EP2074199A2 - Procédé d'isomérisation utilisant un tamis moléculaire mtt à petit grain cristallin modifié par un métal - Google Patents

Procédé d'isomérisation utilisant un tamis moléculaire mtt à petit grain cristallin modifié par un métal

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Publication number
EP2074199A2
EP2074199A2 EP07843768A EP07843768A EP2074199A2 EP 2074199 A2 EP2074199 A2 EP 2074199A2 EP 07843768 A EP07843768 A EP 07843768A EP 07843768 A EP07843768 A EP 07843768A EP 2074199 A2 EP2074199 A2 EP 2074199A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
metal
molecular sieve
dewaxing
mtt
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.)
Withdrawn
Application number
EP07843768A
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German (de)
English (en)
Inventor
Stacey I. Zones
Kamala Krishna
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.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
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Filing date
Publication date
Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Publication of EP2074199A2 publication Critical patent/EP2074199A2/fr
Withdrawn legal-status Critical Current

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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins 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
    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1062—Lubricating oils
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C10G2300/1085—Solid paraffins
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • 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
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4025—Yield
    • 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
    • C10G2400/06—Gasoil
    • 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
    • C10G2400/10—Lubricating oil

Definitions

  • This invention is directed to a process for isomerizing a feed which includes straight chain and slightly branched paraffins having 10 or more carbon atoms using a catalyst comprising a small crystallite MTT molecular sieve loaded with metals.
  • This invention is also directed to dewaxing methods producing products with improved viscosity indexes at lower pour points.
  • zeolites useful in dewaxing include ZSM-48, ZSM-57, SSZ-20,EU-l, EU-13, ferrierite, SUZ-4, theta-1 , NU-10, NU-23, NU-87,ISI-1 , ISI-4,KZ-1 ,and KZ-2.
  • U.S. Pat. No. 5,252,527 and 5,053,373 disclose a zeolite such as SSZ-32 which is prepared using an N-lower alkyl-N'-isopropyl-imidazolium cation as a template.
  • 5,053,373 discloses a silica to alumina ratio of greater than 20 to less than 40 and a constraint index, after calcination and in the hydrogen form, of 13 or greater.
  • the zeolite of 5,252,527 is not restricted to a constraint index of 13 or greater.
  • 5,252,527 discloses loading zeolites with metals in order to provide a hydrogenation- dehydrogenation function.
  • Typical replacing cations can include hydrogen, ammonium, metal cations, e.g., rare earth, Group UA and Group VIII metals, as well as their mixtures.
  • metal cations e.g., rare earth, Group UA and Group VIII metals, as well as their mixtures.
  • a method for preparation of MTT-type zeolites such as SSZ-32 or ZSM-23 using small neutral amines is disclosed in U.S. Pat. No. 5,707,601.
  • U.S. Pat. No. 5,397,454 discloses hydroconversion processes employing a zeolite such as SSZ-32 which has a small crystallite size and a constraint index of 13 or greater, after calcination and in the hydrogen form.
  • the catalyst possesses a silica to alumina ratio of greater than 20 and less than 40.
  • U.S. Pat. No. 5,300,210 is also directed to hydrocarbon conversion processes employing SSZ-32.
  • the SSZ-32 of U.S. Pat. No. 5,300,210 is not limited to a small crystallite size.
  • U.S. Pat. No. 7,141 ,529 discloses a method of metal-modifying molecular sieves with different metals (a metal or metal selected from the group consisting of Ca 1 Cr, Mg, La, Ba, Pr, Sr 1 K and Nd and also with a Group VIII metal) to provide catalysts with improved isomerization selectivity using an nC 16 feed. None of the processes produced a molecular sieve with a small crystallite size. None of the isomerization methods gave a slope of the Vl of the product boiling at 650°F (343°C) and above versus the pour point of zero or less.
  • different metals a metal or metal selected from the group consisting of Ca 1 Cr, Mg, La, Ba, Pr, Sr 1 K and Nd and also with a Group VIII metal
  • U.S. Pat. Publication No. 2007/0041898A1 discloses a method of making a small crystallite MTT catalyst. Nothing is disclosed of metal-modifying the molecular sieve.
  • a process for dewaxing a hydrocarbon feed to produce an isomerized product comprising contacting the feed under isomerization conditions in the presence of hydrogen with catalyst comprising a molecular sieve having MTT framework topology and having a crystallite diameter of about 200 to about 400 Angstroms in the longest direction, the catalyst containing at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd and at least one Group VIII metal.
  • a dewaxing method comprising isomerization dewaxing a hydrocarbon feed having at least 5 wt% wax over a catalyst to produce two or more isomerized products boiling at 343°C (650°F) or higher, each isomerized product having: a. a pour point between 0 and -30°C, and b. a corresponding viscosity index of 95 or higher; wherein a line fit to a chart of the pour points on an x-axis and the viscosity indexes on a y-axis has a slope of the line for y of zero or less.
  • a dewaxing process comprising isomerization dewaxing a hydrocarbon feed having at least 5 wt% wax over a catalyst to produce two or more isomerized products boiling at 343°C (650°F) or higher, each isomerized product having: a. a pour point between 0 and -30°C, and b.
