolling and carrying out.Important factor is under the condition of suitable time, temperature and vapour concentration all β zeolite granulars to be handled uniformly.For example, the β zeolite should be placed on contact β zeolite piece surface and the inner visibly different place of quantity of steam.The β zeolite can carry out steam treatment having to flow through to provide under the atmosphere of the flowing steam of the equipment of low vapour concentration.This certain amount (positive amount) that can be described as vapour concentration is lower than 50 moles of %.Extend to greater concn with small-scale laboratory operations, vapour concentration can from 1 to 20 mole of % or from 5 to 10 moles of %.Can be less than or equal to 1 or 2 hour or 1 to 2 hour inherent temperature is less than or equal under 600 ℃ (1112 ℉) under atmospheric pressure and the certain content (positive content) of steam is less than or equal under 5 moles of % and carries out steam treatment in the positive time period (positive time period).Can be less than or equal to 2 hours in the positive time period is less than or equal under 650 ℃ (1202 ℉) under atmospheric pressure and the certain content of steam is less than or equal under 10 moles of % and carries out steam treatment in temperature.Steam content is based on the weight meter of the steam of contact β zeolite.Obtain the β zeolite in the temperature steam treatment that is higher than 650 ℃ (1202 ℉), wherein because the β zeolite SF that obtains 6Absorptivity is too low, so useless in its disclosed herein process.Can use the temperature that is lower than 650 ℃ (1202 ℉), and vapor temperature can perhaps be lower than 600 ℃ (1112 ℉) from 600 ℃ (1112 ℉) to 650 ℃ (1202 ℉).Prior art is instructed to exist between time of common steam treatment and the temperature and is influenced each other, and temperature raises then that required time shortens.Yet,,, can use 1/2 to 2 hour or time period of 1 to 11/2 for good result if steam treatment is finished.Carrying out steam treatment process on commercial size can rely on and have so that keep the rotary kiln of the steam that the speed of the atmosphere of 10 moles of % steam injects.
[0023] exemplary laboratory scale steam treatment process is carried out in the clamshell bucket stove with the zeolite in the silica tube that remains on 6.4cm (2-1/2 foot).By slowly the raise temperature of stove of controller.When the temperature of zeolite reached 150 ℃ (302 ℉), the steam that produces in the deionized water that keeps from bottle allowed to enter into the silica tube bottom and upwards passes through.Other gases can access tube to reach the steam content that needs.If desired flask is filled again.In this exemplary process, it is 1 hour that input steam and zeolite reach 600 ℃ of times between (1112 ℉).When the set steam time finishes by reset controller with stove in temperature reduce to 20 ℃ (68 ℉).Allow stove to reduce to 400 ℃ (752 ℉) (about 2 hours), and stop in the steam inflow silica tube.Take out down sample at 100 ℃ (212 ℉), and put into the lab oven at that has air purge and keep a night down at 110 ℃ (230 ℉).
[0024] process and the β zeolite in the composition disclosed herein are handled to finish the deoxygenated reactive aluminum without acid solution.In this, notice and place acid to reduce synthetic residual basic metal (for example sodium) concentration in all raw materials (for synthetic) β zeolite in essence.This step of β zeolite manufacture is not the part of the β zeolite treatment of manufacturing described herein.In one embodiment, in treating processes and catalyzer manufacturing processed, only in incidental manufacturing processed, for example the colloidal sol in moulding or metal impregnation process just places acid with the β zeolite on.In another embodiment, after the steam treatment process without acid elution β zeolite from the hole, to remove aluminium " fragment ".
[0025] also comprises Y zeolite in disclosed herein process and the composition in addition with unit cell dimension from 24.33 to 24.38 dusts.This Y zeolite is called as Y zeolite II herein sometimes, this Y zeolite is different from the optional extra Y zeolite that has different unit cell dimensions and be described below.Y zeolite II preferably has the unit cell dimension of 24.34 to 24.36 dusts.In one embodiment, the mol ratio that Y zeolite II can have overall silica and aluminum oxide is 5.0 to 12.0, is 5.0 to 11.0 in another embodiment, and still is 5.0 to 10.0 in another embodiment.Process disclosed herein and composition need Y zeolite II.
[0026] randomly and except Y zeolite II, disclosed process and composition can comprise extra Y zeolite, it is called as Y zeolite I herein sometimes.The unit cell dimension that Y zeolite I has is different with the unit cell dimension of Y zeolite II.The unit cell dimension of Y zeolite I preferably is at least little 0.04 dust of unit cell dimension than Y zeolite II.The unit cell dimension of Y zeolite I is 24.25 to 24.32 dusts more preferably, and even 24.26 to 24.30 dusts more preferably.In one embodiment, the mol ratio that Y zeolite I can have overall silica and aluminum oxide is 5.0 to 12.0, is 5.0 to 11.0 in another embodiment, and still is 5.0 to 10.0 in another embodiment.
[0027] scheme that adds Y zeolite I in the manufacturing processed product that satisfies various hydrocracking unit operation demands for catalyst manufacturers produces provides handiness.The existence of Y zeolite I has changed the performance of catalyzer in catalyzer, and need not to change the consumption of the preparation method of Y zeolite II itself or the Y zeolite II in catalyzer.But in some instances, adding Y zeolite I has reduced the demand to Y zeolite II, and when can not get the Y zeolite II of capacity, this is extra advantage.The hydrocracking unit operation, particularly those make the process of overhead products, can use the catalyzer that contains Y zeolite I and Y zeolite II as instrument, satisfy that they are active and optionally special and be distinctive demand sometimes for hydrocracking catalyst.
