CN1208431A - Catalytically converting a hydrocarbonaceous feed - Google Patents
Catalytically converting a hydrocarbonaceous feed Download PDFInfo
- Publication number
- CN1208431A CN1208431A CN97191694A CN97191694A CN1208431A CN 1208431 A CN1208431 A CN 1208431A CN 97191694 A CN97191694 A CN 97191694A CN 97191694 A CN97191694 A CN 97191694A CN 1208431 A CN1208431 A CN 1208431A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- spent catalyst
- spent
- moving
- regenerated
- 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.)
- Pending
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- 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
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Process for the catalytic conversion of a hydrocarbonaceous feed comprising contacting the hydrocarbonaceous feed in a moving-bed reactor with particulate catalyst, to obtain reactor effluent and spent catalyst, separating spent catalyst from reactor effluent, regenerating spent catalyst in a regenerator by contacting spent catalyst with air under conditions to combust coke deposited on the catalyst to obtain regenerated catalyst which is supplied to the moving-bed reactor, wherein at regular intervals spent catalyst or regenerated catalyst is contacted with a coating fluid comprising precursors of a substantially non-acidic meso- or macroporous oxidic or oxyanionic material.
Description
The present invention relates to a kind of catalysis conversion method of hydrocarbon feed, comprise hydrocarbon feed is contacted with beaded catalyst in moving-burden bed reactor, obtain reactor effluent and spent catalyst, from reactor effluent, isolate spent catalyst, by spent catalyst can contacted with regeneration of spent catalyst under the condition of the coke on the catalyzer by burnt deposit with air, thereby the acquisition regenerated catalyst is transported to moving-burden bed reactor with regenerated catalyst.
This method is referred to as fluid catalytic cracking (FCC) method.In the method, hydrocarbon feed is catalytically conveted to lighter crackate, and these products can be used as motor spirit, diesel-fuel, oil plant and chemical feedstocks.In the FCC method, raw material is to contact with suitable beaded catalyst under the pressure of the temperature of 450-800 ℃ raising and 0.1-1Mpa.The quality ratio of catalyzer and raw material to be transformed is 3: 1-100: 1, and duration of contact was less than 10 seconds.Appropriate catalyst comprises acidic molecular sieve crystal, clay and binding agent.This catalyzer is known, for example, and can be referring to the pending trial European application 95201948.7 of applicant in application on July 14 nineteen ninety-five.In this manual, term " molecular sieve catalyst " just is meant this beaded catalyst.
In recent years, often will transform the hydrocarbon feed of high boiling range, this raw material contains a spot of metal, as nickel and vanadium.In conversion process, these metals can be deposited on the granules of catalyst that forms coke.In regenerative process, coke is burned, and metal is retained on the beaded catalyst.Vanadium has disadvantageous effect to the stability of the molecular sieve that is used for catalyzer, and nickel also is deleterious, and this is because select to form coke and hydrogen, nickel content is high more, then can form many more gaseous product, hydrogen and lighter hydrocarbons,, have many more sedimentation of coke on granules of catalyst as methane.
The pending trial European application 95201948.7 that the applicant applied for July 14 nineteen ninety-five relates to a kind of method of catalyzed conversion hydrocarbon feed, is included in hydrocarbon feed is contacted with beaded catalyst.Granules of catalyst comprises a core that is centered on by shell, and its SMIS is a molecular sieve catalyst, and shell comprises and is essentially nonacid mesopore or macropore oxidation or oxo-anions (oxyanionic) material.
These granules of catalyst wherein are coated with fluid and contain the precursor that is essentially nonacid mesopore or macropore oxidation or oxo-anions material by making freshly prepd molecular sieve catalyst particle and a kind of fluid contact preparation that is coated with.
The applicant found in the FCC process, and when using this coating fluid handling spent catalyst, catalyzer gathers the harmful effect that is produced and can be cancelled.
Therefore, the present invention relates to a kind of method of hydrocarbon feed catalyzed conversion, comprise hydrocarbon feed is contacted with beaded catalyst in moving-burden bed reactor, obtain reactor effluent and spent catalyst, from reactor effluent, isolate spent catalyst, by spent catalyst can contacted with regeneration of spent catalyst under the condition of the coke on the catalyzer by burnt deposit with air, thereby acquisition regenerated catalyst, regenerated catalyst is transported to moving-burden bed reactor, wherein spent catalyst or regenerated catalyst regularly contact with a kind of coating fluid, and this coating fluid contains the precursor that is essentially nonacid mesopore or macropore oxidation or oxo-anions material.
