Technologies For The Synthesis of Ethylene and Propylene From Natural Gas

ISSN 20799780, Review Journal of Chemistry, 2016, Vol. 6, No. 1, pp. 83–123. © Pleiades Publishing, Ltd.
, 2016
Technologies for the Synthesis of Ethylene

and Propylene from Natural Gas
Yu. A. Treger and V. N. Rozanov
LLC Sintez Research and Engineering Center, pr. Vernadskogo 86, Moscow, 117571 Russia
email: yurytreger@gmail.com, RozanovVN@yandex.ru
Received September 2, 2015; in final form, October 2, 2015
Abstract—Different technologies for the synthesis of ethylene and propylene from natural gas are
considered. The simplest ethylene synthesis method is the oxidative condensation (or dimerization) of
methane (OCM process), but the implementation of this method is discouraged by a low ethylene
yield. Among the relatively simple methods for the synthesis of ethylene (together with acetylene)
immediately from methane are thermooxidative pyrolysis (TOP process) and pyrolysis in the presence
of chlorine (Benson process), whose disadvantages are a high temperature and a great number of by
products. A wide range of processes for the synthesis of ethylene and propylene with a small amount
of butylenes are based on the intermediate synthesis of syngas from methane and its further use for the
direct synthesis of lower olefins or products for subsequent catalytic pyrolysis to lower olefins, such as
methanol (methanoltoolefins (MTO) and methanoltopropylene (MTP) processes), dimethyl
ether, and liquid fuel (Fischer–Tropsch method). The methyl chloridetoolefins (MCTO) process
consisting of the synthesis of methyl chloride via the oxidative chlorination of methane and the cata
lytic pyrolysis of methyl chloride differ from these threestage processes in the absence of the syngas
production stage. The direct oxidation of methane to methanol and the homologyzation of methanol
to ethanol with further dehydration of ethanol to ethylene are also considered.
Keywords: natural gas, methane, ethylene, propylene.

DOI: 10.1134/S2079978016010039
CONTENTS
1. Introduction
2. Natural gas purification
3. Separation of methane homologues and their conversion into ethylene and propylene
3.1 Synthesis of ethylene via the pyrolysis of an ethane fraction
3.2. Pyrolysis of ethane fractions and C3–C4 and higher hydrocarbons
4. Oxidative condensation (dimerization) of methane and its homologues to ethylene (OCM process)
5. Pyrolysis of methane to ethylene and acetylene (thermooxidative pyrolysis (TOP) process)
6. Chloropyrolysis of methane to ethylene and acetylene (Benson process)
7. Partial oxidation of methane to methanol for further conversion into lower olefins
8. Conversion of methane into syngas for further processing into lower olefins by different methods
9. Direct synthesis of lower olefins from syngas
10. Methanoltoolefins (MTO) process: methane–syngas–methanol–olefins (predominantly ethyl
ene and propylene or only propylene: MTP process)
11. Dimethyl ethertoolefins process: methane–syngas–dimethyl ether–lower olefins
12. Methyl chloridetoolefins (MCTO) process: methane–methyl chloride–lower olefins
13. Synthesis of liquid fuel from syngas by the Fischer–Tropsch method (gastoliquid conversion
(GTLC process) with further pyrolysis of fuel to lower olefins
14. Chain of conversions: methane–methanol–homologyzation to ethanol–dehydration of ethanol to
ethylene
15. Conclusions
83
84 TREGER, ROZANOV
1. INTRODUCTION
At proven world oil resources of 156.7 billion tonnes (2003) and their constant current consumption of
4.265 billion tonnes in 2005 [1], oil will be sufficient for ∼37 years. Similarly, natural gas will be sufficient
for 68 years at its proven world resources of 175.77 trillion Nm3 (2003) and constant consumption at a level
of 2.6 trillion Nm3 in 2005 [1]. Russian reserves account for up to 40% of natural gas and no more than
10% of oil and gas condensate resources. Gas is much cheaper than oil.
In view of this fact, the problem of replacing the oil products used as feedstocks for the synthesis of
lower olefins for natural gas under Russian conditions is urgent and seems worthy of detailed consider
ation.
Ethylene is the most heavytonnage organic product in the world and finds wide application as an ini
tial intermediate product for the synthesis of organic compounds in the chemical and petrochemical
industry. The world production of ethylene in 2008 was 113 million tonnes, and its annual growth was at
a level of 2–3% [2]. In [3], it is pointed out that the rate of increase in natural gas chemistry production
in the world exceeds the gross domestic product growth rate.
There is almost no ethylene market in Russia, as the greater volume of produced ethylene is processed
at domestic facilities. The consumption of ethylene in 2006 was 2355 t [4]. In the Russian Federation, eth
ylene is produced at ten Russian enterprises located in the Southern, Volga, and Siberian Federal Districts.
The world production of propylene in 2006 was ∼67 million tonnes [5]. The overall propylene capaci
ties in the Russian Federation in 2004 were at a level of 1.4 million tonnes [5]. Propylene was produced at
12 Russian enterprises concentrated in the Central, Southern, Volga, and Siberian Federal Districts.
The main industrial method for the synthesis of lower olefins is the pyrolysis of liquid oil distillates and
lower saturated hydrocarbons in tubular furnaces at 800–950°C [2]. In Western Europe, 90% of lower ole
fins are synthesized via the pyrolysis of gasoline; in the United States, nearly 30% of lower olefins are
obtained via the pyrolysis of liquid oil products; among them, 42% are synthesized from ethane and 29%
from liquefied gases [2]. Different feedstocks are used in the Russian Federation; in particular, ethane sup
plied by the Orenburg Helium Plant, which plans to process ethane at its own facilities in the future, is
converted at the Kazanorgsintez enterprise. However, the main feedstocks are gasoline and natural gas liq
uids (NGL).
2. NATURAL GAS PURIFICATION

The production of ethylene and propylene requires the separation of natural gas into fractions which
can be used for the synthesis of target products. The flowsheets of the purification of natural gas and its
separation into fractions are described below.
When natural gas fractions are used for the synthesis of ethylene and propylene, it is necessary to purify
the gas from sulfurcontaining compounds and carbon dioxide. Since natural gas is separated via low
temperature distillation, the gas must also be dried to the water vapor dew point of around 60°C. Gas pro
cessing plants use twostage ethanol amine regenerative technology for the simultaneous purification of
the gas from sulfurcontaining compounds and carbon dioxide and treatment with ethylene glycol for dry
ing [6, 7]. Since the latter does not give the required dew point, the gas is passed after this stage through
an additional unit of drying with the use of 5 Å molecular sieves. The gas purification and drying flowsheets
are shown in Fig. 1.
A highpressure gas (20–40 atm) is fed to the firststage absorber C1. The absorber is irrigated with
regenerated ethanol amine. The gas from absorber C1 enters the secondstage absorber C3. Ethanol
amine saturated with hydrogen sulfide and carbon dioxide is passed from the bottom of absorber C1 into
the firststage desorber C2, where ethanol amine is regenerated and hydrogen sulfide and carbon dioxide
are removed owing to pressure relief absorbent heating. The desorber bottom temperature of ~130°C is
maintained by supplying heat to the boiler. The regenerated ethanol amine from the bottom of desorber
C2 is delivered to absorber C1. Fresh ethanol amine is introduced into this circuit to compensate losses.
The vaporgas mixture from the top of desorber C2 is fed to the second purification stage.
The second absorption stage (absorber C3 and desorber C4) is operated in the same way as the first
stage. The purified gas from absorber C3 is fed for drying. The vapors from the top of desorber C4 are
recycled into desorber C2.
Twostage ethanol amine purification guarantees the content of hydrogen sulfide and carbon dioxide
in the purified gas of less than 10 ppm each.
The gas purified from sour compounds is delivered for preliminary drying in the diethylene glycol
washing unit in absorber C5. The saturated glycol from the bottom of the absorber enters regenerator
REVIEW JOURNAL OF CHEMISTRY Vol. 6 No. 1 2016

