PROVEN TECHNOLOGIES OF BI-ZEOLITE FCC CATALYSTS IN JSC "GAZPROM NEFT", EXPERIENCE OF MANUFACTURE AND USE. Газпром нефть. Russia & CIS BBTC 2015

Transcription

1 PROVEN TECHNOLOGIES OF BI-ZEOLITE FCC CATALYSTS IN JSC "GAZPROM NEFT", Russia & CIS BBTC 2015 EXPERIENCE OF MANUFACTURE AND USE 1

2 CATALYST MANUFACTURING FACILITY AT JSC "GAZPROMNEFT-OMSK REFINERY" - Facility for manufacture of microspheroidal zeolite-containing FCC catalyst has been in operation within the refinery since The achieved capacity in production of microspheroidal zeolite catalyst is 3 thousand tons per year - Microspheroidal zeolite catalysts of in-house manufacture are used at Gazprom Neft in three oil refining units with total capacity of 6 million tons/year on feed. - Manufacturing process for FCC catalysts was developed in close cooperation with HYDROCARBON PROCESSING INSTITUTE (SIBERIAN BRANCH OF RUSSIAN ACADEMY OF SCIENCES) Following new requirements to motor fuels the technology for production of bi-zeolite FCC catalysts featuring a capability to boost octane characteristics in cracked gasoline and to increase olefins content in PP and BB streams was implemented at the JSC "Gazpromneft-Omsk Refinery" Catalyst Manufacturing Facility in the years

3 HYDROCARBONS PROCESSING INSTITUTE (SIBERIAN BRANCH OF RUSSIAN ACADEMY OF SCIENCES) - OMSK REFINERY'S STRATEGIC PARTNER More than 25 years of cooperation between SB RAS Hydrocarbons Processing Institute and Omsk Refinery in the field of development, deployment and support of FCC catalysts; Availability of advanced experimental facilities and laboratory-scaled plants for research on FCC catalysts; Jointly developed local technology for manufacture of catalysts and additives thereto (with grant of 6 patents); Experiences gained from technical support during operation of the FCC catalysts in process units at Omsk Refinery and Moscow Refinery; Onward long-term joint work under General Agreement on Cooperation with HPI SB RAS for the years of is continued. Over the last 5 years the following state-of-the-art manufacturing technologies have been commercialized: - bi-zeolite catalysts based on ultrastable HREY zeolite (in 2010); - bi-zeolite catalysts based on ultrastable HREY zeolite featuring lowered Rare-Earths content (in 2013). 3

4 BI-ZEOLITE CATALYSTS TECHNOLOGY Y zeolite ZSM-5 zeolite Bi-zeolite FCC catalysts increased olefins content in the gaseous cracked products, octane boost for the gasoline fraction. Octane booster additive to FCC catalyst improved octane characteristics of the gasoline fraction when used with monozeolite catalyst. Technology of bi-zeolite catalysts based on ultrastable HREY zeolite and ZSM-5 zeolite allows to improve octane characteristics of cracked gasoline while retaining its yield. 4

5 COMPARISON DATA ON MICROACTIVITY OF JSC GAZPROMNEFT-OMSK REFINERY'S CATALYSTS According to microactivity tests the proven bi-zeolite catalysts demonstrate higher activity: they increase yields of gasoline and gaseous products. Mono-zeolite catalyst* Bi-zeolite catalyst* Bi-zeolite catalyst with lowered RE content* Conversion, wt. % Gasoline yield, wt. % Dry gas yield, wt. % PP/BB fraction yield, wt. % 6.8 / / / 14.7 Yield of C 2 - C 4 olefins, wt. % Light gas oil yield, wt. % Heavy gas oil yield, wt. % Coke yield, wt. % * Laboratory data on microactivity of catalysts (ASTM ) 5

6 OPERATING EXPERIENCE WITH BI-ZEOLITE CATALYSTS (GRADES A & B) Operation results from with bi-zeolite catalysts of Grades A & B in FCCU and КТ-1/1 Complex (Unit 200) at JSC "Gazpromneft-Omsk Refinery" did confirm effectiveness of the technology: Section 200 KT-1/1 Complex Grade А Bi-zeolite Catalyst Gasoline Yield up to 55% wt.; RON Increased by 1.5 points; Zeolite ZSM-5 Filler FCCU Grade B Bi-zeolite Catalyst Gasoline Yield up to 50% wt.; RON Increased by 1,0 point Y zeolite Binder 6

7 Temperature of zeolite destruction, o C Conversion, wt. % TECHNOLOGY OF BI-ZEOLITE CATALYSTS WITH LOWERED RE CONTENT ,0 zeolite + matrix , zeolite 75, RE content in zeolite, wt. % 70,0 0,0 0,5 1,0 1,5 2,0 RE content in catalyst, wt. % Effect of RE content on FCC catalysts performance: + increase in activity due to formation of Bronsted acid sites in the zeolite structure; + improved thermal stability of zeolitic component and maintained high activity of equilibrium catalyst; - more intensive hydrogen transfer reactions, which downgrades octane properties of cracked gasoline. 7

