EP0663434B1 - Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques - Google Patents
Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques Download PDFInfo
- Publication number
- EP0663434B1 EP0663434B1 EP94403062A EP94403062A EP0663434B1 EP 0663434 B1 EP0663434 B1 EP 0663434B1 EP 94403062 A EP94403062 A EP 94403062A EP 94403062 A EP94403062 A EP 94403062A EP 0663434 B1 EP0663434 B1 EP 0663434B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- charge
- reaction zone
- zone
- stage
- 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.)
- Expired - Lifetime
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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
-
- 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
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
Definitions
- the present invention relates to a method of catalytic cracking in a fluidized bed of a charge hydrocarbons, especially a filler with a high content of basic nitrogen compounds.
- cracking of the charge is carried out at a temperature of the order of 500 ° C., at a pressure close to atmospheric pressure, in the absence of hydrogen.
- the catalyst is coated with coke and heavy hydrocarbons, and continuously regenerates it outside the cracking reactor. The heat resulting from the combustion of coke and traces of hydrocarbons remaining in the presence of air or oxygen serves to bring the desired temperature the catalyst particles, which are recycled to the reactor.
- the catalysts can be of various types and we can refer on this point, for example, to EP-A-0 206 871.
- the invention also aims to remove or limit, in such a process, the wall effects of the reactor and the back-movements of the particles of catalyst.
- the process according to the invention has the advantage of lending itself to cracking in good nitrogen load conditions, on the one hand, because the low acidity of the catalyst, which reduces its activity, is offset by the increase in reaction temperature, made possible by use of a downflow reactor and by lowering the resulting reaction time, and, on the other hand, because that increasing the reaction temperature allows shift towards desorption the adsorption-desorption balance basic molecules at the acid sites of the catalyst.
- the flow rate of catalyst used may advantageously be increased, which will increase the number of active sites.
- the ratio of the mass of catalyst present in the hydrocarbon mass reactor may, in particular, advantageously be greater than 5 and, from preferably between 7 and 15.
- the new catalyst used could, for example, include a limited amount of alumina (s), not exceeding not 30% by weight, at least one zeolite, in an amount representing 15 to 40% by weight, the balance to 100% which may consist of kaolin, a basic clay or weakly acidic, such as sepiolite and vermiculite, a silica-based binder and optionally a metal trap such as for example a metal oxide.
- alumina s
- zeolite in an amount representing 15 to 40% by weight
- the balance to 100% which may consist of kaolin, a basic clay or weakly acidic, such as sepiolite and vermiculite, a silica-based binder and optionally a metal trap such as for example a metal oxide.
- the device shown comprises a reactor downflow tubular 1, or "downer”, supplied at its upper part, from an enclosure 2, which is concentric, in regenerated catalyst particles.
- a valve 3, intended to regulate the mass ratio of catalyst to the charge mass to be treated in the reactor, is interposed between reactor 1 and enclosure 2. Above this valve there is a line 4, fitted with a valve 5, supplying the reactor 1 in the hydrocarbon charge to be treated, preheated by in a manner known per se.
- This charge is sprayed into fines droplets by injectors at the top from reactor 1, towards the bottom of it, to come to mix with the catalyst particles, on contact from which the cracking reaction takes place. As we will see below, these particles have been brought to a temperature suitable for cracking by the operation of regeneration of spent catalyst.
- the particles of catalyst and the charge to be treated therefore flow from high below, co-current, in reactor 1.
- the stripped catalyst particles are removed by gravity of the enclosure 6, by an inclined conduit 22, towards an ascending column 12, in which they are routed upwards, towards a regenerator 13, using of a carrier gas, diffused at 14 at the base of the column 12, from line 15.
- the regenerated catalyst particles are removed by gravity through conduit 19 towards the enclosure 2, without thermal losses.
- Type of load processed A low nitrogen
- B very nitrogenous
- - density 17.7 18.5 - sulfur
- % by weight 2.42
- 0.9 - hydrogen % by weight
- ppm 11.6 11.95 -
- Conradson carbon % by weight
- ppm basic nitrogen
- ppm 350 1015 - PT 50% TBP (° C) 470 475 - vanadium (ppm) 1.5 1.0 - nickel (ppm) 1.1 1.9
- the catalyst used is that described according to the invention.
