EP2276565A2 - Gasoline synthesis catalyst - Google Patents

Gasoline synthesis catalyst

Info

Publication number
EP2276565A2
EP2276565A2 EP09734615A EP09734615A EP2276565A2 EP 2276565 A2 EP2276565 A2 EP 2276565A2 EP 09734615 A EP09734615 A EP 09734615A EP 09734615 A EP09734615 A EP 09734615A EP 2276565 A2 EP2276565 A2 EP 2276565A2
Authority
EP
European Patent Office
Prior art keywords
matrix
catalyst
nanostructural
catalyst according
copper ions
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Withdrawn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
EP09734615A
Other languages
German (de)
French (fr)
Inventor
Dobieslaw Nazimek
Stanislaw Jablonski
Waldemar Zaniuk
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.)
Uniwersytet Marii Curie Sklodowskiej
Original Assignee
Uniwersytet Marii Curie Sklodowskiej
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 Uniwersytet Marii Curie Sklodowskiej filed Critical Uniwersytet Marii Curie Sklodowskiej
Publication of EP2276565A2 publication Critical patent/EP2276565A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
    • B01J29/68—Iron group metals or copper
    • 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
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • C10G2400/02—Gasoline
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the subject of the present invention is a nanostructural catalyst for the synthesis of gasolines, in particular via a low alcohol route, where water is a by-product, e.g.
  • n and x in the above equation are dependent on the temperature and pressure in the system as well as the catalyst used in the process. This means that the catalyst, which, beside enabling the very synthesis reaction to occur, also influences the degree of the coupling process related to the degree of isomerisation of hydrocarbons to increase the octane number of the gasoline to be obtained. Also important is the catalyst's resistance to water present as a by-product of the synthesis.
  • the objective of the present invention is to provide a novel catalyst formula for the synthesis of gasolines from methanol or its homologues, in particular its matrix, having high catalytic resistance to water, even above 100 ppm, that would also allow active sites to be appropriately deposited thereon for high and long-lasting activity of the catalyst and its selectivity towards increasing the degree of isomerisation of hydrocarbons in order to increase octane number of the gasoline to be obtained.
  • the catalyst according to the present invention characterises in that its active sites in the form of copper ions are introduced in a coordinated octahedral structure and at a preferable amount of Cu in a range of 0,2 to 0,5 % by weight of the metal, by known methods, onto nanostructural aluminosilicate matrixes, in particular 10-channel matrixes of monoclinic crystal structure with channel dimensions from 7,6 A to 3,0 A, of high adsorptive capacity and ion exchange selectivity, thermal stability in the range 973 - 1023 K, and, preferably, Al 2 O 3 to SiO 2 molar ratio of max 10, and total surface area not greater than 40 m2/g, in particular in the form of ferrierite or clinoptilolite granules.
  • Example 1 The present invention is illustrated by the following embodiments. Example 1.
  • a catalyst named FERR-Cu was prepared, where as the matrix there were used 1,5 to 3 mm diameter granules of ferrierite, a hydrated aluminosilicate of sodium, potassium and magnesium in sodium form, of general formula (Na 5 K) 2 Mg[OHZAl 3 Si 15 O 36 ] • 9H 2 O, crystallised in a rhomboidal system in the form of needle-shaped crystals characterised by the following physicochemical data:
  • a catalyst named KLIP-Cu was prepared, where as the matrix there was used clinoptylolite, a natural zeolite of identical chemical composition to that of ferrierite, crystallised in a monoclinical system (Cm symmetry group), in the form of granules of 1,5 to 3 mm in diameter, characterised by the following physicochemical data:
  • the catalysts according to the present invention were subjected to evaluation in kinetic tests in ethanol coupling processes, assuming that an indicator of catalyst activity will be the reaction rate expressed as TOF (Turnover Frequency) towards the formation of ETBE (ethyl tert-butyl ether) as the most desirable product, as well as towards the formation of isomeres above C 5 hydrocarbons.
  • TOF Treatment Frequency
  • ETBE ethyl tert-butyl ether

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The subject of the present invention is a catalyst for the synthesis of gasolines from methanol or its homologues, in particular its nanostructural matrix having high catalytic resistance to water, even as high as above 100 ppm and making it possible to appropriately deposit active sites onto it, which results in high and long-lasting activity of the catalyst and its selectivity towards increasing the degree of hydrocarbons isomerisation to increase the octane number of the gasoline to be obtained. Preferably the catalyst is in form of copper ions supported on an aluminosilicate matrix.

