WO2016157015A1 - Procédé de craquage catalytique en lit fluide - Google Patents

Procédé de craquage catalytique en lit fluide Download PDF

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Publication number
WO2016157015A1
WO2016157015A1 PCT/IB2016/051537 IB2016051537W WO2016157015A1 WO 2016157015 A1 WO2016157015 A1 WO 2016157015A1 IB 2016051537 W IB2016051537 W IB 2016051537W WO 2016157015 A1 WO2016157015 A1 WO 2016157015A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
zsm
group
sapo
fcc
Prior art date
Application number
PCT/IB2016/051537
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 EP16771477.3A priority Critical patent/EP3277779A4/fr
Publication of WO2016157015A1 publication Critical patent/WO2016157015A1/fr

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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
    • 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
    • C10G2400/20—C2-C4 olefins

Definitions

  • the present disclosure relates to a fluid catalytic cracking (FCC) process.
  • FCC fluid catalytic cracking
  • Propylene is an unsaturated organic compound having the chemical formula C33 ⁇ 4. It is the second most important starting product in the petrochemical industry after ethylene. It is used as a raw material for a wide variety of products. Nearly two-third of the demand for propylene is from plastic polypropylene manufacturers.
  • Propylene is obtained as a component of natural gas during oil and gas extraction.
  • propylene can also be produced by catalytic cracking of the leftover of vacuum distillation of crude oil, i.e. Vacuum Gas Oil (VGO).
  • VGO Vacuum Gas Oil
  • Other competing products obtained during the catalytic cracking of VGO include gaseous olefins, light cycle oil (LCO), gasoline and allied products.
  • a fluid catalytic cracking (FCC) process comprises contacting a feedstock containing vacuum gas oil (VGO) with a catalyst composition in an FCC reactor at pre-determined conditions to obtain a resultant product comprising 7 % to 16 % propylene.
  • the catalyst composition comprises an FCC catalyst and an additive.
  • the additive used in the present disclosure comprises at least one zeolite loaded with at least one Group V element in an amount ranging from 0.1 % to 5 % of the total weight of the zeolite; and at least one metal promoter in an amount ranging from 1 % to 3 % of the total weight of the zeolite.
  • at least one excipient in a ratio of 1 : 1 to 2.5:1 with respect to the zeolite is also present in the additive.
  • the Group V element is phosphorus
  • the metal promoter is an element selected from the group consisting of magnesium, calcium, strontium, barium, copper, iron, nickel, zinc, gallium, indium, thallium and any of the lanthanide series metal.
  • the present disclosure provides an FCC process using a catalyst composition resulting in a product having 7 % to 16 % propylene.
  • the process includes the step of contacting a feedstock containing vacuum gas oil (VGO) with a catalyst composition in an FCC reactor at a pre-determined feed flow rate, a pre-determined weight hourly space velocity, a pre-determined temperature and a pre-determined pressure to obtain a product having 7 % to 16 % propylene.
  • VGO vacuum gas oil
  • the catalyst composition includes an FCC catalyst and an additive.
  • the FCC catalyst is FCC-e-Cat.
  • the ratio of the FCC catalyst to the additive is in the range of 90: 10 to 95:5, preferably, 93:7.
  • the additive used in the catalyst composition comprises:
  • the Group V element is phosphorus.
  • the metal promoter is at least one element selected from the group consisting of magnesium, calcium, strontium, barium, copper, iron, nickel, zinc, gallium, indium, thallium and any of the lanthanide series metals.
  • the metal promoter is at least one element selected from the group consisting of magnesium, calcium, strontium and barium.
  • the metal promoter is a combination of zinc and gallium.
  • 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, SAPO-17, SAPO-18, SAPO-34, SAPO-44, MCM- 22, an intergrowth of ZSM-11, zeolite Y and zeolite Beta.
  • an excipient in a ratio of 1.1 to 2.5:1 with respect to the zeolite is also present in the catalyst composition of the present disclosure.
  • the excipient in accordance with the present disclosure is at least one selected from the group consisting of a binder, a filler and a matrix.
  • the binder is pseudoboehmite.
  • the filler is alpha alumina. In an embodiment of the present disclosure, the matrix is silica.
  • the process in accordance with the present disclosure is carried out in the temperature range of 500 °C to 550 °C and pressure range of 0.5 atm to 2 atm.
  • An inert gas such as, nitrogen is used as a carrier gas.
  • the feed flow rate is in the range of 5 ML/h to 7 ML/h and the weight hourly space velocity (WHSV) is in the range of 5.2 h "1 to 5.3 h "1 .
  • WHSV weight hourly space velocity
  • the liquid products obtained were weighed using an integrated balance.
  • the liquid products were analyzed by Simulated Distillation of Petroleum Products (LTSIMDIST) and Paraffins, Iso-paraffins, Olefins Naphthenes and Aromatics (PIONA) analyzer equipped with a Prefractionator.
  • LTSIMDIST Simulated Distillation of Petroleum Products
  • PIONA Paraffins, Iso-paraffins, Olefins Naphthenes and Aromatics
  • Table-2 summarizes the amount of the different products obtained when the reaction was carried out using only the FCC catalyst (without the additive).
  • the yield of propylene using the FCC catalyst (having a composition as mentioned hereinabove) is 6.2 %, which is lower as compared to that of the yields of the other products obtained.
  • the ratio of the FCC catalyst to the additive is 93:7, from experiments 2 onwards. Experiments 2 to 6:
  • ZSM-5 loaded with phosphorus along with metal promoters (Group II metals) magnesium, calcium, strontium and barium in varying amounts were used as the additive along with the FCC catalyst as given in Table-5 below.
  • Five grams of dried zeolite was mixed with the solution of nitrate of metal promoter (magnesium, calcium, strontium and barium) and orthophosphoric acid.
  • the slurry obtained was stirred at room temperature for 3 hours. After 3 hours, the slurry was evaporated in a rotary evaporator that was maintained at 75 °C under vacuum.
  • the dried sample obtained was calcined at 550 °C for 5 hours.
  • the calcined sample obtained was then ground into fine powder and sieved to obtain particles in size ranging from 600 ⁇ to 800 ⁇ . Thereafter, the fine powder was pressed into pellets and used along with the FCC catalyst, as the catalyst composition.
  • the yield of propylene was highest, when calcium (see experiment 8) was used in the catalyst composition and the yield of propylene was least when barium (see experiment 10) was used in the catalyst composition.
  • the catalyst compositions of experiments 11 to 13 were prepared similarly as in experiments 7 to 10, except that instead of Group II metal salts, salts of nickel, iron and copper as the Metal Promoters were used, as given in Table-7 below.
  • Experiment 14 was similar to experiments 11 to 13, except that instead of nickel, iron and copper, a mixture of zinc and gallium was used as metal promoter 1 and metal promoter 2. The details of the additive are given below in Table-9.
  • the catalyst compositions of experiments 15 to 16 were prepared similar to experiments 11 to 13, except that instead of nickel, iron and copper; lanthanum and cerium were used as the metal promoters as given below in Table- 11.
  • extrudates of the additives were formed.
  • H-ZSM-5 having S1O2/AI2O 3 ratio of 23 was loaded with 1 % to 14 wt % of phosphorus.
  • the loading of the phosphorus was carried as previously mentioned in the experiments 2 to 6.
  • the phosphorus loaded zeolite was mixed thoroughly with 3.5 g of pseudoboehmite as the binder, for 3 hours to achieve a composite containing pseudoboehmite and zeolite in a ratio of 1.5: 1.
  • Fifty percent solution of nitric acid in water was added to the composite containing pseudoboehmite and zeolite, under stirring.
  • the final material obtained was extruded into 2 mm extrudates.
  • the extrudates were calcined at a temperature of 700 °C for 5 hours and then used as the additive along with the FCC catalyst as the catalyst composition.
  • Table- 13 gives the amount of different products obtained by using the extrudates containing different amount of phosphorus.
  • Table- 15 below provides the amount of different products obtained when using the catalyst composition as given in experiments 23 and 24.
  • Cat/oil the catalyst to the feedstock weight ratio
  • the fluid catalytic cracking process of the present disclosure results in a product having a high propylene yield.
  • Use of calcium and iron in the catalyst composition gives the highest propylene yield (15.1 %). It is also found that addition of phosphorus (0.1 % to 5 %) in the catalyst composition gives high propylene yields, however, more than 5 % phosphorous in the catalyst composition, results in decreased propylene yield. This may be due to the higher suppression/moderation of acid sites, thereby reducing the number and the strength of the acid sites.