8 TECHNOLOGY OF BI-ZEOLITE CATALYSTS WITH LOWERED RE CONTENT Principles of Manufacture Technology Relevant to Bi-zeolite Catalysts with Lowered RE Content: - Increased content of ultrastable HREY zeolite in the composition increased catalyst activity; - Decreased RE content in zeolite and, consequently, decrease of RE content in the catalyst by 1.5 times improved octane characteristics of naphtha fraction; - Modified sequence of H + and RE ion exchange in zeolite increased thermal stability of the catalyst. Isobutane Content of Butane-Butadiene Fraction, % wt 55,0 50,0 45,0 40,0 35,0 0,0 0,5 1,0 1,5 2,0 Catalyst RE Content, % wt Lowering catalyst RE content decreases activity of hydrogen transfer reactions, which, in turn, is reflected by decreased isobutane content of butane-butadiene fraction and increased butylene content of butane-butadiene fraction, improved octane characteristics of the gasoline fraction. 8

9 Microactivity Gasoline Yield, % wt MICROACTIVITY DATA ON BI-ZEOLITE CATALYSTS WITH LOWERED RE CONTENT Laboratory data on microactivity show that microactivity of equilibrium catalyst increased up to 81.5 and gasoline yield increased up 47.5% wt during catalyst changeout on the Section 200 of Complex KT-1/1. 82,0 48,0 81,0 80,0 Grade M 47,5 47,0 46,5 Grade M 79,0 46,0 78,0 Grade A 45,5 45,0 77,0 76,0 44,5 44,0 Grade A 75,0 Varied Degrees of Catalyst Replacement in the System 43,5 Varied Degrees of Catalyst Replacement in the System Laboratory data on catalyst microactivity (ASTM ) 9

10 OPERATING EXPERIENCE RELEVANT TO BI-ZEOLITE CATALYSTS WITH LOWERED RE CONTENT (GRADES M and N) Results obtained using bi-zeolite catalysts with lowered RE content (grades M and N) at the FCCU and Section 200 of Complex KT-1/1 of JSC Gazpromneft-Omsk Refinery ( ) confirmed efficiency of the technology: Section 200 of KT-1/1 Complex Grade M Bi-zeolite Catalyst Gasoline Yield up to 55% wt RON Increased by 1.5 points Propylene in Propane-Propylene Fraction up to 86% wt Butylenes in Butane-Butadiene Fraction up to 53% wt Zeolite ZSM-5 Filler FCCU Grade N Bi-zeolite Catalyst Gasoline Yield up to 50% wt RON Increased by 1.5 points Propylene in Propane-Propylene Fraction up to 83% wt Butylenes in Butane-Butadiene Fraction up to 55% wt Y zeolite Binder 10

11 COMPARATIVE TESTS OF CATALYST MANUFACTURED BY JSC "GAZPROMNEFT- OMSK REFINERY" VS COMPETING CATALYST (PERFORMED BY CPERI, GREECE) Comparative tests of a catalyst manufactured by JSC Gazpromneft-Omsk Refinery vs a competing catalyst were performed on an FCC pilot plant in CPERI (Greece) in PROPERTY COMPETING CATALYST GRADE M CATALYST CONVERSION GASOLINE YIELD COKE YIELD LIGHT GASOIL YIELD LPG YIELD PROPANE-PROPYLENE FRACTION, Propylene in PROPANE-PROPYLENE FRACTION BUTANE-BUTYLENE FRACTION, ΣС 4 olefins in BUTANE-BUTYLENE FRACTION 7.1 / / / / 0.6 DRY GAS YIELD Results of tests performed at the FCC pilot unit indicate that the catalyst manufactured by JSC Gazpromneft- Omsk Refinery as compared to a competing catalyst has: - an increased yield of gasoline fraction (by 4 relative percent) - a decreased yield of dry gas, which is a non-desired FCC product (by 6 relative percent) 11

12 MICROACTIVITY DATA RELEVANT TO REPLACEMENT OF CATALYST SYSTEM OF FCCU G AT MOSCOW REFINERY WITH GRADE M BI-ZEOLITE CATALYST Gasoline Yield, % wt Grade M catalyst manufactured by JSC Gazpromneft-Omsk Refinery has been in use at the FCC Unit G of JSC Gazpromneft-Moscow Refinery since Laboratory data show that gasoline yield increased by about 2 2.5% wt with system replacement rate of about 50%. 47,0 46,5 46,6 % 46,0 45,5 45,0 44,5 44,1 % 44,0 43,5 43,0 2 мар апр июн июл сен ноя дек фев 6 апр 6.04 Выход Gasoline бензина, Yield, % 12

13 FUTURE FCC BI-ZEOLITE CATALYSTS EXISTING BI-ZEOLITE CATALYST FUTURE BI-ZEOLITE CATALYST OF OCTANE SERIES PRODUCT YIELD % wt PRODUCT YIELD % wt GASOLINE YIELD 55.0 COKE YIELD 4.3 GASOLINE YIELD 55.0 COKE YIELD 4.4 LGO YIELD 11.4 LGO YIELD 8.1 LPG YIELD 18.7 LPG YIELD 22.5 DRY GAS YIELD 2.1 DRY GAS YIELD 3.2 HGO YIELD 8.5 HGO YIELD

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