PBE-1 zeolite based

Proprietary catalyst

Polimeri EuropaPolimeri Europa – the petrochemicalcompany of Eni – manages the productionand marketing of Basic Chemicals,Polyethylene, Elastomers and Styrenics.

With its 17 production sites throughoutEurope and a widespread sales network,Polimeri Europa can present itself to the intermediates, thermoplastic resinsand elastomers market as a sound andcomprehensive supplier whose key strengthis its integration. From raw materials toproduction plants, from research laboratoriesto technology, through to the interface withthe market which can turn to a single sourcewith the certainty of finding solutions to itsrequirements not only in terms of products,but also in terms of assistance and service. Thanks to the definition of the e-commerceand the logistic portal express, Polimeri Europacan offer to its customers the opportunity to use their tailored made e-shopping and logistics. Saving time and money.

On the basis of its first hand experience,Polimeri Europa can also license its proprietaryproduction technologies aiming to satisfy the even more specific customers needs.

Polimeri Europa’s commitment to quality,improvement and innovation continues, as does its pledge to promote sustainablegrowth with regard to the community and the environment.

POLIMERI EUROPA CATALYSTS NOW AVAILABLE FOR LICENSING AND SALES

LicensingProprietary process technologiesPhenol and derivativesPBE-1 Zeolite catalyst based Cumene *Phenol, Acetone, Alphamethylstyrene *Isopropyl Alcohol Acetone hydrogenation *Isopropyl Alcohol to Cumene *PBE-1 Zeolite catalystTS-1 Titanium silicalite catalyst based AmmoximationDMC and derivativesDimethylcarbonatevia Carbon Monoxide and Methanol *Dimethylcarbonate / Diphenylcarbonate *PolyethyleneLDPEHDPEEVAStyrenicsPBE-1 and PBE-2 Zeolite catalyst based EthylbenzeneStyrene monomerGPPSHIPSEPSABS continuous mass polymerizationSANElastomerse-SBRs-SBRSBS / SB / LCBRPolybutadiene

Proprietary catalyst technologiesTitanium silicalitePBE-1 ZeolitePBE-2 Zeolite

* Co-licensing in cooperation with Lummus Technology

General informationPBE-1 catalyst is a high-performancecomposite material specifically designed for industrial cumene and ethylbenzenesynthesis in fixed bed reactors. PBE-1 catalyst is the result of long-termresearch within Eni associated with direct Polimeri Europa (former EniChem)experience in both cumene and ethylbenzeneindustrial production.

ApplicationsPBE-1 is the catalyst of choice in zeolitebased Polimeri Europa Cumene andEthylbenzene Technologies through benzenealkylation with respectively propylene andethylene. Benzene is first alkylated with theolefin forming the monoalkylated product(cumene or ethylbenzene). A small amount of dialkylated by-products are fully recovered in a separatetransalkylation step with benzene formingaddtional cumene. PBE-1 catalyst is equallyeffective for alkylation and transalkylationreactions carried out in liquid phase as wellas in mixed phase. It allows both recycle and once-through reactor mode operations. PBE-1 catalyst can effectively replace otherzeolite based catalysts in both cumene andethylbenzene applications affording superiorperformances in terms of lower impuritiesformation and higher catalyst lifetime.

PBE-1 industrial catalyst can be fullyregenerated by coke burning in properconditions without any zeolite structuraldamage (as proved by XRD techniques).

Up to five reaction/regeneration cycles have been tested at pilot plant scale showing unchanged catalyst structure andperformances as well as stable Al state intothe zeolite (as proved by Al-MAS-NMR andFT-IR spectroscopy). Both in-situ or ex-situindustrial regeneration are possible for PBE-1catalyst. Based on an economic stand-pointand thanks to the extremely long lifetime of every reaction cycle, ex-situ regeneration,which inherently allows a better control ofcoke burning conditions, is preferred forPBE-1 catalyst. This in turn allows industrialreactors in carbon steel with a consistentinvestment saving.