TECHNOLOGIES FOR THE SYNTHESIS OF ETHYLENE 85
H2S, CO2
S1
C5 C6 Vacuum
C1 A1
CH4 after regeneration
C2
C3 CH4 to regeneration
C4
Natural gas
C2 Water Dried gas
Second
First natural gas purification
purification stage Natural gas drying
stage
Fig. 1. Natural gas purification and drying: (C) absorption column, (S) separators, (A) adsorber.
C6, where the water vapor is withdrawn from the top. The regenerated diethylene glycol from the bottom
of regenerator C6 is fed for irrigation to absorber C5.
The gas from the glycolic drying unit enters the unit of adsorption drying with 5 Å molecular sieves.
The gas from adsorber A1 has a dew point no higher than 60°C and is further fed to the separation unit.
The adsorber is operated in a periodic mode: adsorption cycles alternate with regeneration cycles. The
adsorber is regenerated with methane heated in a furnace.
It should be noted that hydrogen sulfide removed from an initial gas cannot be exhausted into the
atmosphere. It must be fed to a Claus unit for the synthesis of sulfur of oxidized in an alkali solution to
thiosulfate.
Natural gas contains inert compounds (nitrogen, argon, helium), which do not produce any effect on
the process, but must be removed by blowdown from the recycled gas.
In the production of methanol, the total concentration of sulfurcontaining compounds in the purified
gas must not exceed 0.2 mg/m3 [8] at their usual initial content of up to 100 mg/m3. To remove sulfur
containing compounds, natural gas is subjected to twostage purification [9]. At the first stage, organic sul
furcontaining compounds are hydrated to hydrogen sulfide on an aluminumcobaltmolybdenum or alu
minumnickelmolybdenum catalyst at a temperature of 350–450°C. To accomplish this, a small amount
of hydrogen (~0.15 vol %) is introduced into the natural gas [9]:
RSH + H2 → RH + H2S.
At the second stage, hydrogen sulfide is adsorbed by zinc oxide on GIAP10 adsorbent containing zinc
oxide with copper oxide additive:
ZnO + H2S → ZnS + H2O + 76.7 kJ/mol (heat release),
ZnO + COS → ZnS + CO2 + 111.3 kJ/mol.
In the production of chloromethanes via the chlorination of methane, the destructive hydrogenation
of methane homologues to methane is performed on a nickelchromium catalyst simultaneously with puri
fication from sulfur to the ethane content at a level of 0.01%:
C2H6 + H2 → 2CH4 + 65.1 kJ/mol,
C3H8 + 2H2 → 3CH4 + 120.9 kJ/mol,
C4H10 + 3H2 → 4CH4 + 173.5 kJ/mol,
C5H12 + 4H2 → 5CH4 + 228.2 kJ/mol.

86 TREGER, ROZANOV
E11 To initial gas

E10 compression
CH4
T9 S3
S2 S4
C1
Natural gas
E1 E2 E3 S3H8 C4H10
S1 S2 S3
S4 C5
E4 E5 C H C2H6

3 8
E8 Stable gasoline

E7 E6
C2H6
Fig. 2. Purified natural gas and gas condensate separation: (E) heat exchangers, (S) separators, (C) distillation columns.
3. SEPARATION OF METHANE HOMOLOGUES AND THEIR PROCESSING INTO

ETHYLENE AND PROPYLENE. SEPARATION OF METHANE HOMOLOGUES
The flowsheet of the separation of condensate from natural gas and the separation of homologues con
tained in it is shown in Fig. 2 [9]. The initial gas with a pressure of 35–37 atm is separated into three frac
tions to recuperate the cold of the flow withdrawn from the unit.
The first gas fraction is passed through heat exchangers E1, E2, and E3, where it is cooled by the
methane withdrawn from separator S2, the feed of column C1, and the ethane from the cooling circuit.
The second gas fraction is cooled in heat exchangers E4 and E5 by the methane withdrawn from sepa
rator S3 and the ethane of the cooling circuit. The third gas fraction is cooled in heat exchangers E8, E7, and
E6 by the ethane withdrawn from separator S4 and the propane and ethane of the cooling circuit.
All three fractions of natural gas cooled to a temperature of around 50°C are fed to separator S1, where
the liquid and gas phases are separated. The liquid phase after heat exchanger E2 serves as a feed to col
umn C1 (demethanizer). The gas phase is cooled in heat exchanger E9 by the ethane of the cooling cir
cuit to a temperature of 60 to 75°C.
This flow is further cooled in heat exchanger E10 by the methane expanded to a pressure of 6–12 atm.
The liquid phase from separator S2 with a temperature of around 85°C is delivered for refluxing to col
umn C1. This column is operated at a pressure of 30–35 atm and a top temperature of around 75°C. The
methane withdrawn from the top of this column is cooled in heat exchanger E11 by the gas flow expanded
to a pressure of 6–12 atm from separator S3. The liquid phase from this separator is delivered for refluxing
to column C1. The gas from separators S2 and S3 after heating in heat exchangers E10, E1, E11,
and E4 are combined into one flow and fed for compression, where it is brought to a pressure required
for further use. The proposed flowsheet provides the ethane recovery of ~85%. There also exist other pos
sible flowsheets.
C2+ hydrocarbons are accumulated at the bottom of column C1, where the temperature is 20–40°C.
This enables the removal of methane to the level at which ethane with a concentration of no lower than
95 wt % will be obtained. The residue of column C1 serves as a feed to column C2 (deethanizer). Its dis
tillate is ethane. This column is operated at a pressure of 25–30 atm. The condenser of this column is
cooled by the propane from the cooling circuit. The ethane from the separator is passed through heat
exchanger E8 and supplied to consumers. The residue of this column represents a C3+ fraction and serves
as a feed to column C4 (depropanizer).
The gas condensate contained in the initial gas and separated upon its compression is fed to column
C3 (compression gasoline). It is operated at a pressure of 18–20 atm. Methane and ethane dissolved in
the feed are withdrawn from the top of this column and recycled for compression.
Stable gasoline separated as a residue of column C5 serves as a reflux of column C3. The residue of
column C3 is mixed with the residue of column C2 and supplied to depropanizer C4 as a feed.
The distillate of column C4 is propane. The column is operated at a pressure of 16–20 atm, which
enables the use of recycled water in the reflux condenser of column C4. The residue of depropanizer C4
is a fraction of C4+ hydrocarbons, which serve as a feed to debutanizer C5. The distillate is a mixture of
n and isobutanes. The residue of column C5 is stable gasoline (hexane fraction).

