WO2016157014A1 - Procédé de craquage catalytique de fluide pour la production de naphta direct craqué à faible teneur en oléfines - Google Patents

Procédé de craquage catalytique de fluide pour la production de naphta direct craqué à faible teneur en oléfines Download PDF

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Publication number
WO2016157014A1
WO2016157014A1 PCT/IB2016/051536 IB2016051536W WO2016157014A1 WO 2016157014 A1 WO2016157014 A1 WO 2016157014A1 IB 2016051536 W IB2016051536 W IB 2016051536W WO 2016157014 A1 WO2016157014 A1 WO 2016157014A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
zsm
rare earth
earth metal
additive
Prior art date
Application number
PCT/IB2016/051536
Other languages
English (en)
Inventor
Ravishankar Raman
Venkata Chalapathi Rao PEDDY
Venkateswarlu Choudary Nettem
Original Assignee
Hindustan Petroleum Corporation Limited
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 Hindustan Petroleum Corporation Limited filed Critical Hindustan Petroleum Corporation Limited
Priority to EP16771476.5A priority Critical patent/EP3277777A4/fr
Publication of WO2016157014A1 publication Critical patent/WO2016157014A1/fr

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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
    • 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
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • 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
    • C10G2300/70—Catalyst aspects
    • 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

Definitions

  • the present disclosure relates to a fluid catalytic cracking process for preparing cracked run naphtha with low olefin content.
  • Vacuum distillation of crude oil results in a variety of petroleum products with a wide range of molecular weights.
  • the heavier hydrocarbon fractions, usually, the left-overs from vacuum distillation process are converted and refined into more valuable lower molecular weight hydrocarbons with the help of a fluid catalytic cracking (FCC) unit.
  • FCC fluid catalytic cracking
  • Vacuum Gas Oil (VGO), a component of the heavy hydrocarbons, is subjected to cracking in an FCC unit resulting in cracked run naphtha (CRN), fuel oil and off gas as the end-products.
  • the cracked run naphtha (CRN) produced by the cracking of VGO typically, contains around 45-55% liquid olefins. When these liquid olefins come in contact with dissolved oxygen, they form hydroperoxides as immediate products, which undergo further reactions to form insoluble oxidized species.
  • These oxidized species that include peroxides, aldehydes, acids, ketones as well as components with molecular weights 200-600 g/mol are commonly referred to as gum.
  • CN 102794195 A suggests one such catalyst.
  • the catalyst is prepared from the following raw materials in percentage by mass: 25-50% of aluminum trioxide hydrate on the basis of AI2O 3 , 1-5% of P on the basis of P2O5, 0.1-5% of rare-earth oxide on the basis of (rare-eartff Os and 50-75% of modified shape-selective molecular sieve.
  • the catalyst has the advantages of high gasoline octane number, low olefin content, high gasoline yield and low dry gas yield.
  • the rare earth component in the cracking catalyst restricts the formation of liquid olefins. However, these catalysts show a tendency to lose the expensive rare earth metal component due to which the catalyst activity cannot be recovered. The catalyst is required to be replenished frequently.
  • An object of the present disclosure is to provide an FCC process to produce cracked run naphtha with low olefin content. Another object of the present disclosure is to provide an FCC process that makes use of a non-rare earth metal promoter based catalyst composition.
  • Still another object of the present disclosure is to provide an FCC process that makes use of a non-rare earth metal promoter that has a long service life
  • the disclosure relates to a fluid catalytic cracking (FCC) process for the production of cracked run naphtha with low olefin content.
  • FCC fluid catalytic cracking
  • Vacuum gas oil is subjected to a catalytic cracking process in a fixed bed down-flow reactor unit in the presence of a catalyst composition comprising a FCC equilibrated catalyst (ECAT) and an additive, wherein the additive comprises a zeolite and at least one non-rare earth metal promoter selected from the group consisting of Zn and Ga.
  • the resultant product containing cracked run naphtha has a liquid olefinic content less than 45 wt%.
  • the disclosure relates to a fluid catalytic cracking (FCC) process for production of cracked run naphtha with low olefin content.
  • FCC fluid catalytic cracking
  • the disclosure relates to a process that makes use of an additive in combination with an FCC equilibrated catalyst (ECAT), the mixture thereof reduces the concentration of olefin in the cracked run naphtha prepared while processing a vacuum gas oil feedstock.
  • ECAT FCC equilibrated catalyst
  • an FCC process for obtaining cracked run naphtha with low olefin content from vacuum gas oil is disclosed.
  • the catalytic reactor which is a fixed bed down-flow reactor, is maintained at a pressure in the range of 1 atm to 2 atm and temperature in the range of 400 °C to 700 °C.
  • the feedstock is vacuum gas oil (VGO) obtained as a left-over from vacuum distillation of crude oil.
  • the feedstock in-flow is maintained at 6 ml/hr and a weight hourly space velocity (WHSV) of 9 hr "1 .
  • An inert gas a non-limiting example of which is nitrogen, is selected as a carrier gas.
  • the VGO is contacted with a catalyst composition comprising an FCC equilibrated catalyst (ECAT) and an additive comprising a zeolite and at least one non-rare earth metal promoter, to obtain a resultant product containing cracked run naphtha having a liquid olefinic content less than 45 wt%.
  • the zeolite is at least one selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-48, ZSM-57, SAPO-5, SAPO-11, SAP017, SAPO-18, SAPO-34, SAPO-44, MCM-22, ZSM-Y and Beta.
  • the non-rare earth metal promoter is at least one selected from a group consisting of Zn and Ga.
  • the precursor for the non-rare earth metal promoter is a salt of the non-rare earth metal.
  • the precursor of the non-rare earth metal promoter is a nitrate salt of the non-rare earth metal.
  • the FCC equilibrated catalyst, ECAT is present in the range of 80 wt% to 93 wt% of the catalyst composition and the additive is present in the range of 7 wt% to 20 wt% of the catalyst composition.
  • the non-rare earth metal promoter in the additive used in the process is in the range of 1 wt% to 10 wt% of the additive.
  • Example 1 A comparative example for FCC of VGO with 100% conventional catalyst - FCC equilibrated catalyst (ECAT)
  • the FCC reaction was carried out using VGO as the feedstock.
  • the reaction was carried out in a fixed bed down-flow reactor unit with a high pressure liquid gas separator.
  • the reaction parameters are listed in Table 1.
  • the catalyst used was an equilibrated catalyst 100% FCC equilibrated catalyst (EC AT).
  • the liquid products obtained were weighed using an integrated balance.
  • the liquid products were analyzed by SIMDIST (Simulated Distillation) and PIONA (paraffins, isoparaffins, olefins, naphthenes and aromatics) analyzers equipped with a pre-fractionator.
  • Table 1 FCC Reaction Parameters
  • Example 2 Catalytic Cracking of VGO with 93% FCC ECAT and 7% P-ZSM-5 (Comparative Example)
  • ZSM-5 with Si/Al ratio of 23 was loaded with 1% phosphorus in the following manner. 10 g of ZSM-5 sample was mixed with 2.65 g ortho phosphoric acid solution and the resultant slurry was agitated thoroughly at 25 °C for 3 hours for allowing phosphorus to impregnate the zeolite. The resulting slurry was then evaporated in a rotary evaporator maintained at 75 °C under vacuum to obtain a dried mass which was calcined at 550 °C for 5 hours to result in a calcined mass.
  • Example 1 The calcined mass was ground into fine powder, sieved to obtain particles having particle sizes ranging from 600 ⁇ to 800 ⁇ and pressed into pellets to obtain the final sample P-ZSM-5 (phosphorus impregnated ZSM-5). 93% of the catalyst used in Example 1 and 7% of P-ZSM-5 were mixed and the mixture was used as the catalyst in the present example and the catalytic cracking was carried out in a manner similar to Example 1. The resultant products obtained in Example 2 and their percentage composition are discussed in Tables 4 and 5.
  • Table 2 shows the composition of the samples as prepared in Example 1 and Example 2.
  • Table 2 FCC equilibrated catalyst (ECAT) and a composite of ECAT and ZSM-5 with P loading
  • Examples 3-6 were carried out using the process and catalyst composition in accordance with the present disclosure.
  • ZSM-5 with Si/Al molar ratio of 23 was loaded with individual or a mixture of non-rare earth metal promoters, Zn and Ga as listed in Table 3.
  • the nitrate salts of the metals were used as the precursor. 1.186 g of metal salts were dissolved in 30 ml of water and made into their respective solutions. 10 g of ZSM-5 was added to this metallic salt solution and was made into a slurry. The slurry was agitated at 75 °C for 3 hours for allowing the non-rare earth metal promoters to impregnate into ZSM-5.
  • the non-rare earth metal promoter impregnated ZSM-5 slurry was evaporated in a rotary evaporator maintained at 75 °C under vacuum to obtain a dried mass which was calcined at 550 °C for 5 hours to result in a calcined mass.
  • the calcined mass was ground into fine powder, sieved to obtain particles having particle sizes ranging from 600 ⁇ to 800 ⁇ and pressed into pellets to obtain the final sample M-ZSM-5 (non-rare earth metal promoter impregnated ZSM-5).
  • 93% of the catalyst used in Example 1 and 7% of M-ZSM-5 were mixed and the mixture was used as the catalyst in the present example and the FCC was carried out in a manner similar to Example 1.
  • the resultant products obtained in Examples 3-6 and their percentage composition are discussed in Tables 4 and 5.
  • Table 3 Catalyst compositions used in Examples 3-6 with their metal loadings
  • Table 4 Composition of the CRN from Example 1 and Examples 2-6
  • n-Olefins (wt%) 11.9 12.0 10.0 17.4 12.5 12.6
  • the process of the current disclosure employing a catalyst composition comprising a non- rare earth metal promoter, is successful in achieving the desired results, i.e. an olefin content less than that obtained by FCC equilibrated catalyst, ECAT and ECAT with a phosphorus loaded additive.

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

Abstract

La présente invention concerne un procédé de craquage catalytique de gazole sous vide pour la préparation de naphta direct craqué à faible teneur en oléfines. Le procédé fait usage d'une composition de catalyseur qui est un mélange d'un catalyseur équilibré FCC et d'un additif comprenant une zéolithe et au moins un promoteur de métal non des terres rares qui est sélectionné parmi Zn et Ga. Le procédé est couronné de succès en ce qui concerne l'obtention de teneur en oléfines inférieure dans le naphta direct craqué résultant par rapport à un catalyseur de base FCC ECAT.
PCT/IB2016/051536 2015-03-31 2016-03-18 Procédé de craquage catalytique de fluide pour la production de naphta direct craqué à faible teneur en oléfines WO2016157014A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16771476.5A EP3277777A4 (fr) 2015-03-31 2016-03-18 Procédé de craquage catalytique de fluide pour la production de naphta direct craqué à faible teneur en oléfines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1326/MUM/2015 2015-03-31
IN1326MU2015 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016157014A1 true WO2016157014A1 (fr) 2016-10-06

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830728A (en) * 1986-09-03 1989-05-16 Mobil Oil Corporation Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture
EP1112336B1 (fr) * 1998-05-05 2004-06-16 ExxonMobil Chemical Patents Inc. Procede relatif a la production selective d'olefines c 3? dans un processus de craquage catalytique fluide
US20060260981A1 (en) * 2005-05-19 2006-11-23 Gosling Christopher D Integrated fluid catalytic cracking process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4834867A (en) * 1986-08-25 1989-05-30 W. R. Grace & Co.-Conn. A process for producing gasoline under FCC conditions employing a cracking catalysts having aromatic selectivity
US4927522A (en) * 1988-12-30 1990-05-22 Mobil Oil Corporation Multiple feed point catalytic cracking process using elutriable catalyst mixture
US6852214B1 (en) * 1998-08-31 2005-02-08 Mobil Oil Corporation Gasoline sulfur reduction in fluid catalytic cracking

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830728A (en) * 1986-09-03 1989-05-16 Mobil Oil Corporation Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture
EP1112336B1 (fr) * 1998-05-05 2004-06-16 ExxonMobil Chemical Patents Inc. Procede relatif a la production selective d'olefines c 3? dans un processus de craquage catalytique fluide
US20060260981A1 (en) * 2005-05-19 2006-11-23 Gosling Christopher D Integrated fluid catalytic cracking process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3277777A4 *

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Publication number Publication date
EP3277777A4 (fr) 2018-09-26
EP3277777A1 (fr) 2018-02-07

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