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CN101490217A - 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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Publication number
CN101490217A
CN101490217A CNA2007800271976A CN200780027197A CN101490217A CN 101490217 A CN101490217 A CN 101490217A CN A2007800271976 A CNA2007800271976 A CN A2007800271976A CN 200780027197 A CN200780027197 A CN 200780027197A CN 101490217 A CN101490217 A CN 101490217A
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CN
China
Prior art keywords
zeolite
weight
composition
catalyzer
catalyst
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CNA2007800271976A
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Chinese (zh)
Inventor
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
    • B01J29/08—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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • 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

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

Abstract

Increased selectivity of middle distillate and increased catalyst activity are obtained in a hydrocracking process by the use of a catalyst containing a hydrogenation component, a beta zeolite having an overall silica to alumina mole ratio of less than 30 and a SF6 adsorption capacity of at least 28 wt%, a Y zeolite having a unit cell size of from 24.25 to 24.32 angstrom, and a support.

Description

Contain the hydrocracking catalyst of β and Y zeolite and be used to prepare the method for overhead product
Invention field
[0001] the present invention relates to catalyst composition and, particularly the purposes in the hydrocracking at hydroconversion process.The present invention more specifically relates to and comprises Y zeolite and the β zeolite catalyst composition as active cracking component.The present invention is specifically related to produce the method for hydrogen cracking of middle distillate.
Background of invention
[0002] oil refinery be usually by producing the product of wanting from the hydrocarbon charging hydrocracking of crude oil, and for example turbine fuel, diesel oil fuel and other are known as the hydrocarbon liquid of middle distillate, and low-boiling point liquid, for example petroleum naphtha and gasoline.Hydrocracking also has other useful result, for example removes desulfuration and nitrogen by hydrotreatment from charging.The most normal charging of carrying out hydrocracking is gas oil and the heavy gas oil that reclaims by distillation from crude oil.
[0003] hydrocracking is generally undertaken by gas oil or other hydrocarbon charging contacts down in the condition (comprising the existence of temperature, elevated pressure and the hydrogen of rising) that is fit to suitable hydrocracking catalyst in the reactor that is fit to, and contains the product that hangs down the overall average boiling point that hydrocarbon product that refinery wants distributes so that produce.Although the operational condition in the hydrocracking reactor has certain influence to product yield, hydrocracking catalyst is the principal element of the described productive rate of decision.
[0004] hydrocracking catalyst carries out preliminary classification according to the character of the main cracking component of this catalyzer.This classification is divided into hydrocracking catalyst based on amorphous cracking component, for example those of silica-alumina and based on the zeolite as cracking component, for example those of β or Y zeolite.Hydrocracking catalyst is also classified according to the main products of their expections, and wherein two kinds of main productss are petroleum naphtha and " overhead product ", and term " overhead product " represents that in hydrocracking refining field boiling range is higher than the retortable petroleum derived fraction of petroleum naphtha.Overhead product is usually included in the refinery product that reclaims as kerosene and diesel oil fuel.At present, overhead product demand height.Therefore, refinery pays close attention to the hydrocracking catalyst that selectivity is produced the overhead product cut.
[0005] three main catalytic performances estimating the performance of the hydrocracking catalyst be used to make overhead product are active, selectivity and stability.Can measure activity in this wise, promptly by relatively adopting same feedstock, must using so that produce the temperature at required scope (for example being lower than 371 ℃ (700 ℉)) ebullient product of given percentage (common 65%) down at it for overhead product at the constant various catalyzer down of other hydrocracking condition.The temperature that given catalyzer needs is low more, and to compare this catalyst activity high more with the catalyzer of the temperature of having relatively high expectations.The selectivity of hydrocracking catalyst can be measured in aforementioned activity test process, and is measured as in required overhead product product scope, and for example 149 ℃ (300 ℉) is to the percentage of 371 ℃ of (700 ℉) interior ebullient product cuts.Stability be catalyzer when under the condition of activity test, handling given hydrocarbon charging in long-time better its active measurement standard of maintenance.Stability is generally measured by maintenance 65% or required temperature variation every day of other given transformation efficiency.
[0006], need be used to produce overhead product having excellent selectivity under the given activity and/or under given selectivity, have excellent active new hydrocracking catalyst all the time although being used to produce the cracking catalyst of overhead product is known and is used in industrial environment.
Summary of the invention
[0007] finds, compare, contain unit cell dimension or size a with present commercially available other hydrocracking catalyst of the method for hydrogen cracking that is used to produce overhead product 0For the Y zeolite of 24.25-24.32 dust and contain preferred total silica/alumina (SiO 2/ Al 2O 3) mol ratio is less than 30 and SF 6Loading capacity has quite big improved selectivity and have quite big improved activity under given selectivity for the hydrocracking catalyst of the β zeolite of at least 28 weight % under the given activity.This catalyzer also contains metal hydrogenation component for example nickel, cobalt, tungsten, molybdenum or its arbitrary combination.This catalyzer contains in dry substance greater than 2 weight % to the β zeolite of maximum 5 weight %, and based on the gross weight of β zeolite, Y zeolite and carrier, and the Y zeolite of this catalyzer/β zeolite weight ratio is 2.5-12.5, in dry substance.Total silica/alumina mole ratio of Y zeolite is 5.0-11.0.In another embodiment, catalyzer does not contain other zeolite or does not contain other β zeolite or Y zeolite.
[0008] in one embodiment, catalyzer is made up of such material or mainly is made up of such material, and promptly hydrogenation component, total silica/alumina mole ratio are less than 30 and SF 6Loading capacity is the β zeolite of at least 28 weight %, Y zeolite and the carrier that unit cell dimension is the 24.25-24.32 dust, wherein total silica/alumina mole ratio of Y zeolite is 5.0-11.0, wherein catalyzer contains in dry substance greater than the β zeolite of 2 weight % to maximum 5 weight %, gross weight based on β zeolite, Y zeolite and carrier, and wherein the Y zeolite of catalyzer/β zeolite weight ratio is 2.5-12.5, in dry substance, wherein the surface-area of Y zeolite is less than 800m 2/ g.
[0009] it is believed that the hydrocracking catalyst that contains described Y zeolite and described β zeolite is new in this field.
[0010], comprises under the existence of the temperature and pressure of rising and hydrogen that described catalyzer is for being than harmonic(-)mean boiling point and effective than the product height of low average molecular weight with gas oil and other hydrocarbon feedstock conversion at common hydrocracking condition.In one embodiment, product contains larger proportion ebullient component in overhead product scope (being defined as 149 ℃ (300 ℉) herein to 371 ℃ (700 ℉)).