The butane fraction can be separated into components. This requires another column. This is reason
able when there exists a consumer of isobutane. Alternatively, butanes are used in the mixture fed for
pyrolysis or as liquefied household gas. Steam is used as a heating agent in the boilers of all the columns.
The natural gas separation unit must incorporate ethane and propane cooling circuits.
3.1 Synthesis of Ethane via the Pyrolysis of an Ethane Fraction

The pyrolysis of ethane is performed in such a regime that its conversion is 60–65% [10, 11]. The
unconverted ethane is separated in the gas separation system and recycled for pyrolysis. At complete
ethane conversion, the yield of pyrolysis products is the following (wt %): H2, 5.5; C3H6, 2.1; C4H8, 0.85;
CH4, 11.6; C3H8, 0.5; C5+, 2.25; C2H4,75.1; C4H6, 2.1.
The ethane pyrolysis reaction is endothermic and follows a radical chain mechanism. To increase the
yield and decrease the process temperature, it is possible to perform oxidative dehydrogenation in the
presence of carbon dioxide or oxygen, which bonds the liberated hydrogen:
C2H6 → C2H4 + H2 – 32.4 kJ/mol,
2C2H6 + O2 → 2C2H4 + 2H2O + 419.1 kJ/mol.
A variant of the process flowsheet for the synthesis of ethane via the pyrolysis of ethane is shown in
Fig. 3. The feedstock and recycled ethane is fed to a section in the convection zone of a furnace for heating
to a temperature of ~150°C. The heated ethane is delivered to column C1, where it is saturated with water
vapor at a temperature of ~ 140°C to a water content of ~30 wt % with respect to ethane. The steamethane
mixture is passed through three sections in the convection zone of furnace F1 and enters into a radiant
coiled tube located in the combustion chamber at a temperature of ~670°C. The combustion chamber is
heated by its own hydrogenmethane fraction.
The pyrolysis of ethane is performed at a temperature of 830–850°C. The ethane conversion is 60–
65%. The pyrolysis products from the radiant coiled tube are quickly cooled to ~370°C in quenching and
evaporating heat exchanger E1. The heat is withdrawn owing to the regeneration of steam at 40–120 atm.
The steam obtained is separated from water in steam separator S1 and superheated in one of the sections
in the convection zone of furnace F1.
The pyrogas is further cooled to ~200°C in heat exchanger E2 by heating of the feed water for the
quenching and evaporating heat exchanger and then enters washing column C2. In this column, the
pyrogas is cooled to 35–40°C and the products are condensed. The condensed liquid consists of water and
a small amount of heavy tar, which are separated in vessel S3.
The water heated to ~140°C from vessel S2 is delivered for irrigation of column C1. Excess water is
recycled to vessel S2.
The cooled pyrogas from column C2 is fed to the suction line of five or sixstage compressor Com1
(only two stages are shown in the figure). After compression at each stage, the gas is cooled (heat exchang
ers E3 and E4), and water and liquid hydrocarbons are condensed. The water is recycled to vessel S3,
and the liquid hydrocarbons from vessel S4 are also passed to vessel S3, where they are withdrawn from
the system.
Before the last compressor stage, the gas is washed from sulfurcontaining compounds and carbon
dioxide in column C3 with an alkali solution. In the top section of column C3, the gas is washed from
trace alkali with water. At the last stage, the gas is finally compressed to ~40 atm. Water is removed in sep
arator S5, and the gas is fed to acetylene hydrogenation reactor R1. It represents a shellandtube appa
ratus with heat removal owing to the evaporation of methanol.
The purified gas is cooled in heat exchanger E5 to ~15°C and then is passed through drier D1.
The driers are operated in a periodic regime: one is used to dry the gas, and the other is used to regenerate
the hot methane fraction. The dried gas is cooled in heat exchanger E6 to 30°C.
The cooled gas enters separator S6. The liquid phase from this separator is fed to column C4, at the
bottom of which C3+ hydrocarbons are withdrawn. Column C5 is operated at a pressure of ~20 atm.
A temperature of ~80°C is maintained at its bottom to blow away C2 hydrocarbons. The gas from separator
S6 is passed through multiflow heat exchanger E7, where it is cooled to 60°C. Here, hydrocarbons are
partially condensed and removed in separator S7.
Column C5 (demethanizer) has two feed flows, one of which is the liquid from separator S7 and the
other is the vapor from the top of column C4. Column C5 is operated at a pressure of 11 atm. An ethane
ethylene fraction is withdrawn at its bottom. The gas from separator S7 is passed through multiflow heat
exchanger E8, where it is cooled to 85°C. The condensate formed in this case flows from separator S8

88 TREGER, ROZANOV
S8
F1
Com1 Com2 S10
Ethane H2
C1 T3 T4 R1 70°C 93°C
CH4
S4 S5 E8 E11
E7
S2 −93°C
S7
from C6 T5 T6 S6 −37°C
Hydro T9 S9
Water carbons
C2 Water
S1 C3 to S1 −19°C Ethylene
C4 C5 C6
T10
S3
NaOH solution
E1 E2 to F1
Tar Water S3+
Condensate
Fig. 3. Production of ethylene via the pyrolysis of ethane: (F) pyrolysis furnace, (C) distillation columns, (S) separators,
(R) reactor, (D) dryer, (E) heat exchangers, (Com) compressors.
into separator S9. The vapor condensate from column C5 after cooler E9, in which boiling ethylene
with a temperature of 93°C is used as a heattransfer fluid, enters the same separator. The liquid phase
from separator S9 is fed to column C5 as a reflux. The gas from separator S7 represents a methane frac
tion, which serves as a cooling fluid in heat exchangers E8 and E7.
The gas from separator S8 is cooled by the recycled flows from separator S10 in multiflow cooler E10
to 120°C. The gas flow from separator S10 represents a hydrogen fraction, which serves as a cooling fluid
in multiflow heat exchangers E10, E8, and E7. The condensed methane from separator S10 is
expanded and fed to separator S9 after heating in heat exchanger E10.
The cold of recycled flows is insufficient for multiflow heat exchangers E7 and E8. The deficient
amount of cold in them is supplied via the evaporation of ethylene at temperatures of 70 and 93°C, respec
tively.
The ethaneethylene fraction from the bottom of column C5 is passed by a pump through heat
exchanger E10, where it is heated owing to the cooling of its heattransfer fluid and then fed to column
C6. Commercial ethylene is withdrawn at the top of this column, and ethane is withdrawn at its bottom
and recycled for pyrolysis. Column C6 is operated at a pressure of 20 atm. Liquid propylene with a tem
perature of 37°C serves as a cooling fluid in its reflux condenser, and propylene vapor at a temperature of
0°C is used as a heating fluid in its boiler.
The yield of ethylene in the pyrolysis of an ethane fraction can be as high as 80%.
Hydrogen and methane fractions are used for combustion in pyrolysis furnaces. As can be judged from
the balance, their fuel must be sufficient at a good thermal efficiency of pyrolysis furnaces.
3.2. Pyrolysis of Ethane and C3–C4 (and Higher) Hydrocarbon Fractions