Description

Gasoline synthesis catalyst.
The subject of the present invention is a nanostructural catalyst for the synthesis of gasolines, in particular via a low alcohol route, where water is a by-product, e.g.
catalyst nCH3O CnHn+x + H2O
The values n and x in the above equation are dependent on the temperature and pressure in the system as well as the catalyst used in the process. This means that the catalyst, which, beside enabling the very synthesis reaction to occur, also influences the degree of the coupling process related to the degree of isomerisation of hydrocarbons to increase the octane number of the gasoline to be obtained. Also important is the catalyst's resistance to water present as a by-product of the synthesis.
So far, syntheses of gasoline from methanol or its homologues have been carried out using known catalysts e.g. copper catalyst, supported on an aluniinosilicate matrix in the form of a zeolite, characterised by high molecular Al2O3ZSiO2 ratio, at about 40, denominated by the symbol ZSM-5. Polish patent specification PL 244883. The relatively high content of Al2O3 in the matrix results in zeolite catalysts' high vulnerability to water present in the reaction environment, which directly affects their activity.
The objective of the present invention is to provide a novel catalyst formula for the synthesis of gasolines from methanol or its homologues, in particular its matrix, having high catalytic resistance to water, even above 100 ppm, that would also allow active sites to be appropriately deposited thereon for high and long-lasting activity of the catalyst and its selectivity towards increasing the degree of isomerisation of hydrocarbons in order to increase octane number of the gasoline to be obtained.
The catalyst according to the present invention characterises in that its active sites in the form of copper ions are introduced in a coordinated octahedral structure and at a preferable amount of Cu in a range of 0,2 to 0,5 % by weight of the metal, by known methods, onto nanostructural aluminosilicate matrixes, in particular 10-channel matrixes of monoclinic crystal structure with channel dimensions from 7,6 A to 3,0 A, of high adsorptive capacity and ion exchange selectivity, thermal stability in the range 973 - 1023 K, and, preferably, Al2O3 to SiO2 molar ratio of max 10, and total surface area not greater than 40 m2/g, in particular in the form of ferrierite or clinoptilolite granules.
The present invention is illustrated by the following embodiments. Example 1.
A catalyst named FERR-Cu was prepared, where as the matrix there were used 1,5 to 3 mm diameter granules of ferrierite, a hydrated aluminosilicate of sodium, potassium and magnesium in sodium form, of general formula (Na5K)2Mg[OHZAl3Si15O36] • 9H2O, crystallised in a rhomboidal system in the form of needle-shaped crystals characterised by the following physicochemical data:
- Al2O3ZSiO2 molecular ratio - approx. 10
- approximate channel dimensions: width - 7,6 A and height 3 A
- total surface area determined by BET method (argon absorption at liquid nitrogen temperature) - Sog- approx. 35 m2Zg,
- thermal stability - 973 K
Onto the matrix thus prepared, Cu active sites were deposited by ion exchange from an ammoniacal solution, at an amount of 0,2 % by weight, and then, after recovery from the solution, drying and calcination, the final catalyst was obtained.
Example 2.
A catalyst named KLIP-Cu was prepared, where as the matrix there was used clinoptylolite, a natural zeolite of identical chemical composition to that of ferrierite, crystallised in a monoclinical system (Cm symmetry group), in the form of granules of 1,5 to 3 mm in diameter, characterised by the following physicochemical data:
- Al2O3ZSiO2 molar ratio - approx. 4
- approximate channel dimensions: width- 7,6 A and height 3 A - total surface area determined by BET method (argon absorption at liquid nitrogen temperature) - Sog - approx. 40 m2/g,
- thermal stability - 1023 K
Onto the matrix thus prepared, Cu ions were deposited by impregnation at an amount of 0,5 % from its nitrate solution, using EDTA as the complexing agent. After recovery from the solution, drying and calcination, the final catalyst was obtained.
The catalysts according to the present invention were subjected to evaluation in kinetic tests in ethanol coupling processes, assuming that an indicator of catalyst activity will be the reaction rate expressed as TOF (Turnover Frequency) towards the formation of ETBE (ethyl tert-butyl ether) as the most desirable product, as well as towards the formation of isomeres above C5 hydrocarbons.
The test results indicate that for both the FEER-Cu and the KLIP-Cu catalyst the apparent reaction activation energy, ΔE, is approx. 300 kJ/mol, selectivity towards ETBE - approx. 45%, and towards isomeres above C5 - approx. 30% while the selectivity towards undesirable products - CO2 and CO not greater than 10 - 12%. A comparison of the above data with those of known zeolite catalysts allows one to state that the catalyst according to the present invention is highly active, selective and relatively resistant to the presence of water, which makes it possible to favorably use it in ethanol coupling processes to obtain higher, more technologically desired hydrocarbons even with 5% by volume of water in it.