  • a corresponding viscosity index of 95 or higher wherein a line fit to a chart of the pour points on an x-axis and the viscosity indexes on a y-axis has a slope of the line for y of zero or less; and wherein the yield of the two or more isomerized products boiling at 343°C (650°F) or higher is 90 wt% or greater based on the feed.
  • Figure 1 shows yield versus pour point for isomerization of a heavy neutral (500N) feed using a standard MTT-containing catalyst ("Std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal- modified SSZ-32X”).
  • Std SSZ-32 standard MTT-containing catalyst
  • metal-modified SSZ-32 metal-modified standard MTT-containing catalyst
  • metal-modified, small crystallite MTT-containing catalyst metal-modified, small crystallite MTT-containing catalyst
  • FIG. 2 shows Viscosity Index (Vl) versus pour point for isomerization of a heavy neutral (500N) feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Figure 3 shows gas make (production of C 1 -C 4 products) versus pour point for isomerization of a heavy neutral (500N) feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Figure 4 shows yield of C 5 products versus pour point for isomerization of a heavy neutral (500N) feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Figure 5 shows yield versus pour point for isomerization of a 150N feed using a standard MTT-containing catalyst ("std SSZ-32”), a small crystallite MTT-containing catalyst without metal loading (“small crystal SSZ-32), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal- modified SSZ-32X").
  • Figure 6 shows Viscosity Index (Vl) versus pour point for isomerization of a 150N feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal- modified standard MTT-containing catalyst ("metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X”).
  • Figure 7 shows gas make versus pour point for isomerization of a 150N feed using a standard MTT-containing catalyst (“std SSZ-32”), a metal-modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the small crystallite MTT-containing catalyst ("metal-modified SSZ-32X”).
  • Figure 8 shows yield of Light Naphtha (C 5 -250°F) products versus pour point for isomerization of a 150N feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal-modified standard MTT-containing catalyst ("metal- modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Figure 9 shows yield versus pour point for isomerization of a Medium Neutral feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal- modified standard MTT-containing catalyst (“metal-modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Figure 10 shows Viscosity Index (Vl) versus pour point for isomerization of a Medium Neutral feed using a standard MTT-containing catalyst ("std SSZ-32”), a metal-modified standard MTT-containing catalyst ("metal- modified SSZ-32”) and the metal-modified, small crystallite MTT-containing catalyst ("metal-modified SSZ-32X").
  • Vl Viscosity Index
  • Figure 11 shows a comparison of the X-ray diffraction patterns of a standard MTT molecular sieve (“STANDARD SSZ-32”) and a small crystallite MTT molecular sieve (“SSZ-32X”).
  • the catalyst is comprised of a molecular sieve having the MTT framework topology.
  • the catalyst employed comprises from 5 to 85 wt% molecular sieve.
  • Molecular sieves as used herein can include “zeolites”.
  • the terms "MTT type zeolite”, “MTT molecular sieve”, or variations thereof refers to the framework structure code for a family of molecular sieve materials.
  • the Structure Commission of the International Zeolite Association (IZA) gives codes consisting of three alphabetical letters to zeolites (a type of molecular sieve) having a structure that has been determined. Zeolites having the same topology are generically called by such three letters.
  • the code MTT is given to the structure of molecular sieves including: ZSM-23, SSZ-32, EU-13, ISI-4, and KZ-1.
  • zeolites having a framework structure similar to that of ZSM- 23 and SSZ-32 are named a MTT-type zeolite.
  • molecular sieves useful for isomerization dewaxing are intermediate pore size molecular sieves having a framework topology of MTT, TON, AEL or FER.
  • the small crystallite MTT-type zeolites used in one embodiment of the catalyst have a crystallite diameter of about 200 Angstroms to about 400 Angstroms in the longest direction.
  • small crystallite MTT molecular sieves are prepared from an aqueous solution containing sources of an alkali metal oxide or hydroxide, an alkylamine (such as isobutylamine), an organic carbon compound source of quaternary ammonium ion which is subsequently ion-exchanged to the hydroxide form, an oxide of aluminum (e.g., wherein the aluminum oxide source provides aluminum oxide which is covalently dispersed on silica), and an oxide of silicon.
  • sources of an alkali metal oxide or hydroxide such as isobutylamine
  • an organic carbon compound source of quaternary ammonium ion which is subsequently ion-exchanged to the hydroxide form
  • an oxide of aluminum e.g., wherein the aluminum oxide source provides aluminum oxide which is covalently dispersed on silica
  • an oxide of silicon e.g., wherein the aluminum oxide source provides aluminum oxide which is covalently dispersed on silica
  • the organic carbon compound source of quaternary ammonium ion which is subsequently ion-exchanged to the hydroxide form is N-lower alkyl-N'- isopropyl-imidazolium cation (for-example N, N'-diisopropyl-imidazolium cation or N-methyl-N'-isopropyl-imidazolium cation).
  • the aqueous solution has a composition in terms of mole ratios falling within the following ranges: Table 1 - Composition of mole ratios
  • Q is the sum of Q a and Q b ; M is the alkali metal oxide or hydroxide; and M+ is the alkali metal cation derived from the alkali metal oxide or hydroxide.
  • the alkali metals are the series of elements comprising Group 1 (IUPAC style) of the periodic table: lithium (Li) 1 sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr).
