CN1078105C - In-situ regeneration process of fisher-tropsch synthesis catalyst - Google Patents

In-situ regeneration process of fisher-tropsch synthesis catalyst Download PDF

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Publication number
CN1078105C
CN1078105C CN98106777A CN98106777A CN1078105C CN 1078105 C CN1078105 C CN 1078105C CN 98106777 A CN98106777 A CN 98106777A CN 98106777 A CN98106777 A CN 98106777A CN 1078105 C CN1078105 C CN 1078105C
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China
Prior art keywords
reactor
light oil
add
temperature
pressure
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Expired - Lifetime
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CN98106777A
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Chinese (zh)
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CN1230467A (en
Inventor
李国辉
周敬来
李煜
胡靖文
张荣乐
张青运
方勇
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Zhongke Synthetic Oil Technology Co Ltd
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The present invention relates to an in-situ regeneration method for a Fisher-Tropsch synthesis catalyst. Part of light oil distillate in a Fisher-Tropsch synthetic product is used for regenerating an in-situ deactivated catalyst in a subcritical or supercritical state; meanwhile, the pressure drop of a bed is reduced to normal reaction level, and reducing gas is used for reducing the treated catalyst. The treated catalyst has good activity and high stability, the regenerated Fe system catalyst has high stability, the activity is restored, the pressure drop of the reactor bed is normal, and the level of the fresh catalyst can be achieved.

