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Friedel-Crafts Alkylation of Xylenes With Tert-Butanol Over Me So Porous Superacid UDCaT-5

Friedel-Crafts Alkylation of Xylenes With Tert-Butanol Over Me So Porous Superacid UDCaT-5

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Published by Bharadwaj Santhosh
Friedel-Crafts Alkylation of Xylenes With Tert-Butanol Over Me So Porous Superacid UDCaT-5
Friedel-Crafts Alkylation of Xylenes With Tert-Butanol Over Me So Porous Superacid UDCaT-5

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04/21/2013

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Friedel-Crafts alkylation of xylenes with
tert 
-butanol over mesoporous superacid UDCaT-5
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Abstract
Friedel-Crafts alkylation of 
xylenes
with
tert 
-butanol in the presence of novelmesoporous superacidic catalysts named as UDCaT-4, UDCaT-5 and UDCaT-6 wasinvestigated. The catalysts are modified versions of zirconia showing high catalyticactivity, stability and reusability. The catalytic activity is in the order:
UDCaT-5 (mostactive)
>
UDCaT-6
>
UDCaT-4
> sulfated zirconia
(least active)
. Synergistic effect of very high sulfur content present (9% w/w S) and preservation of tetragonal phase inUDCaT-5, in comparison with sulfated zirconia (4% w/w S), were responsible for highercatalytic activity.
The performance of UDCaT-5 in alkylation of xylenes was studied with
tert 
-butanol with reference to selectivity and stability. Alkylation of 
m
-xylene over UDCaT-5 gives 96% conversion of 
tert 
-butanol with 82% selectivity towards 5-
tert 
- butyl-
m
-xylene (5-TBMX) under optimum reaction conditions. The formation of productsis correlated with the acidity of the catalyst.
The reactions were conducted in liquid phase
at relatively low reaction temperatures
(130–
160 °C
). A systematic investigation of theeffects of various operating parameters was done to describe the reaction pathway.
Thereaction was carried out without any solvent in order to make the process cleaner andgreener. An overall second order kinetic equation was used to fit the experimental data,under the assumption that both xylene and
tert 
-butanol are weakly adsorbed. Anindependent dehydration study of 
tert 
-butanol (TBA) was also done.
Keywords:
Friedel-Crafts alkylation;
tert 
-Butyl xylenes; Mesoporous superacidiccatalysts UDCaT-5;
Sulfated zirconia
; Green chemistry.
Introduction
Alkylation processes normally require Friedel–Crafts acid catalysts such as AlCl
3
,BF
3
, TiCl
4
, liquid HF, and AlCl
3
with elemental iodine.
1,2
Several problems are associatedwith these catalysts such as toxicity, corrosiveness, low reaction selectivity, and disposalof effluents.
3–5
Relatively high concentration of catalyst is needed; often the amounts aremore than stoichiometric making the reactions inherently polluting.
6
Due to ever increasing societal, environmental, and economic pressure, efforts are devoted to thedevelopment of environmentally friendly catalysts for the production of industriallyimportant chemicals and intermediates.
7–9
Alkylation of xylenes with
tert 
-butanol (TBA) is an important reaction both inorganic synthesis and chemical manufacturing. Some dimethyl alkylbenzenes haveassumed practical significance. In particular, 1,2-dimethyl-4-
tert 
-butylbenzene or 4-
tert 
- butyl-
o
-xylene (4-TBOX) was proposed as the starting substance for the production of 1
 
novel phthalocyanine pigments, plasticizers, photographic materials and other valuable products.
10–13
 
tert 
-Butylated xylenes are usually manufactured by reacting xylenes in the presence of liquid acid catalysts, with pure isobutylene or C
4
fraction from naphthacrackers containing isobutylene, giving wide product distribution. These processes suffer from problems associated with the use of highly corrosive liquid acids and also the sourceof isobutylene. The development of a technologically efficient, highly productive andenvironmentally safe method for the synthesis of dimethyl-
tert 
-butylbenzene (DMTBB)is challenging. There is a tremendous scope for devising a new catalytic process for thesynthesis of 
tert 
-butylated xylenes to replace conventional homogenously catalyzed,highly polluting processes. Besides, due to the problems associated with unavailability,transportation and handling of isobutylene, particularly for usage in low-tonnage fine andspeciality chemical industry (typically 10-100 TPA production), it is advantageous togenerate isobutylene
in situ
. Dehydration of 
tert 
-butanol is an attractive source for thesame. Further,
tert 
-butanol is available as a by-product in the ARCO process for  propylene oxide which could be used effectively for this purpose. We have successfullycarried out
tert 
-butylation of several aromatic compounds by using
tert 
-butanol, methyl-
tert 
-butyl ether (MTBE) and isobutene as alkylating agents using ecofriendly solid acidcatalysts.
14–17
The only problem which needs to be considered was activity and stability of solid acid catalysts in the presence of water, which is evolved during the reaction.For the past few years, our laboratory is engaged vociferously in the synthesis,characterization and application of selective, ecofriendly and active catalysts such asUDCaT series catalysts, sulfated zirconia, heteropolyacids and their modified versionssupported on clays. In particular, sulfated zirconia has been extensively studied in anumber of reactions
18–20
and it should be modified to bring in shape selectivity,mesoporosity and better acidity. Recently we prepared novel mesoporous superacidsnamed as UDCaT-4, UDCaT-5 and UDCaT-6, which are modified versions of zirconiaand have found a great potential for industrially important reactions.
21–23
We havereported, for the first time, that a sulfated zirconia, with sulfur content as high as 9% w/w,was produced with preservation of tetragonal phase by using chlorosulfonic acid as a newsource for sulfate ion. It was designated as UDCaT-5. The acronym “UDCaT” symbolizesour research institute, formerly called
U
niversity
D
epartment of 
C
hemical
T
echnology(
UDCT
), which is now renamed as
I
nstitute of 
C
hemical
T
echnology (
ICT
). The work summarizes the investigation of activity and selectivity of these new breed of catalyticmaterials in alkylation of xylenes with
tert 
-butanol, including reaction kinetics. Thecatalyst can be used as the basis for a high performance and environmentally safe methodfor the synthesis of DMTBB. The model studies were done with
m
-xylene and thenextended to other xylene isomers.
Experimental SectionChemicals and Catalysts
Pure xylene isomers,
tert 
-butanol, zirconium oxychloride, aluminum nitrate,ammonium persulfate and aqueous ammonia solution were procured from Aldrich, USA.Hexadecyl amine and chlorosulfonic acid was purchased from Spectrochem Ltd.Mumbai, India. Tetraethyl orthosilicate (TEOS) was procured from Fluka, Germany. Allchemicals were of analytical reagent (A.R.) grade. These were used as received withoutany further purification.
Preparation of Catalysts
2
 
