Chapter 4

Introduction to Hydroprocessing Reactions

While production of new catalytic phases such as phosphides, carbides, and nitrides
may yield interesting catalysts, it is also of interest to understand the mechanisms of
heteroatom removal associated with their use. Thus, we undertook a study of the
hydrodenitrogenation reactions of a series of simple amines: n-pentylamine, neopentylamine, tert-pentylamine, piperidine, and pyridine. The results for the alkyl series
of pentylamines will be presented in Chapter 5, while the results for the C5 ring structures
will be presented in Chapter 6.
The literature reports that the catalytic hydrogenation reactions of amines, thiols, and
alcohols are all generally similar, producing condensation products, olefins, and saturated
hydrocarbons in their conversion reactions. Examples of published reactions of
heteroatomic aliphatic species, cyclic aliphatic species, and simple cyclic aromatics are
summarized in Sections 4.1 to 4.3, respectively, and those involving heteroatom
exchange in Section 4.4.

4.1.

Reactions of alkyl aliphatic species

Schemes 4.1.1 through 4.1.7 summarize the basic reactions of the aliphatic
heteroatom ring molecules, and Table 4.1 lists the references. Condensation reactions of
alkyl species are reported in sections 4.1.1 to 4.1.3. These are facile types of reactions
which occur at low temperature in hydrogen, helium, and vacuum. This type of reaction

72

(for amines) is reported to proceed through quaternization of the nitrogen of a reactant

(alkyl donor) molecule, followed by nucleophilic attack by a non-quaternized (alkyl
acceptor) species (6). The observation is that alkyl chains, protons, and the heteroatoms
themselves are susceptible to exchange (as shown presently in Section 4.4), and that these
reactions can be considered easy under typical conditions. Although a heteroatom
compound (ammonia, hydrogen sulfide, water) can be generated during condensation, the
number of C-X (X = N, S, O) bonds is conserved, so this type of reaction does not lead
directly to free hydrocarbons (olefins or saturates).
Scheme 4.1.4 reports olefins which have been observed in the products of reactions of
alkyl heteroatomic species. The formation of olefins is thought to occur by -elimination
type reactions as reported later in Schemes 5.1 and 5.2.
Dehydrogenation reactions of alcohols, amines, and thiols are summarized in Scheme
4.1.5. These products, like the olefins, are favored by low pressure and lack of hydrogen.
Note that decarbonylation can lead to reduction of the hydrocarbon chain length. Thus,
operating at high pressure (which selects against dehydrogenation and decarbonylation) is
desirable in hydrodeoxygenation situations, such as found in the processing of
biologically derived oils.
Scheme 4.1.6 reports saturated hydrocarbons which have appeared in the products of
reactions of alkyl heteroatomic molecules. Whether these molecules are created as a
result of direct hydrogenolysis of C-N bonds, or by -elimination followed by
hydrogenation is of fundamental interest in this work. We will argue that the elimination pathway is observed to be easier than the direct hydrogenolysis route and is
therefore preferred.

73

Scheme 4.1: Reactions of alkylamines.

4.1.1. Formation of di- and tri- alkyl species

SH
R OH

R
Vac

H
N

H2

H
N

NH2

NH2

H2

NH2

H2
N

H
N

Liq
C8H16

H
N

C8H16

Liq
C8H16

C8H16

NH2

4.1.2. Disproportionation of diamines

NH2

NH

4.1.3. Alkyl transfer

R1
R1

R2
+
R1

R2

R1

CO
R2

R2

74

R2

+
R2

R1

R1

C8H16

Scheme 4.1: cont Reactions of alkylamines.

4.1.4. Production of olefins.

H2, He
H2C CH2

H2S

NH2

H2C CH2

NH3

H2C CH2

SH

N
H

H2C CH2

NH2

H2C CH2

N
H

SH
He

N
H

NH2

NH2

H2N

NH3

H2S

NH3

NH3

H2, He, Vac

H2

SH

H2, He

H2
NH2
H2, He

NH

75

NH2

Scheme 4.1: cont Reactions of alkylamines.

4.1.4. cont Production of unsaturated hydrocarbons.

