GUIDER.

DR Hunh Quyn GROUP 10 V t Nguyn L Vn Quyt Nguyn Hong Minh Tr L Trn Phong Ph

CONTENT
INTRODUCTION COMPOSITIONS AND

PREPARATIONS OF CATALYST CONCLUTION

INTRODUCTION
The development around the

sixties of various processes of selective oxidation of alkanes has constituted a significant breakthrough for the large scale production of chemicals and intermediates.

 Today most of the monomers for the manufacture of plastics and synthetic fibers are produced by selective

catalytic oxidation of hydrocarbons and include large volume products such as ethylene oxide, acrylonitrile, vinyl chloride, maleic and phthalic anhydrides. In addition, the world market for oxidation catalysts may be estimated as around 200-250 million US dollars, about half of which is in Europe.

 On the average, the costs for a chemical product produced

by oxidation processes can be allocated as follows: 60% to raw materials, 20% to capital costs, and 20% to other costs such as labor, utilities, catalysts, etc. Therefore, a larger economic impact for chemical oxidation processes may be realized by technologies using alternate, lessexpensive raw materials. The substitution of expensive alkenes or other hydrocarbons (for example, aromatics) with a less expensive alkane feedstock can thus represent a breakthrough for the realization of shut-down economics technologies able to reduce the transfer price of a product in a fully amortized plant as compared to the existing competitive technologies

 In most cases, in fact, the price of light (C2-C6) alkanes

is the same as that of fuel, due to the reduced number of non-energy applications for these hydrocarbons. Furthermore, the functionalization of alkanes in the presence of oxygen (oxyfunctionalization which includes oxidation, ammoxidation, oxidative dehydrogenation, oxychlorination and oxidative dimerization processes) in comparison to other possible competitive petrochemical processes of alkane conversion is the more interesting process option to obtain selectively high value chemicals.

 most cases, in fact, the price of light (C2-C6) alkanes is

the same as that of fuel, due to the reduced number of non-energy applications for these hydrocarbons. Furthermore, the functionalization of alkanes in the presence of oxygen (oxyfunctionalization which includes oxidation, ammoxidation, oxidative dehydrogenation, oxychlorination and oxidative dimerization processes) in comparison to other possible competitive petrochemical processes of alkane conversion is the more interesting process option to obtain selectively high value chemicals.

 However, the possible utilization of alkane feedstocks for

selective oxidation reactions requires the discovery of a selective catalyst for the reaction, a difficult task due to the relative inertness of the alkane and the two-three order of magnitude higher reactivity of possible products or intermediates. The control of the consecutive reactions up to carbon oxides is thus very critical. The selective oxidation of alkanes thus requires the development of novel concepts and catalytic systems to fulfil the strict requirements of controlled surface reactivity necessary for selective behavior

Introduction to propane oxidation catalyst

Compositions of catalysts
Catalyst preparation Catalyst testing

Compositions of catalysts
particularly for a formulation containing the oxides of

Mo, V, Nb and W. supported on a low-area alumina calcined at 1150C (alumina)

Catalyst preparation
wet impregnation method
incipient wetness (or dry) impregnation method

wet impregnation method

the alumina support precursor (Alcan AA400) was first

calcined at 1150C a sample of 2g of this was then treated sequentially by aqueous solutions of the salts of each metal After leaving the system to equilibrate in an excess of solution overnight (about 15h), the samples were then dried using a rotary evaporator at 80C and were then finally calcined for 6h at 650C.

Al2O3

calcining

1150C

mixture

solutions of the salts of each metal

15h 80C

drying

calcined

6h 650C

catalyst

wet impregnation method

incipient was fed to 2g of the calcined alumina in aliquots wetness impregnation method each solution
of 800L drying between each impregnation (ca. 15min at 130C). The preparation of sample F4 involved a sequence of impregnation steps involving the addition of both species simultaneously whereas F5 and F6 involved impregnation by a single species per sequence (Mo first for the former, V first for the latter) and calcining after each sequence. Catalysts F7 and F8 were prepared by wet impregnation to verify whether or not the presence of Nb and W had any effect on this system.

Catalystprepared were tested in a quartz microreactor testing The materials

using 300mg of each sample (particle size 212-425m) diluted with 100mg of quartz grains of the same size. The WHSV (weight hourly space velocity) based on the weight of catalyst alone was 8000 ml g-1h-1 The catalytic experiments were carried out in the temperature range from 400 to 650C. The effluent from the reactor was analysed by a Varian 3400 Gas Chromatograph.

Figure 4 Results obtained with the catalysts of the F series