The following catalysts were prepared by well-developed procedures andcharacterized in our laboratory: (i) sulfated zirconia (S-ZrO
2
), (ii) UDCaT-4, (iii)UDCaT-5, and (iv) UDCaT-6.
 Preparation of Sulfated Zirconia (S-ZrO
2
 )
Sulfated zirconia (S-ZrO
2
) was prepared by adding aqueous ammonia solution tozirconium oxychloride solution at a pH of 10, as detailed elsewhere.
20
The precipitate wasthoroughly washed with distilled water and made free from ammonia and chloride ions. Itwas dried in an oven at 120 °C for 24 h. The sulfation of the zirconia was done using 15cm
3
g
-1
of 0.5 M sulfuric acid. It was dried at 110 °C and calcined at 650 °C for 3 h.
 Preparation of UDCaT-4
The ordered hexagonal mesoporous silica (HMS) was prepared according to our earlier work.
24
Desired quantities of zirconium oxychloride and aluminum nitrate weredissolved in aqueous solution and added to precalcined HMS by incipient wetnesstechnique. After addition the solid was dried in an oven at 110 °C for 3 h. The driedmaterial was hydrolyzed by ammonia gas and washed with deionized water until a neutralfiltrate was obtained and the absence of chlorine ion in the filtrate was detected by phenolphthalein indicator and silver nitrate tests. It was then dried in an oven for 24 h at110 °C. Persulfation was carried out by immersing the above solid material in to 0.5 Maqueous solution of ammonium persulfate for 30 min. It was dried at 110 °C for 24 h andcalcined at 650 °C for 3 h to get active catalyst called UDCaT-4 with 0.6% w/w of alumina.
21
 Preparation of UDCaT-5
UDCaT-5 was prepared by adding aqueous ammonia solution to zirconiumoxychloride (ZrOCl
2
.8H
2
O) solution at pH of 9-10. The precipitated zirconium hydroxideso obtained was washed with deionized water until a neutral filtrate was obtained. Theabsence of chlorine ion was detected by the AgNO
3
test. A material balance on chlorideions before and after precipitation and washing shows no retention of Cl
 – 
on the solid.Zirconium hydroxide (Zr(OH)
4
) was dried in an oven for 24 h at 100 °C and was crushedto 100 mesh size. Zr(OH)
4
then immersed in 15 cm
3
g
-1
of 0.5 M solution of chlorosulfonic acid and ethylene dichloride. All materials were immersed for 5 min in thesolution and then without allowing moisture absorption were kept in an oven and theheating was started slowly to 120 °C after about 30 min. These materials were kept inoven at 120 °C for 24 h and calcined at 650 °C for 3 h to get the active catalysts UDCaT-5.
22
 Preparation of UDCaT-6 
UDCaT-6 was prepared by adding an aqueous solution of 2.5 g zirconiumoxychloride to 5 g precalcined HMS by incipient wetness technique and it was dried in anoven at 120 °C for 3 h. The dried material was hydrolyzed by ammonia gas and washedwith distilled water until no chloride ions were detected which was confirmed by theAgNO
3
test. It was further dried in an oven for 2 h at 120 °C. Zr(OH)
4
/HMS wasimmersed in 15 cm
3
g
-1
of 0.5 M chlorosulfonic acid in ethylene dichloride. It was soakedfor 5 min in the solution and then without allowing moisture absorption, it was oven driedto evaporate the solvent at 120 °C after about 30 min. The sample was kept in the oven at120 °C for further 24 h and calcined thereafter at 650 °C for 3 h to get the active catalystUDCaT-6.
23
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