Liq

CH3

C5H12

NH3

NH3

H2O

NH2
H2
NH2
H2
OH

4.1.5. Dehydrogenation and decarbonylation.

OH
CH3

C5H12

( + H2 )

Liq.

OH

+
+

H2

H2

2 H2

2 H2

O
Vac

NH2
NH2

NH2

NH
H2, He

H2

76

CO

Scheme 4.1: cont Reactions of alkylamines.

4.1.6. Production of saturated hydrocarbons

H2, He
H3C CH3

SH
H2
NH2
H2
SH

H2S

NH3

H2S

NH3

NH3

NH3

H2O

H2

NH2

H2

NH2

H2
NH2

H2
OH

4.1.7. Isomerization of olefins

H2, He, Vac

H2, He, Vac

H2, He

H2, He

H2

77

Table 4.1: Reactions involving alkyl amines, thiols, and alcohols.

Reaction

Reactant

Product

Citation

4.1.1.1

ethanethiol

diethylsulfide

(1, 2)

4.1.1.2

alkyl alcohol

dialkylether

(3)

4.1.1.3

n-butylamine

di(n-butyl)amine

(4)

4.1.1.4

n-pentylamine

di(n-pentyl)amine

(5, 6, 7, 8)

tri(n-pentyl)amine

(5, 6, 7)

4.1.1.5

neo-pentylamine

di(neo-pentyl)amine

(5, 6)

4.1.1.6

2-(n-octyl)amine

di(n-octyl)amine

(9)

tri(n-octyl)amine

(9)

4.1.1.7

cyclohexylamine

di(cyclohexyl)amine

(10)

4.1.1.8

3-phenylpropylamine

di(3-phenylpropyl)amine

(11)

4.1.2.1

di(n-pentyl)amine

tri(n-pentyl)amine

(8)

4.1.3.1

R3N + R3N

R2RN + R2RN

(12)

4.1.4.1

ethanethiol

C2H4

(1)

4.1.4.2

ethylamine

C2H4

(5)

4.1.4.3

diethylsulfide

C2H4 + C2H5SH

(1)

4.1.4.4

diethylamine

C2H4 + C2H5NH2

(13

4.1.4.5

triethylamine

C2H4 + (C2H5)2NH

(14)

4.1.4.6

diisopropylamine

C3H6 + (C3H7)NH2

(14)

4.1.4.7

n-butylamine

butenes

(4, 15)

4.1.4.8

n-butylthiol

butenes

(16)

4.1.4.9

n-pentylamine

pentenes

(5, 6, 7, 8)

4.1.4.10

tert-pentylamine

methylbutenes

(5, 6)

4.1.4.11

di(n-pentyl)amine

C5H10 + C5H11NH2

(8)

4.1.4.12

2-(n-octyl)amine

octenes

(9)

4.1.4.13

cyclohexylamine

cyclohexene

(8)

4.1.4.14

cyclohexanol

cyclohexene

(8)

78

Table 4.1: cont Reactions involving alkyl amines, thiols, and alcohols.

Reaction

Reactant

Product

Citation

4.1.5.1

n-butanol

n-butanone

(17, 18, 19)

C3 + CO

(17, 18)

4.1.5.2

2-n-octanol

2-n-octanone

(9)

4.1.5.3

n-butylamine

n-butanenitrile

(4)

4.1.5.4

n-pentylamine

n-pentanenitrile

(6)

4.1.5.5

neo-pentylamine

neo-pentanenitrile

(5, 6)

4.1.6.1

ethanethiol

C2H6

(1, 2)

4.1.6.2

n-butylamine

C2H6

(15)

4.1.6.3

n-butanethiol

n-butane

(16)

4.1.6.4

n-pentylamine

n-pentane

(5, 6, 7, 8)

4.1.6.5

neo-pentylamine

neo-pentane

(5)

4.1.6.6

cyclohexylamine

cyclohexane

(8)

4.1.6.7

cyclohexanol

cyclohexane

(8)

4.1.7.1

1-butene

2-butenes

(4, 15, 16)

cis-2-butene

trans-2-butene

(4, 15, 16)

4.1.7.2

1-pentene

2-pentenes

(5, 6, 7, 8)

cis-2-pentene

trans-2-pentene

(5, 6, 7, 8)

4.1.7.3

2-methyl-1-butene

2-methyl-2-butene

(5, 6)

