EP2115100A1 - Procédé d'hydrocraquage sélectif utilisant de la zéolithe bêta - Google Patents

Procédé d'hydrocraquage sélectif utilisant de la zéolithe bêta

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Publication number
EP2115100A1
EP2115100A1 EP07756312A EP07756312A EP2115100A1 EP 2115100 A1 EP2115100 A1 EP 2115100A1 EP 07756312 A EP07756312 A EP 07756312A EP 07756312 A EP07756312 A EP 07756312A EP 2115100 A1 EP2115100 A1 EP 2115100A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
zeolite
beta zeolite
alumina
beta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07756312A
Other languages
German (de)
English (en)
Other versions
EP2115100A4 (fr
Inventor
Li Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP2115100A1 publication Critical patent/EP2115100A1/fr
Publication of EP2115100A4 publication Critical patent/EP2115100A4/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • B01J35/30—
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a hydrocracking process, which produces increased quantities of middle distillate boiling range products and employs a catalyst comprising a beta zeolite as an active cracking component.
  • Hydrocracking is a basic conversion process used in many petroleum refineries worldwide to reduce the molecular weight of petroleum derived feedstocks and convert the feedstock into more valuable products such as motor fuel, diesel fuel and lubricants. Hydrocracking also has other beneficial results such as removing sulfur and nitrogen from the feedstock by hydrodesulfurization. While the overall physical design of a hydrocracking process can be very important to the level of conversion and selectivity achieved by a hydrocracking process, these two measures of performance are always also tied to the abilities of the hydrocracking catalyst employed in the process. [0003] Hydrocracking catalysts are subject to initial classification on the basis of the nature of the predominant cracking component of the catalyst.
  • hydrocracking catalysts are also subject to classification on the basis of their intended predominant product of which the two main products are naphtha and "distillate", a term which in the hydrocracking refining art refers to distillable petroleum derived fractions having a boiling point range which is above that of naphtha. Distillate typically includes the products recovered at a refinery as kerosene and diesel fuel.
  • the process disclosed herein relates to a zeolitic catalyst having improved selectivity for the production of distillate boiling range hydrocarbons.
  • These catalysts normally comprise a zeolite component and a support or other component such as alumina or silica-alumina and a metal hydrogenation component.
  • US 4,757,041 describes the simultaneous hydrocracking and dewaxing of heavy oils using a catalyst comprising zeolite beta plus a second zeolite such as X or Y zeolite.
  • US 5,128,024 and US 5,284,573 describe hydrocarbon conversion processes in which heavy oils are simultaneously subjected to hydrocracking and dewaxing using a catalyst based upon zeolite beta with a hydrogenation component.
  • Japanese unexamined patent publication published June 15, 1999 based upon application 11-156198 describes a hydrocracking process for the production of middle distillates which employs a catalyst comprising beta zeolite which is dealuminated by acid treatment and then hydrothermally treated.
  • a middle distillate hydrocracking catalyst containing beta zeolite that has a silica:alumina molar ratio of less than 30: 1 and a SF 6 adsorption capacity of at least 28 wt-% has good selectivity and activity.
  • the beta zeolite does not require steam treatment, although the beta zeolite can be steamed.
  • the catalyst contains a metal hydrogenation component such as nickel, cobalt, tungsten, molybdenum, or any combination thereof. It is believed that a hydrocracking catalyst containing the subject beta zeolite is novel to the art.
  • One embodiment of the process disclosed herein can be summarized as a hydrocracking process which comprises contacting a feed stream comprising hydrocarbons having boiling points between 34O 0 C and 565 0 C with a catalyst comprising a hydrogenation component and beta zeolite.
  • the hydrogenation component comprises a metal component such as nickel, cobalt, tungsten, molybdenum, or any combination.
  • the beta zeolite has a silica:alumina molar ratio of less than 30:1 and a SF 6 adsorption capacity of at least 28 wt-%.
  • the drawing is a chart of the yield advantage of tested catalysts compared to a reference catalyst plotted versus the activity advantage expressed in terms of reactor temperature compared to the reference catalyst.