Main physical properties

Physical form ExtrudateNominal diameter 2.1 mmABD 500 kg/m3

PackagingPacked in 200 liters steel drums withinternal polyethylene liner.

EXTRAZEOLITEEXTRAZEOLITEAND ZEOLITE PROPERTIES

PBE-1 is a beta zeolite based catalystdisplaying unusual and unrivalledperformances in industrial cumene andethylbenzene synthesis thanks to its uniquecombination of extrazeolite properties (given by binder selection and formingprocedure) and zeolite properties (given by the specific features of the zeolitecontained into the catalyst).

Catalyst pellet Inside catalyst pellet

Model Beta Zeolite structureBeta Zeolite crystals

Zeolite particleBinder particleinter-particle mesoporosity

E PROPERTIES

Catalyst Forming procedureThanks to the proprietary forming procedurebeta zeolite is highly dispersed into the PBE-1 catalyst matrix giving incomparablehigh strength and negligible loss on attritionto the catalyst particle. Mechanicalproperties of the catalyst ensure very lowand constant pressure drop as well as a negligible fine production during loadingand unloading operations for severalreaction/regeneration cycles in industrialcumene and ethylbenzene synthesis.

Extrazeolite porosityPBE-1 catalyst deactivation rate is the lowestone ever seen in a zeolite based catalyst forcumene and ethylbenzene synthesis. This isdue, beside to the specific features of the betazeolite, to the extrazeolite porosity providedby the proprietary forming procedure. Theresulting unusually high and well distributedextrazeolite porosity allows optimal diffusionof reactants and products through the catalystparticle, avoiding consecutive reactionsresponsible for coke precursors formation.

Extra

zeol

ite p

ore

volu

me

Extrazeolite pore diameter

Extrazeolite pore size distribution

Proprietary zeolite based catalyst forming procedure Conventional zeolite based catalyst forming procedure

Zeolite and binder dispersion in catalyst particle

100 µm

ZEOLITE PROPERTIES

Zeolite morphologyZeolite morphology is also a peculiarity of PBE-1 catalyst. The small dimension ofzeolite crystals together with their uniformdistribution allow faster diffusion ofreactants and products into and out of the zeolite crystals leading to betterperformances in terms of monoalkylationselectivity as well as negligible formation of recognized coke precursors.

Zeolite crystals

1700 1400Wavenumber, cm-1

Abso

rban

ce

Skeletal 19a 1545 cm-1 Skeletal 19b 1455 cm-1

N

H

O-

Al Si

N

Al

These unique acid properties give to PBE-1 catalyst an incomparable tolerance to all poisons normally present in benzeneand propylene feedstocks as directly proventhrough pilot plant experiments with doped feedstocks. Both acid sites amountand distribution in the zeolite are strictlyregulated by specifications in PBE-1 catalystproduction and carefully controlled by FT-IR titration after adsorption/desorption of pyridine probe molecule.

Zeolite AcidityThe overall amount of acid sites as well as their distribution between Bronsted and Lewis types into the beta zeolite (BEA)structure are peculiar in PBE-1 catalyst. The combined effects of acid sites amountand distribution leads to an unusually high activity and selectivity to cumene and ethylbenzene in both alkylation andtransalkylation reactions.

Acid sites titration by FTIR-spectroscopy of adsorbed Pyridine

Pyridinium ion formed on Bronsted acid sites

Pyridine adduct on Lewis acid sites

Responsible Care

Polimeri Europa SpAA subsidiary of Eni SpASole shareholder company

Head Office Piazza Boldrini, 120097 San Donato Milanese (Milano) – Italyt +39 02 520.1info@polimerieuropa.comwww.polimerieuropa.com

Licensing Piazza Boldrini, 120097 San Donato Milanese (Milano) – Italyt +39 02 520.32883f +39 02 520.32077info.licensing@polimerieuropa.com

Agent

Euro Support BVKorte Gracht, 263811 KH Amersfoort – The Netherlandst +31 33 4650465f +31 33 4650721eurosupport@eurosupport.nl

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