[0028] term " Y zeolite " that herein uses means and comprises all crystalline zeolites, itself or have US-A-3,130 substantially, the 007 X-ray powder diffraction pattern that proposes, or have and US-A-3,130,007 similar X-ray powder diffraction patterns still have slight, it will be appreciated by those skilled in the art that, since cationic exchange, calcining, or the like, the modified Y zeolite that d-spacing (d-spacings) changes, this need be converted into Y zeolite catalytic activity and stable form usually.With respect to US-A-3,130,007 described Y zeolite, Y zeolite I and Y zeolite II are the Y zeolite of modification.As what use herein, the meaning of unit cell dimension is the unit cell dimension that records by the X-ray powder diffraction.
[0029] Y zeolite that is used for process disclosed herein and composition is to have the large pore zeolite of effective hole dimension greater than 7.0 dusts.Because some holes of Y zeolite are relatively large, Y zeolite allows molecule relatively freely to enter its internal structure.The hole of Y zeolite allow the benzene molecular of reaction product and more macromole to wherein entering, and from wherein passing through.
[0030] as Y zeolite I, Y zeolite II or comprise that the one group of Y zeolite that can be used for process disclosed herein and composition of two kinds of zeolites is meant overstable or hydrophobic Y zeolite sometimes.In essence, the composition and the performance of this group Y zeolite are to be prepared from by four step processes.The first, as alkali metal form (normally sodium) and have the Y zeolite and the aluminum ion generation cationic exchange of 24.65 dust unit cell dimensions usually.The aluminium exchange step is logical produce make the sodium content of initial sodium Y zeolite from usually greater than the value of 8 weight %, from 10 to 13 weight % are (according to Na usually 2O calculates), the value that is reduced to 0.6 to 5 weight % scope is (according to Na 2O calculates).The method of carrying out ion-exchange is known in the art.
[0031] second, the Y zeolite that calcining is obtained by the first step in the presence of water vapour.For example, in three embodiments, at 1.4kPa (definitely) (following kPa (a)) (0.2psi (definitely) (following psi (a))) at least, at least 6.9kPa (a) (1.0psi (a)) or at least the water vapor of 69kPa (a) (10psi (a)) have calcining Y zeolite down.In other two embodiments, basically by or atmosphere by vapor composition in calcine Y zeolite.The Y zeolite calcining is to obtain the unit cell dimension of 24.40 to 24.64 dust scopes.
[0032] the 3rd, will carry out the ammonium exchange by the Y zeolite that second step obtains once more.Ammonium exchange for the second time further is reduced to sodium content 0.5 weight %, usually less than 0.3 weight %, according to Na 2O calculates.
[0033] the 4th, further handle the Y zeolite that obtains by third step and have the Y zeolite of the unit cell dimension of 24.25 to 24.32 dusts or preferred 24.26 to 24.30 dusts, for Y zeolite I with generation.For Y zeolite II, this handles the Y zeolite that produces unit cell dimension from 24.33 to 24.38 dusts or preferred from 24.34 to 24.36 dusts.In one embodiment, the zeolite Y that is obtained by the 4th step has overall silica and alumina molar ratio is 5.0 to 12.0, is 5.0 to 11.0 in another embodiment, and still is 5.0 to 10.0 in another embodiment.The processing of the 4th step can comprise any the be general zeolite and the known technology of overstable Y zeolite deoxygenated aluminium.Especially to produce required unit cell dimension and overall silica and alumina molar ratio.The manages the mol ratio that step can change unit cell dimension and/or framework silica and aluminum oxide everywhere, and changes or do not change the mol ratio of overall silica and aluminum oxide.Normally, finish the deoxygenated aluminium of zeolite, for example use acid (for example HCl), with evaporable muriate (SiCl for example by chemical process 4) or handle with sequestrant (for example ethylenediamine tetraacetic acid (EDTA) (EDTA)).Another current techique be pure steam or in the air mixture to the hydrothermal treatment consists of zeolite, preferably for example the existence of sufficient water vapor (for example substantially by the atmosphere of vapor composition, most preferably by vapor composition) down calcining to produce the unit cell dimension that needs and the mol ratio of overall silica and aluminum oxide.
[0034] owing to added the 4th step, preparation process and the US-A-3 that is used for the Y zeolite of process disclosed herein and composition discussed above, the difference of instruction in 929,672.US-A-3,929,672, wherein all quote in the lump as a reference, the method to overstable Y zeolite deoxygenated aluminium is disclosed.US-A-3,929,672 have instructed a kind of preparation process, wherein sodium Y zeolite I partly with ammonium ion exchange, steam calcination under the temperature of control and vapor partial pressure afterwards, ammonia exchange and the calcining in exsiccant atmosphere, chosen wantonly subsequently again afterwards.Can repeated exchanged and steam calcination steps to reach the degree that the deoxygenated aluminium that needs and unit cell dimension reduce.US-A-3,929,672 zeolite is known runs after fame from UOP LLC with Y-84 or LZY-84, Des Plaines, Illinois, U.S.A is commercially available.Y-84 or LZY-84 zeolite can form by first three step manufacturing of mentioning just now, but randomly may further include the calcining step in dry atmosphere, for example in the air of not moisture and steam, calcining under 482 ℃ (900 ℉) or the higher temperature.