Information disclosure
[0011] advised with β and Y zeolite in conjunction with as multiple different catalysts, comprise the component of hydrocracking catalyst.For example, US-A-5,275,720; US-A-5,279,726; And US-A-5,350,501 have described the method for hydrogen cracking that uses the catalyzer that comprises β zeolite and Y zeolite.US-A-5,275,720 have described the method for hydrogen cracking that uses catalyzer, and described catalyzer comprises Y zeolite that unit cell dimension is 24.25-24.32 dust and the 8.0 weight % that are less than zeolite in 4.6mm steam partial pressure and 25 ℃ of following water vapor loading capacities and β zeolite together with other component.US-A1-2004/0152587 has described the hydrocracking catalyst that comprises carrier, described carrier comprise unit cell dimension be 24.10-24.40 dust, total silica/alumina ratio be higher than 12 and surface-area be 850m at least 2The zeolite of the faujusite structure of/g, and this catalyzer can contain for example Y zeolite of β zeolite, ZSM-5 zeolite or different unit cell dimensions of second kind of zeolite.Also advised with two kinds of different Y zeolite in conjunction with as multiple different catalysts, comprise the component of hydrocracking catalyst, as US-A-4,661,239 and US-A-4, described in 925,546.
Detailed Description Of The Invention
[0012] the method and composition disclosed herein feedstock conversion that can be used for containing organic compound is a product, and particularly by acid catalysis, for example organifying compound, particularly hydrocarbon are hydrocracking into than the harmonic(-)mean boiling point with than the product of low average molecular weight.Said composition comprises β zeolite and Y zeolite, and described composition can be catalyzer and/or support of the catalyst.Said composition can also comprise refractory inorganic oxide.When being used as the catalyzer of hydrocracking, said composition contains β zeolite, Y zeolite, refractory inorganic oxide and hydrogenation component.
[0013] method for hydrogen cracking disclosed herein and composition concentrate on and use the catalyzer that contains concrete β zeolite and concrete Y zeolite.Said composition does not preferably contain other zeolite, does not contain other β zeolite, and/or does not contain other Y zeolite.The β zeolite preferably has lower silica/alumina mole ratio and higher SF 6Loading capacity.The unit cell dimension of Y zeolite is the 24.25-24.32 dust.Find, when described β zeolite is sneaked into hydrocracking catalyst by this way with described Y zeolite, obtain different performances.Compare with the catalyzer that contains a kind of Y zeolite, under the given activity in the overhead product scope selectivity of ebullient product higher or under given selectivity in the overhead product scope ebullient product activity higher.
[0014] the β zeolite is known as the component of hydrocracking catalyst in the art.The β zeolite is described in US-A-3,308,069 and US issue 28341 again, it is introduced in full with for referencial use herein.The silica/alumina mole ratio that is used for the β zeolite of method and composition disclosed herein is less than 30 an embodiment, be less than 25 in another embodiment, in another embodiment greater than 9 and be less than 30, in another embodiment greater than 9 and be less than 25, in another embodiment greater than 20 and be less than 30, or in another embodiment greater than 15 and be less than 25.As used herein, unless otherwise noted, the silica/alumina (SiO of zeolite 2/ Al 2O 3) mol ratio is the mol ratio of measuring according to the total amount of aluminium that exists in the zeolite and silicon (skeleton and non-skeleton), and is called total silica/alumina (SiO sometimes herein 2/ Al 2O 3) mol ratio.
[0015] the β zeolite is synthetic by the reaction bonded thing that contains template usually.For using template, synthetic β zeolite is being known in the art.For example, US-A-3,308,069 and US issue 28341 again and described use tetraethyl ammonium oxyhydroxide and US-A-5,139,759 have described and have used derived from the corresponding halid tetraethyl ammonium ion of tetraethyl ammonium, at this it are introduced in full with for referencial use.Another standard method of preparation β zeolite is by H.Robson (editor) and K.P.Lillerud (XRD Patterns), second revised edition, ISBN0-444-50703-5, Elsevier, 2001 exercise question describe in the book of VerifiedSynthesis of Zeolitic Materials.It is believed that selecting specific template is not crucial for the success of method disclosed herein.In one embodiment, the β zeolite is to calcine the time that is enough to remove template from the β zeolite in air under 500-700 ℃ (932-1292 ℉) in temperature.Remove template calcining can with the β zeolite with carry out before or after carrier and/or hydrogenation component combine.Although it is believed that template can be higher than under 700 ℃ (1292 ℉) in calcining temperature removes, very high calcining temperature can significantly reduce the SF of β zeolite 6Loading capacity.It is believed that for this reason when preparation is used for the β zeolite of method disclosed herein, should avoid calcining temperature to be higher than 750 ℃ (1382 ℉) in order to remove template.For method key disclosed herein is the SF of β zeolite 6Loading capacity is at least 28 weight %.
[0016] although known with zeolite for example β zeolite steam treatment cause the real crystal structural modification of zeolite, the ability of analytical technology can't accurately be monitored and/or these variations of the important structure details aspect of characterize at present.Displacedly be, the various physicalies of using zeolite for example the measuring result of surface-area as the variation that has taken place and the indication of intensity of variation.For example, it is believed that steam treatment zeolite adsorption sulfur hexafluoride (SF afterwards 6) ability reduce to be because the reduction of the size of zeolite crystallinity or zeolite micropore or attainability causes.But the indirect mutual relationship of these variations may not make us expecting in the zeolite, because SF in the used catalyzer in disclosed method and the composition herein 6Loading capacity is higher.In the embodiment of disclosed method and composition, no matter whether pass through steam treatment, the SF of β zeolite herein 6Loading capacity all should be at least 28 weight %.
[0017] therefore, the β zeolite of method and composition disclosed herein can be used SF 6Loading capacity characterizes.This is the generally acknowledged characterization technique such as the poromerics of zeolite.It and other loading capacity are measured, and for example the similar part of water adsorption capacity is, it utilizes weight difference to measure through pre-treatment to the adsorbed SF of sample that does not contain adsorbate substantially 6Amount.SF 6Because its size and dimension holds it back and enters diameter and be used in this test less than the hole of 6 dusts.Therefore it can be used as a kind of measurement approach that obtains aperture and bore dia contraction.This is again a kind of measurement approach of steam treatment to the zeolite influence.In the simplification of this measuring method is described, with sample preferably at first in a vacuum 300 ℃ (572 ℉) predrying 1 hour down, subsequently under atmospheric pressure in air in 650 ℃ (1202 ℉) heating 2 hours down, weigh at last.Be exposed to SF subsequently 6In 1 hour, simultaneously sample is remained under 20 ℃ (68 ℉).SF 6Vapour pressure remain on liquid SF 6Under the pressure that 400 holders (53.3kPa (7.7psi)) are provided down.Sample weigh again to measure adsorbed SF 6Amount.Sample can be suspended on the balance to make things convenient for these steps to carry out in these steps.