When three types of feedstocks, such as ethane, propanebutane fractions, and socalled “stable gaso
line” (more highboiling natural gas fractions), are used for pyrolysis, each of them has its own balance of
decomposition [10, 11]. The weight ratio between propane and butanes in natural gas is 2 : 1. In pyrolysis,
the conversion is ~92% for propane and ~96% for butanes. NButane and isobutane give absolutely dif
ferent yields of products, particularly, ethylene: nC4H10 gives 33–36 wt % of ethylene, whereas isoC4H10
gives only 10–15 wt %:
C3H8 → C3H6 + H2 – 124.3 kJ/mol,
C4H10 → 2C2H4 + H2 – 231.1 kJ/mol.
With allowance for the recycled propane, a mixture of liquefied gases will have the following composi
tion (wt %): C3H8, 70; nC4H10, 20; iC4H10, 10.

For such a feedstock, it is possible to assume the following yields of pyrolysis products (wt %): H2, 1.3;
CH4, 22.4; C2H6, 4.2; C2H4, 36.9; C2H2, 0.6; C3H8, 3.4; C3H6, 14.8; C3H4, 0.7; C4H10, 2.5; C4H8, 2.5;
C4H6, 2.6; ΣC5–C8, 2.0; aromatics, 4.1; heavy liquid fuel, 2.0.
A variant of the ethylene production flowsheet in which all the natural gas components except methane
serve as a feedstock is described below (Fig. 4).
The feedstock ethane together with the recycled ethane is pyrolyzed in furnace F1 as shown in Fig. 3.
The liquid feedstock incorporating liquefied propane and butanes, stable gasoline, and the recycled
propane is pyrolyzed in furnace F2. Furnaces F1 and F2 differ from each other in the configurations
of coiled tubes in the combustion chambers and the regimes of pyrolysis. The mixture of feedstock with
vapor is heated to a temperature of ~570°C. The pyrolysis temperature for this feedstock can fall in the
range of 840–870°C.
The further sequence of separation for the total pyrolysis products does not radically differ from the
flowsheet of separation for ethane pyrolysis products in Fig. 3 before the stage of separation of commercial
ethylene and recycled ethane. Propylene and butylenes are separated on the separation unit consisting of
three columns.
C3+ hydrocarbons are fed to the depropanizer, where a propanepropylene fraction is withdrawn at the
top, and C4+ hydrocarbons are withdrawn at the bottom. The propanepropylene fraction is fed to the pro
pylene column. To obtain propylene with a concentration of 99.8% (polymerizationgrade quality), this
column must have no less than 200 trays. It usually consists of two parts (splittype column): the liquid
from the stripping section is pumped as a reflux to the enriching section, and the vapor from the enriching
section is fed to the bottom of the stripping section.
The residue from the depropanizer is fed to the debutanizer. A C4 hydrocarbon (butylenedivinyl) frac
tion is separated at the top of this column. A C5+ fraction representing pyrogasoline is withdrawn at the
bottom of the debutanizer. It can be used as a highoctane gasoline component, but only after the hydro
genation of dienes contained in it. The butanebutylene fraction can be used for the separation of divinyl.
To decrease the feedstock consumption, the C3 and C4 hydrocarbon fractions can be subjected to
exhaustive hydrogenation to propane and butanes, which will be recycled for pyrolysis. In the pyrolysis of
a propanebutane fraction, the yield of ethylene with allowance for the formed ethane and unconverted
propane recycle is ~42–43 wt %.
When the C5+ fraction of natural gas is used in addition to ethane and a propanebutane fraction, the
yield of ethylene from it with allowance for recycles is ~34 wt %.
The yields of ethylene and propylene synthesized via the steam cracking of different hydrocarbon feed
stocks are given in Table 1.
4. OXIDATIVE CONDENSATION (DIMERIZATION) OF METHANE TO ETHYLENE

The synthesis of ethylene via the catalytic oxidative dimerization of methane was discovered in 1982.
Since that time, several thousand papers and patents have been published, but the process was never
implemented in industry. In [13], it was concluded that, despite a relatively short time after the oxidative
condensation of methane to ethylene was discovered, there is a fair amount of reliable information known
about this catalytic process: mechanism, catalysts, kinetics, and different techniques for increasing the
efficiency of the reaction.
The studies conducted by different authors show that the maximum yield of C2 hydrocarbons per reac
tor run under laboratory conditions is 17–20% at an ethylene/ethane ratio of 24. The conversion of meth
ane per single pass through a reactor is 30–35%. At a higher methane conversion, the yield of C2 hydro
carbons does not grow and, consequently, only the amount of formed byproducts increases, and the
selectivity of the process becomes lower. The chemistry of this process can be described by the following
reactions:
2CH4 + O2 → C2H4 + 2H2O + 281.9 kJ/mol,
2CH4 + 0.5O2 → C2H6 + H2O + 176.9 kJ/mol,
CH4 + 2O2 → CO 2 + 2H2O + 802.8 kJ/mol,
CH4 + 1.5O2 → CO + 2H2O + 519.7 kJ/mol,
CH4 + 0.5O2 → CO + 2H2 + 35.7 kJ/mol.

90 TREGER, ROZANOV
Ethane recycle
C2 Ethane py
rolysis
fraction furnace F1
Pyrogas compression, Purification Ethylene Propylene

purification, from acetylene separation separation
and drying in 3 columns in 3 columns
and drying
C3C4
C3C4
pyrolysis
fraction furnace F2
Propane recycle
Fig. 4. Flowchart for the pyrolysis of C2–C4 methane homologues.
All these reactions produce a great deal of heat. The optimal process temperature lies within a range of
800–940°C depending on the catalyst.
The methane conversion is 20% on a mixture of rareearth oxides with lithium salt additives at a selec
tivity to C2 hydrocarbons of 80% in an autothermal process regime when oxygen is used as an oxidizer
[14]. The C2H4/C2H6 ratio is 2.
In [15], the kinetics of the methane oxidative dimerization process on La/Ce catalysts was studied, and
its mathematical modeling and optimization were performed. In addition to the first three of the above
cited reactions, the data [15] were described with consideration for the following reactions:
2C2H6 + O2 → 2C2H4 + 2H2O,
C2H4 + 2O2 → 2CO + 2H2O,
C2H4 + 3O2 → 2CO2 + 2H2O,
CO2 + H2 ←
→ CO + H2O.
The kinetic model was used as a basis to perform the mathematical modeling and theoretical optimi
zation of the methane oxidative dimerization process in a plugflow reactor. The conversion of oxygen and
the selectivities to ethane and ethylene were studied as functions of the conditional contact time, temper
ature, pressure, and the volumetric ratio of reagents.
The paper [16] is devoted to the practical aspects of technology for the production of ethylene from
natural gas via the oxidative dimerization of methane. The analysis of published data shows that the best
catalysts give close results under optimal conditions despite their different nature. The singlepass yield of
C2 hydrocarbons does not exceed 25% on any catalyst, and the same result was obtained when modeling
the catalytic oxidative dimerization of methane. The yields of C2 hydrocarbons above 20% take place only
at a 20 to 35fold dilution of feedstocks (methane and oxygen) with an inert gas.
Table 1. Yield of products in the steam cracking of different hydrocarbon feedstocks [12]
Liquid hydrocarbon feedstocks, wt
Gaseous hydrocarbon feedstocks, wt %
Yield of products %
ethane propane butanes naphtha gasoil
Hydrogen and methane 13 28 24 26 23
Ethylene 80 45 37 30 25
Propylene 1.11 14.0 16.4 14.1 14.4
Butadiene 1.4 2 2 4.5 5
Mixture of butylenes 1.6 1 6.4 8 6