- Test 1 2 3 Catalyst injection temperature (° C) 750 748 733 Charge injection temperature (° C) 233 250 250 Reactor outlet temperature (° C) 520 530 540 C / O report 4.9 5.4 7.8
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
- un réacteur, dans lequel la charge à traiter et le lit fluidisé du catalyseur se déplacent, de façon connue en soi, à co-courant et de haut en bas dans le réacteur ;
- des particules d'un catalyseur qui, à l'état d'équilibre, adsorbe à 150°C, sous une pression de 5mbars, une quantité de pyridine inférieure à 250 micromoles/g et, de préférence, inférieure à 50 micromoles/g, et dont la rétention de pyridine, après chauffage à 350°C sous vide, n'excède pas 20%.
- une étape d'alimentation en particules de catalyseur, au moins en partie régénéré, de la partie supérieure de la zone réactionnelle ;
- une étape d'introduction et de pulvérisation de la charge à traiter dans la partie supérieure de la zone réactionnelle, au-dessous de la zone d'alimentation en catalyseur ;
- une étape de circulation en contact mutuel, dans la zone réactionnelle, du catalyseur et de la charge à traiter, dans des conditions propres à permettre le craquage de la charge ;
- une étape de séparation, à la partie inférieure de la zone réactionnelle, du catalyseur désactivé et des produits de la réaction de craquage ;
- une étape de strippage du catalyseur désactivé ;
- une étape de régénération d'une partie au moins du catalyseur désactivé strippé, dans une zone de régénération ;
- une étape de recyclage du catalyseur régénéré à la partie supérieure de la zone réactionnelle ;
- et une étape de transfert des produits de craquage de la charge hydrocarbonée vers une zone de séparation de ces produits ;
Nature de la charge traitée | A (faiblement azotée) | B (très azotée) |
- densité (°API) | 17,7 | 18,5 |
- soufre (% en poids) | 2,42 | 0,9 |
- hydrogène(% en poids) | 11,6 | 11,95 |
- carbone Conradson (% en poids) | 1,92 | 1,08 |
- azote basique(ppm) | 350 | 1015 |
- PT 50% TBP (°C) | 470 | 475 |
- vanadium (ppm) | 1,5 | 1,0 |
- nickel (ppm) | 1,1 | 1,9 |
Essai | 1 | 2 | 3 |
Température d'injection du catalyseur (°C) | 750 | 748 | 733 |
Température d'injection de la charge (°C) | 233 | 250 | 250 |
Température de sortie du réacteur (°C) | 520 | 530 | 540 |
Rapport C/O | 4,9 | 5,4 | 7,8 |
Essai | 1 | 2 | 3 |
Gaz secs (% en poids) | 4,1 | 4,0 | 4,0 |
Coupe C3 + C4 (% en poids) | 13,4 | 10,0 | 12,1 |
Essence (% en poids) | 41,4 | 38,1 | 41,2 |
Diluant léger (% en poids) | 18,9 | 19,1 | 18,7 |
Diluant lourd (% en poids) | 17,3 | 23,7 | 17,4 |
Coke (% en poids) | 4,9 | 5,1 | 6,6 |
Conversion 220°C (% en poids) | 63,8 | 57,2 | 63,9 |
Conversion 350°C (% en poids) (C3+C4+Essence+diluant léger) | 73,7 | 67,2 | 72,0 |
Delta coke (% en poids) | 1,00 | 0,94 | 0,84 |
Essai | 1 | 2 | 3 |
Catalyseur | A | B | C |
Quantité de pyridine adsorbée à 150°C (micromole/g) | 550 | 200 | 45 |
Rétention de pyridine après chauffage à 350°C sous vide (%) | 40 | 20 | 10 |
Température d'injection du catalyseur (°C) | 737 | 733 | 720 |
Température d'injection de la charge (°C) | 250 | 250 | 250 |
Température sortie réacteur (°C) | 530 | 540 | 550 |
Rapport C/O | 6,2 | 7,8 | 11,5 |
Essai | 4 | 5 | 6 |
Gaz secs (% en poids) | 3,8 | 4,0 | 4,2 |