[0018] in any large-scale production process that comprises such as the technology of steam treatment and heating, each particle may stand different degree of treatments.For example, the particle in the bottom of the heap that moves along rotary oven (pile) may not can be subjected to atmosphere or the temperature identical with the particle that covers this heap top.This factor must be considered in manufacturing processed and in the analysis of the finished product and test process.Therefore, recommend any experimental measurement that described material is carried out all on the representative composite sample of the finished product of all amts, to carry out, with avoid by on the single particle or the test result of on nonrepresentative sample, carrying out mislead.For example, carrying out loading capacity on the representative composite sample measures.
[0019] although method and composition disclosed herein can use the β zeolite without steam treatment, method and composition disclosed herein also can use the β zeolite through steam treatment, and condition is to compare gentleness of steam treatment with the steam treatment of β zeolite in the document.Under the condition that is fit to and through the suitable time, steam treatment β zeolite can produce the catalyzer that can be used in the method and composition disclosed herein.
[0020] to be used for the zeolite of hydrocracking catalyst be disadvantageous relatively means to hydrothermal treatment consists.For any given zeolite, steam treatment has reduced the acidity of zeolite.When the zeolite that uses steam treatment to cross during as hydrocracking catalyst, significantly the result is that total overhead product productive rate improves but catalyst activity reduces.This significantly compromise meaning between productive rate and the activity just do not wanted steam treatment β zeolite in order to realize high reactivity, but this can be a cost with lower product yield.This significantly trading off between productive rate and the activity must be considered, and limit and it seems by the attainable improvement of steam treatment β zeolite.As if as if when the β zeolite that uses steam treatment to cross in the disclosed catalyzer herein, the catalyst activity that only contains Y zeolite improves limited, and described catalyst production is improved and improved a lot.
[0021] if to β zeolite steam treatment, this steam treatment mode can successfully be carried out by different way, and the greatly influence and the method that may determine industrial actual use of the type of available equipment and throughput.Can the β zeolite remain fixing material or the situation of upset when the β zeolite is limited in the container or is being limited in the converter under carry out steam treatment.Important factor be all β zeolite particles under the felicity condition of time, temperature and vapour concentration by even processing.For example, it is significantly different with inner quantity of steam that the β zeolite should not be placed to the surface that causes contacting β zeolite material.The β zeolite can carry out steam treatment in the atmosphere of the flowing steam that flows through the equipment that low vapour concentration is provided.This can be described as being less than under the positive quantity vapour concentration of 50 moles of %.Vapour concentration can be 1-20 mole % or 5-10 mole %, and small-scale laboratory operations needs greater concn.Steam treatment can be under the temperature that is less than or equal to 600 ℃ (1112 ℉), at normal atmosphere be less than or equal to the positive time period that is less than or equal to 1 or 2 hour or 1-2 hour under the positive steam content of 5 moles of %.Steam treatment can under the temperature that is less than or equal to 650 ℃ (1202 ℉) at normal atmosphere be less than or equal under the positive steam content of 10 moles of % and be less than or equal to 2 hours positive time period.Steam content is based on the weight of the steam of contact β zeolite.Be higher than 650 ℃ of steam treatment under (1202 ℉) in temperature and as if be created in disabled β zeolite in the method disclosed herein, because the SF of gained β zeolite 6Loading capacity is too low.Can use the temperature that is lower than 650 ℃ (1202 ℉), and the steam treatment temperature can or be lower than 600 ℃ (1112 ℉) for 600 ℃ (1112 ℉)-650 ℃ (1202 ℉).Usually influence each other between the time of instruction steam treatment and the temperature in this area, temperature raises, and required time reduces.But,,, it seems the time period that can use 1/2-2 hour or 1-11/2 hour in order to have obtained the result if carry out steam treatment.Carrying out plant-scale steam treatment process can be by rotary oven, and wherein steam injects with the speed of the atmosphere that keeps 10 moles of % steam.
[0022] zeolite that is contained in 6.4cm (2-1/2 inch) silica tube in the clam shell grab bucket stove (clam shell furnace) is carried out exemplary lab scale steam treatment program.By the controller furnace temperature that slowly raises.After the zeolite temperature reaches 150 ℃ (302 ℉), make the steam of the deionized water generation that is contained in the flask enter silica tube bottom and up.Other gas can be transported in the pipe to obtain required steam content.Again load flask as required.In this exemplary process, reaching 600 ℃ of times between (1112 ℉) at incision steam and zeolite is 1 hour.Last in the steam treatment time of setting makes furnace temperature be reduced to 20 ℃ (68 ℉) by reseting controller.Make stove be cooled to 400 ℃ (752 ℉) (about 2 hours), and stop steam inflow silica tube.Under 100 ℃ (212 ℉), shift out sample, and place the laboratory stove under air purge, to keep whole night down in 110 ℃ (230 ℉).
[0023] the β zeolite of method and composition disclosed herein is handled without acid solution and is carried out dealuminzation.It is to be noted that in this respect the thick β zeolite of all substantially (for example synthetic) all is exposed in the acid to reduce the concentration of basic metal (for example sodium) residual in synthetic.This step in β zeolite manufacturing course is not regarded as the part of processing to β zeolite finished product described herein.In one embodiment, handle and the catalyzer manufacturing processed in, the β zeolite only is exposed in the acid in incidental preparation behavior (for example in the forming process or the peptization in the metal impregnation process).In another embodiment, the β zeolite after the steam treatment program not by pickling from the hole, to remove aluminium " chip (debris) ".
[0024] comprises that also unit cell dimension is the Y zeolite of 24.25-24.32 dust in disclosed method and the composition herein.The unit cell dimension that Y zeolite preferably has is the 24.26-24.30 dust.Total silica/alumina mole ratio that Y zeolite can have is 5.0-12.0 in one embodiment, is 5.0-11.0 in another embodiment, and is 5.0-10.0 in another embodiment.Method and composition disclosed herein needs Y zeolite.
