Development in TIPS RAS of novel advanced
processes for conversion of gaseous
feedstock and polymer wastes to valueadded chemical products
INOVACE 2013
Innovation technologies for unconventional chemical
feedstock transformation
1. New technology for synthesis gas production
2. New technology for production of olefins or
gasoline from natural , associated or biogas
3. New technologies for synthesis gas
transformation in slurry systems
4. Novel processes for polymer waste to fuel
transformation
OXIDATION OF NATURAL GASES TO SYN-GAS IN REACTOR SYSTEM WITH
FEEDING OF OXIDANT AND HYDROCAARBON IN DIFFERENT REACTORS
Regenerator
Natural or
associated
gas,
Biogas
Syn-gas formation
reactor
H2 + CO
(syn-gas)
Metal oxide
(MeO)
Metal (Me)
Conversion hydrocarbons in syn-gas:
CnHm + nMeO → nCO + ½m H2 + nMe
CO2+CH4 = 2CO+2H2
Catalyst regeneration:
O2 + 2Me0 → 2MeO
Nitrogen
ADVANTAGES OF NEW TECHNOLOGY
OF SYNGAS PRODUCTION:
Air
•44 % less capital costs and 16% less syngas
production costs
in comparison to
traditional steam reforming;
•Processing of associated petroleum gas
with a wide range of C2-C4 hydrocarbons
and CO2 into synthesis gas ;
•Using air as an oxidant without dilution of
syngas with nitrogen;
•Elimination of the formation of explosive
oxygen-hydrocarbon mixtures;
•Low rate of catalyst deactivation due to
coke removal during regeneration;
•Production of considerable amounts of
pure nitrogen
3
DIAGRAM OF OLEFINS (ETHYLENE AND PROPYLENE) SYNTHESYS
TIPS RAS
NEW NANOSTRUCTURATED CATSLYST
BASED ON ZSM-5
NATURAL GAS
Men+
Men+
0,5-0,7 ть
SYNGAS
DME synthesis
Men+
Catalyst production on
Industrial scale
Olefins
production
PROPYLENE
(TILL 60%)
ETHYLENE
(TILL 40 %)
The 2600 м3 of natural or associated gas gives
1 t of olefins
Gasoline or
naphtha
production
The yield of gasoline is 40- 50000 t per 1 mln.
m3 of gas.
4
DESIGN OF PILOT PLAN
РДС-4
FRC
P
РРГ-1
Синтез-газ
Сдувка на факел
1
Т-23
Т-22
ВЗ-89
F
РГ-1
P
1/2
ВТР-87
ВТР-86
2/2
T
3/5
ВЗ-19
Т-54
ВЗ-36
AC
Р
ВЗ-82
Ч-28
На анализ
На второй реактор при
увеличении
производительности
T
5/4
T
вода
P
T
ВЗ-20
Т-16
ВЗ-22
AC
Ч-25
На
анализ
ВЗ-80
ВЗ-31
ВЗ-81
8/4
На
анализ
ВЗ-17
ВЗ-27
газы
регенерации
6/5
9/4
Водород / азот / кислород
L
L
ВЗ-24
Т-15
ВЗ-25
5
ВЗ-26
Вода
Т-29
ВЗ-38
Ч-19
ВЗ-79
ВЗ-23
Т-14
L
10/4
ВТР-37
вода
На
анализ
ВЗ-21
ВЗ-33
Конденсат
Смесь
оксигенатов
6
2
3
7
5/5
ВЗ-90
L
ВЗ-32
Ч-26
Ч-17
L
4/2
P
Олефинсодержащий
газ
T
6/4
5/2
Водород / азот / кислород
РДС-2
Т-13
вода
в вентвыброс
ВЗ-28
AC
ВЗ-18
ВЗ-35
Т-24
AC
вода
Т-55
AC
4
7/4
Р
ВЗ-88
4/5
РДС-3
3/2
Process
Convers
ion
Olefin esynthesis
Катализатор
Т,оС
%
Пиролиз
70
-
1000
>99
Mobil
50-70
ZSM-5
350400
UOP/Norskhydro
70
SAPO-34
Lurgi (DME)
70
Van
(DME)
DME TIPS
Dijk >80
С2-С4
olefins, %
Selectivity
С2=
С3=
47
31
17
47-75 26-56
7-24
20-28
450
До
100
75-90
38-50 32-36
ZSM-5
430450
99
>69
0
70
SAPO-34
450
70
49
70
0
ZSM-5
340450
95100
80-88
30-50 20-47
THREE-PHASE SYSTEM SLURRY TECHNOLOGY
Catalysis in three-phase
systems
(slurry technologies)
15
mV
10-50
7
Газгольдер
H2
6
1
M
M
M
10
К
2
5
Буферная емкость
12
9
H2O
N2
CO
H2
11
3
1
Catalyst productivity
– 0,14-0,67 kg/kg(kat)*h
.
Olefins production
DME conversion : 73% mass.
Selectivity on C2-C6: >80% mass.
Ethylene + Propylene : 95%
14
К
M
13
4
DME production
Conversion СО: 30-56% mass.
Selectivity on DME: 91% mass.
DME in product : 95%
На сброс
8
17
Combination
of
homogeneous
and
heterogeneous catalysis advantages
+ Heat and mass transfer from the catalyst
grain by the liquid medium
+Use of undiluted feed
16
0-100
deg
Polymer wastes for production of motor fuels and petrochemical
feedstock
Oil fractions
Motor fuels
Mixing
(dissolution)
Dissolved (solubilized)
wastes
Polymer
wastes
Polymers and polymer wastes:
Polyethylene (PE);
Polypropylene (PP);
Polystyrene (PS);
Poly(ethylene terephthalate)
Oil fractions:
Light gas oil;
Heavy gas oil;
Vacuum distillate
Catalytic cracking
Feedstock for
petrochemistry
MAIN ADVANTAGES
- Surplus production of motor
fuels and petrochemical
products;
- Relatively low capital costs due
to potential of application of the
technology at existing catalytic
cracking units