In most works, the oxidative dimerization process was studied at 700–800°C and a methane/oxygen
ratio of 3–6. At such ratios, the adiabatic heating is 500–1100°C. Calculations show that the number of
reactors in a cascade must be 5–6 at a singlepass methane conversion of 25–30%. Each reactor needs an
individual feed with oxygen, which will nearly completely be consumed in it. When a single adiabatic reac
tor is used, an initial mixture must be diluted with water vapor.
Some economic aspects of ethylene production via the catalytic oxidative dimerization of methane are
discussed in [17]. It is noted that the studies of this reaction at the AllRussian Research Institute of
Organic Synthesis enabled the development and calculation of the process flowsheet. The engineering and
economic evaluation of this process was performed for its implementation both in a gas producing region
and at a chemical enterprise which consumes ethylene for further processing and incurs a deficit of it. The
calculations were performed for an industrial unit with a capacity of 200 000 t of ethylene per year.
The work presents the comparative data for the developed process of ethylene production from meth
ane and the known process of ethylene production from ethane. The consumption of feedstocks, auxiliary
materials, and energy sources, the ethylene prime cost compositions, and the costs of units for both pro
cesses are given.
The work has a number of subjective and objective shortcomings. For example, the cost of the unit for
the production of ethylene from methane and the prime cost of ethylene proved to be 25% higher than the
same parameters of the ethane pyrolysis process. However, the unit for the preliminary separation of
ethane from natural gas was not taken into consideration in this case.
The objective difficulties consisted in that the gas prices were under government control, and the
ethane price was free (commercial). The prime cost of ethylene produced via the oxidative dimerization
of methane at a gas processing enterprise proved to be 1.7–1.9 times lower than at a similar chemical
enterprise unit, because the average price of natural gas for enterprises in the gas production industry was
more than two times lower than for enterprises of other industry branches.
The data obtained at the AllRussian Research Institute of Organic Synthesis on catalyst samples
developed together with the Institute of Chemical Physics of the Russian Academy of Sciences were used
as a basis to develop a process flowsheet for the production of polymerizationgrade ethylene. The flow
chart of this production is shown in Fig. 5.
In view of large heat release and high temperatures, a reactor for the catalytic oxidative dimerization
of methane must be adiabatic. The maximum singlepass methane conversion in one reactor may be 20–
25% at a selectivity to C2 hydrocarbons of ~75%, which provides their yield of ~14%. To attain a methane
conversion of 32–35%, a cascade of two reactors with intermediate withdrawal of heat between them was
installed.
The adiabatic regime with a maximum catalyst bed temperature of 850–870°C is implemented at a
volumetric ratio CH4/O2 ~ 6 for the operation with one reactor. In the case of a cascade of two reactors,
oxygen is fed to each of them at a ratio CH4/O2 ~ 6. In a twostage reactor, an increase in the methane
conversion by 1.6 times leads to a growth in the yield of C2 hydrocarbons by 1.3 times; i.e., the selectivity
decreases, and the consumption of oxygen grows by two times in this case. However, the methane recycle
and, consequently, the load of the gas separation system decrease.
The initial natural gas together with the recycled methane and ethane are fed to reaction unit (1),
which consists of one reactor or a cascade of two reactors. The flow with a temperature of 860–890°C
from the reactors is cooled in quenching and evaporating heat exchangers with generation of highpres
sure steam. The flow is further cooled to 30°C with condensation of reaction water and fed to reaction gas
compressor (2). The gas is purified from a predominant amount of CO2 in ethanolamine purification unit
(3). The afterpurification of this flow by alkali washing and its drying and cooling to –100°C with the use
of propylene and ethylene cooling cycles are performed in unit (4). The fuel gas comprising hydrogen, car
bon monoxide, nitrogen, residual oxygen, and some methane is separated in unit (5). This flow is
expanded to a pressure of 0.3–0.5 MPa through turboexpander (6). The unconverted methane is separated
in column (7) and recycled to the reaction unit through turboexpander (8). A C2+ fraction fed to column
(9) is withdrawn at the bottom of column (7). An ethaneethylene fraction containing ~0.4% of acetylene
is withdrawn at the top of this column. Acetylene is removed by dimethylformamide washing (10). Com
mercial ethylene is separated in column (11). The quality of ethylene corresponds to the requirements
imposed on the feedstocks used in vinyl chloride and polymer synthesis processes. Ethane representing
the residue of this column is recycled to the reaction unit.
The obtained experimental data and the developed process flowsheet were used as a basis to calculate
the consumption coefficients for feedstocks and energy utilities in the synthesis of ethylene by oxidative
dimerization. The consumption per 1 t of ethylene is as follows: methane, 3.05 t; oxygen, 4.07 t; electrical

92 TREGER, ROZANOV
Steam
CO2
Feedstocks
3
1
2
4
Fuel gas
Ethylene
5 10
8
9
11
C3+ hydrocarbons
Fig. 5. Flowchart for the production of ethylene via the catalytic oxidative dimerization of methane: (1) reaction unit;
(2) compressor; (3) ethanolamine purification from CO2; (4) alkali purification, drying, and cooling; (5) fuel gas separa
tion; (6, 8) turboexpanders; (7) methane separation column; (9) ethaneethylene fraction separation column; (10) purifi
cation from acetylene; (11) commercial ethylene separation column.
power, 1650 kW h; thermal energy, 0.866 Gcal. Byproducts per 1 t of ethylene are as follows: thermal
energy, 26.9 Gcal; fuel gas, 0.9 t; carbon dioxide, 0.65 t.
The capital expenditures on the creation of a plant with a capacity of 200000 t of ethylene and the
prime cost of ethylene are now out of date, being determined with the use of average prices as of the begin
ning of 2001.
5. PYROLYSIS OF METHANE AND ITS HOMOLOGUES