[0025] term " Y zeolite " meaning used herein is to comprise having as US-A-3,130, all crystalline zeolites of listed basic X-ray powder diffraction pattern in 007, or have and US-A-3, similar in 130,007 but as those skilled in the art recognize that because cationic exchange, calcining etc. the modified Y zeolite of the X-ray powder diffraction pattern of (its generally be Y zeolite is changed into catalytic activity and stable form is necessary) and d-spacing offset slightly.With US-A-3, to compare these Y zeolite are modified Y zeolites to the Y zeolite of instruction in 130,007.As used herein, " unit cell dimension " is meant the unit cell dimension that records by X-ray powder diffraction.
[0026] used Y zeolite is the large pore zeolite of effective hole size greater than 7.0 dusts in the method and composition disclosed herein.Because some holes of this Y zeolite are big relatively, this Y zeolite allows molecule relatively freely to enter in their internal structure.The hole of this Y zeolite allow benzene molecular and more macromole enter wherein and allow reaction product therefrom to pass through.
Be known as the zeolite of overstable or super-hydrophobic Y zeolite when [0027] one group of Y zeolite of available includes in the method and composition disclosed herein.This group is formed and the Y zeolite of character prepares by four step rule substantially.At first, Y zeolite and the ammonium ion that is alkali metal form (normally sodium) and has 24.65 dust unit cell dimensions usually carries out cationic exchange.The ammonium exchange step usually with the sodium content of initial sodium Y zeolite from pressing Na 2The O meter is usually greater than 8 weight %, and the value of 10-13 weight % is reduced to by Na usually 2The value of O meter 0.6-5 weight %.The method of carrying out ion-exchange is well known in the art.
[0028] second, calcining is from the Y zeolite of the first step in the presence of water vapor.For example, in three embodiments at the (0.2psi (definitely) (hereinafter being psi (a)) of 1.4kPa (definitely) (hereinafter being kPa (a)) at least, at least 6.9kPa (a) (1.0psi (a)), or calcining Y zeolite under the water vapor of 69kPa (a) (10psi (a)) exists at least.In two other embodiments, in substantially by vapor composition or atmosphere, calcine Y zeolite by vapor composition.The calcining Y zeolite is to produce the unit cell dimension of 24.40-24.64 dust.
[0029] the 3rd, will be from the Y zeolite ammonium exchange once more in second step.Ammonium exchange is for the second time further reduced to sodium content by Na 2The O meter is lower than 0.5 weight %, is usually less than 0.3 weight %.
[0030] the 4th, will further handle from the Y zeolite in the 3rd step, to produce the Y zeolite that unit cell dimension is 24.25-24.32 dust or preferred 24.26-24.30 dust.The total silica/alumina mole ratio that derives from the Y zeolite in the 4th step is 5.0-12.0 in one embodiment, is 5.0-11.0 in another embodiment, and is 5.0-10.0 in another embodiment.The processing in the 4th step can comprise the technology of any known generally speaking zeolite and particularly overstable Y zeolite dealuminzation, to produce required unit cell dimension and total silica/alumina mole ratio.The manages step everywhere can change unit cell dimension and/or framework silica/alumina molar ratio, changes or do not change total silica/alumina mole ratio simultaneously.Usually, the zeolite dealuminzation is for example used for example HCl of acid by chemical process, with volatile halogenated SiCl for example 4, or with sequestrant for example ethylenediamine tetraacetic acid (EDTA) (EDTA) handle to realize.Another common technology be pure water steam or in the air mixture hydrothermal treatment consists zeolite, preference as in the presence of enough water vapors, calcine (for example substantially by vapor composition, and most preferably in the atmosphere by vapor composition) to produce required unit cell dimension and total silica/alumina mole ratio.
[0031] the above-mentioned preparation procedure and the US-A-3 of used Y zeolite in the method and composition disclosed herein, the difference of the Y zeolite preparation procedure of instruction is to have increased by the and manages step everywhere in 929,672.US-A-3,929,672 disclose the method with overstable Y zeolite dealuminzation, at this it are introduced in full with for referencial use.US-A-3,929,672 have instructed a kind of preparation method, wherein sodium Y zeolite and ammonium ion are partly exchanged, and the exchange of steam calcination under controllable temperature and vapor partial pressure, and then ammonium subsequently is the calcining step of choosing wantonly in dry atmosphere subsequently.Exchange and steam calcination steps can repeat to reduce with dealuminzation that obtains required degree and unit cell dimension.US-A-3,929,672 zeolite known with trade(brand)name Y-84 or LZY-84 available from UOP LLC, Des Plaines, Illinois, U.S.A.Y-84 or LZY-84 zeolite can be by first three step manufacturings of just having mentioned, but optional further calcining step that can be included in the dry atmosphere is for example calcined in 482 ℃ (900 ℉) or higher temperature under in the air of anhydrous and dry-steam.
[0032] the above-mentioned preparation procedure and the US-A-5 of used Y zeolite in the method and composition disclosed herein, the difference of the Y zeolite preparation procedure of instruction is that also the manages the condition of step everywhere in 350,501, it causes the critical range of Y zeolite unit cell dimension.US-A-5,350,501, at this it is introduced in full with for referencial use, disclosed the 4th step is included in enough water vapors and exists down (in substantially by vapor composition or the atmosphere by vapor composition) calcining from the resulting zeolite of the 3rd treatment step, be lower than 24.40 to obtain unit cell dimension, and most preferably be not more than 24.35 dusts, and the loading capacity lower to water vapor.By US-A-5, the Y zeolite that four steps programs in 350,501 are produced is the UHP-Y zeolite, at US-A-5, is defined as super-hydrophobic Y zeolite in 350,501.US-A-5,350,501 are defined as in its character unit cell dimension with " UHP-Y " zeolite or size is less than 24.45 dusts and at 25 ℃ and P/P 0Value is the zeolite aluminosilicate that 0.10 time adsorptive power is less than 10.00 weight %.US-A-5, most preferred UHP-Y zeolite is the LZ-10 zeolite in 350,501.