[0035] preparation process and the US-A-5 that is used for the Y zeolite of process disclosed herein and composition discussed above, the similar process of the Y zeolite of 350,501 instructions.But that discusses in the above the manages everywhere and selects special conditions to think that Y zeolite II and optional Y zeolite I make the unit cell dimension of critical range in the step.US-A-5,350,501, wherein all quote in the lump as a reference, disclose the 4th step its be included in capacity water vapor (basic by steam or atmosphere by vapor composition in) calcine the zeolite that obtains from the 3rd treatment step down, be lower than 24.40 to produce unit cell dimension, and most preferably be not more than 24.35 dusts, and have relatively low receptivity water vapor.At US-A-5, the Y zeolite by the process manufacturing of four steps in 350,501 is a kind of UHP-Y zeolite, and at US-A-5,350,501 are defined as a kind of super-hydrophobic Y zeolite.US-A-5,350,501 are defined as the zeolite aluminosilicate with " UHP-Y " zeolite, it has unit cell dimension or the yardstick that is equal to or less than 24.45 dusts, and under 25 ℃ to the receptivity that has of water vapor, and at the P/P that has 0.10 less than 10.00 weight % 0Value and other performances.At US-A-5, most preferred UHP-Y zeolite is LZ-10 in 350,501.
[0036] being used for process disclosed herein and composition can form by mol ratio with overall silica and aluminum oxide is carried out the deoxygenated aluminum less than 5 Y zeolite fully as another group Y zeolite of Y zeolite I, Y zeolite II or both, and at US-A-4,503,023, US-A-4,597,956 and US-A-4,735, describe in detail in 928, wherein full content is quoted as a reference in the lump.US-A-4,503,023 disclose the another kind of process to Y zeolite deoxygenated aluminium, comprise Y zeolite is contacted with control ratio, temperature and the aqueous solution of the silicofluoride of pH condition, and it is avoided aluminium to propose extraction and is not had the silicon displacement.US-A-4,503,023 record silicofluorides are used for as the aluminium extract, and as the source of external silicon, and wherein silicon is used for replacing extracting aluminium and is embedded into the Y zeolite structure.This salt has general formula:
(A) 2/b?SiF 6
Wherein, except H +, A is metal or the non-metal cations with valency " b ".Positively charged ion with " A " representative is aluminum alkyls, NH 4 +, Mg ++, Li +, Na +, K +, Ba ++, Cd ++, Cu ++, H +, Ca ++, Cs +, Fe ++, Co ++, pb ++, Mn ++, Rb +, Ag +, Sr ++, Ti +, and Zn ++
[0037] known this group preferred member is LZ-210, and is a kind of from UOP LLC, DesPlaines, Illinois, the zeolite aluminosilicate molecular sieves that U.S.A. is commercially available.Other zeolites of LZ-210 zeolite and this group are the parent material preparation by Y zeolite easily.In one embodiment, the mol ratio that the LZ-210 zeolite has overall silica and aluminum oxide is 5.0 to 12.0, is 5.0 to 11.0 in another embodiment, still is 5.0 to 10.0 in another embodiment.Under the situation of Y zeolite I, unit cell dimension can be preferably 24.25 to 24.32 dusts and 24.26 to 24.30 dusts more preferably.Under the situation of Y zeolite II, unit cell dimension can or be preferably 24.34 to 24.36 dusts for 24.33 to 24.38 dusts.The LZ-210 class zeolite that uses in disclosed herein process and the composition has the composition of expressing according to oxide mol ratio with following general formula:
(0.85-1.1)M 2/nO:Al 2O 3:xSiO 2
Wherein " M " is the positively charged ion with " n " valency, and " x " is 5.0 to 12.0 value.
[0038] as a rule, the LZ-210 zeolite can be by using the aqueous solution of silicofluoride, and preferred hexafluorosilicic acid ammonium solution forms fully to y-type zeolite deoxygenated aluminum.Deoxygenated aluminium can be by with Y zeolite, usually but must not be a kind of Y zeolite of ammonium exchange, puts into water reaction medium for example in the ammonium acetate aqueous solution, and the aqueous solution that slowly adds ammonium silicofluoride is finished.After reaction is carried out, obtained having the zeolite that overall silica and alumina molar ratio increase.The size that increases depends in part on the amount that silicofluoride contacts with zeolite at least, and depends on the reaction times of permission.Normally, 10 to 24 hours reaction times is enough to reach balance.What obtain can be from being the form of LZ-210 zeolite by conventional filtration technology isolating solid product from water reaction medium.In some cases, this product can carry out steam calcination by means known in the art.For example depress at 482 ℃ (900 ℉) to the temperature of 816 ℃ (1500 ℉) at the branch of 1.4kPa (a) (0.2psi (a)) at least, product can contact 1/4 to 3 hour time with water vapor, so that bigger crystallization-stable to be provided.In some cases, the product of steam calcination can carry out the ammonium exchange by methods known in the art.For example product can form slurry for water, adds ammonium salt afterwards in slurry.The mixture that obtains heats a few hours usually, filters, and washes with water.US-A-4,503,023; US-A-4 has described the method to LZ-210 zeolite steam treatment and ammonium exchange in 735,928 and US-A-5,275,720.