TO ETHYLENE AND ACETYLENE
Acetylene is a highly reactive compound. For this reason, a number of industrially important syntheses
with the use of acetylene are much simpler than with ethylene. For example, the synthesis of acetaldehyde
is performed in a single stage via the hydrogenation of acetylene in the presence of a catalyst in contrast to
the multistage synthesis with the use of ethylene. The vinyl chloride synthesis process is also performed in
a single stage and is simple in equipment implementation.
Acetylene can be synthesized from different hydrocarbons, including natural gas by pyrolysis [18]. The
yield of acetylene in the methane pyrolysis process is much higher than for ethylene and its byproducts.
Both of these products (ethylene and acetylene) are obtained together in the pyrolysis of hydrocarbons.
Their yield depends on the employed technology and process conditions. In most cases, it is possible to
attain selective ethylene synthesis. The only hydrocarbon from which ethylene cannot be synthesized via
noncatalytic pyrolysis without a considerable amount of acetylene, is methane, i.e., natural gas in
essence.
The synthesis of acetylene via the thermooxidative pyrolysis of methane (TOP process) has gained the
widest recognition. In this case, the target product is acetylene with a low concentration of ethylene.
The production of an acetyleneethylene mixture can be of interest for the synthesis of vinyl chloride,
especially if it is an equimolar mixture suitable for the development of a combined vinyl chloride synthesis

method. In this case, hydrogen chloride obtained in the pyrolysis of dichloroethane is completely utilized
at the acetylene hydrochlorination stage.
Such a mixture is obtained in the pyrolysis of methane at its low conversion of nearly 40%. The yield
of acetylene grows with an increase in the conversion owing to a growth in the temperature or reaction
time, whereas the yield of ethylene begins to decrease.
At a 40% methane conversion, the concentration of acetylene and ethylene in the reaction gas is rather
small, thus resulting in a complicated technology for the separation of target products. A methane recycle
is used to attain high acetylene and ethylene yields per supplied methane. The separation of methane from
reaction products requires deep cold. It is also necessary to compress the flow to a pressure of ~4.0 MPa
and create at least one cooling cycle with an isotherm of around 100°C (flowsheet for the separation of
pyrolysis products with production of ethylene is given in section 3).
The pyrolysis of methane requires a high temperature of no less than 1300°C. To stop when an equimo
lar acetyleneethylene mixture is obtained, the reaction time must be very short, i.e., about 5⋅10–5 s (at a
temperature of ~1500°C).
The ethylene and acetylene yields in the pyrolysis of ethane can attain 30–35% (for each product).
This requires a temperature of ~1400°C and a reaction time of ~10–3 s. Since the pyrolysis process occurs
in an adiabatic reactor, the initial temperature must be ~1700°C. The conversion of ethane is more than
90% and, in all likelihood, there will be no need for its separation and return as a recycle. However, to
obtain such high temperatures, the pyrolysis of ethane must be performed in a hightemperature heat
transfer fluid flow obtained via the combustion of a hydrogencontaining gas or methane in oxygen with
water vapor added to control the process temperature.
The technology for the production of an equimolar acetyleneethylene mixture can be implemented in
the best way when liquefied gases, such as propane, butane, and their mixtures, are used as feedstocks.
Their pyrolysis in a hightemperature heattransfer fluid flow obtained via the combustion of a hydrogen
containing gas in oxygen can give acetylene and ethylene yields at a level of 50–52% at their total concen
tration in products of nearly 20 vol %. The temperature is ~1700°C in the reactor zone for the mixing of
feedstocks with a heattransfer fluid and ~1200°C before the zone for the quenching of pyrolysis products
(flash cooling by water injection for the prevention of side reactions). In this case, the reaction time is
~3⋅10–3 s.
The principal flowsheet of the process is shown in Fig. 6. Fuel (hydrogencontaining gas or methane)
and oxygen are fed to the top section of reactor R1, where combustion occurs. Water vapor is injected
into the combustion chamber to maintain a desired heattransfer fluid temperature. At the outlet from the
combustion chamber, the hightemperature heattransfer fluid is mixed with the evaporated liquefied
gases heated in heating furnace F1 to a temperature of ~500°C. The vapor mixture of feedstocks and the
heattransfer fluid is passed through the reaction zone of reactor R1, at the end of which it is subjected
to flash cooling (“quenching”). Cooling to ~90°C is performed via the injection of water through nozzles
owing to its partial evaporation.
The unevaporated water together with soot and heavy tar particles is collected in separator S1. The gas
flow from this separator is fed to column C1, where it is cooled with water to a temperature of ~30°C.
The water from separator S1 and column C1 is fed for purification from coke and tar, cooled in a service
cooling tower, and recycled back into the process.
The water is partially withdrawn to wastewater treatment facilities. The cooled gas is delivered for com
pression through gas holder H1. The compressor compresses the gas to a pressure of 0.7–0.8 MPa. The
gas is cooled in interstage coolers E1 to ~35°C. The condensed water is fed to the system for its purifica
tion. The gas is further cooled in the system of heat exchangers E2 to around 25°C. This freezes the mois
ture out to a required level. Moisture can also be removed by adsorption over alumina or zeolites.
The gas is fed to the kerosene washing system to remove C3 hydrocarbons, divinyl, and aromatics. The
cooling gas enters absorber C2 irrigated with kerosene with a temperature of 15°C. The washed gas is
delivered for acetylene hydrochlorination. The kerosene saturated with admixtures is heated in heat
exchanger E3 and delivered for irrigation into intermediate desorber C3. The dissolved gas recycled to
the gas holder is blown from this desorber at a decreasing pressure. The kerosene from the bottom of col
umn C3 is delivered for irrigation into desorber C4 through heat exchanger E4. The blown gases from
column C4 are flared. The regenerated kerosene is fed for the irrigation of absorber C2.
The gas obtained in the process of pyrolysis has approximately the following composition (vol %): H2,
26.8; CH4, 16.2; CO, 14.5; CO2, 15.8; C2H2, 11.4; C2H4, 11.0; N2 + O2, 4.3; C3+, <0.01.
This composition corresponds to the following rough reaction equation:

94 TREGER, ROZANOV
E1 E2
Fuel Water
S1
Steam
Com1
Water to
H1
purification To flare
Oxygen Water to
R1
“quenching” To hydrochlo
Liquefied rination
gases C1
E4
Steam
C3 C4
R1
E3
Water to C2
purification
Fig. 6. Production of an equimolar acetyleneethylene mixture: (F) pyrolysis furnace, (R) reactor, (C) absorption and dis
tillation columns, (H) gas holder, (E) heat exchangers.
100 CH4 + 90.5 O2 → 14.7 C2H4 + 15.2 C2H2 + 19.3 CO + 21 CO2 + 35.7 H2 + 119.8 H2O. The
enthalpy of such a reaction is 427 kJ/(mol methane).
One of the shortcomings in the production of an equimolar acetyleneethylene mixture is the cumbrous
system for the purification of quenching water and the utilization of soottar wastes. Moreover, the hydro
chlorination of acetylene is performed on a mercurycontaining catalyst, and this requires an environ
mentally hazardous system for the preparation of a catalyst and the utilization of mercurycontaining
wastes.
It is interesting that the waste of this production represents a mixture of carbon oxides and hydrogen,
i.e., actually syngas, which can be used for the production of methanol. Such an application of syngas
takes place in Novomoskovsk.
In the first approximation, it is possible to use an acetyleneethylene mixture containing ~100000 t of
each component per year for the production of vinyl chloride instead of 200000 t of ethylene per year. The
unit consumption of propanebutane feedstocks is ~2 t per 1 t of an acetyleneethylene mixture.
Hence, there exists an industrially commercialized technology for the production of an acetyleneeth
ylene mixture from methane, ethane, and C3–C4 fractions, which can be used for the synthesis of vinyl
chloride. However, as shown in practice, the prime cost of vinyl chloride obtained from acetylene is much
higher than for acetylene synthesized from ethylene by the balanced flowsheet.
The capital expenditures on the production of an acetyleneethylene mixture are quite comparable with
the expenditures on the organization of ethylene production.
6. CHLOROPYROLYSIS OF METHANE
TO ETHYLENE AND ACETYLENE
Higher hydrocarbons are also formed in the thermolysis of a methanechlorine mixture (Benson pro
cess) [19]. The radicalchain mechanism of this process is considered in [20].
Initiation: CH4 → CH3· + H·
Cl2 + M → 2Cl· + M
Chain transfer: H· + CH4 → H2 + CH3·
H· + Cl2 → HCl + Cl·
Chain continuation: CH3· + Cl2 → CH3Cl + Cl·
Cl· + CH4 → HCl + CH3·
Termination: 2CH3· → C2H6

A process developed by Département de Chimie Physique des Réactions (France) for the synthesis of
vinyl chloride from methane was reported at the Seventh Symposium on the Conversion of Natural Gas
[21]. The process consists in the chlorination of methane to methyl chloride with simultaneous pyrolysis
of the latter to acetylene, ethylene, and vinyl chloride. The effect of temperature on the CH3Cl conversion
and the yield of three main products, i.e., vinyl chloride, ethylene, and acetylene, are illustrated in Fig. 7.
The results represent a continuation of the earlier performed works [21]. According to the data [22],
the yield of hydrocarbons per unconverted methane was 77% at a temperature of 1000°C, a contact time
of nearly 1 s, and a Cl2 concentration in a mixture with methane of 1%, and the remainder was methyl
chloride. Among the hydrocarbons, 91% was due to unsaturated compounds (ethylene, propylene, and
acetylene) and the remainder was ethane.
In [21], the yield of target products (C2H3Cl, C2H2, and C2H4) per converted methyl chloride at a tem
perature of 950°C, a contact time of 10 ms, and a chlorine content of 15% in a mixture with methyl chlo
ride was nearly 40%, and the methyl chloride conversion was 30%. The authors consider these results to
be encouraging, but they are confused by a very high CH2Cl2 yield of ∼35%. However, in our opinion, the
yield of more chlorinated methyl chlorides strongly depends on the chlorine concentration, which
increased by 15 times in comparison with the prior experiments [22].
The performed works have a laboratory research character and, in addition, are of interest only for the
production of vinyl chloride. There is also a need for at least a preliminary evaluation of economic advan
tages.
The flowchart of the possible process could appear as follows (Fig. 8). Reactor 1 is supplied with meth
ane and chlorine and the recycled methyl chloride and ethane from separation system 2. Vinyl chloride
and propylene are withdrawn from separation system 2 as finished products, and ethylene and acetylene
are separated as feedstocks for further processing. Ethylene and acetylene are used at stage 3 for the pro
duction of vinyl chloride by the combined method: chlorination of ethylene to dichloroethane, pyrolysis
of dichloroethane to vinyl chloride, and synthesis of vinyl chloride from separated hydrogen chloride and
acetylene.
7. PARTIAL OXIDATION OF METHANE TO METHANOL

The direct oxidation of natural gas to methanol and the abovediscussed oxidative condensation of
methane to ethylene and ethane are currently considered among the most promising direct methods for
the conversion of natural gas [13, 23]. A principal distinction of these reactions from the hightemperature
processes of syngas production and further catalytic synthesis of products is their unsteadystate kinetic
character. For this reason, the thermodynamic methods, which are well developed for steadystate high
temperature catalytic processes, are inapplicable here for the analysis of the composition of synthesized
products and the optimization of reactions. It is necessary to perform a detailed kinetic analysis, i.e., to
apply intensive efforts to study the mechanisms of these complex chainbranching reactions:
CH4 + 0.5O2 → CH3OH − 94.7 kJ/mol.
Just this circumstance was a reason for a nearly halfcentury delay in the development of a technology
for the direct oxidation of hydrocarbons despite the fact that the first industrial plants were successfully
operated for their time as long ago as the 1940s. In the opinion of the authors [13, 23], new opportunities
are now opened in this direction, in particular, for the catalytic effect on the complex chemical process of
the oxidation of hydrocarbons.
A detailed review of results for both the catalytic and noncatalytic (highpressure) direct gasphase oxi
dation of methane to methanol was performed [13].
According to the engineering and economic evaluation [24], the direct methane oxidation process
CH4 +1/2O2 → CH3OH undoubtedly proves to be more profitable than the traditional synthesis through
syngas at a selectivity to methanol higher than 77%. The existing engineering solutions have made it pos
sible to increase the selectivity to methanol to 60% and higher, i.e., to closely approach the limit of prof
itability.
As a result of pilot tests on a unit with a capacity of 100 t of methanol per year at a temperature of 380–
480°C, a pressure of 5–10 MPa, and an oxygen concentration of 2.8%, the conversion of oxygen was 95–
98%, and the yield of crude methanol was 20 kg per 1000 m3 of transmitted gas or 0.63 kg per kilogram of
processed gas.
The most substantial shortcoming of the partial oxidation of natural gas to methanol is the need to
maintain a low initial oxygen concentration (∼3%) to attain a satisfactory selectivity in the conversion of
methane to methanol, and as a result, it is impossible to provide a rather considerable conversion of nat

96 TREGER, ROZANOV
Conversion, %
80
70 (a)
60
50
40
30
20
10
0
500 600 700 800 900 1000 1100 1200
Temperature, °C
Yield, %
35
30 (b)
25
20
15
10
5
0
500 600 700 800 900 1000 1100 1200
Temperature, °C
C2H3Cl C2H4 C2H2
Fig. 7. Effect of temperature on (a) CH3Cl conversion and (b) the yield of three main products.
Cl2 C2H4
1 2 3
CH4 C2H2
C2H6, CH3Cl C2H3Cl
Fig. 8. Flowchart for the processing of natural gas by the Benson method: (1) pyrolysis reactor, (2, 3) separation units.
ural gas per single pass through a reactor. To increase the total conversion, it is desirable to use a recycling
flowsheet. Another shortcoming is a low quality of synthesized crude methanol, which contains small
amounts of formaldehyde and ethanol. However, in the opinion of the authors [25], this process can be
profitable even at a low capacity, since it does not require expensive equipment.
The proposed flowchart for the production of methanol via the direct oxidation of methane looks
rather simple (Fig. 9). Partial oxidation stage 1 is supplied with the purified methane, the recycled meth
ane, and a limited amount of oxygen (3%). Crude methanol and the methane recycle are obtained at sep
aration stage 2. The crude methanol is further passed to purification stage 3.
8. CONVERSION OF METHANE INTO SYNGAS

The main method for the conversion of an inert methane molecule into reactive compounds is the syn
thesis of syngas.