[0033] another group Y zeolite of available can prepare by total silica/alumina mole ratio being lower than 5 Y zeolite dealuminzation in the method and composition disclosed herein, and at US-A-4,503,023, US-A-4,597,956 and US-A-4,735, describe in detail in 928, it is introduced in full with for referencial use at this.US-A-4,503,023 disclose another kind of program with the Y zeolite dealuminzation, and it comprises and utilizes controlled ratio, temperature and the pH condition avoiding the aluminium to be extracted and do not have under the silicon replacement situation that Y zeolite is contacted with the silicofluoride aqueous solution.US-A-4,503,023 point out that silicofluoride is used as the aluminium that aluminium extraction agent and replacement extract and the source of inserting the outside silicon in the Y zeolite structure.This salt has following general formula:
(A) 2/bSiF 6
Wherein A is the non-H with " b " valency +Metal or non-metal cations.Positively charged ion shown in " A " is alkylammonium, NH 4 +, Mg ++, Li +, Na +, K +, Ba ++, Cd ++, Cu ++, H +, Ca ++, Cs +, Fe ++, Co ++, Pb ++, Mn ++, Rb +, Ag +, Sr ++, Ti +And Zn +
[0034] the preferred member of this group is known as LZ-210, can be available from UOP LLC, and Des Plaines, Illinois, the zeolitic aluminosilicate molecular sieve of U.S.A.Other zeolite of LZ-210 zeolite and this group is easily by the Y zeolite feed preparation.Total silica/alumina mole ratio of LZ-210 zeolite is 5.0-12.0 in one embodiment, is 5.0-11.0 in another embodiment, and is 5.0-10.0 in another embodiment.Under the situation of Y zeolite I, unit cell dimension can or be preferably 24.26-24.30 for the 24.25-24.32 dust.Under the situation of Y zeolite II, unit cell dimension can or be preferably 24.34-24.36 for the 24.33-24.38 dust.In the method and composition disclosed herein used LZ-210 class zeolite have as shown in the formula in the composition of representing with oxide mol ratio:
(0.85-1.1)M 2/nO:Al 2O 3:xSiO 2
Wherein " M " is " n " valency positively charged ion, and " x " has the value of 5.0-12.0.
[0035] generally speaking, the LZ-210 zeolite can be by using the silicofluoride aqueous solution, and preferred hexafluorosilicic acid ammonium solution prepares Y-type zeolite dealuminzation.Dealuminzation can followingly be realized: with Y zeolite, normally but needn't be the Y zeolite that ammonium exchanged, place water-containing reacting medium, for example in the ammonium acetate solution, and slowly add the ammonium silicofluoride aqueous solution.After reaction is carried out, produce the zeolite that total silica/alumina mole ratio increases.This increasing degree depends in part on the amount and the reaction times of the silicate fluoride solution that contacts with zeolite at least.Usually, 10-24 hour reaction times is enough to realize balance.Can be the LZ-210 forms of zeolite by traditional filtering technology and the isolating gained solid product of water-containing reacting medium.In some cases, this product can carry out steam calcination by means commonly known in the art.For example, this product can be depressed at 482 ℃ (900 ℉)-816 ℃ (1500 ℉) at the branch of 1.4kPa (a) (0.2psi (a)) at least with water vapor and contact 1/4 to 3 hour so that bigger crystallization-stable to be provided down.In some cases, the steam calcination product can carry out the ammonium exchange by means commonly known in the art.For example, this product can water slurrying, after this ammonium salt is being joined in this slurry.Usually with resulting mixture heating up several hours, filter also washing.The method of steam treatment and ammonium exchange LZ-210 zeolite is described in US-A-4, in 503,023, US-A-4,735,928 and US-A-5,275,720.
[0036] by above-mentioned preparation method preparation and be used in basic X-ray powder diffraction pattern and and unit cell dimension or the size a that the Y zeolite in the method and composition disclosed herein has zeolite Y 0Be the 24.25-24.32 dust, preferred 24.26-24.30 dust.Total silica/alumina mole ratio that Y zeolite has is 5.0-12.0 in one embodiment, is 5.0-11.0 in another embodiment, and is 5.0-10.0 in another embodiment.The surface-area that Y zeolite can have (BET) is 500m at least 2/ g is less than 800m 2/ g is less than 700m usually 2/ g and typically be 500-650m 2/ g.
[0037] stability and/or another method of tart of raising Y zeolite are with Y zeolite and multivalent metal cation, the positively charged ion, magnesium cation or the calcium positively charged ion that for example contain rare earth element, or the combined exchange of ammonium ion and multivalent metal cation, reduce sodium content thus until the low above-mentioned value that arrives after the first or second ammonium exchange step.The method of carrying out ion-exchange is as known in the art.
[0038] in the method disclosed herein used catalyzer mainly as the alternative catalysts in the existing industrial hydroeracking unit.Therefore, its size and shape preferred class are similar to traditional industrial catalyst.It preferably makes the cylindrical extrudate of diameter 0.8-3.2mm (1/32-1/8 inch).But this catalyzer can be made any other desired form, for example spheroid or sheet.This extrudate can be cylindrical form in addition, for example in the known trilobal or other shape that have advantage aspect reduction diffusion length or the pressure drop.
[0039] industrial hydrocracking catalyst contains multiple non-zeolitic materials.This is for a plurality of reasons, for example particle intensity, cost, porosity and performance.Therefore, even other catalyst component is not as active cracking component, still whole catalyzer had positive contribution.These other components are known as carrier herein.Some traditional components of carrier, for example silica-alumina has certain contribution to the cracking ability of catalyzer usually.In the embodiment of disclosed method and composition, catalyzer contains the β zeolite of less content herein.Catalyzer contains more than 2 weight % to maximum 5 weight %, preferably more than the β zeolite of 2 weight % to maximum 3 weight %, based on the gross weight of β zeolite, Y zeolite and carrier, in dry substance.As used herein, be thought of as under 500 ℃ (932 ℉) weight after in the dry air heating 6 hours in the weight of dry substance.The weight ratio of Y zeolite that catalyzer has and β zeolite is 2.5-12.5, and preferred 2.5-3.0 is in dry substance.
[0040] rest part of catalyst particle except that zeolitic material can be mainly by traditional hydrocracking material, and for example aluminum oxide and/or silica-alumina are formed.Silica-alumina have a desired properties characteristic that helps obtain catalyzer.In one embodiment, catalyzer contains at least 25 weight % aluminum oxide and at least 25 weight % silica-aluminas, all based on the gross weight of zeolite and carrier, in 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 %, all based on the gross weight of zeolite and carrier, in dry substance.But, it is believed that aluminum oxide only as tackiness agent, rather than active cracking component.Support of the catalyst can contain and be higher than 50 weight % silica-aluminas or be higher than 50 weight % aluminum oxide, based on the weight of carrier, in dry substance.Use the roughly silica-alumina and the aluminum oxide of equivalent in one embodiment.Except silica-alumina and aluminum oxide, can comprise for example silicon-dioxide, zirconium white, titanium dioxide, boron oxide (boria) and Zirconia-alumina as other inorganic refractory of carrier.These aforementioned carrier materials can be separately or arbitrary combination use.
[0041] except β zeolite, Y zeolite and other solid support material, this catalyzer contains metal hydrogenation component.Hydrogenation component preferably provides as one or more underlying metals (base metal) that are evenly distributed in the catalyst particle.Hydrogenation component is one or more element components of the 6th, 9 and 10 families of periodictable.Can use precious metal, for example platinum and palladium, but use the combination of two kinds of underlying metals to obtain optimum.Particularly, nickel or cobalt match with tungsten or molybdenum respectively.The preferred composition of metal hydrogenation component is nickel and molybdenum or nickel and tungsten.The amount of nickel or cobalt is preferably the 2-8 weight % of final catalyzer.The amount of tungsten or molybdenum is preferably the 8-22 weight % of final catalyzer.The total amount of base metal hydrogenation component is the 10-30 weight % of final catalyzer.
[0042] catalyzer of present method can utilize the industry standard technique preparation.This can usually be summarised as β zeolite and Y zeolite and other inorganic oxide components and liquid, and for example water or gentle acid mix the extrudable thickener of formation, extrude by foraminous die plate then.Collect extrudate, and preferably at high temperature with its calcining so that the extrudate sclerosis.Sieve the particle of extruding then by size, and as by dipping or known incipient wetness technique adding hydrogenation component.If catalyzer contains two kinds of metals in hydrogenation component, these can add in succession or simultaneously.Catalyst particle can add calcining and calcining again behind the adding metal between the step at metal.
[0043] in another embodiment, can make things convenient for or preferably with porous, inorganic refractory oxide, β zeolite, Y zeolite and metallic compound combination, then the bonded material is ground altogether, the material that will grind is altogether extruded subsequently, at last with the calcined material of extruding.Adopt the source of metal, for example the another kind of Ammonium Heptamolybdate or ammonium metawolframate and another kind of metal is originated, and for example nickelous nitrate or Xiao Suangu are realized grinding altogether, and described two kinds are come source compound generally to introduce in the bonded material with aqueous solution form.Other metal can add with the moisture form of dissolved or as salt similarly.Similarly, can for example introduce non-metallic element in the phosphoric acid adding aqueous solution, for example phosphorus by with soluble composition during use.
[0044] at US-A-5, other preparation method has been described in 279,726 and US-A-5,350,501, at this it is introduced in full with for referencial use.
[0045] catalyzer by method for preparing contains the metal hydride that is oxide form.Oxide form generally is converted to sulphided form and is used for hydrocracking.This can realize by any known sulfurization technology, comprise the outside prevulcanize (ex situ presulfiding) before packing into catalyzer in the hydrocracking reactor, after packing into catalyzer in the hydrocracking reactor and the prevulcanize before using at elevated temperatures, and vulcanization in situ, promptly use the catalyzer of oxide form comprising the hydrocarbon charging hydrocracking that makes sulfocompound under the hydrocracking condition that the temperature of rising, pressure and hydrogen exist.
[0046] method for hydrogen cracking disclosed herein carries out in the industrial now general condition scope in method for hydrogen cracking.Operational condition is refinery or treatment unit special use in many cases.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 be 232 ℃ (450 ℉)-454 ℃ (850 ℉), inlet pressure should be 5171kPa (g) (750psi (g))-24132kPa (g) (3500psi (g)), and is generally 6895kPa (g) (1000psi (g))-24132kPa (g) (3500psi (g)).Incoming flow is mixed with enough hydrogen, to record volume of hydrogen cycle rate/unit volume charging under 0 ℃ (32 ℉) and the 101.3kPa (a) (14.7psi (a)) be 168-1684 standard (normal) ltr/ltr (the 1000-10000 standard cubic feet per barrel (SCFB) that records under 15.6 ℃ (60 ℉) and 101.3kPa (a) (14.7psi (a))) to be provided at, and send into one or more comprising in the catalyst fixed bed reactor.Hydrogen is mainly from circulating current, and it can be by purifying plant to remove acid gas, although this not necessarily.With charging with contain at least 75 moles of % hydrogen usually with any recycle hydrocarbons blended hydrogen-rich gas in one embodiment.For hydrocracking producing overhead product, the feeding rate of representing with LHSV is usually at 0.3-3.0 hour -1Wide region in.As used herein, the LHSV meaning is the liquid hourly space velocity rate, and it is defined as liquid volume flow velocity hourly divided by catalyst volume, and wherein liquid volume and catalyst volume are with the equal volume unit representation.
[0047] typical feed of method disclosed herein is the many different hydrocarbon of fractionation recovery from crude oil and the mixture of azeotropic compound.It has the component of the upper limit that boiling point is higher than 149 ℃ (300 ℉)-371 ℃ of (700 ℉) boiling ranges usually to make overhead product.Usually, it has boiling range and starts from and be higher than 340 ℃ (644 ℉) and end to be lower than 482 ℃ (900 ℉) in one embodiment, be lower than 540 ℃ (1004 ℉) in another embodiment, in the 3rd embodiment, be lower than the boiling range of 565 ℃ (1049 ℉).This petroleum derived feed can be the materials flow mixture that produces in refinery, for example atmospheric gas oil, coker gas oil, straight run gas oil, diasphaltene gas oil, vacuum gas oil and FCC turning oil.Typical gas oil comprises the component that boiling point is 166 ℃ of (330 ℉)-566 ℃ (1050 ℉).In addition, the charging of method disclosed herein can be single cut, for example heavy vacuum gas oil.Typical heavy gas oil fraction has higher proportion, and the boiling point of at least 80 weight % is the hydrocarbon component of 370 ℃ of (700 ℉)-566 ℃ (1050 ℉) usually.Synthetic hydrocarbon mixture for example also can be handled in the method from the synthetic hydrocarbon mixture of shale oil or coal recovery.Charging can be before sending into present method through hydrotreatment or as handle with sulphur, nitrogen or other pollutent of removing total amount bituminous matter for example by solvent extraction.
[0048] expection present method becomes to have more volatile hydrocarbon, for example hydrocarbon of overhead product boiling range with most of feedstock conversion.Typical transformation efficiency is 50-100 volume % (hereinafter being volume %), and this greatly depends on the composition of charging.Transformation efficiency is 60-90 volume % in the embodiment of disclosed method herein, is 70-90 volume % in another embodiment, is 80-90 volume % in another embodiment, is 65-75 volume % in another embodiment.In fact the effluent of this method contains multiple hydrocarbon, is higher than the feed hydrocarbon that does not become substantially of the boiling range of any required product from methane to the boiling point.The effluent of this method is carried from the reactor that contains catalyzer usually, and usually by the known method of those of ordinary skills (comprise be separated or distill) separation, has the product of any required final boiling point with production.The hydrocarbon that boiling point is higher than the final boiling point of any desired product is known as unconverted product, even the decrease to some degree in the method for their boiling point.Most of unconverted hydrocarbon are recycled in the reaction zone, and few percentage is gone as drag stream (drag stream) as 5 weight %.In order to produce overhead product, at least 30 weight %, and the effluent of preferred at least 50 weight % is being lower than 371 ℃ (700 ℉) boiling down.