[0039] prepares by preparation process discussed above and be used for X-ray powder diffraction pattern and unit cell dimension or the yardstick a that the optional Y zeolite I of process disclosed herein and composition has basic zeolite Y oBe preferably 24.25 to 24.32 dusts, more preferably 24.26 to 24.30 dusts.Prepare and be used for X-ray powder diffraction pattern and unit cell dimension or the yardstick a that the Y zeolite II of process disclosed herein and composition has basic zeolite Y by preparation process discussed above oBe preferably 24.33 to 24.38 dusts, more preferably 24.34 to 24.36 dusts.In one embodiment, the mol ratio that Y zeolite I, Y zeolite II or both can have overall silica and aluminum oxide is 5.0 to 12.0, is 5.0 to 11.0 in another embodiment, still is 5.0 to 10.0 in another embodiment.Y zeolite I and/or Y zeolite II can have surface-area (BET) and be at least 500m 2/ g is less than 800m 2/ g is usually less than 700m 2/ g, and be generally 500 to 650m 2/ g.
[0040] another kind of increase Y zeolite stability and/or tart method are by exchanging with polyvalent metallic cation and Y zeolite, for example contain positively charged ion, magnesium cation, calcium positively charged ion or the ammonium ion of rare earth and combining of multivalent metal cation, thereby reduce sodium content until it is low to moderate above-mentioned numerical value after first or second ammonium exchange step.The method of carrying out ion-exchange is known in the art.
[0041] catalyzer that uses in the process disclosed herein is intended at first as the existing commercial unitary alternative catalysts of hydrocracking.So its size and dimension, preferred class is similar to conventional commercial catalysts.Preferably manufacture and have the form that diameter is the cylindrical extrudate of 0.8-3.2mm (1/32-1/8in).But the form that catalyzer can manufacture any other hope is sphere or particle for example.Extrudate can the columniform form of right and wrong, for example known trilobal, or other are favourable or reduce the shape that diffusion length or pressure fall.
[0042] Shang Ye hydrocracking catalyst contains many non-zeolitic materials.This is for a variety of reasons, for example granule strength, cost, porousness and performance.Even but not as active cracking component, other catalyst components still have positive contribution to whole catalyzer.These other components are called as carrier herein.Some traditional carrier component for example silica-alumina have some contributions to the cracking ability of catalyzer usually.In the embodiment of disclosed herein process and composition, catalyzer contains the β zeolite of relatively small amount.Be exsiccant β zeolite, Y zeolite I (if any), Y zeolite II and carrier based on all, catalyzer contains 0.5 to 5 weight %, the β zeolite of preferred 0.7 to 2.6 weight %.As what use, think the weight after 500 ℃ (932 ℉) heat 6 hours down in dry air herein based on the weight of dry substance.The weight ratio that catalyzer has Y zeolite I and β zeolite is 0.5 to 5, is preferably 0.5 to 2.0, based on dry substance.When having optional Y zeolite I, the weight ratio that catalyzer has Y zeolite I and β zeolite is 1.5 to 8, is preferably 2 to 6.5, based on dry substance.When having optional Y zeolite I, be exsiccant β zeolite, Y zeolite I, Y zeolite II and carrier based on all, catalyzer contain from more than 5 weight % to maximum 15 weight %Y zeolite I and Y zeolite II.
[0043] except zeolitic material, the residuum of granules of catalyst mainly constitutes (take up) by the conventional hydrocracking material of for example aluminum oxide and/or silica-alumina.The existence of silica-alumina helps the performance characteristic that catalyzer reaches to be needed.In one embodiment, catalyzer contains the aluminum oxide of at least 25 weight % and the silica-alumina of at least 25 weight %, and the both is based on the gross weight of zeolite and carrier, all based on dry substance.In another embodiment, the alumina content that the silica-alumina content of catalyzer is higher than 40 weight % and catalyzer is higher than 20 weight %, and the both is based on the gross weight of zeolite and carrier, all based on dry substance.But aluminum oxide is considered to only play the effect of binding agent, and is not active cracking component.Support of the catalyst can contain silica-alumina that surpasses 50 weight % or the aluminum oxide that surpasses 50 weight %, based on the weight of carrier drying.Use the silica-alumina and the aluminum oxide of about equivalent in one embodiment.Except silica-alumina and aluminum oxide, can comprise for example silicon-dioxide, zirconium white, titanium dioxide, boron oxide (boria), Zirconia-alumina as other inorganic fire proof materials of carrier.Above-mentioned these solid support materials can be used in combination separately or arbitrarily.
[0044] except β zeolite, Y zeolite and other solid support materials, catalyzer of the present invention contains metallic hydrogenation component.This metallic hydrogenation component preferably is provided as one or more and is evenly distributed on base metal in the granules of catalyst.Hydrogenation component is the elementary composition from the periodic table of elements the 6th, 9 and 10 families.Can application examples such as the precious metal of platinum and palladium, but best result obtains with two kinds of base metals combinations.Especially, nickel or cobalt are paired with tungsten or molybdenum respectively.The metallic hydrogenation component preferred compositions is nickel and molybdenum or nickel and tungsten.The consumption of nickel or cobalt is preferably between 2 to the 8 weight % of final catalyzer.The consumption of tungsten or molybdenum is preferably between 8 to the 22 weight % of final catalyzer.The total amount of base metal hydrogenation component is 10 to 30 weight % of final catalyzer.