The coating fluid is the dispersion of precursor in gas or liquid solvent, and suitable is the colloidal dispersion of precursor, can be aerosol (dispersion of solid in gas), or the water-sol (dispersion of solid in liquid).
During being coated with, granules of catalyst is hot, and when particle contacts with the coating fluid of the dispersion form of precursor in gas, precursor will be deposited on the granules of catalyst, forms the shell that is essentially nonacid mesopore or macropore oxidation or contains anionic materials.When with coating fluid coated heat granules of catalyst, solvent will be evaporated, and form the shell that is essentially nonacid mesopore or macropore oxidation or contains anionic materials.
Should select to be coated with the fluidic amount, make that it is the shell of 0.05-20 micron to obtain thickness that enough precursors are arranged.
Suitable nonacid mesopore oxidation or oxo-anions material comprise nonacid oxidation or the oxygenatedchemicals that is selected from 2A in the periodic table of elements, 2B, 3A, 3B, 4A, 4B and lanthanon, for example, clay, as kaolin and metakaolin, aluminum oxide, silicon-dioxide, magnesium oxide, calcium oxide, titanium oxide, zirconium white, ytterbium oxide, cerium oxide, lanthanum trioxide, stannic oxide, aluminum phosphate, magnesium aluminate, with and composition thereof.Macropore oxidation or oxo-anions examples of material comprise Alpha-alumina and silicon-dioxide, as the silicon-dioxide of amorphous forms.
In this specification sheets and claims, term " poromerics " is meant that the aperture is less than 1.0nm (nanometer), suitable is the material of 0.3-0.9nm, term " large pore material " is meant that the aperture is greater than 50nm (nanometer), the material that suitable is greater than 100nm, and " mesopore material " is meant the material of aperture between poromerics aperture and large pore material aperture.
Useless or regenerated catalyst can several modes contact with the coating fluid, coating liquid can be sprayed to revivifier, or be expelled to from the transport pipe of reactor and revivifier extension.
In addition, can be from revivifier the pump-around stream of one regenerated catalyst of extraction, and deliver in the independent container that member is housed, this member can form fluidized-bed in this container under normal operation.Then, coating liquid is sprayed in this container, and discharges the granules of catalyst that was coated with from container.
The applicant in the pending trial European application 95201948.7 of July 14 nineteen ninety-five application embodiment 1A-1J and the coating liquid described in the following examples can be used for the present invention.Those skilled in the art can prepare coating liquid according to these information, and these coating fluid physical efficiencys produce in common FCC process and are essentially nonacid mesopore or macropore oxidation or contain the oxygen material.
Below with embodiment the present invention is described in more detail.
In an embodiment, beaded catalyst contacts with the raw material of description in the table 1 in small-sized activity experiment unit, and its temperature is 540 ℃, and pressure is a normal atmosphere.
Raw materials used composition among embodiment and the Biao: %m represents mass percent, and ppm represents with ppm of quality.
Table 1 proportion, API 21.8 hydrogen, %m 12.3 sulphur, %m 0.85 nitrogen, %m 0.20 vanadium, ppm 8.60 nickel, ppm 4.10 Kang Laxun carbon, the kinematic viscosity of %m 3.66 in the time of 100 ℃, mm
2/ s 16.2 aromatic carbons, %m 15.5
In example, use spent catalyst, this catalyzer is the AdvanceR927 catalyzer available from AKZO Nobel, takes a sample from industrial FCC unit.Spent catalyst contains the coke of the 1%m that has an appointment.A collection of spent catalyst uses not according to embodiments of the invention, and the spent catalyst (this catalyzer is referred to as to be coated with spent catalyst) that another batch is coated with silicon-dioxide uses by the embodiment of the invention.
Before experiment, spent catalyst is handled in air to remove the dealkylation settling under 600 ℃ temperature in small-sized activity test unit.
The preparation process of painting catalyst is as follows.With 400 the gram spent catalyst pack into the spraying coating apparatus in, equipment is the STREA-1 type, is made by Niro-Aeromatic Fielder.Solid is a fluidisation in 80 ℃ the airflow in temperature in.The atomizing pressures that use 2 crust are sprayed to 354 gram silica hydrosol Nyacol 2040NH4 (silicon-dioxide that contains 40%m) in the fluidized-bed by exit diameter nozzle as 0.5mm, flow be 600 milliliters/minute.Product in an independent stove 120 ℃ air drying 2 hours, 550 ℃ of calcinings 2 hours in air, then in air, remove any hydrocarbon settling then at 600 ℃.The product that so obtains is a coating spent catalyst sample of the present invention.