[0049] exist or do not exist under the situation of hydrotreatment in advance, method and composition disclosed herein can be used on this area and is called in a step and the two step process flow processs.These terms are as outstanding by J.Scherzer and A.J.Gruia, the book of Hydrocracking Science and Technology by name, ISBN0-8427-9760-4, Marcel Dekker Inc., New York, such use that institute defines and explains in 1996.In two step process, this catalyzer can be used in first or second step.At the hydrotreating catalyst that can have before this catalyzer in reactor independently, or this catalyzer can be packed in the reactor identical with hydrotreating catalyst or different hydrocracking catalyst.The upstream hydrotreating catalyst can be used for feed pretreatment step or is used for hydrotreatment round-robin unconverted materials.Hydrotreating catalyst can be used for the specific end use of hydrotreatment polynuclear aromatic (PNA) compound, to promote the conversion of these compounds in hydrocracking catalyst bed subsequently.This catalyzer also can with second kind of different catalyzer, for example based on Y zeolite or the catalyst combination that mainly has an amorphous cracking component use.
[0050] herein in some embodiments of disclosed method, catalyzer use with charging or in the charging by catalyzer as charging or be similar in the structure of charging and use.Crude oil and the sulphur content that enters the charging of this method thus change greatly according to its source.As used herein, charging is meant without hydrotreatment or still contains and causes sulphur content to be higher than the organosulfur compound of 1000 ppm by weight or still contain the charging that causes nitrogen content to be higher than the organic nitrogen compound of 100 ppm by weight (0.01 weight %).
[0051] herein in other embodiment of disclosed method, catalyzer uses with the charging through hydrotreatment.The hydrotreatment of charging is known and can be implemented to the those of ordinary skill of hydrocarbon process field, to produce the charging that will be fed to the hydrotreatment in the method disclosed herein.Although the sulphur content of the charging of hydrotreatment can be the 500-1000 ppm by weight, the sulphur content of the charging of hydrotreatment is lower than 500 ppm by weight in the embodiment of disclosed method herein, is the 5-500 ppm by weight in another embodiment.The nitrogen content of the charging of hydrotreatment is lower than 100 ppm by weight in one embodiment, is the 1-100 ppm by weight in another embodiment.
[0052] mentions all book about all of the family of elements of periodictable herein by CRC Handbookof Chemistry and Physics by name, ISBN 0-8493-0480-6, 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 ".Mention to using about all of surface-area as ASTMD4365-95 herein, Standard Test Method for Determining Micropore Volume andZeolite Area of a Catalyst (measuring the micro pore volume of catalyzer and the standard method of test of zeolite surface area) and by people such as S.Brunauer, J.Am.Chem.Soc., 60 (2), the described nitrogen adsorption technology of the article of 309-319 (1938) by BET (Brunarer-Emmett-Teller) method measure at nitrogen partial pressure P/P 0It is the single-point surface-area under 0.03.Mention to by ASTM D2887 the boiling point that Standard Test Method for Boiling Range Distribution ofPetroleum Fractions by Gas Chromatography (standard test methods of the boiling Range Distribution Analysis by the gas chromatography determination petroleum fractions) measures herein about all of boiling point.The ASTM method can be available from ASTMInternational, 100Barr Harbor Drive, P.O.Box C700, West Conshohocken, Pennsylvania, U.S.A..
[0053] provides the following example to be used to illustrate, rather than will limit method and composition as limiting in the claim.
Embodiment 1
Sample 1
[0054] Y zeolite by the exchange of steam treatment ammonium prepares modified Y zeolite, and (Des Plains, Illinois USA) and in the literature is called with Na the Y zeolite of described ammonium exchange available from UOP LLC 2O meter sodium content is less than the Y-84 of 0.2 weight %.Resulting modified Y zeolite is called sample 1 and total silica/alumina (SiO herein 2/ Al 2O 3) mol ratio be 5.0-5.5, unit cell dimension be 24.28 and surface-area be 540-640m 2/ g.
Embodiment 2
[0055] by with sample 1, total silica/alumina (SiO 2/ Al 2O 3) mol ratio is 23.8 and SF 6If loading capacity is 29 weight % and contains β zeolite, soft silica-aluminum oxide and the HNO that exists in the template of using in its building-up process 3The Catapal of-peptization TMC boehmite aluminum oxide is combination preparation two kinds of catalyzer (A and B) in shredder.Soft silica-aluminum oxide is the CCIC silica-alumina that nominal consists of 75 weight % silicon-dioxide and 25 weight % aluminum oxide.The CCIC silica-alumina is available from Catalysts ﹠amp; Chemicals Industries Co.Ltd. (CCIC).In each final catalyzer, list in the table in the amount of these components of dry substance.Resulting mixture is extruded into the cylindrical particle that length is 1.6mm (1/16 inch) diameter of 3.2mm (1/8 inch)-12.7mm (1/2 inch).With wet extrudate 104 ℃ (220 ℉) dry down minimum 4 hours, then minimum 90 minutes of the temperature lower calcination that surpasses 550 ℃ (1022 ℉).For catalyst A and B, will be enough in final catalyzer subsequently provides the nickelous nitrate of 5 weight % nickel (in Ni) and is enough to provide the ammonium metawolframate of 17.5 weight % tungsten (in W) to join in the incinerating extrudate to incipient wetness in final catalyzer.Then extrudate is dried to unrestricted flow, then by calcining oxidation in minimum 90 minutes down at 500 ℃ (932 ℉).
Embodiment 3
[0056] above-mentioned two kinds of catalyzer are by making by 10 volume %H 2S and surplus H 2It is that 149 ℃ (300 ℉) also slowly rise to 413 ℃ (775 ℉) and 6 hours catalyst bed prevulcanized of maintenance under this temperature that the air communication that constitutes is crossed initial temperature.