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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de craquage catalytique en lit fluide. Le procédé de la présente invention consiste à mettre en contact une charge contenant du gasoil sous vide (VGO) avec une composition de catalyseur dans un réacteur de craquage catalytique en lit fluide (FCC), avec des paramètres de réaction prédéterminés, pour obtenir un produit résultant ayant un rendement élevé de propylène.
PCT/IB2016/051537 2015-03-31 2016-03-18 Procédé de craquage catalytique en lit fluide WO2016157015A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16771477.3A EP3277779A4 (fr) 2015-03-31 2016-03-18 Procédé de craquage catalytique en lit fluide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1340MU2015 2015-03-31
IN1340/MUM/2015 2015-03-31

Publications (1)

Publication Number Publication Date
WO2016157015A1 true WO2016157015A1 (fr) 2016-10-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2016/051537 WO2016157015A1 (fr) 2015-03-31 2016-03-18 Procédé de craquage catalytique en lit fluide

Country Status (2)

Country Link
EP (1) EP3277779A4 (fr)
WO (1) WO2016157015A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128325A1 (en) * 2006-11-07 2008-06-05 Saudi Arabian Oil Company Advanced control of severe fluid catalytic cracking process for maximizing propylene production from petroleum feedstock
US20130023710A1 (en) * 2011-07-21 2013-01-24 Reliance Industries Limited Fcc catalyst additive and a method for its preparation

Family Cites Families (5)

* 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
TWI259106B (en) * 2003-06-30 2006-08-01 China Petrochemical Technology Catalyst conversion process for increasing yield of light olefins
BRPI0602678B1 (pt) * 2006-07-14 2015-09-01 Petroleo Brasileiro Sa Aditivo para maximização de glp e propeno adequado a operação da unidade de craqueamento catalítico fluido em baixa severidade e processo de preparo do mesmo
AU2012202584B2 (en) * 2011-05-11 2013-10-17 Bharat Petroleum Corporation Limited A multifunctional catalyst additive composition and process of preparation thereof
EP2729553A4 (fr) * 2011-07-06 2015-04-29 Reliance Ind Ltd Procédé et composition de catalyseur/additif pour la réduction de la quantité de combustible gazeux produit dans un procédé de craquage catalytique fluide (fcc)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128325A1 (en) * 2006-11-07 2008-06-05 Saudi Arabian Oil Company Advanced control of severe fluid catalytic cracking process for maximizing propylene production from petroleum feedstock
US20130023710A1 (en) * 2011-07-21 2013-01-24 Reliance Industries Limited Fcc catalyst additive and a method for its preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3277779A4 *

Also Published As

Publication number Publication date
EP3277779A4 (fr) 2018-09-26
EP3277779A1 (fr) 2018-02-07

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