[0045] catalyzer of process of the present invention can be prepared with industrial standard technology.Very briefly, this can be summarized as: with the liquid mixing of β zeolite and Y zeolite and other inorganic oxide component and for example water or gentle acid, to form extrudable cream group, extrude by the porous mould then.Collect extrudate and preferably at high temperature with its calcining so that extrudate is hardened.The particle of extruding by size selection then, and add hydrogenation component by dipping dipping or known incipient wetness technology.If catalyzer contains two kinds of metals in hydrogenation component, these can side by side or sequentially add so.Granules of catalyst can add between the step and metal adding calcining once more later at metal
[0046] in another embodiment, can be easily or preferably with porous, inorganic refractory oxide, β zeolite, Y zeolite with contain (multiple) compound of (multiple) metal, grind this mixing material then, extrude the material of this grinding subsequently, and calcine this material of extruding at last.Can finish grinding with metal source, other sources of Ammonium Heptamolybdate or ammonium metawolframate and other metals for example, for example nickelous nitrate or Xiao Suangu, two kinds are come source compound to be incorporated in the blended material with the form of the aqueous solution or as salt usually.In dissolved water form or as salt, can introduce other metals similarly.Similarly, when using, can merge to and introduce non-metallic element in the aqueous solution, for example phosphorus by for example soluble constituent of phosphoric acid.
[0047] US-A-5,279,726 and US-A-5,350,501 have still described other preparation methods, and its full content is quoted as a reference in the lump at this.
[0048] catalyzer for preparing by process discussed above contains the metal hydride of oxide form.Oxide form is converted into the sulphided form that is used for hydrocracking usually.
This can finish by any known sulfurization technology, be included in catalyzer is added outside (ex situ) prevulcanized before the hydrocracking reactor, catalyzer is being added back and the prevulcanized before elevated temperature uses in the hydrocracking reactor, and original position sulfuration, promptly by using the catalyzer of oxide form, to make the hydrocarbon feed hydrocracking that contains sulphur compound under the hydrocracking condition that exists of elevated temperature and pressure and hydrogen comprising.
[0049] hydrocracking process disclosed herein will be operated with the condition that present commercialization ground is used for the general range of hydrocracking process.Operational condition depends on refining or process unit in many examples.That is to say that their major parts are made up of and the decision of required product the structure of existing hydroeracking unit (it can not change usually) and restriction, charging under the condition that does not have sizable expense.The temperature in of catalyst bed should for 232 ℃ (450 ℉) to 454 ℃ (850 ℉), and inlet pressure should for 5171kPa (g) (750psi (g)) to 24132kPa (g) (3500psi (g)), and be preferably 6895kPa (g) (1000psi (g)) to 24132kPa (g) (3500psi (g)).Feed stream mixes with enough hydrogen, with the hydrogen cycle rate of the raw material of per unit volume that 168 to 1684 normal (normal) ltr/ltr are provided, it is at following conditioned measurement: 0 ℃ (32 ℉) and 101.3kPa (a) (14.7psi (a)) (1000 to 10000 standard ft 3/ bucket (SCFB) is at 15.6 ℃ (60 ℉) and 101.3kPa (a) (14.7psi (a))) measure down), and by containing catalyst fixed bed one or more reactors.Mainly produce hydrogen from circulating current, although wherein not necessarily, this air-flow also can be flowed through purifier apparatus to remove acid gas.Hydrogen-rich gas mixes with raw material, and any in one embodiment round-robin hydrocarbon will contain the hydrogen of 75mol% at least usually.For hydrocracking producing overhead product, according to the feed rate of LHSV usually in 0.3 to 3.0hr-1 wide region.As what use herein, the meaning of LHSV is a liquid hourly space velocity, and it is defined as liquid rate of volume flow hourly divided by catalyst volume, and wherein liquid volume is identical volume unit with catalyst volume.
[0050] typical raw material is from the azeotropic product of crude oil recovery and the mixture of many different hydrocarbon by fractionation in the process disclosed herein.Be to make overhead product, have boiling point usually and be higher than component in 149 ℃ (300 ℉) to 371 ℃ (700 ℉) this boiling spread upper end.Usually having boiling spread begins from being higher than 340 ℃ (664 ℉) and ending to be lower than 482 ℃ (900 ℉) at an embodiment, be lower than 540 ℃ (1004 ℉) in another embodiment, and in the 3rd embodiment, be lower than 565 ℃ (1049 ℉).The raw material of this petroleum derivation can be the mixture of the logistics made in the rectifying, for example atmospheric gas oil, coker gas oil (coker gas oil), straight run gas oil, diasphaltene gas oil (deasphalted gas oil), vacuum gas oil and FCC turning oil.Typical gas oil contains boiling point in 166 ℃ (330 ℉) scope to 566 ℃ (1050 ℉).Perhaps, the raw material in the process disclosed herein can be independent cut, for example heavy vacuum gas oil.Typical heavy gas oil fraction has the hydrocarbon component of significant proportion, at least 80 weight % usually, boiling point from 371 ℃ (700 ℉) to 566 ℃ (1050 ℉).For example also can this process, process from the synthetic hydrocarbon mixture of shale oil or coal recovery.Before entering process of the present invention, raw material can carry out hydrogen treatment or handle with sulphur, nitrogen or other pollutents of removing total amount (gross amount) pitch for example by solvent extraction.