79

In general, the selectivity for dehydrogenated species is favored by low pressures and
inert atmosphere, while saturated hydrocarbons are favored by higher pressure and
hydrogen atmosphere. However, changing the hydrogen pressure does not significantly
influence the conversion of aliphatic amines (8), indicating that the rate determining step
in C-N bond cleavage does not involve hydrogen.
The isomerization reactions of olefins, reported in Scheme 4.1.7, are thought to be
secondary reactions. That is, once the primary olefin is generated via -elimination, it
subsequently participates in isomerization. Later, in Scheme 5.3, we show a possible
mechanism for how these reactions occur on acid-base sites.

4.2.

Reactions of aliphatic ring compounds

Schemes 4.2.1 through 4.2.3 summarize the basic reactions of the aliphatic
heteroatom ring molecules, and Table 4.2 lists the references. Scheme 4.2.1 reports some
of the condensation products which have been observed. Note that free hydrocarbon ends
on these species could not have been produced by condensation reactions acting alone. It
is thus logical to assume that an elimination reaction (and hydrogenation of the so formed
olefin) has occurred, leading to the formation of e.g. n-pentylamine from piperidine. This
intermediate then combines with a second reactant molecule (here piperidine) via a
condensation reaction to create the observed product, in this case N-(n-pentyl)-piperidine.
The usual decomposition products of aliphatic rings are summarized in Scheme 4.2.2. In
these situations, intermediate alkyl species are thought to be highly reactive and are thus
infrequently seen. The presence of monoolefins and saturated hydrocarbons is common.

80

Scheme 4.2.: Reactions of aliphatic ring compounds.

4.2.1. Condensation reactions.

H2
NH

H2
NH

4.2.2. Formation of alkyl heteroatomics, alkanes, and alkene from aliphatic rings.

H2

NH2

SH

OH

N
H
H2
S
H2
O
H2

NH2

N
H

81

Scheme 4.2.: cont Reactions of aliphatic ring compounds.

4.2.3. Production of diolefins from aliphatic rings.

NH3

NH3

SH2

N
H

N
H

82

Table 4.2: Reactions of aliphatic ring compounds.

Reaction

Reactant

Product

Citation

4.2.1.1

pyrrolidine

N-(n-butyl)pyrrolidine

(8)

4.2.1.2

piperidine

N-(n-pentyl)piperidine

(5, 20)

4.2.2.1

pyrrolidine

n-butylamine

(8)

butenes

(8)

n-butane

(8)

4.2.2.2

tetrahydrothiophene

n-butanethiol

(16)

butenes

(16)

n-butane

(16)

4.2.2.3

tetrahydrofuran

n-butanol

(17, 18, 19)

butenes

(17, 18, 19)

n-butane

(17, 18, 19)

4.2.2.4

piperidine

n-pentylamine

(20, 21, 22)

pentenes

(5, 20, 21, 22)

pentane

(5, 20, 21, 22)

4.2.3.1

piperidine

pentadienes

(23)

4.2.3.2

piperidine

cyclopentene

(8)

4.2.3.3

tetrahydrothiophene

butadiene

(16)

4.2.3.4

tetrahydrofuran

butadiene

(19)

Scheme 4.2.3 reports some diene species which have been produced from aliphatic rings.
The formation of dienes is infrequent, but their identification backs up our position that
the heteroatom removal step is likely occurring via an elimination mechanism. In this
case two C=C bonds are formed, once for each C-X (X = N, S, O) bond broken.

83

4.3.

Reactions of aromatic heterocyclic hydrocarbons.

Scheme 4.3 reports common reactions of aromatic heterocycles. Here, the

hydrogenation reactions of the heteroatomic ring are usually the first to occur, and the so
formed aliphatic ring structure may then react according to the examples for aliphatic
rings given in Schemes 4.1 and 4.2. Thus the typical products are hydrogenated aliphatic
rings, alkyl species, monoolefins and saturates. Occasionally, dienes are observed in the
products, as well as condensation products typical of the aliphatic ring, which are
summarized in Scheme 4.3.2.
Thus, we have built up to the reactions of the simplest aromatic heterocycles, based
upon reactions observed for intermediates of their decomposition. It is relevant to note
that the hydrogenation reactions of heterocyclic rings are thought to occur on different
catalytic sites from those responsible for reactions of aliphatic species. This point is
exemplified by the conversion of piperidine over alumina and alumina/phosphate
catalysts, while pyridine displayed no reaction under the same conditions (23). The dual
function hydroprocessing catalyst, having hydrogenation and hydrogenolysis
capabilities, is indeed much discussed in the literature (22).