Coupe C3 + C4 (% en poids) | 10,8 | 12,1 | 14,3 |
Essence (% en poids) | 39,1 | 41,2 | 43,8 |
Diluant léger (% en poids) | 20,7 | 18,7 | 17,4 |
Diluant lourd (% en poids) | 20,0 | 17,4 | 11,8 |
Coke (% en poids) | 5,6 | 6,6 | 8,5 |
Conversion 220°C (% en poids) | 59,3 | 63,9 | 70,8 |
Conversion 350°C (C3+C4+essence+diluant léger) | 70,6 | 72,0 | 75,5 |
Delta coke (% en poids) | 0,90 | 0,84 | 0,74 |
Claims (5)
- Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques, dans une zone réactionnelle tubulaire, ce procédé comprenant une étape d'alimentation en particules de catalyseur, au moins en partie régénéré, de la partie supérieure de la zone réactionnelle,une étape d'introduction et de pulvérisation de la charge à traiter dans la partie supérieure de la zone réactionnelle, au-dessous de la zone d'alimentation en catalyseur, une étape de circulation à co-courant et en contact mutuel, dans la zone réactionnelle, du catalyseur et de la charge à traiter, dans des conditions propres à permettre le craquage de la charge, une étape de séparation, à la partie inférieure de la zone réactionnelle, du catalyseur désactivé et des produits de la réaction de craquage, une étape de strippage du catalyseur désactivé, une étape de régénération d'une partie au moins du catalyseur désactivé strippé, dans une zone de régénération, une étape de recyclage du catalyseur régénéré à la partie supérieure de la zone réactionnelle, et une étape de transfert des produits de craquage de la charge hydrocarbonée vers une zone de séparation de ces produits,
ce procédé étant caractérisé en ce que la charge et le catalyseur circulent de haut en bas et à co-courant dans la zone tubulaire et en ce que l'on utilise un catalyseur qui, à l'état d'équilibre , à 150 °C, sous une pression de 5 mbars, adsorbe une quantité de pyridine inférieure à 250 micromoles/g et, de préférence, inférieure à 50 micromoles/g, et dont la rétention de pyridine, après chauffage à 350°C sous vide, n'excède pas 20 %, et de préférence 10 %, de la quantité adsorbée à 150°C. - Procédé selon la revendication 1, caractérisé en ce que le rapport de la masse du catalyseur à la masse de la charge d'hydrocarbures est supérieur à 5 et, de préférence, compris entre 7 et 15.
- Procédé selon l'une des revendications 1 et 2, caractérisé en ce que, à la sortie de la zone réactionnelle, la vitesse de déplacement des particules de catalyseur est sensiblement égale à celle des gaz.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que, à la sortie de la zone réactionnelle, la vitesse de déplacement des particules de catalyseur est de l'ordre de 25 m/s.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le catalyseur comprend, en % en poids, au plus 30 % d'alumine, entre 15 et 40 % d'au moins une zéolithe, le complément à 100 % étant constitué au moins partiellement d'un diluant choisi dans le groupe constitué par le kaolin, les argiles basiques ou faiblement acides, telles que la sépiolite et la vermiculite, d'un liant à base de silice, et éventuellement d'un piège à métaux.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9400472A FR2715163B1 (fr) | 1994-01-18 | 1994-01-18 | Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques. |
FR9400472 | 1994-01-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0663434A1 EP0663434A1 (fr) | 1995-07-19 |
EP0663434B1 true EP0663434B1 (fr) | 1998-04-15 |
Family
ID=9459131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94403062A Expired - Lifetime EP0663434B1 (fr) | 1994-01-18 | 1994-12-30 | Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques |
Country Status (11)
Country | Link |
---|---|
US (1) | US5660716A (fr) |
EP (1) | EP0663434B1 (fr) |
JP (1) | JPH0834980A (fr) |
CN (1) | CN1050625C (fr) |
AT (1) | ATE165111T1 (fr) |
CA (1) | CA2140418A1 (fr) |
DE (1) | DE69409623T2 (fr) |
ES (1) | ES2116557T3 (fr) |
FR (1) | FR2715163B1 (fr) |
GR (1) | GR3026682T3 (fr) |
ZA (1) | ZA95399B (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2753453B1 (fr) * | 1996-09-18 | 1998-12-04 | Total Raffinage Distribution | Procede et dispositif de craquage catalytique en lit fluidise d'une charge d'hydrocarbures, mettant en oeuvre une zone de mise en contact amelioree |
FR2753454B1 (fr) * | 1996-09-18 | 1999-06-04 | Inst Francais Du Petrole | Procede et dispositif de craquage catalytique descendant mettant en oeuvre l'injection d'une charge sous un angle adequat sur un catalyseur conditionne |
JP3574555B2 (ja) * | 1996-11-15 | 2004-10-06 | 新日本石油株式会社 | 重質油の流動接触分解方法 |
JP3553311B2 (ja) * | 1997-03-14 | 2004-08-11 | 財団法人石油産業活性化センター | 炭化水素油の接触分解方法 |
IT1299034B1 (it) * | 1998-04-07 | 2000-02-07 | Agip Petroli | Procedimento per determinare il tenore in azoto dell'effluente del reattore di pretrattamento in un impianto di cracking catalitico |
FR2785907B1 (fr) * | 1998-11-13 | 2001-01-05 | Inst Francais Du Petrole | Procede et dispositif de craquage catalytique comprenant des reacteurs a ecoulements descendant et ascendant |
KR100322663B1 (ko) * | 2000-03-20 | 2002-02-07 | 곽호준 | 폐플라스틱을 이용한 휘발유, 등유 및 경유의 연속식제조방법 및 그 시스템 |
US20040206669A1 (en) * | 2001-06-08 | 2004-10-21 | Andrea De Rezende Pinho | Process for fluid catalytic cracking |
ES2187387B1 (es) * | 2001-11-20 | 2004-04-16 | Universidad Politecnica De Valencia. | Una unidad de ensayo para el estudio de catalizadores en reacciones de corto tiempo de contacto entre el catalizador y los reactivos. |
GB2403434B (en) | 2002-04-26 | 2005-09-14 | China Petroleum & Chemical | A downflow catalytic cracking reactor and its application |
CN100400141C (zh) * | 2005-10-14 | 2008-07-09 | 浙江大学 | 连续型变压流化吸附制取高纯气体的装置 |
AT502901B1 (de) * | 2005-10-31 | 2009-08-15 | Electrovac Ag | Vorrichtung zur wasserstoffherstellung |
US9944862B2 (en) * | 2013-11-18 | 2018-04-17 | Indian Oil Corporation Limited | Process and a system for enhancing liquid yield of heavy hydrocarbon feedstock |
CN108369162B (zh) * | 2015-12-16 | 2021-08-27 | 环球油品公司 | 用于催化剂取样的方法和装置 |
EP3575384A1 (fr) | 2018-05-28 | 2019-12-04 | Total Research & Technology Feluy | Procédé catalytique de solvants à deux phases pour la production de molécules mono-oxygénées à partir de matières premières biologiques comprenant des glucides et utilisation desdites molécules mono-oxygénées dans un processus de craquage catalytique fluide |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835029A (en) * | 1972-04-24 | 1974-09-10 | Phillips Petroleum Co | Downflow concurrent catalytic cracking |
US4411773A (en) * | 1980-12-18 | 1983-10-25 | Mobil Oil Corporation | Heat balance in FCC process and apparatus with downflow reactor riser |
US4412914A (en) * | 1981-08-10 | 1983-11-01 | Ashland Oil, Inc. | Endothermic removal of coke deposited on sorbent materials during carbo-metallic oil conversion |
JPS6032887A (ja) * | 1983-08-02 | 1985-02-20 | Asia Sekiyu Kk | ペンタン留分からlpgを選択的に製造する方法 |
DE3661989D1 (de) * | 1985-06-19 | 1989-03-09 | Inst Francais Du Petrole | Stabilized and dealuminated zeolite omega |
JPS624784A (ja) * | 1985-07-16 | 1987-01-10 | コンパニ−・フランセ−ズ・ド・ラフイナ−ジユ | 炭化水素仕込物の接触クラツキングのための方法および装置の改良 |
JPH07108980B2 (ja) * | 1985-10-18 | 1995-11-22 | アクゾ・ナ−ムロ−ゼ・フエンノ−トシヤツプ | 炭化水素原料のクラツキング方法 |
US4708786A (en) * | 1986-03-26 | 1987-11-24 | Union Oil Company Of California | Process for the catalytic cracking of nitrogen-containing feedstocks |
US4693808A (en) * | 1986-06-16 | 1987-09-15 | Shell Oil Company | Downflow fluidized catalytic cranking reactor process and apparatus with quick catalyst separation means in the bottom thereof |
JP2801686B2 (ja) * | 1989-10-16 | 1998-09-21 | 旭化成工業株式会社 | 炭化水素の接触転化法 |
AU643736B2 (en) * | 1989-12-29 | 1993-11-25 | Chevron Research And Technology Company | Dual component cracking catalyst and process for vanadium passivation and improved sulfur tolerance |
FR2659346B1 (fr) * | 1990-03-09 | 1994-04-29 | Inst Francais Du Petrole | Procede de craquage avec oligomerisation ou trimerisation des olefines presentes dans les effluents. |
FR2667609B1 (fr) * | 1990-10-03 | 1993-07-16 | Inst Francais Du Petrole | Procede et dispositif de craquage catalytique en lit fluide a courant descendant. |
FR2669037A1 (fr) * | 1990-11-08 | 1992-05-15 | Total France | Procede et dispositif d'homogeneisation, a l'interieur d'un reacteur tubulaire de craquage d'hydrocarbures a lit de particules solides fluidisees, du melange de ces particules et des vapeurs d'hydrocarbures a traiter. |
-
1994
- 1994-01-18 FR FR9400472A patent/FR2715163B1/fr not_active Expired - Fee Related
- 1994-12-30 EP EP94403062A patent/EP0663434B1/fr not_active Expired - Lifetime
- 1994-12-30 ES ES94403062T patent/ES2116557T3/es not_active Expired - Lifetime
- 1994-12-30 AT AT94403062T patent/ATE165111T1/de not_active IP Right Cessation
- 1994-12-30 DE DE69409623T patent/DE69409623T2/de not_active Expired - Fee Related
-
1995
- 1995-01-17 CN CN95101700A patent/CN1050625C/zh not_active Expired - Fee Related
- 1995-01-17 CA CA002140418A patent/CA2140418A1/fr not_active Abandoned
- 1995-01-18 US US08/374,236 patent/US5660716A/en not_active Expired - Fee Related
- 1995-01-18 JP JP7005825A patent/JPH0834980A/ja not_active Ceased
- 1995-01-18 ZA ZA95399A patent/ZA95399B/xx unknown
-
1998
- 1998-04-16 GR GR980400880T patent/GR3026682T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
JPH0834980A (ja) | 1996-02-06 |
US5660716A (en) | 1997-08-26 |
FR2715163B1 (fr) | 1996-04-05 |
CN1111274A (zh) | 1995-11-08 |
CA2140418A1 (fr) | 1995-07-19 |
ZA95399B (en) | 1995-09-26 |
FR2715163A1 (fr) | 1995-07-21 |
CN1050625C (zh) | 2000-03-22 |
DE69409623D1 (de) | 1998-05-20 |
EP0663434A1 (fr) | 1995-07-19 |
GR3026682T3 (en) | 1998-07-31 |
DE69409623T2 (de) | 1998-08-27 |
ES2116557T3 (es) | 1998-07-16 |
ATE165111T1 (de) | 1998-05-15 |
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