  • the relative values of the different products of a petroleum refinery are set by a variety of factors including local consumption patterns, and climate. In some locations there is a great economic advantage to producing naphtha boiling range hydrocarbons. In other locations there is a preference for producing the heavier (higher boiling) diesel and kerosene fractions. While the product distribution from an existing hydrocracking unit can be adjusted to a limited extent by changes in feed stock and operation conditions, the yield characteristics of the catalyst used in the process is often of high if not determining importance. As the relative demand for distillate is increasing in many areas faster than the demand for naphtha boiling hydrocarbons, many refineries are attempting to increase their distillate production.
  • Beta zeolite is well known in the art as a component of hydrocracking catalysts. Beta zeolite is described in US 3,308,069 and US Re 28,341, which are incorporated herein for their description of this material. The cited references also indicate that hydrocracking conditions and procedures are widely described in the literature.
  • the zeolite beta that is used in the process disclosed herein has a silica:alumina molar ratio (SiO 2 )Al 2 O 3 ) of less than 30:1 in one embodiment, of less than 25:1 in another embodiment, of more than 9:1 and less than 30:1 in yet another embodiment, of more than 9:1 and less than 25:1 in a fourth embodiment, of more than 20:1 and less than 30:1 in a fifth embodiment, and of more than 15:1 and less than 25:1 in a sixth embodiment.
  • SiO 2 )Al 2 O 3 silica:alumina molar ratio
  • the beta zeolite is usually synthesized from a reaction mixture containing a templating agent.
  • templating agents for synthesizing beta zeolite is well known in the art.
  • US 3,308,069 and US Re 28,341 describe using tetraethylammonium hydroxide
  • US 5,139,759 which is incorporated herein, describes using the tetraethylammonium ion derived from the corresponding tetraethylammonium halide. It is believed that the choice of a particular templating agent is not critical to the success of the process disclosed herein.
  • the beta zeolite is calcined in air at a temperature of from 500 to 700 0 C for a time sufficient to remove to remove the templating agent from the beta zeolite. Calcination to remove the templating agent can be done before or after the beta zeolite is combined with the support and/or the hydrogenation component. Although it is believed that the templating agent could be removed at calcination temperatures above 700 0 C, very high calcination temperatures could significantly decrease the SF 6 adsorption capacity of beta zeolite. For this reason it is believed that calcination temperatures above 75O 0 C for removing the templating agent should be avoided when preparing the beta zeolite for use in the process disclosed herein. It is critical to the process disclosed herein that the SF 6 adsorption capacity of the beta zeolite is at least 28 wt-%.
  • the hydrocracking process disclosed herein centers on using relatively low amounts of a zeolite beta having a relatively low silica:alumina molar ratio and a relatively high SF 6 adsorption capacity. It has been found that differing performance results when such zeolite beta is incorporated in hydrocracking catalysts in this way. Not only is the activity of the hydrocracking catalyst higher than that of catalysts containing steamed beta zeolite, but unexpectedly the product yield is higher too.
  • the catalyst used in the process disclosed herein is intended primarily for use as a replacement catalyst in existing commercial hydrocracking units. Its size and shape is, therefore, preferably similar to those of conventional commercial catalysts. It is preferably manufactured in the form of a cylindrical extrudate having a diameter of from 0.8 -3.2 mm. The catalyst can however be made in any other desired form such as a sphere or pellet. The extrudate may be in forms other than a cylinder such as the form of a well-known trilobe or other shape which has advantages in terms or reduced diffusional distance or pressure drop.
  • Commercial hydrocracking catalysts contain a number of non-zeolitic materials. This is for several reasons such as particle strength, cost, porosity, and performance.
  • the catalyst of the process disclosed herein contains a positive amount less than 3 percent beta zeolite by weight based on the combined weight of the beta zeolite and the support on a volatile-free basis. Volatile-free basis means the weight of each of the beta zeolite and the support is determined after each has been heated at 500°C to drive off all volatile matter.
  • the zeolite content of the catalyst used in the process disclosed herein is a positive amount less than 2 wt-% in another embodiment, less than 1.5 wt-% in a third embodiment, less than 1 wt-% in a fourth embodiment, less than 0.5 wt-% in a fifth embodiment, and from 0.1 to 2 wt-% in a sixth embodiment.
  • the remainder of the catalyst particle besides the zeolitic material may be taken up primarily by conventional hydrocracking materials such as alumina and/or silica-alumina. The presence of silica- alumina helps achieve the desired performance characteristics of the catalyst.
  • the catalyst contains at least 25 wt-% alumina and at least 25 wt-% silica- alumina based on the weight of the catalyst.