  • Q a is an organic carbon compound source of quaternary ammonium ion and Q b is an amine.
  • Q a is an N-lower alkyl-N'-isopropyl- imidazolium cation (for example an N, N'-diisopropyl-imidazolium cation or N- methyl-N'- isopropyl-imidazolium cation).
  • a number of different Q b amines are useful, In one embodiment, isobutyl amine, neopentyl amine, monoethyl amine, or mixtures thereof are suitable examples of Q b .
  • the molar concentration of Q b is greater than the molar concentration of Q a Generally, the molar concentration of Q b is in the range from 2 to about 9 times the molar concentration of Q a .
  • U.S. Pat No. 5,785,947 (herein incorporated by reference) describes how a zeolite synthesis method employing two organic sources of nitrogen, one source being an amine containing from one to eight carbons provides significant cost savings over a method in which the quaternary ammonium ion source (such as imidazolium) is the only source of organic component.
  • the combination of the two organic nitrogen sources allows the possibility of the primary template (used in smaller quantity) to nucleate the desired zeolite structure and then the amine to contribute to filling the pores in a stabilizing manner, during crystal growth. Empty pores of high silica zeolites are susceptible to re-dissolution under the synthesis conditions.
  • the amine also can contribute to maintaining an elevated alkalinity for the synthesis.
  • the organic carbon compound source of quaternary ammonium ion also provides hydroxide ion.
  • the organic carbon compound source of quaternary ammonium ion, Q a , of the aqueous solution is derived from a compound of the formula:
  • R is lower alkyl containing 1 to 5 carbon atoms, for example -CH3 or isopropyl.
  • An anion (A ⁇ ) which is not detrimental to the formation of the MTT molecular sieve is associated with the cation.
  • an anion include halogens (e.g., fluoride, chloride, bromide and iodide), hydroxide, acetate, sulfate, carboxylate, etc. Hydroxide is a particularly useful anion.
  • the reaction mixture is prepared using standard zeolitic preparation techniques.
  • Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, and aluminum compounds, such as aluminum-coated silica colloids (one example is Nalco 1056 colloid sol), AI 2 (SO 4 .) 3 , and other zeolites.
  • the aluminum oxide is in a covalently dispersed form on silica.
  • Aluminum oxide in a covalently dispersed form allows molecular sieve with increased aluminum content to be crystallized. Increased aluminum content in the molecular sieve promotes isomerization.
  • zeolites of pentasil structure and lower silica/alumina ratios (approximately 10) can be used as aluminum oxide sources or feedstocks for the synthesis of small crystallite MTT molecular sieve. These zeolites are recrystallized to the small crystallite MTT molecular sieve in the presence of the organic sources Q a and Q b described above.
  • Mordenite and ferrierite zeolites constitute two such useful sources of aluminum oxide or feedstocks. These latter zeolites have also been used in the crystallization of ZSM- 5 and ZSM-11 (U.S. Pat. No. 4,503,024).
  • an alumina coated silica sol such as that manufactured by Nalco Chem. Co. under the product name 1056 colloid sol (26% silica, 4% alumina).
  • use of the sol generates crystallites of less than
  • the catalytic performance of MTT molecular sieves (in the hydrogen form) for cracking capability is manifested by Constraint Index values (as defined in J. Catalysis 67, page 218) of 13 or greater and in one embodiment the MTT molecular sieve (in the hydrogen form) has a Constraint Index from 13 to 22. Determination of Constraint index is also disclosed in U.S. Pat. No. 4,481 ,177. In general, lowering the crystallite size of a zeolite leads to decreased shape selectivity. This has been demonstrated for ZSM-5 reactions involving aromatics as shown in J. Catalysis 99,327 (1986). In addition, zeolite ZSM-22, (U.S. Pat. No.
  • Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silicas, tetraalkyl orthosilicates, and silica hydroxides. Salts, particularly alkali metal halides such as sodium chloride, can be added to or form in the reaction mixture. They are disclosed in the literature as aiding the crystallization of zeolites while preventing silica occlusion in the lattice.
  • the reaction mixture is maintained at an elevated temperature until the crystals of the molecular sieve are formed.
  • the temperatures during the hydrothermal crystallization step are typically maintained from about 140° C. to about 200° C, for example from about 160° C. to about 180° C. or from about 170° C. to about 180° C.
  • the crystallization period is typically greater than 1 day, and in one embodiment the crystallization period is from about 4 days to about 10 days.
  • the hydrothermal crystallization is conducted under pressure and usually in an autoclave so that the reaction mixture is subject to autogenous pressure.
  • the reaction mixture can be stirred while components are added as well as during crystallization.
  • the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration or centrifugation.
  • the crystals are water-washed and then dried, e.g., at 90° C. to 150°C. for from 8 to 24 hours, to obtain the as-synthesized molecular sieve crystals.
  • the drying step can be performed at atmospheric or subatmospheric pressures.
  • the crystals can be allowed to nucleate spontaneously from the reaction mixture.
  • the reaction mixture can also be seeded with MTT crystals both to direct, and accelerate the crystallization, as well as to minimize the formation of undesired aluminosilicate contaminants.
  • the small crystallite MTT-type zeolites used in the catalyst have a crystallite diameter of about 200 Angstroms to about 400 Angstroms in the longest direction.