Claims

Claims
1. A gasoline synthesis catalyst with active sites in the form of copper ions supported on an aluminosilicate matrix, characterised in that copper ions are introduced in a coordinated octahedral structure at an amount between 0,2 to 0,5 % by weight of metal, onto a nanostructural aluminosilicate matrix of monoclinic crystallographic structure, high adsorptive capacity and ion exchange selectivity, as well as at Al2O3 to SiO2 molar ratio of max. 10 and thermal stability in the range 973 - 1023 K.
2. The catalyst according to claim 1, characterised in that its nanostructural matrix has a 10-channel structure with channel dimensions from 7,6 A to 3,0 A.
3. The catalyst according to claim 1, characterised in that the total surface area of its nanostructural matrix is not greater than 40 m2/g.
4. The catalyst according to claim 1, characterised in that its nanostructural matrix is in the form of ferrierite granules.
5. The catalyst according to claim 1, characterised in that its nanostructural matrix is in the form of clinoptylolite granules.
EP09734615A 2008-04-22 2009-04-21 Gasoline synthesis catalyst Withdrawn EP2276565A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL384999A PL207580B1 (en) 2008-04-22 2008-04-22 Petrol synthesis catalyst
PCT/PL2009/000037 WO2009131474A2 (en) 2008-04-22 2009-04-21 Gasoline synthesis catalyst

Publications (1)

Publication Number Publication Date
EP2276565A2 true EP2276565A2 (en) 2011-01-26

Family

ID=40940550

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09734615A Withdrawn EP2276565A2 (en) 2008-04-22 2009-04-21 Gasoline synthesis catalyst

Country Status (4)

Country Link
EP (1) EP2276565A2 (en)
AU (1) AU2009238764A1 (en)
PL (1) PL207580B1 (en)
WO (1) WO2009131474A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111696619B (en) * 2019-03-13 2023-06-20 赣南师范大学 Method for predicting influence degree of reaction environment on reaction activation energy

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA801758B (en) * 1979-04-04 1981-03-25 Mobil Oil Corp Steam-resistant zeolite catalyst
PL135292B1 (en) 1983-12-02 1985-10-31 Inst Chemii Przemyslowej Method of manufacture of zsm-5 type high-silicon zeolite
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US5491273A (en) * 1994-11-17 1996-02-13 Mobil Oil Corporation Catalytic conversion of methanol to linear olefins
GB0607395D0 (en) * 2006-04-12 2006-05-24 Bp Chem Int Ltd Process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009131474A2 *

Also Published As

Publication number Publication date
WO2009131474A2 (en) 2009-10-29
AU2009238764A1 (en) 2009-10-29
PL384999A1 (en) 2009-10-26
WO2009131474A3 (en) 2009-12-17
PL207580B1 (en) 2011-01-31

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