Description

A kind of in-situ regeneration method of taking a Tropsch synthesis catalyst
The invention belongs to a kind of renovation process of catalyzer, relate in particular to a kind of in-situ regeneration method of expense one Tropsch synthesis catalyst.
Expense one holder is synthetic be grow up 1920's by CO+H 2The technology of synthetic liquid fuel is taken the synthetic Fe series catalysts that adopts of a holder, carries out building-up reactions in fixed bed, fluidized-bed or slurry attitude bed, can obtain required hydrocarbon products.But catalyzer is reactivity worth variation progressively in reaction process, and the yield of product and selectivity are descended, and meanwhile, the reactor bed pressure drop constantly increases, and finally can cause reactor plugs.The method that South Africa Sasol company adopts the gap to inject synthetic oil is cleaned beds, bed pressure drop is decreased, but catalyst stability is still not enough.
Goal of the invention of the present invention provides the in-situ regeneration method of a kind of expense one Tropsch synthesis catalyst, and the catalyzer after the regeneration has that reactivity worth is good, good stability and reactor bed pressure drop are normal.
Goal of the invention of the present invention is to realize like this, adopt a part of light oil fraction that takes in the holder sintetics, under subcritical or supercritical state, the original position decaying catalyst is carried out surface treatment, reduce bed pressure drop simultaneously to the normal reaction level, with reducing gas the catalyzer of handling with light oil is carried out in-situ reducing again.The catalyzer of handling has like this reached the effect of active good, good stability, and its reactivity worth and live catalyst are suitable.
Method of the present invention comprises the steps:
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 15Light oil with 0.1-10.0h -1The liquid air speed add reactor from an end of reactor, in reactor, be heated and be pressurized to subcritical or supercritical state.Keeping under the constant condition of reactor temperature pressure the material in the reactor being discharged continuously from the other end of reactor, becoming transparently until the outward appearance of ejecta, stopping to add light oil to reactor;
(2) expense one is held in the palm C in the sintetics then 5-C 15Light oil from (1) step a rightabout end add reactor, in reactor, be heated, be pressurized to subcritical or supercritical state, under the constant condition of temperature, pressure in keeping reactor, material in the reactor is discharged continuously from the other end of reactor, become transparently until the outward appearance of ejecta, stop to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 100-300 ℃, pressure becomes 0.1-3.0MPa, makes reducing gas with 10-1000h -1Gas space velocity enter reactor from reactor head, under the constant condition of temperature, the pressure in keeping reactor, make the material in the reactor discharge the H in ejecta continuously from the bottom of reactor 2O or CO 2Continuous 2 hours of content is constant, stops to add reducing gas.
Aforesaid reducing gas is H 2, CO or synthetic gas.
The present invention compared with prior art has following advantage:
(1) in-situ regeneration.
(2) method is simple.
(3) the Fe series catalysts good stability after the regeneration, active high, the pressure drop of reactor bed is normal, reaches the level of live catalyst.
Embodiment 1
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 8Light oil add reactor from the bottom of reactor, be heated to 250 ℃, be pressurized to 3.0MPa, reach supercritical state, keeping under the constant condition of reactor temperature pressure then, the interior material of reactor is discharged continuously from the top of reactor, keeping liquid air speed 0.5h -1, become transparently until the outward appearance of ejecta, stop to add light oil to reactor;
(2) will take C in the holder sintetics then 5-C 8Light oil add from the top of reactor, be heated to 250 ℃, be pressurized to 3.0MPa, reach supercritical state, under the constant condition of the temperature, pressure in keeping reactor, the material in the reactor is flowed out continuously from the bottom of reactor, keep liquid air speed 0.5h -1, become transparently until the outward appearance of ejecta, stop to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 250 ℃, pressure becomes 0.2MPa, makes reducing gas with CO+H 2Synthetic gas be 100h with the gas space velocity -1Enter reactor from reactor head, make the material in the reactor discharge the H in ejecta continuously from the bottom of reactor 2Continuous 2 hours of O content is constant.
Catalyst performance after the regeneration sees Table 1.
Embodiment 2
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 8Light oil add reactor from the top of reactor, be heated to 240 ℃, be pressurized to 2.5MPa, reach subcritical state, keeping under the constant condition of reactor temperature pressure the material in the reactor being discharged continuously from the bottom of reactor, keep liquid air speed 5.0h -1, become transparently until the outward appearance of ejecta, stop to add light oil to reactor;
(2) will take C in the holder sintetics then 5-C 8Light oil add from the bottom of reactor, be heated to 240 ℃, be pressurized to 2.5MPa, reach subcritical state, under the constant condition of the temperature, pressure in keeping reactor, the material in the reactor is flowed out continuously from the top of reactor, keep liquid air speed 5.0h -1, the outward appearance in ejecta becomes transparent, stops to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 220 ℃, pressure becomes 2.5MPa, makes reducing gas with CO+H 2Synthetic gas be 1000h with the gas space velocity -1Enter reactor from reactor head, make the material in the reactor discharge the CO in ejecta continuously from the bottom of reactor 2Continuous 2 hours of content is constant.
Catalyst performance after the regeneration sees Table 1.
Embodiment 3
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 15Light oil add reactor from the bottom of reactor, be heated to 200 ℃, be pressurized to 2.0MPa, reach subcritical state, keeping under the constant condition of reactor temperature pressure the material in the reactor being discharged continuously from the top of reactor, keep liquid air speed 1.0h then -1, become transparently until the outward appearance of ejecta, stop to add light oil to reactor;
(2) will take C in the holder sintetics then 5-C 15Light oil add from the top of reactor, be heated to 200 ℃, be pressurized to 2.0MPa, reach subcritical state, under the constant condition of the temperature, pressure in keeping reactor, the material in the reactor is flowed out continuously from the bottom of reactor, keep liquid air speed 1.0h -1, become transparently until the outward appearance of ejecta, stop to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 150 ℃, pressure becomes 3.0MPa, makes reducing gas CO with gas space velocity 500h -1Enter reactor from reactor head, make the material in the reactor discharge the CO in ejecta continuously from the bottom of reactor 2Continuous 2 hours of content is constant.
Catalyst performance after the regeneration sees Table 1.
Embodiment 4
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 15Light oil add reactor from the top of reactor, be heated to 240 ℃, be pressurized to 2.5MPa, reach subcritical state, keeping under the constant condition of reactor temperature pressure, the interior material of reactor is discharged continuously from the bottom of reactor, keeping liquid air speed 10.0h -1, become transparently until the outward appearance of ejecta, stop to add light oil to reactor;
(2) will take C in the holder sintetics then 5-C 15Light oil add from the bottom of reactor, be heated to 240 ℃, be pressurized to 2.5MPa, reach subcritical state, under the constant condition of temperature, pressure in keeping reactor, the material in the reactor is flowed out continuously from the top of reactor, keep liquid air speed 10.0h -1, the outward appearance in ejecta becomes transparent, stops to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 280 ℃, pressure becomes 0.2MPa, makes reducing gas H 2With gas space velocity 100h -1Enter reactor from reactor head, make the material in the reactor discharge the H in ejecta continuously from the bottom of reactor 2Continuous 2 hours of O is constant.
Catalyst performance after the regeneration sees Table 1.
Table 1
Project Live catalyst Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Before the regeneration After the regeneration Before the regeneration After the regeneration Before the regeneration After the regeneration Before the regeneration After the regeneration
CO transformation efficiency (%) 80 66 82 72 75 76 86 68 83
CH 4Selectivity (%) 5.0 2.9 1.3 4.6 0.9 3.7 3.0 5.9 3.1
C in the hydrocarbon 5 +Selectivity (%) 70 60 71 55 74 56 65 56 71
C 5 +Yield g/Nm (CO+H 2) 90 56 96 56 84 65 80 52 90
Bed pressure drop (MPa) 0.05 0.9 0.75 0.8 0.5 0.85 0.5 1.1 0.2
Reaction conditions: T=250 ℃ (I section)/280 ℃ (II section), P=2.5MPa, GHSV=400h -1, unstripped gas H 2/ CO ratio=1.84, tail gas recycle ratio R=3.0.