  • the small crystallite MTT molecular sieve can be used as- synthesized or can be thermally treated (calcined).
  • the calcination is advantageously conducted at a temperature of about 750 F.
  • the molecular sieve can be leached with chelating agents, e.g., EDTA or dilute acid solutions, to increase the silica alumina mole ratio.
  • the molecular sieve can also be steamed. Steaming helps stabilize the crystalline lattice to attack from acids.
  • the calcined molecular sieve is then loaded with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd.
  • metals are known for their ability to modify performance of the catalyst by reducing the number of strong acid sites on the catalyst and thereby lowering the selectivity for cracking versus isomerization. In one embodiment, modification also involves increased metal dispersion such that acid or cation sites in the catalysts are blocked.
  • metal loading is accomplished by a variety of techniques, including impregnation and ion exchange. Typically, the metal is loaded such that the catalyst contains 0.5 to 5 wt.% metal on a dry basis. In one embodiment the catalyst contains 2 to 4 wt% metal on a dry basis.
  • Typical ion exchange techniques involve contacting the extrudate or particle with a solution containing a salt of the desired replacing cation or cations.
  • a salt of the desired replacing cation or cations is selected from the group of chlorides and other halides, nitrates, sulfates, and mixtures thereof.
  • Representative ion exchange techniques are disclosed in a wide variety of patents including U.S. Pat. Nos. 3,140,249; 3,140,251 ; and 3,140,253, each of which is incorporated herein by reference. Ion exchange can take place either before or after the extrudate or particle is calcined. Calcination is carried out in a temperature range from 400 to 1100 T.
  • the molecular sieve is dried at temperatures ranging from 149° F. to about 599° F.
  • the molecular sieve is then further loaded using a technique such as impregnation with a Group VIII metal to enhance the hydrogenation function.
  • the Group VIII metal at once, as disclosed in U.S. Pat. No. 4,094,821.
  • the Group VIII metal is platinum, palladium or a mixture of the two.
  • the material can be calcined in air or inert gas at temperatures from 500 to 900 °F.
  • step (c) extruding or forming the mixture of step (b) to form an extrudate or formed particle;
  • step (d) drying the extrudate or formed particle of step (c);
  • step (e) calcining the dried extrudate or formed particle of step (d); (f) impregnating the calcined extrudate or formed particle of step (e) with at least one metal selected from the group consisting of Ca, Cr, Mg, La, Ba, Na 1 Pr, Sr, K and Nd to prepare a metal-modified extrudate or formed particle;
  • step (g) drying the metal-modified extrudate or formed particle of step (f);
  • step (j) calcining the dried catalyst precursor of step (i) to form a finished, bound catalyst.
  • an active material in conjunction with the synthetic molecular sieve, i.e., combined with it, tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes.
  • active materials are hydrogenating components and metals added to affect the overall functioning of the catalyst.
  • the overall functioning of the catalyst includes enhancement of isomerization and reduction of cracking activity.
  • small crystallite MTT molecular sieve can be used in intimate combination with hydrogenating components for those applications in which a hydrogenation-dehydrogenation function is desired.
  • Typical hydrogenating components can include hydrogen, ammonium, metal cations, e.g. rare earth, Group MA and Group VII metals, as well as their mixtures.
  • metal hydrogenating components include tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, platinum, palladium (or other noble metals).
  • the Group VIM metal is a noble metal selected from the group of platinum, palladium, rhenium, and mixtures thereof.
  • the Group VIII metal is a noble metal selected from the group of platinum, palladium, and mixtures thereof.
  • the metal hydrogenating component is added such that it constitutes about 0.3 to about 5 wt.% of the catalyst on a dry basis.
  • Metals added to affect the overall functioning of the catalyst include magnesium, lanthanum (and other rare earth metals), barium, sodium, praseodymium, strontium, potassium and neodymium.
  • Other metals that might also be employed to affect the overall functioning of the catalyst include zinc, cadmium, titanium, aluminum, tin, and iron.
  • Hydrogen, ammonium as well as metal components can be exchanged into the molecular sieve.
  • the zeolite can also be impregnated with the metals, or, the metals can be physically intimately admixed with the molecular sieve using standard methods known to the art.
  • the metals can be occluded in the crystal lattice by having the desired metals present as ions in the reaction mixture from which the zeolite is prepared.
  • the molecular sieve zeolite described is converted to its acidic form and then is mixed with a refractory inorganic oxide carrier precursor and an aqueous solution to form a mixture.
  • the aqueous solution is acidic.
  • the aqueous solution acts as a peptizing agent.
  • the carrier also known as a matrix or binder
  • Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and metal oxides.
  • the carrier occurs naturally.
  • the carrier is in the form of gelatinous precipitates, sols, or gels, including mixtures of silica and metal oxides.
  • the molecular sieve is composited with porous matrix materials and mixtures of matrix materials such as silica, alumina, titania, magnesia, silica-alumina, silica- magnesia, silica-zirconia, silica-thoria, silica- beryllia, silica- titania, titania-zirconia as well as ternary compositions such as silica- alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the matrix can be in the form of a cogel.
  • the matrix materials are alumina and silica.
  • Inactive materials can suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically without using other means for controlling the rate of reaction.