[0051] process of the present invention wishes most of feedstock conversion is more high-volatile hydrocarbon, for example overhead product boiling spread hydrocarbon.Typical transformation efficiency largely depends on raw material and forms from 50 to 100 volume % (following volume %) difference.Herein in disclosed process embodiment, transformation efficiency is between 60 to 90 volume %, in another embodiment between from 70 to the 90 volume %, still in another embodiment between from 80 to the 90 volume %, still in another embodiment between from 65 to the 75 volume %.In fact the ejecta of process will contain the hydrocarbon of broad variety, from methane to unaltered in any above ebullient raw material hydrocarbon of boiling spread of wishing product in essence.The ejecta of process is usually by containing the reactor of catalyzer, and is separated and distills with well known to a person skilled in the art the method separation, comprising usually, makes the product with required final boiling point.Be meant unconverted product at the above ebullient hydrocarbon of the final boiling point of any required product, reduce even their boiling point has had in a way during the course.Most of unconverted hydrocarbon are circulated to conversion zone, and small percentage for example 5 weight % be removed as resistance logistics (drag stream).In order to make overhead product, at least 30 weight %, the ejecta of preferred at least 50 weight % is being lower than 371 ℃ (700 ℉) boiling down.
[0052] process disclosed herein and composition can be applied to this area and be called single step and two step process processes, with or hydrogen treatment in advance.(ISBN 0-8247-9760-4, Marcel Dekker Inc., New York, 1996) define and have illustrated these terms in the book of J.Scherzer and AJ.Gruia Hydrocracking Science and Technology by name.In two step processes, catalyzer of the present invention can be used for first or second step.Catalyzer can be by hydrogenation catalyst in isolating reactor, or can be used as the hydrogen treatment catalyzer or different hydrocracking catalysts is inserted same reactor.Upstream hydrogen treatment catalyzer can be used for feed pretreatment step or be used for round-robin unconverted materials hydrogen treatment.The hydrogen treatment catalyzer can be used for the specific purpose of hydrogen treatment polynuclear aromatics (PNA) compound, to promote their conversions in follow-up (a plurality of) hydrocracking catalyst bed.Catalyzer of the present invention can also be used for the catalyzer combination different with second kind, for example based on Y zeolite or catalyzer with main unformed cracking component.
[0053] herein openly in some embodiments of process, catalyzer uses with raw material or is newly to advance raw material or the similar form of newly advancing raw material (raw feed) is used with the raw material of the catalyzer of flowing through.The crude oil and the therefore sulphur content of the raw material of this process, according to its source a great difference is arranged, as what use herein, newly advancing raw material is meant and does not also pass through hydrotreated raw material, or still contain the raw material that causes sulphur content to be higher than the organosulfur compound of about 1000 ppm by weight, perhaps still contain the raw material that causes nitrogen content to be higher than the organic nitrogen compound of about 100 ppm by weight (0.01 weight %).
[0054] herein openly in some embodiments of process, catalyzer uses with hydrotreated raw material.Hydrocarbon processing field those of ordinary skill is known and the hydrogen treatment that can newly advance raw material is carried out technology disclosed herein to make hydrotreated raw material.Though the sulphur content of hydrotreated feed can be between 500 to 1000 ppm by weight, but disclose herein in the embodiment of process, the sulphur content of hydrogen treatment raw material is lower than 500 ppm by weight, and from 5 to 500 ppm by weight in another embodiment.Openly in the embodiment of process, the nitrogen list of hydrogen treatment raw material is lower than 100 ppm by weight herein, and from 1 to 100 ppm by weight in another embodiment.
[0055] mentions all book about all of the family of elements of periodictable herein by CRC Handbookof Chemistry and Physics by name, ISBN0-8493-0480-6, CRC Press, BocaRaton, Florida, U.S.A., the 80th edition, the IUPAC on the periodic table of elements in the interior front cover of 1999-2000 " New Notation ".The surface-area of all references is to be 0.03 time at nitrogen partial pressure P/Po herein, the single-point surface-area that uses the nitrogen adsorption technology to record by BET (Brunauer-Emmett-Teller) method, this method is at ASTM D4365-95, people's such as " Standard Test Method forDetermining Micropore Volume and Zeolite Area of a Catalyst " and S.Brunauer article (J.Am.Chem.Soc, 60 (2), 309-319 (1938)) the middle description.The boiling point of all references is by ASTM D2887 herein, the boiling point that " Standard Test Method forBoiling Range Distribution of Petroleum Fractions by GasChromatography " records.The ASTM method can be from ASTM International, 100Barr Harbor Drive, and P.O.Box C700, West Conshohocken, Pennsylvania, U.S.A. obtains.
[0056] following Example is used for illustration purpose, and does not limit process and the composition that defines in the claim.
Embodiment 1
Sample 1
[0057] (Y zeolite of the ammonium of USA) selling exchange is prepared the Y zeolite of modification, and it is meant to have according to Na in the literature for Des Plaines, Illinois by steam treatment UOP LLC 2The sodium content that O calculates is less than the Y-84 of 0.2 weight %.The Y zeolite of the modification that obtains is meant sample 1 herein, and has overall silica and aluminum oxide (SiO 2/ Al 2O 3) mol ratio be 5.0 to 5.5, unit cell dimension is 24.28 dusts, and surface-area is 540 to 640m 2/ g.As the example of Y zeolite I, sample 1 refers to Y1 in table.