  • the silica-alumina content of the catalyst is above 40 wt-% and the alumina content of the catalyst is above 35 wt-%, both based on the weight of the catalyst.
  • the alumina is believed to function only as a binder and to not be an active cracking component.
  • the catalyst support may contain over 50 wt-% silica-alumina or over 50 wt-% alumina based on the weight of the support. Approximately equal amounts of silica-alumina and alumina are used in an embodiment.
  • inorganic refractory materials which may be used as a support in addition to silica-alumina and alumina include for example silica, zirconia, titania, boria, and zirconia-alumina. These aforementioned support materials may be used alone or in any combination.
  • the subject catalyst contains a metallic hydrogenation component.
  • the hydrogenation component is preferably provided as one or more base metals uniformly distributed in the catalyst particle.
  • Noble metals such as platinum and palladium could be applied but best results have been obtained with a combination of two base metals.
  • nickel or cobalt is paired with tungsten or molybdenum, respectively.
  • the preferred composition of the metal hydrogenation component is both nickel and tungsten, with the amount by weight of the elemental metal of tungsten being two to three times the amount of nickel.
  • the amount of nickel or cobalt is preferably between 2 and 8 weight percent of the finished catalyst.
  • the amount of tungsten or molybdenum is preferably between 8 and 22 weight percent of the finished catalyst.
  • the total amount of a base metal hydrogenation component is from 10 to 30 weight percent.
  • the catalyst of the subject process can be formulated using industry standard techniques. This can, with great generalization, be summarized as admixing the beta zeolite with the other inorganic oxide components and a liquid such as water or a mild acid to form an extrudable dough followed by extrusion through a multihole die plate.
  • the extrudate is collected and preferably calcined at high temperature to harden the extrudate.
  • the extruded particles are then screened for size and the hydrogenation components are added as by dip impregnation or the well known incipient wetness technique. If the catalyst contains two metals in the hydrogenation component these may be added sequentially or simultaneously.
  • the catalyst particles may be calcined between metal addition steps and again after the metals are added.
  • the finished catalyst should have a surface area between 300 and 550 m2/g and an average bulk density (ABD) of 0.9 to 0.96 g/cc.
  • the subject hydrocracking process will be operated within the general range of conditions now employed commercially in hydrocracking processes.
  • the operating conditions in many instances are refinery or processing unit specific. That is, they are dictated in large part by the construction and limitations of the existing hydrocracking unit, which normally cannot be changed without significant expense, the composition of the feed and the desired products.
  • the inlet temperature of the catalyst bed should be in the range of from 232 to 454°C, and the inlet pressure should be above 6895 kPa(g).
  • the feed stream is admixed with sufficient hydrogen to provide hydrogen circulation rate of 168 to 1684 n.1/1 and passed into one or more reactors containing fixed beds of the catalyst.
  • the hydrogen will be primarily derived from a recycle gas stream which may pass through purification facilities for the removal of acid gases although this is not necessary.
  • the hydrogen rich gas admixed with the feed and in one embodiment any recycle hydrocarbons will contain at least 90 mol percent hydrogen.
  • the feed rate in terms of liquid hourly space velocity (L.H.S.V.) will normally be within the broad range of 0.3 to 1.5 hr-1, with a L.H.S.V. below 1.2 being used in one embodiment.
  • the typical feed to the subject process is a mixture of many different hydrocarbons and coboiling compounds recovered by fractional distillation from a crude petroleum.
  • Such a petroleum derived feed may be a blend of streams produced in a refinery such as coker gas oil, straight run gas oil, deasphalted gas oil and vacuum gas oil. Alternatively, it can be a single fraction such as a heavy vacuum gas oil. Synthetic hydrocarbon mixtures such as recovered from shale oil or coal can also be processed in the subject process. The feed may be subjected to hydrotreating or treated as by solvent extraction prior to being passed into the subject process to remove gross amounts of sulfur, nitrogen or other contaminants such as asphaltenes.
  • the subject process is expected to convert a large portion of the feed to more volatile hydrocarbons such as naphtha and diesel boiling range hydrocarbons.
  • Typical conversion rates vary between 50 and 90 vol-% depending greatly on the feed composition.
  • the conversion rate is between 60 and 90 vol-% in an embodiment of the process disclosed herein, between 70 and 90 vol-% in another embodiment, between 80 and 90 vol-% in yet another embodiment, and between 65 and 75 vol-% in still another embodiment.
