THE CATALYTIC VAPOR PHASE DEHYDROGENATION OF SECONDARY AND TERTIARY ALCOHOLS

114 Pages·4.463 MB·English

by  LAKE, DONALD BIXBY

69-17,863
LAKE, Donald Bixby, 1925-
THE CATALYTIC VAPOR PHASE DEHYDRO­
GENATION OF SECONDARY AND TERTIARY
ALCOHOLS.
University of Delaware, Ph.D., 1952
Chemistry, organic
University Microfilms, Inc., Ann Arbor, Michigan
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The C atalytic Vapor Phase
Dehydrogenation of
Secondary and T ertiary A lcohols
By
Donald B. Lake
A Thesis
Submitted to the Faculty of the U niversity of Delaware
in p a rtia l fu lfillm en t o f the requirem ents for the
degree of Doctor of Philosophy.
September, 19S2
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Approved
Pro a or in Charge of Ih esis
Approved
Head of Department
,„V»_ _ _ _
Approved
Dean of School of a£ts and Science
Approved
Dean of School of Graduate Studies
!4caJo f
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Acknowl edgme nt
The author w ishes to express h is
appreciation to Dr. W.A. Mosher under
whose d irectio n th is research was
conducted.
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Dedicated
To
M. M. L.
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Table of Contents
Statement of The Problem.....................................................*........................ 1
Summary..........................................*............................... ^
Introduction................................................................................................................. 5
D iscu ssion ......................*....................................... 9
Adsorption on The C atalyst Surface*........................................... 9
Copper C a ta ly sis................................................................................................
Chromia C a ta ly sis.............................................................................................. 21
C onclusions................................................. 36
Experimental ................................................... 57
Determ ination of I-I.E.T.'. of Practiona- ing Columns •• 57
Preparation of Starting M aterials.................................................. 59
Pinacol hydrate anfl P inacolone..................................................... 59
Pinaeolyl a lc o h o l........................................ 59
Methyl isopropyl ca rb in o l »........................................... 42
Butanol-2 ............. 44
Methyl eye 1 opr opyl carb in ol*.................................................... 45
Methyl cyclopentyl carb in ol. . . . . . ........................ 47
2 ,3 -dime thy lbuta.no 1-2 ........................... 53
M ethylethyl t-b u tyl carbinol .................................................. 53
Dim ethylneopentyl carbinol ............................................................. 54
Isooctane • • • ................ 55
Experimental C atalytic Techniques ..................................................... 56
Apparatus Tor Chromia C atalysis ................... 56
Preparation of A ctive Chromia C atalyst ............................. 58
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Procedure For R eactivating Hie Chromia C a ta ly st.........* 59
Procedure For a Typical Dehydrogenation Over Chromia . 60
A nalysis of Products From Chromia C atalysis ......................... 62
Preparation of A ctive Copper C a ta ly st........................ ................ 65
Apparatus For Copper C atalysis ............................................................ 66
Procedure For a Typical Dehydrogenation Over Copper .. 68
Experimental C atalytic Studies . . . . ................ 69
Explanatory ITote . . . . . . . . . ........................................................................... 69
Run ITo.
A-2 P inacolyl alcohol over cop p er.......................................... 70
A-4 P inacolyl alcohol over cop p er . .................................. 70
A-5 P inacolyl alcohol over cop p er................................... 71
A-6 P inacolyl alcohol over a cid icc hrom ia......................... 71
A-7 P inacolyl alcohol over acid icc hrom ia ......... 73
A-9 P inacolyl alcohol over acidicc hrom ia......................... 74
A-10 P inacolyl alcohol over acid ic chromia ......................... 76
A -ll P inacolyl alcohol over "basic chrom ia....................... 76
B -l Tert. butyl alcohol over co p p er.......................................... 77
B-2 .Tert. butyl alcohol over co p p er......................................... 79
C-4 Butanol-2 over a cid ic chromia ............................................... 79
C-5 Butanol-2 over b asic chromia ................. 81
C-6 Butanol-2 over b asic chromia ................................................. 82
R -l M ethylisopropyl carbinol over acid ic chromia . . . . 83
P-2L. Methyl isopropyl carbinol over basic chrom ia 84
F -l M ethyleye1opropyl carbinol over acid ic chromia .. 86
F-2 M ethyleye1opropyl carbinol over b asic chromia . . . 87
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D-2 K ethylcyclopentyl carbinol over b asic chromia . . . . 88
G -l Dim ethylisopropyl carbinol over acid ic ch rom ia.... 89
•G-2 D im ethylisopropyl carbinol over acid ic chromia . . . 90
G-3 D im ethylisopropyl carbinol over b asic chromia . . . . 91
K -l H ethylethyl t-b u tyl carbinol over acid ic chrom ia.. 93
II-2 K ethylethyl t-b u tyl carbinol over basic chromia .. 94
II—3 Hethylethj:^ t-b u ty l carbinol over b asic chrom ia... 96
J -l Dim ethylneopentyl carbinol over acid ic chromia . . . 97
J-2 Dim ethylneopentyl carbinol over b asic ch ro m ia ..... 98
K-l Isooctane over basic chrom ia.. ........................ 99
L -l O xidation of lie thyl ethyl t-b u tyl carbinol Q 35-40°C.100
bibliography ........................................................................................ 102
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-1-
Statement of The Problem
During the past several years the research of many
students at th is U niversity has been directed toward the
elucid ation of a g en era lized mechanism far the homogeneous
liq u id phase oxidation of alcohols with chromic acid.
Such a mechanism has been proposed and the supporting evidence
is quite convincing.
On the contrary, " little is known about the hetero­
geneous vapor phase dehydrogenation of alcohols prim arily be­
cause in terest in th is fie ld has been along p ractical lin e s
rather than th eo retica l. No account is given in the
litera tu re of the dehydrogenation of alcohols of the type
that cleave read ily upon oxidation with chromic acid, nor is
there any statem ent concerning the dehydrogenation products
of tertia ry alcoh ols.
Therefore, it was decided to study the ca ta ly tic vapor
phase dehydrogenation of alcoh ols and from the nature of the
products to see i f there was any p ossib le relation sh ip between
the type of mechanism currently postulated here for chromic
acid oxidation of alcohols and the mechanism which can be
postulated to sa tisfa c to r ily explain the resu lts obtained.
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-2-
Summary
The ca ta ly tic vapor phase dehydrogenation of p in acolyl
o
alcohol and te r t. butyl alcohol over copper at 350 c. was
studied.
A sim ilar study was made over chromia ca ta ly sts at
400° c. using the follow ing compounds: p in acolyl alcohol,
butandl-;r2, methyl isopropyl carbinol, methyl cyclopropyl
carbinol, methyl cyclopentyl carbinol, dim ethyl isopropyl
carbinol, m ethylethyl te r t. - butyl carbinol, dim ethylneopentyl
carbinol and 2 ,2 ,4 - trim ethylpentane. Both an acid ic and
b asic ca ta ly st was used.
Basic chromia p referen tia lly catalyzed dehydrogenation
and tertia ry alcohol cleavage w hile acid ic chromia catalyzed,
equally, dehydration and dehydrogenation and caused no cleavage.
Chromic acid oxidation o f m ethylethyl te r t. b utyl carbinol
was found to y ie ld a large amount of plnacolone.
Basic concepts and current th eories of heterogeneous
ca ta ly tic reaction s were d iscu ssed .
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