  • zeolite materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials e.g. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in petroleum refining the catalyst is often subjected to rough handling. This tends to break the catalyst down into powders which cause problems in processing.
  • Metal-modified in this disclosure means that the catalyst molecular sieve contains at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd; and at least one Group VIII metal.
  • Group VIII metals are Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
  • naturally occurring clays are composited with the synthetic small crystallite MTT molecular sieve.
  • naturally occurring clays include the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite.
  • Fibrous clays such as sepiolite and attapulgite can also be used as supports. Such clays can be used in the raw state as originally mined or can be initially subjected to calcination, acid treatment or chemical modification.
  • the mixture of molecular sieve and binder can be formed into a wide variety of physical shapes.
  • the mixture can be in the form of a powder, a granule, or a molded product, such as an extrudate having a particle size sufficient to pass through a 2.5-mesh (Tyler) screen and be retained on a 48-mesh (Tyler) screen.
  • the catalyst is molded, such as by extrusion with an organic binder
  • the mixture can be extruded before drying, or dried or partially dried and then extruded.
  • Small crystallite MTT molecular sieve can also be steamed. Steaming helps stabilize the crystalline lattice to attack from acids.
  • the dried extrudate is then thermally treated, using calcination procedures.
  • the level of molecular sieve is between 5 and 85 wt %, or in another embodiment between 5 and 60 wt%.
  • the level of molecular sieve is varied for different molecular sieve types.
  • the metal-modified small crystallite MTT catalyst gives superior yields and exceptional Viscosity Index (Vl) on a variety of feeds.
  • Vl Viscosity Index
  • the byproduct selectivity is significantly changed compared to catalysts containing standard MTT-type zeolite, e.g., the catalyst results in very low gas and naphtha make.
  • the product yield was 97% at a pour point of -15 C and a Vl of 120 - 121.
  • a much larger drop is seen from waxy Vl to dewaxed Vl.
  • the resultant product Vl was about 111.
  • a metal- modified standard MTT-type zeolite catalyst gave a Vl of 115.
  • Gas make and naphtha make were both much reduced by the use of the small crystallite MTT molecular sieve loaded with metals.
  • Such a high yield and product Vl very close to the waxy feed Vl after dewaxing was very surprising.
  • the yield of 700 F+ dewaxed lube product in this instance was as high as 97%.
  • the slope of the product Vl versus pour point is unusual in that it was not lowered at lower pour point.
  • the resultant 650 F+ product had exceptional Vl's of 165-170 at pour points between -25 and - 30 °C.
  • the 750 °F+ boiling product was further split into two fractions, the 750-850 °F fraction had a kinematic viscosity at 100 °C of 3.8 mm 2 /s and a very high Vl of 151 at a pour point of -18°C, and the 850 °F+ fraction had a viscosity of 9.7mm 2 /s, a pour point of -11°V, and a Vl of 168.
  • Kinematic viscosity was measured by ASTM D445-06, pour point was measured by ASTM D5950-02, and Vl was measured by ASTM D2270-04.
  • the process using the catalyst comprising a molecular sieve having a small crystallite MTT topology and loaded with metals is used to dewax a variety of feedstocks ranging from relatively light distillate fractions such as kerosene and jet fuel up to high boiling stocks such as whole crude petroleum, reduced crudes, vacuum tower residua, cycle oils, synthetic crudes (e.g., shale oils, tars and oil, etc.), gas oils, vacuum gas oils, foots oils, Fischer-Tropsch derived waxes and intermediate products, slack waxes, deoiled slack waxes, waxy lubricant raffinates, n-paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, other heavy oils, and mixtures thereof.
  • relatively light distillate fractions such as kerosene and jet fuel up to high boiling stocks
  • synthetic crudes e.g., shale oils
  • the feedstock is a hydrocarbon having a weight percent wax of at least 5 %.
  • Weight percent wax in the feed is measured by heating the waxy sample until it is just above its pour point, pouring 100 grams of the heated waxy sample into a tared 1 liter beaker and recording the weight of the heated waxy sample to two decimal places; adding 400 mL of a 1 :1 mixture of toluene: methyl ethyl ketone (MEK) to the beaker and dissolving the waxy sample with gentle stirring over a hot plate until homogeneous. Cover the beaker with a piece of aluminum foil and place it in the freezer which has been preset to the pour point temperature of the feed. Allow the sample to sit undisturbed overnight. After cooling in the freezer overnight, filter the mixture using a filter assembly installed in the freezer. Use No.
  • Perform the filtration by connecting the funnel to heavy-duty vacuum, prewetting the filter paper with cold MEK, pulling the vacuum, quantitatively transfering the entire mixture in the beaker into the funnel using a spatula, rinsing the beaker with cold MEK, and filtering the rinsate. Close the freezer and wait until the solvent has completely drained through the filter, and the freezer has dropped to its original preset temperature. Wash the wax filter cake thoroughly using cold MEK. Allow the wax cake to dry, disconnect the vacuum, and remove the filter-funnel assembly from the freezer.
  • waxes Straight chain n-paraffins either alone or with only slightly branched chain paraffins having 16 or more carbon atoms are sometimes referred to herein as waxes.
  • the feedstock will often be a C10+ feedstock generally boiling above about 350°F, since lighter oils will usually be free of significant quantities of waxy components.