84

Scheme 4.3: Reactions of aromatic heterocyclic compounds.

4.3.1. Hydrogenation of aromatics to form aliphatic rings, alkanes, and alkenes.

H2

NH3

NH3

H2S

H2O

N
H

H2
N
H

H2
S

H2
O

85

Scheme 4.3: cont Reactions of aromatic heterocyclic compounds

4.3.2. Secondary reactions of aromatic heterocycles. Formation of condensation

products.

H2
N
N
H2
or

N
N
H2
N
N
CH3
H2
N
N

CH3

86

Table 4.3: Reactions of aromatic heterocyclic compounds.

Reaction

Reactant

Product

Citation

4.3.1.1

pyrrole

pyrrolidine

(8, 24)

n-butylamine

(8, 24)

butadiene

2-butenes

(8, 24)

butane

(8, 24)

4.3.1.2

thiophene

tetrahydrothiophene

(25)

n-butanethiol

butadiene

(25)

butenes

(17, 25, 26)

butane

(17, 25, 26)

4.3.1.3

furan

tetrahydrofuran

(17, 18, 19)

n-butanol

(17)

butenes

(17, 18, 19)

butane

(17, 18, 19)

butanone

(17, 18)

C3 + CO

(17, 18, 19)

4.3.1.4

pyridine

piperidine

(5, 27, 28)

n-pentylamine

(29)

pentenes

(5, 27, 28, 29)

pentane

(5, 27, 28, 29)

4.3.1.5

2-methylthiophene

tetrahydro-2-methylthiophene

(8, 17)

pentenes

(8, 17)

pentane

(8, 17)

4.3.1.6

2-methylpyridine

2-methylpiperidine

(30)

87

Table 4.3: cont Reactions of aromatic heterocyclic compounds.

Reaction

Reactant

Product

Citation

4.3.2.1

pyrrole

N-(n-butyl)pyrrolidine

(8)

4.3.2.2

pyridine

N-(n-pentyl)piperidine

(5, 8, 31)

4.3.2.3

pyridine

N-(cyclopentyl)piperidine

(5)

4.3.2.4

2-methylpyridine

N-(2-hexyl)-2-methylpiperidine

(30)

4.4.

Heteroatom exchange reactions

Scheme 4.4 summarizes heteroatomic exchange reactions, and the references are
listed in Table 4.4. These exchange reactions are likely of the condensation type
(nucleophilic substitution), proceeded or followed by hydrogenation/dehydrogenation
reactions yielding the listed product. One interesting reaction is the combined cyclization
and heteroatom exchange found in the conversion of 1-pent-4-entylamine. This reactant
can be considered to be the reactive intermediate formed by the cleavage of the first C-N
bond in piperidine. As noted, the cyclization and heteroatom exchanged product thiane is
also observed in the conversion of piperidine.

88

Scheme 4.4: Exchange reactions of heteroatoms.

He/H2S
OH

SH

H2O

H2O

NH3

NH3

NH3

NH3

NH3

He/H2S
SH

OH

H2/H2S
NH2

SH

H2/H2S
N
H

S
H2/H2S

S
H2/H2O
O

S
H2/H2S
NH2

89

Table 4.4: Exchange reactions of heteroatoms.

Reaction

Reactant

Product

Citation

4.4.1

n-propanol

n-propanethiol

(32)

4.4.2

iso-propanol

iso-pentanethiol

(32)

4.4.3

n-pentylamine

n-pentanethiol

(5, 6)

4.4.4

neo-pentylamine

neo-pentanethiol

(6)

4.4.5

1-pent-4-enylamine

thiane

(33)

4.4.6

piperidine

thiane

(5, 33)

4.4.7

pyridine

thiane

(5)

4.4.8

2-methylthiophene

2-methylfuran

(17)

90

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92