[0057] hydrogenation cracking activity and the selectivity (being product yield) of these two kinds of catalyzer of comparison in the test of the mimic the first step.Particularly, these two kinds of catalyzer of test are with lightweight Arabian vacuum gas oil (VGO) the charging hydrocracking of hydrotreatment separately, this charging 15.6 ℃ (60 ℉) down proportion be that 0.877 (API gravity is 30.05 °), initial boiling point are that 107 ℃ (224 ℉), 5 weight % boiling points are that 195 ℃ of (382 ℉), termination boiling point are that 550 ℃ (1021 ℉) and 50 weight % boiling points are 424 ℃ (795 ℉), and 13 weight % boiling and 26 weight % are being lower than under 371 ℃ (700 ℉) and are seething with excitement down being lower than 288 ℃ (550 ℉).
[0058] by being 1.5 hours at LHSV with charging -1, total pressure is 13786kPa (g) (2000psi (g)) and is the reactor of chamber scale by experiment under the 1684 standard ltr/ltr (at the 10000SCFB that records under 15.6 ℃ (60 ℉) and the 101.3kPa (a) (14.7psi (a))) in the hydrogen feed volume speed/unit volume charging that records under 0 ℃ (32 ℉) and the 101.3kPa (a) (14.7psi (a)), test each catalyzer and be used for the operation of the mimic the first step.In charging, add the hydrogen sulfide containing atmosphere be enough to provide the curing di-t-butyl of 2.1 weight % sulphur and exist in simulation as the industrial the first step hydrocracking reactor thus.In addition, adding is enough to provide the hexahydroaniline of 780 ppm by weight nitrogen and simulates the ammoniated atmosphere that exists in the industrial the first step hydrocracking reactor thus in charging.
[0059] for the hydrocracking test of producing overhead product, attemperation condition on demand is to keep changing into the clean transformation efficiency of 65 weight % that boiling point is lower than the material of 371 ℃ (700 ℉) in 100 hours.To be the boiling point effluent that is lower than 371 ℃ (700 ℉) deduct the per-cent that boiling point is lower than the charging of 371 ℃ (700 ℉) as the per-cent of charging to clean transformation efficiency.After 100 hours, record keeps the required temperature of the clean transformation efficiency of 65 weight %, and calculates the relative reactivity and the selectivity of each catalyzer.Data are summed up in table.Each selectivity of catalyst value is total overhead product (that is, 149 ℃ (300 ℉)-371 ℃ (700 ℉)), lightweight overhead product (that is, 149 ℃ (300 ℉)-288 ℃ (550 ℉)) and heavy overhead product (288 ℃ (550 ℉)-371 ℃ (700 ℉)).The relative reactivity value record of each catalyzer is for keeping the required catalyst temperature of the clean transformation efficiency of 65 weight % poor with for the identical reference temperature of all nine catalyzer.The value of relative reactivity is low more, and activity of such catalysts is high more.
Table
The catalyzer title A B
Form the zeolite of weight % and carrier
Zeolite 9.0 20.0
The Y1 zeolite 6.5 20.0
The β zeolite 2.5 --
Carrier 91.0 80.0
The CCIC silica-alumina 60.0 50.0
Aluminum oxide 31.0 30.0
Y1: β zeolite ratio, wt/wt 2.6 NA
149 ℃ (300 ℉)-371 ℃ of (700 ℉) cuts
Relative reactivity, ℃ (℉) 5.6(10) 8.3(15)
Selectivity, weight % 51.0 49.9
149 ℃ (300 ℉)-288 ℃ of (550 ℉) cut selectivity, weight % 33.6 34.1
288 ℃ (550 ℉)-371 ℃ of (700 ℉) cut selectivity, weight % 17.4 15.8
Optional ratio: (288 ℃ of-371 ℃ of cuts): (149 ℃ of-288 ℃ of cuts) 0.52 0.46
NA=is inapplicable
[0060] in table, relative catalyst activity is higher than acquisition with temperature of reactor and represents with respect to the required reference temperature of the clean transformation efficiency of VGO of total overhead product cut 65 weight %.Compare with catalyst B, catalyst A demonstrates higher total overhead product selectivity, activity is more arranged and demonstrates with respect to the obvious higher heavy overhead product selectivity of lightweight overhead product.

Claims (10)

1, a kind of composition comprises by having hydrogenation component, total silica/alumina mole ratio to be less than 30 and SF 6Loading capacity is the catalyzer of the composition of the β zeolite of at least 28 weight %, Y zeolite that unit cell dimension is the 24.25-24.32 dust and carrier, wherein total silica/alumina mole ratio of Y zeolite is 5.0-11.0, wherein catalyzer contains the β zeolite to maximum 5 weight % greater than 2 weight %, gross weight based on β zeolite, Y zeolite and carrier, in dry substance, and wherein the Y zeolite of catalyzer/β zeolite weight ratio is 2.5-12.5, in dry substance.
2, the composition of claim 1, wherein the surface-area of Y zeolite is less than 800m 2/ g.
3, the composition of claim 1, wherein hydrogenation component is selected from the group of molybdenum, tungsten, nickel, cobalt and oxide compound thereof and sulfide composition.
4, the composition of claim 1, wherein Y zeolite is prepared by a method comprising the following steps:
A) the sodium Y zeolite is carried out the exchange of part ammonium;
B) in the presence of water vapor, calcine the zeolite that derives from step (a);
C) zeolite that derives from step (b) is carried out the ammonium exchange; With
D) in the presence of water vapor, calcine the zeolite that derives from step (c).
5, the composition of claim 1, wherein Y zeolite is prepared by a method comprising the following steps:
A) the sodium Y zeolite is carried out the exchange of part ammonium;
B) in the presence of water vapor, calcine the zeolite that derives from step (a);
C) feasible zeolite from step (b) contacts with the silicofluoride that is aqueous solution form; With
D) in the presence of water vapor, calcine the zeolite that derives from step (c).
6, the composition of claim 1, wherein Y zeolite is prepared by a method comprising the following steps:
A) the sodium Y zeolite is contacted with the silicofluoride that is aqueous solution form; With
B) in the presence of water vapor, calcine the zeolite that derives from step (a).
7, the composition of claim 1, wherein the unit cell dimension of Y zeolite is the 24.26-24.30 dust
8, the composition of claim 1, wherein Y zeolite/β zeolite weight ratio is 2.5-3.0, in dry substance.
9, the composition of claim 1, wherein catalyzer contains the β zeolite to maximum 3 weight % greater than 2 weight %, based on the gross weight of β zeolite, Y zeolite and carrier, in dry substance.
10, a kind of method of hydrocracking of hydrocarbon feedstock, it is included in hydrogen and has to descend to be 232 ℃-454 ℃ in temperature to be that charging is contacted with each catalyst composition in the aforementioned claim with pressure.
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