Catalysts, Process and Fluidized Bed Reactor Technology...

FLOTULightAlkaneDehydrogenationProcessforPropyleneProduction
INTRODUCTION
The FLOTU process is a catalytic dehydrogenation of lightparaffinstolightolefins.Onespecificapplication of this technology produces propylene from propane/butane. Propylene is the words second largest petrochemical commodity and is used in the productionofpolypropylene,acrylonitrile,acrylicacid, acrolein, propylene oxide and glycols, plasticizer oxo alcohols, cumene, isopropyl alcohol, and acetone. The growthinpropyleneproductionisprimarilydrivenby their derivatives in particular industry demand for polypropylene, which is used in manufacturing of everyday products. The growth rate of polypropylene iscontinuouslyincreasingandisexpectedtobe6%per yearinnearfuture. The FLOTU dehydrogenation process utilizes FLOTUs (Tsinghua University, Beijing) proprietary equipment (GSSFBR), Ptbased SAPO34 supported catalyst and systems for optimal operations. Integration of intensified catalyst with sophisticated design of fluidizedbedreactorandprocessresultsinsignificant capitalandoperatingcostsavings. ADVANTAGESOFFLOTUTECHNOLOGY At present many technologies for alkane dehydrogenation are available, while our proposed process and technology has added advantages. FLOTU processprovides: Highpropyleneselectivityupto9497wt.%dueto superiorcontrolofreactionatmolecularlevel. Stableconversionbetween3545wt.%withlonger stabilityupto810hr. Ptbased Zeolite supported environmentally friendlycatalyst. Easyregenerationschemeusingsteamwith98100 %regenerationefficiency. Proposed integrated design of bimodal Fluidized bed reactor (GSSFBR) provides unique opportunityofheatsupply. Interconnection of reactor further optimized heat inventory of the process. Potential for process integrationwithexistingdownstreamtechnologies. Lower capital and running costs and highquality propyleneproduction. Continuous onstream propylene production opportunity.

PROCESSCHEMISTRY

This simplest reaction is very complex in his engineeringconstraintsasreactionconstraintsaretied up with each other. High temperature requires due to endothermic nature of reaction requirements which furtheraffectdesiredproductselectivity. FEEDSTOCK The feedstock to a FLOTU dehydrogenation process unit is propane and butane. Propane and butane are recoveredfromrichLPGstreamsfromdifferentplants. Thisfeedstockisalsoavailableinsmallerquantitiesas a byproduct from such refinery operations as hydrocracking, fluidized catalytic cracking (FCC) and residcatalyticcrackingunits(RCC),etc. CATALYST The FLOTU Dehydrogenation Technology uses a platinumbased zeolitesupported catalyst to promote the dehydrogenation reaction with superior control at molecular level. The ZeeFLOTU13 catalyst, introductedin2008,demonstratesveryhighpropylene selectivity. Later in 2009 the catalyst was further intensified(ZeeFLOTU29)forindustrialapplicationin fluidized bed reactor that not only maintain the high activity and selectivity and almost zero attrition requiredforthedehydrogenationprocess. Its the first time that any high hydrothermally stable Pt-based zeolitesupported catalyst is introduced for dehydrogenation activity.

LABORATORYEXPERIENCE
Light alkane dehydrogenation to propylene is endothermic and thermodynamically limited reaction, and does not

enjoy the plethora of mechanistic subtleties for commercialization. Therefore, our laboratory conducts extensive experimentation to design suitable catalyst and reactor, with superior operational benefits. In extensive analysis of light alkane dehydrogenation over various catalysts, it is observed that the support plays vital role in catalyst stability and propylene selectivity. Here we intensified Pt-based catalyst using SAPO-34 as a support, prepared by sequential impregnation and characterized by number of physico-chemical techniques. Propylene selectivity of above 95 % is achieved. The possible reasons for improvement are: larger surface area, shape selectivity, bifunctionality due to weak surface acidity, and superior Pt, Sn and support interaction. The only hydrogen attached to a -carbon in propane was attacked by Pt to form propoxy species (ZOC3H7); those were selectivity converted to propylene over support. The optimum catalytic combination and operating conditions were investigated in detail before constructing the proto-type unit. In order to get into mechanistic understanding and hydrothermal stability, severe hydrothermal treatment was carried out with pure steam and characterized thoroughly. The catalyst activity is found to be 99% recoverable by re-dispersed Pt using chlorination technique and credit goes to hydrothermally stable support.

proposed ( x = ( ) ( S ) ( K ) (t ) ), that successfully calculate attrition debris of any catalyst in a bimodal/multi-particle fluidization system.
5 0.44 1.53 m

The mixing behavior and hydrodynamics of fine particles with coarse particles was investigated in 2D and 3D fluidized beds, respectively. A distinct phenomenological mixing behavior of bi-modal particle system was observed, where strong interparticle forces between fine particles broken. Gas bubble disassociation strategy was found to be significant reason for distinct increase in mixing.

A complete dehydrogenation technology has been proposed, includes intensified catalysts, integrated reactor and process. A pilot scale fluidized bed reactor is designed for propane dehydrogenation to propylene using Pt-based SAPO-34 supported novel catalyst (ZeeFLOTU-29). The results showed that the propane conversion and propylene selectivity were enhanced using GSS-FBR due to uniform heat transfer and coke transfer to secondary catalyst.

The state-of-the-art idea of bi-modal particles fluidized bed reactor (Gas-Solid-Solid fluidization) is proposed first time, in order to overcome operational barriers in particular the continuous heat supply. Mechanical degradation propensity of catalysts is investigated in a bimodal distribution environment using a Gas Jet Attrition - ASTM standard fluidized bed test apparatus. The investigation suggests about the parameters of fluidized bed catalyst and a generalized relationship has been

FORMOREINFORMATION FLOTUtechnologicalservicesareavailableonrequest. Formoreinformationcontact: Prof.Dr.FeiWEI email:wfdce@tsinghua.edu.cn Phone:+861062784654 Dr.ZeeshanNawaz email:engr.dr.zeeshan@gmail.com Phone:+923004443249