  • the effluent of the process will actually contain a broad variety of hydrocarbons ranging from methane to essentially unchanged feed hydrocarbons boiling above the boiling range of any desired product.
  • the hydrocarbons boiling above the boiling point of any desired product are referred to as unconverted products even if their boiling point has been reduced to some extent in the process.
  • the subject catalyst can be employed in what are referred to in the art as single stage and two stage process flows, with or without prior hydrotreating. These terms are used as defined and illustrated in the text Hydrocracking Science and Technology by J. Scherzer and AJ. Gruia, 1996, Marcel Dekker Inc., ISBN 0-8247-9760-4.
  • the subject catalyst can be employed in either the first or second stage or in both stages.
  • the catalyst may be preceded by a hydrotreating catalyst in a separate reactor or may be loaded into the same reactor as a hydrotreating catalyst or a different hydrocracking catalyst.
  • An upstream hydrotreating catalyst can be employed as feed pretreatment step or to hydrotreat recycled unconverted materials.
  • the hydrotreating catalyst can be employed for the specific purpose of hydrotreating polynuclear aromatic (PNA) compounds to promote their conversion in subsequent hydrocracking catalyst bed(s).
  • PNA polynuclear aromatic
  • the subject catalyst can also be employed in combination with a second, different catalyst, such as a catalyst based upon Y zeolite or having primarily amorphous cracking components.
  • the catalyst is employed with a feed or in a configuration that the feed passing through the catalyst is a raw feed or resembles a raw feed. The sulfur content of crude oil, and hence the feed to this process, varies greatly depending on its source.
  • a raw feed is intended to refer to a feed which has not been hydrotreated or which still contains organic sulfur compounds which result in a sulfur level above 1000 wt-ppm or which still contains organic nitrogen compounds that result in a nitrogen level above 100 wt-ppm (0.01 wt-%).
  • the catalyst is used with a feed that has been hydrotreated. Persons of ordinary skill in the art of hydrocarbon processing know and can practice hydrotreating of a raw feed to produce a hydrotreated feed to be charged to the process disclosed herein.
  • the sulfur level of the feed may be between 500 and 1000 wt-ppm
  • the sulfur level of the hydrotreated feed is less than 500 wt- ppm in one embodiment of the process disclosed herein and from 5 to 500 wt-ppm in another embodiment.
  • the nitrogen level of the hydrotreated feed is less than 100 wt-ppm in one embodiment and from 1 to 100 wt-ppm in another embodiment.
  • the SF6 adsorption capacity of the beta zeolite should be at least 28 wt-%.
  • the beta zeolite has not been subjected to a steaming treatment
  • the beta zeolite may be subjected to steaming, but the steaming is relatively mild in comparison to steaming of beta zeolite in the literature.
  • steaming zeolite beta has been found to yield a catalyst that can be used in the process disclosed herein.
  • Steam concentrations may range from 1 to 20 mol-% in one embodiment and from 5 to 10 mol-% in another embodiment, with small-scale laboratory operations extending toward higher concentrations.
  • the steaming in one embodiment is performed for a positive time period of less than or equal to 1 or 2 hours or for 1 to 2 hours at a temperature of less than or equal to 600 0 C at atmospheric pressure and a positive content of steam of less than or equal to 5 mol- %.
  • the steaming in another embodiment is performed for a positive time period of less than or equal to 2 hours at a temperature of less than or equal to 650 0 C at atmospheric pressure and a positive content of steam of less than or equal to 10 mol-%.
  • the steam contents are based on the weight of vapors contacting the zeolite beta. Steaming at temperatures above 65O 0 C appears to result in zeolite that is not useful in the process disclosed herein since the SF6 adsorption capacity of the resulting zeolite beta is too low. Temperatures below 65O 0 C can be used, and the steaming temperature can be from 600 0 C to 650 0 C in one embodiment and less than 600 0 C in another embodiment. It is taught in the art that there is normally an interplay between time and temperature of steaming, with an increase in temperature reducing the required time. Nevertheless, if steaming is done, for good results it appears a time period of 1 A to 2 hours can be used in one embodiment and 1 to 1 1 A hours in another embodiment.
  • the method of performing steaming on a commercial scale is by means of a rotary kiln having steam injected at a rate which maintains an atmosphere of 10 mol-% steam.
  • the beta zeolite of the process disclosed herein is in one embodiment not treated with an acid solution to effect dealumination.
  • essentially all raw (as synthesized) zeolite is exposed to an acid to reduce the concentration of sodium which remains from synthesis. This step in the zeolite manufacture procedure is not considered part of the treatment of manufactured zeolite as described herein.
  • the zeolite is only exposed to an acid during incidental manufacturing activities such as peptization during forming or during metals impregnation. In one embodiment, the zeolite is not acid washed after the steaming procedure as to remove aluminum "debris" from the pores.
  • An exemplary lab scale steaming procedure is performed with the zeolite held in a 6.4 cm quartz tube in a clam shell furnace. The temperature of the furnace is slowly ramped up by a controller. After the temperature of the zeolite reaches 15O 0 C steam generated from deionized water held in a flask is allowed to enter the bottom of the quartz tube and pass upward. Other gas can be passed into the tube to achieve the desired steam content.
  • the flask is refilled as needed.
  • the time between cutting in the steam and the zeolite reaching 600°C was one hour.
  • the temperature in the furnace is reduced by resetting the controller to 20 0 C.
  • the furnace is allowed to cool to 400 0 C (2 hours) and the flow of steam into the quartz tube is stopped.
  • the sample is removed at 100 0 C and placed in a lab oven held overnight at 110 0 C with an air purge.
  • the beta zeolite of the process disclosed herein may also be characterized in terms of SF6 adsorption. This is a recognized technique for the characterization of microporous materials such as zeolites.
  • SF6 adsorption capacity measurement
  • SF6 is used in this test since because of its size and shape hinders its entrance into pores having a diameter of less than 6 Angstroms. It thus can be used as one measurement of available pore mouth and pore diameter shrinkage. This in turn is a measurement of the effect of steaming on the zeolite.
  • the sample is preferably predried in a vacuum at 350 0 C and weighed. It is then exposed to the SF6 for one hour while the sample is maintained at a temperature of 20 0 C. The vapor pressure of the SF6 is maintained at that provided by liquid SF6 at 400 Torr. The sample is again weighed to measure the amount of adsorbed SF6.
  • the sample may be suspended on a scale during these steps to facilitate these steps.
  • any mass production procedure involving techniques such as steaming and heating there is a possibility for individual particles to be subjected to differing levels of treatment. For instance, particles on the bottom of a pile moving along a belt may not be subjected to the same atmosphere or temperature as the particles which cover the top of the pile. This factor must be considered during manufacturing and also during analysis and testing of the finished product. It is, therefore, recommended that any test measure done on the catalyst is performed on a number of randomly obtained individual pellets to avoid being misled by measurements which performed simultaneously on several particles. For instance, an adsorption capacity measurement made using several pellets reports the average adsorption of all the pellets and does not indicate whether individual particles match adsorption criteria. The average adsorption value could be within specification while the individual particles are not within the specification.
  • Beta zeolite was obtained from a commercial source and was calcined in air for two hours at a temperature of 650 0 C to remove templating agent. After calcination, the beta zeolite had a silica:alumina molar ratio of 24.2: 1 and the SF6 adsorption capacity found in an analytical test of the beta zeolite was 29.3 %.
  • Catalyst A was prepared by mixing 0.5 parts by weight of beta zeolite, 48 parts by weight of silica-alumina, and 51.5 parts by weight of alumina in a muller to form a powder mixture. The parts by weight were determined on a volatile-free basis.
  • the silica-alumina had a silica:alumina weight ratio of 78:22.
  • An amount of water and nitric acid that was 4% of the powder mixture on a volatile-free basis was added to the powder mixture to form an extrudable dough.
  • the dough was extruded to form 1.6 mm extrudate, which was calcined at 566 0 C.
  • the calcined extrudate was impregnated to incipient wetness with a solution containing NiN03 and ammonium metatungstate.
  • the wet extrudate was dried and calcined at 510 0 C using a belt calciner to form Catalyst A.
  • Catalyst A contained 5.4 % Ni and 17.8% W.
  • Catalyst B was prepared following the same procedure as that used for preparing Catalyst A, except that the powder mixture was formed by mixing 1 part by weight of beta zeolite, 47.8 parts by weight of silica-alumina, and 51.2 parts by weight of alumina.
  • Catalyst C was prepared following the same procedure as that used for preparing Catalyst A, except that the powder mixture was formed by mixing 3 parts by weight of beta zeolite, 46.5 parts by weight of silica-alumina, and 50.5 parts by weight of alumina.
  • Catalysts D-H Five catalysts, Catalysts D-H, were prepared using as a starting material the same commercial beta zeolite that was used in the preparation of Catalyst A.
  • the beta zeolite for each of Catalysts D-H was calcined to remove templating agent in the manner described in Example 1.
  • preparation of some of Catalysts D-H beta zeolite was hydrothermally treated at a temperature of 880°C for 110 minutes.
  • During the preparation of the remaining Catalysts D-H beta zeolite was hydrothermally treated at a temperature of 920 0 C.
  • the amount of beta zeolite for each of Catalysts D-H was within the range of from 5 to 20 wt-% based on the combined weight of beta zeolite and support on a volatile-free basis.
  • the SF6 adsorption capacity of the beta zeolite used for each catalyst was within the range of from 12.7 to 17.1 wt-% following hydrothermal treatment.
  • Catalysts A-H were measured by pilot plant scale testing using a vacuum gas oil (VGO) having an API gravity of 22.48 and an end boiling point temperature by simulated distillation of 557°C.
  • VGO vacuum gas oil
  • the VGO contained 2.24 wt-% sulfur and 730 wt-ppm nitrogen.
  • the catalysts were presulfided and subjected to a high space velocity in-use aging procedure prior to testing to ensure the test operation was free of startup artifacts.
  • the temperature of the reaction zone during each test was controlled to result in the specified conversion to a collected liquid product at a L.H.S.V. of 1.0 hr-1.
  • the reaction zone was operated at a pressure of 14,479 kPa(g) (2100 psi(g)) with hydrogen being circulated at a rate of 1684 n.1/1 (10,000 SCFB). Conversion during the testing periods varied between 50 and 80 vol-%. Conversion was defined to be the yield of hydrocarbons boiling below 371 0 C resulting from cracking of feed boiling above 371 0 C. [0035]
  • the drawing is a chart of the 149 - 371 0 C cut distillate yield advantage of Catalysts A-H compared to a reference catalyst plotted versus the activity advantage compared to the reference catalyst also and expressed in terms of reactor temperature required to achieve 70% conversion of the VGO. Lower delta reactor temperature requirement indicates higher catalyst activity.
  • Catalyst A showed a higher yield by 2 wt-% than the curve for Catalysts D-H at a given delta temperature. Although a slight extrapolation of the curve for Catalysts D-H is required, Catalyst A also appeared to show a higher activity than the curve for Catalysts D- H at a given delta yield.
  • Catalyst B showed a higher yield by 2.5 wt-% than the curve for Catalysts D-H at a given delta temperature and a higher activity by 5°C than the curve for Catalysts D-H at a given delta yield.
  • Catalyst C appeared to show a higher yield than the curve for Catalysts D-H at a given delta temperature and a higher activity than the curve for Catalysts D-H at a given delta yield.

Abstract

L'invention concerne un procédé d'hydrocraquage permettant d'obtenir des rendements accrus en produits distillés intermédiaires au moyen d'un catalyseur contenant une zéolithe bêta. Dans certains modes de réalisation, la zéolithe bêta n'a pas été traitée de manière hydrothermique. Dans d'autres, la zéolithe bêta a été traitée de manière hydrothermique à une température relativement basse. Dans encore d'autres autres modes de réalisation, le catalyseur contient une quantité relativement basse de zéolithe bêta.
EP07756312A 2007-01-12 2007-01-12 Procédé d'hydrocraquage sélectif utilisant de la zéolithe bêta Ceased EP2115100A4 (fr)

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US8685231B2 (en) * 2009-11-27 2014-04-01 Shell Oil Company Process for conversion of paraffinic feedstock
CN105457672B (zh) * 2014-09-11 2018-01-05 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法和加氢裂化反应的方法

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US6133186A (en) * 1997-03-06 2000-10-17 Shell Oil Company Process for the preparation of a catalyst composition
WO2007056045A1 (fr) * 2005-11-04 2007-05-18 Uop Llc Catalyseur d’hydrocraquage contenant des zeolites beta et y et procede pour son utilisation en vue de fabriquer du naphte
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CN101578353B (zh) 2013-01-16
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CN101578353A (zh) 2009-11-11
KR20100014272A (ko) 2010-02-10

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