Claims (2)

1. in-situ regeneration method of taking a Tropsch synthesis catalyst is characterized in that the preparation method is as follows:
(1) catalyzer of inactivation adopts in former reactor and takes C in the holder sintetics 5-C 15Light oil with 0.1-10.0h -1The liquid air speed add reactor from an end of reactor, in reactor, be heated and be pressurized to subcritical or supercritical state, keeping under the constant condition of reactor temperature pressure, material in the reactor is discharged continuously from the other end of reactor, become transparently until the outward appearance of ejecta, stop to add light oil to reactor;
(2) expense one is held in the palm C in the sintetics then 5-C 15Light oil from (1) step a rightabout end add reactor, in reactor, be heated, be pressurized to subcritical or supercritical state, under the constant condition of temperature, pressure in keeping reactor, material in the reactor is discharged continuously from the other end of reactor, outward appearance in ejecta becomes transparent, stops to add light oil;
(3) after the light oil processing finishes, the temperature of reactor is become 100-300 ℃, pressure becomes 0.1-3.0MPa, makes reducing gas with 10-1000h -1Gas space velocity enter reactor from reactor head, under the constant condition of temperature, the pressure in keeping reactor, make the material in the reactor discharge the H in ejecta continuously from the bottom of reactor 2O or CO 2Continuous 2 hours of content is constant, stops to add reducing gas.
2. a kind of renovation process that takes a Tropsch synthesis catalyst according to claim 1 is characterized in that described reducing gas is H 2, CO or synthetic gas.
CN98106777A 1998-03-30 1998-03-30 In-situ regeneration process of fisher-tropsch synthesis catalyst Expired - Lifetime CN1078105C (en)

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Publication number Priority date Publication date Assignee Title
CN104588038B (en) * 2013-11-03 2016-10-19 中国石油化工股份有限公司 A kind of renovation process inactivating heavy oil hydrogenating treatment catalyst
KR20180087437A (en) * 2015-12-15 2018-08-01 사우디 아라비안 오일 컴퍼니 Supercritical reactor systems and processes for petroleum upgrading
CN111686824A (en) * 2020-06-11 2020-09-22 中科合成油内蒙古有限公司 In-situ regeneration method for ruthenium-based catalyst synthesized by Fischer-Tropsch fixed bed

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61271035A (en) * 1985-05-28 1986-12-01 Chiyoda Chem Eng & Constr Co Ltd Regenerating method for hydrogen-treated catalyst
GB2222531A (en) * 1988-06-30 1990-03-14 Shell Int Research Regeneration process for a Fischer-Tropsch catalyst
US5283216A (en) * 1992-09-24 1994-02-01 Exxon Research And Engineering Company Rejuvenation of hydrocarbon synthesis catalyst
GB2299767A (en) * 1995-04-07 1996-10-16 Norske Stats Oljeselskap Catalyst regeneration in a Fischer-Tropsch reaction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61271035A (en) * 1985-05-28 1986-12-01 Chiyoda Chem Eng & Constr Co Ltd Regenerating method for hydrogen-treated catalyst
GB2222531A (en) * 1988-06-30 1990-03-14 Shell Int Research Regeneration process for a Fischer-Tropsch catalyst
US5283216A (en) * 1992-09-24 1994-02-01 Exxon Research And Engineering Company Rejuvenation of hydrocarbon synthesis catalyst
GB2299767A (en) * 1995-04-07 1996-10-16 Norske Stats Oljeselskap Catalyst regeneration in a Fischer-Tropsch reaction

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