  • waxy distillate stocks such as middle distillate stocks including gas oils, kerosenes, and jet fuels, lubricating oil stocks, heating oils and other distillate fractions whose pour point and viscosity need to be maintained within certain specification limits.
  • Lubricating oil stocks will generally boil above 230°C. (450°F.), more usually above 315°C. (600°F.).
  • Hydroprocessed stocks are a convenient source of stocks of this kind and also of other distillate fractions since they normally contain significant amounts of waxy n- paraffins.
  • the feedstock of the present process will normally be a C10 + feedstock containing paraffins, olefins, naphthenes, aromatic and heterocyclic compounds and with a substantial proportion of higher molecular weight n- paraffins and slightly branched paraffins which contribute to the waxy nature of the feedstock.
  • the n-paraffins and the slightly branched paraffins undergo some cracking or hydrocracking to form liquid range materials which contribute to a low viscosity product.
  • the degree of cracking which occurs is, however, limited so that the yield of products having boiling points below that of the feedstock is reduced, thereby preserving the economic value of the feedstock.
  • Typical feedstocks include hydrotreated or hydrocracked gas oils, hydrotreated lube oil raffinates, bright stocks, lubricating oil stocks, synthetic oils, foots oils, Fischer-Tropsch synthesis oils, high pour point polyolefins, normal alphaolefin waxes, slack waxes, deoiled waxes, microcrystalline waxes, and mixtures thereof.
  • Fischer-Tropsch waxes can be obtained by well-known processes such as, for example, the commercial SASOL® Slurry Phase Fischer-Tropsch technology, the commercial SHELL® Middle Distillate Synthesis (SMDS) Process, or by the non-commercial EXXON® Advanced Gas Conversion (AGC-21) process.
  • Fischer-Tropsch synthesis product usually comprises hydrocarbons having 1 to 100, or even more than 100 carbon atoms, and typically includes paraffins, olefins and oxygenated products. Fischer Tropsch is a viable process to generate clean alternative hydrocarbon products, including Fischer-Tropsch waxes.
  • the conditions under which the isomerization dewaxing process is carried out generally include a temperature which falls within a range from about 392°F to about 800°F 1 and a pressure from about 15 to about 3000 psig. Typically, the pressure is from about 100 to about 2500 psig.
  • the liquid hourly space velocity during contacting is generally from about 0.1 to about 20, for example from about 0.1 to about 5.
  • the contacting is carried out in the presence of hydrogen.
  • the hydrogen to hydrocarbon ratio can fall within a range from about 2000 to about 10,000 standard cubic feet H 2 per barrel hydrocarbon, for example from about 2500 to about 5000 standard cubic feet H 2 per barrel hydrocarbon.
  • the isomerization dewaxing product is further treated, for example by hydrofinishing or adsorbent treatment.
  • the hydrofinishing can be conventionally carried out in the presence of a metallic hydrogenation catalyst, for example, platinum on alumina.
  • the hydrofinishing can be carried out at a temperature of from about 374°F to about 644°F and a pressure of from about 400 psig to about 3000 psig. Hydrofinishing in this manner is described in, for example, U.S. Pat. 3,852,207 which is incorporated herein by reference.
  • Table 2(a) shows the peak listing and relative intensity of peaks of standard SSZ-32, a standard MTT molecular sieve.
  • Table 2(b) shows the peak listing and relative intensity of peaks of small crystallite MTT molecular sieve prior to metal loading.
  • Table 2(b) magnifies peak width so that major peaks of small crystallite MTT molecular sieve and standard SSZ-32 are easily compared.
  • Figure 11 shows the X-ray diffraction patterns of these two types of MTT molecular sieves, and demonstrates clearly the broader x-ray diffraction peaks of the small crystallite MTT molecular sieve.
  • Small crystallite MTT molecular sieve was synthesized as follows: A Hastelloy C liner for a 5 gallon autoclave unit was used for the mixing of reagents and then in the subsequent thermal treatment. At a rate of 1500 RPM and for a period of 1 ⁇ 2 hour, the following components were mixed once they had been added in the order of description. 300 grams of a 1 Molar solution of N, N' Diisopropyl imidazolium hydroxide was mixed into 4500 grams of water. The salt iodide was prepared as in US 4, 483,835, Example 8, and then subsequently was ion-exchanged to the hydroxide form using BioRad AG1-X8 exchange resin. 2400 grams of 1 N KOH were added.
  • Example 2 In a concern that the product might be a mix of small crystals and considerable amorphous material, a TEM (Transmission Electron Microscopy) analysis was carried out. The microscopy work demonstrated that the product of Example 1 was quite uniformly small crystals of MTT molecular sieve with very little evidence of amorphous material. The crystallites were characterized by a spread of small, broad lathe-like components having a diameter in the range of about 200 to about 400 Angstroms in the longest direction. The SiO 2 /AI 2 O 3 ratio of this product w EXAMPLE 2
  • Example 1 The product of Example 1 was calcined to 1100°F in air with a ramp of 1 deg. C/min(1.8F/min) and plateaus of 250°F for 3 hours, 1000 F for 3 hours and then 1100°F for 3 hours.
  • the calcined material retained its x-ray crystallinity.
  • the calcined zeolite was subjected to 2 ion-exchanges at 200°F (using NH 4 NO 3 ) as has been previously described in US Pat. No. 5,252,527.
  • the ion- exchanged material was recalcined and then the microporosity measurements were explored, using a test procedure also described in 5,252,527.
  • the new product, small crystallite MTT molecular sieve had some unexpected differences vs. conventional SSZ-32.
  • the Ar adsorption ratio for small crystallite MTT molecular sieve (Ar adsorption at 87K between the relative pressures of 0.001 and 0.1)/(total Ar adsorption up to relative pressure of 0.1) is larger than 0.5. In one embodiment the Ar adsorption ratio is in the range of 0.55 to 0.70. In contrast for the conventional SSZ-32, the Ar adsorption ratio is less than 0.5, typically between 0.35 and 0.45.
  • the small crystallite MTT molecular sieve of Examples 1 and 2 demonstrated an Argon absorption ratio of 0.62.
  • the external surface area of the crystallites jumped from about 50 m 2 /g (SSZ- 32) to 150 (small crystallite MTT molecular sieve) m 2 /g, indicating the considerable external surface as a result of very small crystals.
  • the micropore volume for small crystallite MTT molecular sieve had dropped to about 0.035 cc/gm, as compared with about 0.06 cc/gm for standard SSZ-32.
  • Small crystallite MTT zeolite was composited with alumina, extruded, dried, and calcined. The dried and calcined extrudate was impregnated with a solution containing both platinum and magnesium , and then finally dried and calcined. The overall platinum loading was 0.325 wt.%. This metal-modified catalyst was then tested for isomerization on a waxy 500N hydrocrackate feed having 21% wax, a kinematic viscosity at 100°C of 10.218 mm 2 /s, and a pour point of +51 °C.
  • Isomerization process conditions used were a LHSV of 1.0 hr- 1 , 4000 scf/bbl gas to oil ratio, and a total pressure of 2300 psig. Following isomerization the products were hydrofinished over a Pt/Pd silica alumina hydrofinishing catalyst at 450 °F.
  • the Vl of the waxy 500N hydrocrackate feed was 122, and the Vl of the solvent dewaxed waxy 500 hydrocrackate feed was 106 when solvent dewaxed at -18°C.
  • the difference between the waxy Vl and the catalytic isomerized product Vl was only two (122-120), which was exceptional.
  • Figures 1 and 2 show the yield and product Vl versus pour point achieved with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst ("metal-modified SSZ-32X").
  • the results are compared with two other catalysts, a standard MTT-containing catalyst (“Std SSZ-32) and a metal-modified standard MTT-containing catalyst ("metal- modified SSZ-32"), tested under the same conditions and using the same feed.
  • the isomerization yield of product boiling at 700°F and above using the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst at the typical product target range of -12 to -15°C pour point was an unprecedented 96 to 97%.
  • the product Vl was approximately 120, which is also excellent, and is believed to be attributable to the exceptional amount of isomerized wax retained in the base oil boiling range product.
  • the slope of the Vl of the product boiling at 700°F and above versus the pour point was negative, approximately -0.15, such that the Vl was actually increased as the pour point was reduced.
  • Example 3 demonstrates where two or more isomerized products boiling at 343°C (650°F) or higher have a corresponding viscosity index of 104, 110, or higher.
  • Figures 3 and 4 show the low yields of Ci to C 4 products (“Gas-make”) and C 5 to C 250 °F product (Naphtha) achieved with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst ("metal-modified SSZ-32X”), compared with two other catalysts.
  • Example 3 The same metal-modified catalyst from Example 3 was also tested for isomerization on a waxy 150N hydrocrackate feed containing 10% wax and a pour point of +32°C.
  • Isomerization process conditions used were a LHSV of 1.0 hr -1 , 4000 scf/bbl gas to oil ratio, and a total pressure of 2300 psig.
  • the products were hydrofinished over a Pt/Pd silica alumina hydrofinishing catalyst at 450 °F.
  • Figures 5 and 6 show the yield and product Vl versus pour point achieved with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst ("metal-modified SSZ-32X").
  • metal-modified SSZ-32X small crystallite MTT zeolite catalyst
  • the results are compared with three other catalysts: a standard MTT-containing catalyst ("Std SSZ32), a metal- modified standard MTT-containing catalyst (“metal-modified SSZ-32”), and a standard small crystallite MTT zeolite catalyst that was not metal-modified (“small crystal SSZ-32X”). All four catalysts were tested under the same conditions and using the same 150N feed.
  • the isomerization yield of product boiling at 650°F and above using the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst at the typical product target range of -12 to -15°C pour point was 94 to 95%.
  • the product Vl was approximately 108.
  • the slope of the Vl of the product boiling at 650°F and above versus the pour point was approximately 0.09, which was significantly less than that obtained with the comparison catalysts.
  • the Vl was not lowered as much as the pour point was reduced with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst.
  • Figures 7 and 8 show the low yields of C 1 to C 4 products (“Gas-make”) and C 5 to C 250°F product (Naphtha) achieved with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst ("metal-modified SSZ-32X”), compared with two other catalysts.
  • Example 3 The same metal-modified catalyst from Example 3 was also tested for isomerization on a waxy medium neutral (220N, MN) feed containing 12.2% wax, a kinematic viscosity at 100°C of 6.149 mm 2 /s, and a pour point of +36°C.
  • Isomerization process conditions used were a LHSV of 1.6 hr '1 , 4000 scf/bbl gas to oil ratio, and a total pressure of 2300 psig.
  • the products were hydrofinished over a Pt/Pd silica alumina hydrofinishing catalyst at 450 °F.
  • Figures 9 and 10 show the yield and product Vl versus pour point achieved with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst ("metal-modified SSZ-32X"). The results are compared with two other catalysts: a standard MTT-containing catalyst ("standard SSZ-32), and a metal-modified standard MTT-containing catalyst ("metal-modified SSZ-32"). All three catalysts were tested under the same conditions and using the same 220N feed. The isomerization yield of product boiling at 650°F and above using the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst at the typical product target range of -15°C pour point was about 92%. The product Vl was 105.
  • the slope of the Vl of the product boiling at 650°F and above versus the pour point over a range of pour points from -12°C to -22°C was essentially zero, which again was significantly less than that obtained with the comparison catalysts.
  • the Vl was not lowered as the pour point was reduced with the metal-modified catalyst comprising the small crystallite MTT zeolite catalyst.
  • EXAMPLE 6 The same metal-modified catalyst from Example 3 was tested for isomerization on a hydrotreated Fischer-Tropsch wax feed having more than 90% wax made by the SASOL® Slurry Phase Fischer-Tropsch process. Isomerization process conditions used were a LHSV of 1.0 hr -1 , 5000 scf/bbl gas to oil ratio, and a total pressure of 300 psig. Following isomerization the products were hydrofinished over a Pt/Pd silica alumina hydrofinishing catalyst at 450 °F. The resultant products boiling at 650°F and above had VIs of 165 to 170 at pour points between -25 and -30°C.
  • the yield of products boiling at 650°F and above were greater than 65 wt.% at a pour point of - 20°C.
  • the products boiling at 650°F and above were further split by vacuum distillation into two fractions, one boiling between 750 to 850°F and the other boiling at 850°F and higher.
  • the lighter boiling fraction had a kinematic viscosity at 100°C of 3.8 mm 2 /s, a Vl of 151 , and a pour point of -18 °C.
  • the heavier boiling fraction had a kinematic viscosity at 100°C of 9.7 mm 2 /s, a Vl of 168, and a pour point of -11 °C.

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

Abstract

L'invention concerne l'enlèvement de cire d'une alimentation en hydrocarbure par l'isomérisation de l'alimentation avec un catalyseur comportant un tamis moléculaire à petit grain cristallin ayant une ossature MTT, le catalyseur contenant au moins un métal sélectionné parmi le groupe constitué de Ca, Cr, Mg, La, Na, Pr, Sr, K et Nd, et au moins un métal du groupe VIII. L'invention concerne un procédé d'enlèvement de cire pour produire des produits bouillant à 343°C (650°F), ou plus, avec des points de figeage bas et des indices de viscosité élevés; la ligne agencée sur le graphique des points de figeage et des indices de viscosité ayant une pente de zéro ou moins. L'invention concerne aussi un procédé d'enlèvement de cire, comportant une alimentation d'enlèvement de cire par isomérisation et ayant une viscosité à 100°C de 2,5 mm2/s, ou plus grande, sur un tamis moléculaire modifié par un métal pour produire des produits ayant des points de figeage bas et des indices de viscosité élevés; la ligne agencée sur le graphique des points de figeage et des indices de viscosité a une pente de zéro ou moins; et le rendement des produits est élevé.
EP07843768A 2006-10-04 2007-10-03 Procédé d'isomérisation utilisant un tamis moléculaire mtt à petit grain cristallin modifié par un métal Withdrawn EP2074199A2 (fr)

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US82819306P 2006-10-04 2006-10-04
US11/866,281 US20080083657A1 (en) 2006-10-04 2007-10-02 Isomerization process using metal-modified small crystallite mtt molecular sieve
PCT/US2007/080340 WO2008042979A2 (fr) 2006-10-04 2007-10-03 Procédé d'isomérisation utilisant un tamis moléculaire mtt à petit grain cristallin modifié par un métal

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US (1) US20080083657A1 (fr)
EP (1) EP2074199A2 (fr)
JP (1) JP2010506010A (fr)
KR (1) KR101385333B1 (fr)
CN (1) CN103031144A (fr)
BR (1) BRPI0717481A2 (fr)
CA (1) CA2662817A1 (fr)
MX (1) MX2009003522A (fr)
RU (1) RU2493236C2 (fr)
SG (1) SG175587A1 (fr)
WO (1) WO2008042979A2 (fr)

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RU2009116476A (ru) 2010-11-10
MX2009003522A (es) 2009-08-25
BRPI0717481A2 (pt) 2014-04-08
JP2010506010A (ja) 2010-02-25
CN103031144A (zh) 2013-04-10
US20080083657A1 (en) 2008-04-10
WO2008042979A2 (fr) 2008-04-10
CA2662817A1 (fr) 2008-04-10
KR101385333B1 (ko) 2014-04-24
KR20090078336A (ko) 2009-07-17
SG175587A1 (en) 2011-11-28
WO2008042979A3 (fr) 2008-07-31
RU2493236C2 (ru) 2013-09-20

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