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TABLE 5. DISTRIBUTION OF PORES BY SIZE IN CATALYSTS №4 AND №1
№4 catalyst
№1 catalyst
R
por
, A
V
por
*10
3
,
sm
3
/g
S
por
, m
2
/g
R
por
, A
V
por
*10
3
,
sm
3
/g
S
por
, m
2
/g
Micropores *
16,0
0,8
11,1
15,9
0,9
12,0
17,2
1,7
20,4
17,2
1,9
23,6
18,6
2,6
30,0
18,6
2,7
32,0
20,1
3,3
37,7
20,1
3,6
40,3
Mesopores *
21,8
4,3
46,3
21,7
4,4
48,1
23,8
5,1
53,3
23,7
5,2
54,8
26,0
6,0
60,5
26,0
6,3
63,4
28,5
7,1
67,9
28,6
7,4
70,6
31,6
8,3
75,2
31,8
8,4
77,4
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35,2
9,6
83,1
35,4
9,5
83,5
40,0
11,2
91,0
40,0
11,0
91,1
45,9
12,7
97,5
46,0
125
97,4
53,4
14,6
104,4
53,7
14,2
103,7
64,2
16,6
110,9
64,5
16,5
111,0
81,2
19,4
117,7
81,1
19,3
117,7
110,2
22,5
123,3
108,9
22,6
123,9
175,3,0
26,8
128,1
166,7
26,6
128,7
Makropores *
544,4
33,9
130,7
511,4
34,4
131,7
* Micro-pores (<20A ̇) meso-pores (20-500A ̇) according to the classification of pores by size
proposed by MM Dubin); macropores (> 500A ̇).
Comparison of the results of the IR spectral analysis of the structure shows that the presence of a
wide absorption band at 914 cm
-1
with a maximum confirms the formation of metal carbides at
the expense of the structure in reactors whose walls are treated with different salts.This can be
proved by the absence (absence) of the above bands and the presence of irregularly structured
carbon in the area of 1350-1500 cm
-1
as a result of the examination of the IR spectra of coke in
reactors whose walls are coated with salts of various metals.The resulting amorphous coke can
be lost by burning at 550-600
℃
in the air stream from the reactor surface for 2-3 hours.The
electron-microscopic analysis also confirmed IR spectroscopy data on the formation of coke as a
result of catalytic changes of C
1
-C
4
-alkanes.
Figure 3. The IR of the structure formed in reactors treated with (1),
(MoO
3
)
x
∙
(ZnO)
y
∙
(ZrO
2
)
z
(2), (MoO
3
)
x
∙
(ZnO)
y
∙
(B
2
O
3
)
z
(3) -spectrums
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Catalytic changes of C
1
-C
4
-hydrocarbons in the gas phase are governed by the first-order
reaction equation:
𝑊 = 𝑘
эф
∙ 𝐶
УВ
Where
𝑘
эф
- the effective constant of the reaction rate, the concentration of
𝐶
УВ
-alkane. Ideal for
reactions leading to extraction reactors
𝑘
эф
=
1
𝜏
𝑙𝑛
1
1 − 𝛼
, 𝐶
−1
Where α is the rate of change of the initial hydrocarbon;
𝜏
-contact time. Using the least-squares
method, the activation energy can be determined experimentally. For this the Arrhenius equation
used a logarithmic form:
𝑙𝑛𝑘
эф
= 𝑙𝑛 𝐴 −
𝐸
а
эф
𝑅𝑇
Where A is the exponential front multiplier;
𝐸
а
𝑒𝑎
-effective activation energy; The R-universal gas
constant is 8,314 j
mol
∙ K.
The parameters A and
𝑙𝑛𝑘
эф
were found based on the lnk_ef and 1/T correlations in the
coordinates. The calculation of the velocity constant was performed according to the first-order
reaction equation, which is confirmed by the straight-line relationship in the coordinates between
ln1/1-a and the contact time
(𝜏)
. The activation energy of the catalytic conversion reaction of
propane was found on the basis of the Arrhenius equation for the relationship between l
nk
and
1/T.
TABLE 6. KINETIC AND ACTIVATION PARAMETERS OF CATALYTIC CHANGE
REACTIONS OF PROPANE-BUTANE FRACTION
Reactor processing
Углеводор
од
T,
0
C
𝑘 ∙ 10
2
, 𝑐
−1
Ea,
кДж/моль
ln k
0
No processing
CH
4
710
800
0,16
3,35
258,5
±
12,9
25,5
±
1,3
C
2
H
4
710
800
0,66
2,88
144,8
±
11,3
12,6
±
1,3
C
3
H
8
710
800
3,47
13,77
132,7
±
10,6
13,0
±
1,2
(MoO
3
)
x
∙
(ZnO)
y
∙
(ZrO
2
)
z
CH
4
710
800
0,33
1,96
171,8
±
9,9
15,3
±
1,2
C
2
H
4
710
800
0,23
1,39
173,7
±
10,0
15,2
±
1,2
C
3
H
8
710
800
1,05
8,47
173,6
±
8,7
16,8
±
0,8
(MoO
3
)
x
∙
(ZnO)
y
∙
(B
2
O
3
)
z
CH
4
710
800
0,6
3,35
160,0
±
8,0
14,5
±
0,7
C
2
H
4
710
800
0,62
2,94
148,6
±
8,1
13,1
±
0,9
C
3
H
8
710
5,2
96,4
±
4,8
8,7
±
0,4
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800
12,5
TABLE 7. C
1
-C
4
- KINETIC AND ACTIVATION PARAMETERS OF PROPANE
DECOMPOSITION IN THE CATALYTIC TRANSFORMATION OF
HYDROCARBONS
(V = 50 ml/min;
𝜏 =
1.34 c; d = 0.6 cm; S/V = 5.6 ∙ 105 cm
-1
)
Реакторга
ишлов
бериш
Углеводород T,
0
C
𝑘 ∙ 10
2
, 𝑐
−1
Ea,
кДж/моль
ln k
0
Ишловсиз
CH
4
710
800
3,7
17,9
150,2±3,6
15,1±0,4
C
2
H
4
710
800
5,1
18,3
124,4±7,7
12,2±0,8
C
3
H
8
710
800
6,1
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