Sample AW1
[0058] part acid elution of sample 1.The Y zeolite of the modification of the pickling that obtains is meant sample AW1 herein, and has overall silica and aluminum oxide (SiO 2/ Al 2O 3) mol ratio be 11.0, unit cell dimension is 24.28 dusts, and surface-area is 570 to 750m 2/ g.As the example of Y zeolite I, sample AW1 refers to AW Y1 in table.
Sample 2
[0059] except steam treatment condition difference, by with sample 1 in the similar method described prepare the Y zeolite of modification.The Y zeolite of the modification that obtains is meant sample 2 herein, and has overall silica and aluminum oxide (SiO 2/ Al 2O 3) mol ratio be 5.0 to 5.5, unit cell dimension is 24.35 dusts, and surface-area is 630 to 730m 2/ g.As the example of Y zeolite II, sample 2 refers to Y2 in table.
Embodiment 2
[0060] by with sample 1 (if present), sample AW1 (if present), sample 2 (if present), β zeolite---it has overall silica and aluminum oxide (SiO 2/ Al 2O 3) mol ratio be 23.8 and SF 6Absorptivity is 29 weight % (if present) and HNO 3The Catapal of-gelatinizing TMThe C boehmite alumina has been mixed with eight kinds of catalyzer (A-H) in shredder.Have overall silica and aluminum oxide (SiO 2/ Al 2O 3) mol ratio be 23.8 and SF 6Absorptivity is the β zeolite of 29 weight %, itself or contain the template of using in its building-up process, perhaps subsequently under mild conditions calcining to remove aforesaid template.In table, the β zeolite that contains template is meant B1, and incinerating β zeolite is meant B2.Unbodied silica-alumina is the CCIC silica-alumina, it is the silicon-dioxide of 75 weight % and the aluminum oxide of 25 weight % that its name is formed (nominal composition), or the Siral silica-alumina, its name consists of the silicon-dioxide of 40 weight % and the aluminum oxide of 60 weight %.The CCIC silica-alumina is from Catalysts ﹠amp; Chemicals Industries Co.Ltd. (CCIC) obtains, and Catapal C aluminum oxide and Siral 40 silica-aluminas obtain from Sasol Germany GmbH.Based on dry substance, the amount of these components in every kind of final catalyzer is listed in the table.The mixture that obtains is extruded to diameter in 1.6mm (1/16in) length at the cylindrical particles of 3.2mm (1/8in) to 12.7mm (1/2in).Wet extrudate drying at least 4 hours under the temperature of 104 ℃ (220 ℉), and subsequently the temperature lower calcination that surpasses 550 ℃ (1022 ℉) at least 90 minutes.For catalyst A-F and H, the nickelous nitrate that adds capacity subsequently to the incinerating extrudate, so that the nickel (calculating with Ni) of 4 weight % to be provided in final catalyzer, and the ammonium metawolframate of capacity, so that the tungsten (calculating with W) of 14 weight % to be provided in final catalyzer, to incipient wetness, and be the nickel of 5 weight % and the tungsten of 17.5 weight % for the corresponding amount of catalyzer G and H.Subsequently extrudate is dried to free-flowing, and made its oxidation at least in 90 minutes by calcining down subsequently at 500 ℃ (932 ℉).Catalyst I is the standard hydrocracking catalyst that contains the tungsten of the nickel of average 5.5 weight % and 17.5 weight %.Think that the different hydrogenation cracking activity and the selectivity results that these examples are described of nickel and W content significantly do not influence.
Embodiment 3
[0061] by making H by 10 volume % 2S and surplus are H 2The air flow stream of forming is crossed catalyst bed, and initial temperature is 149 ℃ (300 ℉) and slowly rise to 413 ℃ (775 ℉) and it was kept 6 hours, and every kind in above-mentioned 9 kinds of catalyzer is all carried out prevulcanized and handles.
[0062] in the mimic Alpha test, compares the hydrogenation cracking activity and the selectivity (being the product productive rate) of 9 kinds of catalyzer.Especially, 9 kinds of catalyzer are measured proportion (API gravity is 30.05 °) to have 0.877 under 15.6 ℃ (60 ℉) respectively, initial boiling point is the hydrocracking of Arabic vacuum gas oil (VGO) raw material of hydrogen treatment lightweight of 107 ℃ (224 ℉), wherein the boiling point of 5 weight % is 195 ℃ (382 ℉), final boiling point is 550 ℃ (1021 ℉), and the boiling point of 50 weight % is 24 ℃ (795 ℉), and 13 weight % are lower than 288 ℃ (550 ℉) boiling, and 26 weight % are lower than 371 ℃ (700 ℉) boiling.
[0063] every kind of catalyzer is tested for the operation of mimic fs in this wise, is about to raw material with 1.5hr -1LHSV by flowing through the reactor of laboratory size, total pressure is 13786kPa (g) (2000psi (g)), the volume hydrogen feed rate of unit volume raw material is 1684 standard ltr/ltr (10000SCFB measures down at 15.6 ℃ (60 ℉) and 101.3kPa (a) (14.7psi (a))) under 0 ℃ (32 ℉) and 101.3kPa (a) (14.7psi (a)).Add enough di-t-butyl disulphide with sulphur that 2.1 weight % are provided and therefore simulation be present in the atmosphere that contains hydrogen sulfide in the commercial fs hydrocracking reactor.In addition, the hexahydroaniline that in raw material, adds capacity with nitrogen that 780 ppm by weight are provided and therefore simulation be present in the atmosphere that contains ammonia in the commercial fs hydrocracking reactor.