The effect of coating is to reduce to finish the charcoal amount, has reduced the amount of gaseous component, hydrogen and methane, the results are shown in table 2 and 3.
Amount of coke is the function of catalyzer to the quality ratio of raw material (C/O is in kg/kg), and wherein amount of coke is represented with the %m of raw materials quality.
Table 2
Amount of coke C/O spent catalyst coating spent catalyst 1.87 7.14-1.95-7.762.62-7.832.74 8.26-3.54-9.033.83 9.55-4.59 11.1-4.81-11.05.60 12.8-6.70-13.4
Hydrogen output is the function of clean transformation efficiency to the ratio of methane production, and clean transformation efficiency is gaseous product and gasoline output sum (in the %m of raw material).
Table 3 hydrogen output is to the clean conversion ratio dead catalyst coating of methane production dead catalyst 35.24 0.5128-37.55-0.435942.99 0.5714-44.07-0.510251.66-0.572851.78 0.6549-55.82 0.6667-57.06-0.610258.03 0.6763-62.22-0.6258
Table 2 and table 3 have clearly illustrated the effect of coating spent catalyst in the FCC process.
Claims (1)
1. the catalysis conversion method of a hydrocarbon feed, comprise hydrocarbon feed is contacted with beaded catalyst in moving-burden bed reactor, obtain reactor effluent and spent catalyst, from reactor effluent, isolate spent catalyst, by spent catalyst can contacted with regeneration of spent catalyst under the condition of the coke on the catalyzer by burnt deposit with air, thereby acquisition regenerated catalyst, regenerated catalyst is transported to moving-burden bed reactor, wherein spent catalyst or regenerated catalyst regularly contact with a kind of coating fluid, and this coating fluid contains the precursor that is essentially nonacid mesopore or macropore oxidation or oxo-anions material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96200088.1 | 1996-01-15 | ||
| EP96200088 | 1996-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1208431A true CN1208431A (en) | 1999-02-17 |
Family
ID=8223586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97191694A Pending CN1208431A (en) | 1996-01-15 | 1997-01-14 | Catalytically converting a hydrocarbonaceous feed |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0882111A1 (en) |
| JP (1) | JP2000503330A (en) |
| CN (1) | CN1208431A (en) |
| AR (1) | AR005446A1 (en) |
| AU (1) | AU698640B2 (en) |
| CA (1) | CA2241548A1 (en) |
| WO (1) | WO1997026313A1 (en) |
| ZA (1) | ZA97249B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10315215A1 (en) * | 2003-04-03 | 2004-10-14 | Basf Ag | In-situ re-coating of catalyst beds |
| FR2920767B1 (en) | 2007-09-06 | 2009-12-18 | Arkema France | REACTIVE GLYCEROL VAPORIZATION PROCESS |
| US8329028B2 (en) | 2009-12-17 | 2012-12-11 | Uop Llc | Solid catalyst hydrocarbon conversion process using stacked moving bed reactors |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232885A (en) * | 1991-12-18 | 1993-08-03 | Amoco Corporation | Process for regenerating a spent resin hydroprocessing catalyst using a group IV metal |
-
1997
- 1997-01-13 ZA ZA97249A patent/ZA97249B/en unknown
- 1997-01-13 AR ARP970100119A patent/AR005446A1/en unknown
- 1997-01-14 CN CN97191694A patent/CN1208431A/en active Pending
- 1997-01-14 JP JP9525695A patent/JP2000503330A/en active Pending
- 1997-01-14 CA CA002241548A patent/CA2241548A1/en not_active Abandoned
- 1997-01-14 AU AU14438/97A patent/AU698640B2/en not_active Ceased
- 1997-01-14 EP EP97901058A patent/EP0882111A1/en not_active Withdrawn
- 1997-01-14 WO PCT/EP1997/000200 patent/WO1997026313A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU1443897A (en) | 1997-08-11 |
| ZA97249B (en) | 1997-07-15 |
| CA2241548A1 (en) | 1997-07-24 |
| JP2000503330A (en) | 2000-03-21 |
| AR005446A1 (en) | 1999-06-23 |
| EP0882111A1 (en) | 1998-12-09 |
| AU698640B2 (en) | 1998-11-05 |
| WO1997026313A1 (en) | 1997-07-24 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |