In The Name of God

Project of Heterogeneous catalysts

Outlines

What is Propene? Production MTP Process Mechanism & Kinetic Catalyst

Template of Catalyst Synthesis

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What is Propene?

Propene,is theknown asmost importantmethylethylene, isin the Propene also second propylene or starting product an unsaturated organic compoundethylene. the chemical all of the petrochemical industry after having Essentially formula C3H6. it isproduced for low-boiling, flammable, and highly a propylene a colorless, chemical purposes is consumed as volatile gas intermediate chemical [1]. processes. in other chemical manufacturing

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Production
The steam cracking of NGL, naphtha or other light fractions of petroleum. By-product of gasoline production from larger FCC units. Other methods : Thermal cracking ofsteam Higher catalyst-to-oil ratios, Higher ethane, MTP, injection rates, Higher temperatures, etc. The propylene production distribution in 2009 was 70% from steam cracking at 52 mln tons, 25% from FCC conversion at 19 mln tons and 5% from other methods (about 4 mln tons)

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MTP
MTP produces propylene selectively from methanol, it can be The rapid increase in the price of crude oil has lowered the produced from synthesis gas, which can be made from any feasibility of these processes for the production of the lower source of carbon-containing materials such coal, petroleum olefins, because they are based on petroleum sources. residue, biomass and natural gas. Furthermore, the consumption of a large amount of energy in the thermal cracking of

naphtha, along with the large carbon dioxide

emissions, increases the production cost of the lower olefins [2].

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MTP

MTP Process MTP Mechanism & Kinetic MTP Catalysts

Coke and Deactivation of Catalyst

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MTP Process

Fixed Beds [3] Fluidized bed :[4] : Simpleet al. proposed Circulating Fluidized Bed as a good Alwahabi in construction

Easy operating process because of : choice for the MTO

Excellent heat transfer catalyst activity fluidized bed permit Minimum scale-up and properties of a studies Minimum regeneration cycles immersed in the reactor. direct steam generation in coils Constant quality because of Continuous regeneration of the catalyst and uniform bed temperature. Transient temperature profiles are also uniform and stable.

The specific throughput in a fluid-bed system is higher.

Specific investment cost is lower.

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MTP Process

In a CFB reactor, Catalyst experiences a fast coking stage. The Mobil Fluidized Bed fastUhde deactivation accompanying a high exothermicity of reaction has become the chief consideration to select reactor . the Lurgi relatively low methanol conversion after a single pass with notable catalyst Trust Liquid Fuels attrition, including the high investment for Fixed Bed scaling up the reactor, are the primary disadvantages [5]. Board (LFTB) The first MTP plant was established in China in 2010 and it has an annual production capacity of 500,000 ton [5].

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Mechanism

A consecutive-type mechanism: ethylene will be first formed in the reaction. Main Mechanism Types [6] A hydrocarbon pool-type mechanism: Dahl & Kolboe proposed that olefin synthesis occurs through a carbonaceous species of unknown stoichiometry, possibly a carbonium ion.

Polyalkylated aromatics Large alkylated olefins Carbonium ions

[5]

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Mechanism

Salehirad and Anderson by means of NMR technique revealed that at low loading (up to one methanol per acid site) the methanol adsorbed in two hydrogen bonded configurations. At higher coverage, methanol may cluster with the involvement of one methoxonium ion [6].

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Kinetic
Because the experiments was carried out at 450 Hydrocarbon pool theory does not represent the activation energies of each steps, so this work could not be useful for conceptual reactor design for MTO process at different Temperatures [7].

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Kinetic
Chenequilibrium constant (K) of Reaction 1 model where the The et al. Deduced an elaborate coking calculated from coking rate equation is obtained. Gayubo et al. over ZSM-5 experimental relationship found by In addition, Chen et al.'s
simulation follows: catalyst as results were in good agreement with the actual data
[8].

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Kinetic

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Catalyst

Molecular sieves ( Zeolites, SAPO, ) are a suitable choice for MTO reaction. Porous structure Concentration acid site External surface

Unblocked sites

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Catalyst

Porous structure [9]:

Medium-pore molecular sieves ( 5-7 A) Large-pore (> 7 A)

C5-C11

MTG process

Rapid coke formation

Small-pore molecular sieves ( < 4 A) C2C4 olefins

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Catalyst
Concentration acid site [10]: The methods used light paraffine (mainly propane) strong acid high selectivity to to reduce the concentration of can also be

sites on zeolites small-pore size zeolites. Decreasing and obtained with are dealumination, cation exchange the
isomorphous substitutionacid sites, which are responsible for concentration of strong of aluminium by other trivalent cations. transfer reactions, is a key factor in reducing the hydrogen conversion of olefins into paraffine.

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Catalyst
External surface [10]: The ratio between the number of acid sites in the external surface and those located on the intracrystalline pore surface plays an important role in this reaction. smaller the crystallite size, the higher this ratio.

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Catalyst
unblocked sites [5]: When methanol initially reaches the catalyst bed there is no

hydrocarbon pool present, but within a very short time an

active hydrocarbon pool is created and full conversion of methanol is achieved. With an increasing time on stream, the catalyst deactivates due to coking and the active hydrocarbon pool moves downstream leaving deactivated catalyst behind.

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Zeolites

Zeolites consist of a frame work built of tetrahedral. Each Tetrahedron comprises a T-atom bound to four O atoms. Oxygen bridges connect the tetrahedral. T-atoms are Si or Al.

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Zeolites

The ERI, LTA and UFI zeolites with 8MR pore entrances also show high selectivity for the lower olefins in the MTO. but they deactivate rapidly in the order of LTA < ERI < UFI . the CHA catalyst have showed a stable conversion [11].

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Zeolites
Increasing the selectivity to light olefins : (1) Modification of the reaction conditions with respect to Increasing its shape selectivity those of the MTG process, by co-feeding water, increasing Increasing hydrothermal stability temperature, decreasing pressure or diluting oxygenates with Reducing the number and strength of acid sites an inert Gas. (2) Modification of the zeolites

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Zeolites
Increasing its shape selectivity
Catalysts of small pore size with pore openings made up of rings of eight units (chabazite, erionite, ZSM-34, offretite, T zeolite, and so on) is selective for MTO . MOR zeolites, regardless of their acid site density, are highly

active and selective for the lower olefins at the initial time.
However, their deactivation rates vary considerably according to their acid site density [12].

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Zeolites
Reducing the number and strength of acid sites:
High Si/Al ratio of zeolite leads to high ratio of propene to ethene

in products of methanol reaction.

Various catalysts such as ZSM-5 zeolites modified with phosphorus and ferro silicalite have shown high selectivity to lower olefins in the MTO reactions [11]. Park et al. Prepared the MOR zeolite with a lower acid site density by careful removal of aluminum atoms from its framework which shows slow deactivation and high selectivity for the lower olefins[12].

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Zeolites
Increasing hydrothermal stability:
A large number of the modifications of the zeolite structure

mentioned above also serve to increase hydrothermal stability,

which does not suffice in view of the severe conditions of high temperature and high water content in the reaction medium required for the MTO process in order to attain high values of activity and selectivity to olefins and to reduce deactivation by coke [13].

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Zeolites
HZSM-5 zeolite shows a moderate deactivation by coke in the MTO process, it suffers from irreversible deactivation (by dealuminisation) under the operating conditions. The incorporation of Ni in the HZSM-5 zeolite implies a decrease in total acidity and in the acid strength of the zeolite. Consequently, the activity of the catalyst decreases. The catalysts with Ni are hydrothermally more stable than the parent zeolite catalyst, and activity is completely recovered in the operation under reaction regeneration cycles [14] .

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SAPOs
Alumino-Phosphate ( AlPO4)

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SAPOs

Sastre et al. found that If the silicon

content is such that island formation is promoted, the acidic character will become strongly dependent on the topology of the material. Acidity directly relates to the concentration of the Si island. Large proportions of

silicon-rich regions were found in

mesoporous SAPOs [6].

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SAPOs
Silicoaluminophosphate materials (SAPO) have a mild acidity and, therefore, they present a very interesting alternative to obtain high selectivity towards light olefins in the MTO process [15]. Chen et al. have Concluded that SAPO-18 and SAPO-34 which have higher acidity and cages smaller than those of SAPO-5 and 17, exhibit high activity towards light olefine [16]. and selectivity

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SAPO-34
SAPO-34 is an analogue to chabazite, it has nearly spherical cages linked throughout the structure by 8-ring windows (diameter cage 4 A). In SAPO-34 silicon only substitutes for phosphorus [16]. SAPO-34 often suffers rapid deactivation although activity is completely recovered subsequent to combustion of coke with air stability than ZSM-5s [14].
[13].

it also shows higher hydrothermal

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SAPO-34
Effects of intracrystalline diffusion on the reactions over SAPO-34 [17]. The selective and stable catalytic performance of the CHA compared to UFI and LTA catalysts in the MTO reaction can be explained by its cages being of suitable shape and size to preserve stably the active intermediates, multialkyl benzenes, in them [11]. The UOP/Hydro MTO process employs a Ni/SAPO-34 molecular sieve as a catalyst and achieves a high yield of the lower olefins of more than 85%
[12]

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SAPO-18

The structure of SAPO-18 is closely related to , but crystallographically distinct The kinetic modelling of the MTO process is studied on a SAPO-18 catalyst, which from SAPO-34. size and shape of cages for both SAPO-18 and SAPO-34 are very is an interesting alternative to SAPO-34, given that it has the following advantages: similar. Since SAPO-18 is expected to have a good performance for MTO . In coke deactivation is significantly slower, its preparation method is simpler and the SAPO-18 silicon substitutes for both AL and P ( the amount of substituted of P is organic template is cheaper [13,18]. larger than of the substituted AL) [16].

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Template of SAPO synthesis

Ye ettemplate exerts thatsignificant influence on both the in the synthesis The al. concluded a the nature of the template used structures and determinesof the molecular Sieves [19]. properties the morphology of final crystals because it influences the rate of

crystalyears ago, Vomscheid et al. demonstrated that, in the synthesis of Some growth [9].
SAPO- 34 with morpholine and TEAOH, the importance of the template SAPO-34 can be synthesized using organic amines as templates, such as appears not only in its role of directing the structure but also of governing tetraethylammonium hydroxide ,isopropylamine ,dipropylamine ,piperidine the distribution of Si in the framework, which clearly affects the catalytic ,morpholine (MOR) ,triethylamine (TEA) ,diethylamine (DEA) ,and properties of the samples [9]. mixtures thereof.

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Template of SAPO synthesis

A comparative study revealed the DEA templated synthesis The mixed templates have also been used in the sample to
have the highest crystallinity and silicon content. MOR had of SAPO-34 .Jun et al. usedn morpholine and TEAOH to the second highest, and and foudLowest [19]. synthesize SAPO-34, TEA the that compared with the SAPO-34 prepared with single template, the lifetime of the catalyst prepared with the mixture template of 75%

morpholine and 25% TEAOH could significantly be

extended [15].

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Template of SAPO synthesis

The gel compositions and structure phases of prepared samples [15]

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REFERENCE
[1] http://en.wikipedia.org/wiki/Propene [2] Ji Won Park et al., Applied Catalysis A: General 356 (2009) 180188 [3] Frerich J. Keil, Microporous and Mesoporous Materials 29 (1999) 4966 [4] Ya-Qing Zhuang et al, Powder Technology xxx (2012) xxxxxx, in press. [5] Uffe V. Mentzel et al., Applied Catalysis A: General 417 418 (2012) 290 297 [6] Zhongmin Liu et al, Current Opinion in Solid State & Materials Science 4 (1999) 80-84 [7] Ali Taheri Najafabadi et al., Journal of Industrial and Engineering Chemistry 18 (2012) 2937 [8] Ya-Qing Zhuang et al, Powder Technology xxx (2012) xxxxxx, in press. [9] Teresa lvaro-Munoz et al., Catalysis Today 179 (2012) 27 34 [10] Michael Stocker, Microporous and Mesoporous Materials 29 (1999) 348 [11] Ali A. Rownaghi et al., Microporous and Mesoporous Materials 151 (2012) 26 33 [12] Ji Won Park et al., Applied Catalysis A: General 349 (2008) 7685

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REFERENCE
[13] [14] [15] [16] [17] [18] [19] Andres T. Aguayo et al., Applied Catalysis A: General 283 (2005) 197207 B. Valle et al., Catalysis Today 106 (2005) 118122 Pengfei Wang et al., Microporous and Mesoporous Materials 152 (2012) 178184. Chen et al.,Studies in Surface Science and Catalysis 84 (1994) 1731-1738 De Chen et al., Microporous and Mesoporous Materials 29 (1999) 191203 A.G. Gayubo et al., Catalysis Today 106 (2005) 112117 LIU Guangyu et al., Chines Journal of Catalyst 33(2012) 174-182

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