[0064] test for hydrocracking and make overhead product, the attemperation condition is lower than 371 ℃ (700 ℉) ebullient material down to remain in 100 hours the process to be converted into the clean transformation efficiency of 65 weight % as required.The clean conversion is to deduct at the per-cent that is lower than 371 ℃ of (700 ℉) ebullient raw materials being lower than the per-cent of 371 ℃ of (700 ℉) ebullient ejectas as raw material.When finishing in 100 hours, note the required temperature of the maintenance clean transformation efficiency of 65 weight %, and calculate the relative reactivity and the selectivity of every kind of catalyzer.These data are summarized in the table.Every kind of selectivity of catalyst numerical value is total overhead product (promptly 149 ℃ (300 ℉) is to 371 ℃ (700 ℉)), lightweight overhead product (promptly 149 ℃ (300 ℉) is to 288 ℃ (550 ℉)), and heavy overhead product (promptly 288 ℃ (550 ℉) is to 371 ℃ (700 ℉)).The relative reactivity records of values of every kind of catalyzer is that catalyzer keeps temperature required poor with for the identical reference temperature of all 9 kinds of catalyzer of the clean transformation efficiency of 65 weight %.The relative reactivity value is low more, and catalyst activity is high more.
Figure A200780027346D00261
Figure A200780027346D00271
[0065] Fig. 1 be 149 ℃ (300 ℉) of catalyst A-I to the figure of 371 ℃ of (700 ℉) part overhead product selectivity to relative catalyst activity, described relative catalyst activity is expressed as and is obtaining the VGO transformation efficiency for for the temperature of reactor more than the required reference temperature of the clean transformation efficiency of 65 weight % of total overhead product part.Catalyst A-F (square) demonstrates under specific relative reactivity total overhead product selectivity greater than catalyzer G-I (rhombus).
[0066] Fig. 2 is the figure to relative reactivity of heavy overhead product part selectivity and lightweight overhead product part selectivity.With respect to catalyzer G-I (rhombus), catalyst A-F (square) demonstrates the obviously higher heavy overhead product selectivity with respect to the lightweight overhead product.

Claims (10)

1. composition, it comprises such catalyzer, and the mol ratio that promptly comprises hydrogenation component, overall silica and aluminum oxide is less than 30 and SF 6Absorptivity is at least the β zeolite of 28 weight %, the Y zeolite (Y zeolite II) and the carrier of unit cell dimension 24.33 to 24.38 dusts, wherein the mol ratio of the overall silica of Y zeolite II and aluminum oxide is 5.0 to 11.0, wherein based on dry substance, gross weight based on β zeolite, Y zeolite II and carrier, catalyzer contains the β zeolite of 0.5 to 5 weight %, and based on dry substance, the Y zeolite II of catalyzer and the weight ratio of β zeolite from 0.5 to 5.
2. the composition of claim 1, wherein the surface-area of Y zeolite II is less than 800m 2/ g.
3. the composition of claim 1, wherein hydrogenation component is selected from the group of being made up of molybdenum, tungsten, nickel and oxide compound thereof and sulfide.
4. the composition of claim 1, wherein the unit cell dimension of Y zeolite II is first unit cell dimension, and catalyzer contains and extra have the 24.25-24.32 dust and at least than the size Y zeolite (Y zeolite I) of second structure cell of little 0.04 dust of first unit cell dimension, its.
5. the composition of claim 1, wherein Y zeolite II is prepared from by the method that may further comprise the steps:
A) the sodium Y zeolite is partly exchanged with ammonium;
B) zeolite that calcining is obtained by step (a) in the presence of water vapour;
C) zeolite that step (b) is obtained exchanges with ammonium; And
D) zeolite that calcining is obtained by step (d) in the presence of water vapour.
6. the composition of claim 1, wherein Y zeolite II is prepared from by the method that may further comprise the steps:
A) the sodium Y zeolite is partly exchanged with ammonium;
B) zeolite that calcining is obtained by step (a) in the presence of water vapour;
C) zeolite that under the aqueous solution form step (b) is obtained contacts with silicofluoride; And
D) zeolite that calcining is obtained by step (d) in the presence of water vapour.
7. the composition of claim 1, wherein Y zeolite II is prepared from by the method that may further comprise the steps:
A) under aqueous solution form, Y zeolite is contacted with silicofluoride;
B) zeolite that calcining is obtained by step (a) in the presence of water vapour.
8. the composition of claim 1, wherein the unit cell dimension of Y zeolite II is 24.34 to 24.36 dusts.
9. the composition of claim 1, wherein based on dry substance, the weight ratio of Y zeolite II and β zeolite is 0.5 to 2.0,
10. method with the hydrocarbon feed hydrocracking, it is included in 232 ℃ to 454 ℃ temperature and 5171kPa (g) to the pressure of 24132kPa (g), in the presence of hydrogen composition any in raw material and the aforementioned claim is contacted.
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