O2 Commercial
1 2 3 methanol
Crude
CH4
CH3OH
CH4
Wastes
Fig. 9. Flowchart for the production of methanol via the direct oxidation of methane: (1) reactor, (2) methane recycle
separation, (3) methanol separation.
Purified natural gas is subjected to conversion (reforming) into carbon oxides and hydrogen with the
use of steam, carbon dioxide, or oxygen, and in this case, the first two reactions are endothermic, and the
third reaction is exothermic:
CH4 + H2O ⇔ CO + 3H2 – 206 kJ/mol, (I)
CH4 + CO2 ⇔ 2CO + 2H2 – 247 kJ/mol, (II)
CH4 + 1/2O2 ⇔ CO + 2H2 + 36 kJ/mol. (III)
The conversion of methane in these processes is high, and the conversion of oxygen in reaction III is
complete. Methane homologues are completely converted into CO and H2, because they are more reac
tive than methane. The catalysts for these processes and their thermodynamics, kinetics, and mechanism
are described in [13].
The reforming conditions result from a compromise between the requirements of thermodynamics,
economics, and materials science. Figure 10 illustrates how the equilibrium constants for the steam and
carbon dioxide conversion of methane (reactions I and II) grow with increasing temperature, and it can
be seen from Fig. 11 how an increase in temperature and a decrease in pressure promote the growth of the
equilibrium conversion of methane to CO + H2 in the oxygen conversion of methane (reaction III) [26].
At a high temperature (800–900°C) and a not very high pressure (1–3 MPa), the thermodynamics of the
lgK
10
6
CH4 + H2O = CO +3H2 (I)
4
−2
−4
−6
−8
CH4 + CO2 = 2CO +2H2 (II)
−10
0 200 400 600 800 1000 1200 1400 1600
Temperature, °C
Fig. 10. Equilibrium constants versus temperature for the production of syngas via the steam conversion (reaction I) and
carbon dioxide conversion (reaction II) of methane.

98 TREGER, ROZANOV
3.2
1 atm
(CO + H2)/CH4, mol/mol

2.4
10 atm
1.6
20 atm
0.8
750 850 950 1050 1150
Temperature, °C
Fig. 11. Maximum yield of syngas per mole of initial methane as a function of the temperature at different pressures for
the oxygen conversion of methane (reaction III).
process is favorable and allows the reaction to be brought to a nearly complete conversion. The econom
ically profitable increase in pressure above the mentioned range would reduce the volume of compressed
gas. In this case, however, there would be a need to increase the reforming temperature to compensate the
effect of pressure on the equilibrium composition of the reaction mixture. Then hardly satisfiable require
ments on construction materials would appear.
To supply heat through a wall, it is necessary to use a tubular reactor, but only special chromiumnickel
steels are stable at a nearly “white heat” temperature of the metal contacting a corrosive medium.
Partial oxidation (reaction III) does not require a heat supply, and the process can be performed in a
conventional shaft reactor. Moreover, reaction III gives the ratio H2 : CO = 2 required for the synthesis of
methanol. However, it is usually 1.5–1.6 in fact [27] because of the side reactions of methane combustion
and hydrogen oxidation to water:
CH4 + 2O2 → CO2 + 2H2O,
H2 + 1/2O2 → H2O.
When the gasphase selective oxidation of methane is performed by reaction ΙΙΙ without a catalyst, the
selectivity under conventional conditions is much lower (∼50%) [27]. For this reason, steam conversion
by reaction I giving excess hydrogen should be additionally performed.
In the process of socalled autothermal reforming, i.e., without heat supply, steam is injected into the
same reactor, but in a small amount, in order not to destroy the heat balance. In this case, hydrogen proves
to be deficient, so CO2 is removed from the obtained syngas to restore the required ratio.
Study [28] gives some recommendations on the selection of a reforming type depending on the capac
ity of a methanol plant. Thus, the authors recommend autothermal reforming for a plant with a capacity
of more than 5000 t of methanol per day. The twostage process, in which steam reforming is followed by
oxygen reforming, is better for a capacity of 1500–7000 t/day. Steam reforming is economically profitable
for smallscale plants.
In the process of onestage steam reforming, natural gas is converted into syngas in a tubular furnace
at a high temperature and a relatively low pressure. In this case, all the required heat is obtained via fuel
combustion, which needs a large reaction chamber in a reforming furnace and leads to a considerable vol
ume of flue gases.
In this case, excess hydrogen is usually withdrawn with a fraction of recycled gas from the production
of methanol and is used as a fuel gas. It is also possible to perform steam conversion with addition of CO2.
Handbook [7] reports some data on the steamoxygen conversion of natural gas with dosing of CO2; i.e.,
all three types of conversion are used in the same process. Carbon dioxide conversion is rarely applied now.
Since the endothermic effect of reaction III is greater than for reaction I, it requires higher fuel consump
tion. Moreover, there is the need for a source of cheap carbon dioxide.
An important engineering technique increasing the selectivity of the natural gas conversion process is
the flash cooling of syngas with the purpose of preventing the reactions between its components with the
formation of methane (inverse to reaction I).
The conclusions drawn from the results of the analysis of different technologies are the following:

Table 2. Typical parameters and performance characteristics of the main natural gas reforming types according to
the data of Haldor Topsoe
Reforming type Steam Steam + autothermal Autothermal
Typical parameters of the main reforming types
Reforming pressure, atm 21 40 75
Temperature at the outlet from a steam reforming 900 720 –
furnace, °C
Temperature at the outlet from a steamoxygen – 1000 1050
reforming reactor, °C
Relative load on a tubular furnace, % 100 35–45 –
Steam/gas ratio 2.5 1.8 1.2
Residual methane content, % (on dry gas basis) 3.1 1.1 2.4
Relative volumetric flow rate from a reforming 100 52 27
furnace, %
Typical parameters of consumption per tonne of methanol
Consumption of natural gas as a feedstock, a fuel, 7.4 7.0 7.5
and an energy source, Gcal/t1)
Process water, m3/t 0.8 0.3 0
Cooling demand, Gcal/t 1.5 1.4 1.5
1) Including an oxygen unit and electrical energy minus generated steam.
Since steam reforming provides a ∼1.5fold excess of hydrogen in comparison with the amount
required for the synthesis of methanol, its integration with oxygen reforming with deficient hydrogen pro
vides a desired ratio between hydrogen and carbon oxides upon the combination of these two reforming
methods.
Steam reforming is performed in a tubular reactor with external heat supply, so it has some temperature
and pressure limitations owing to the instability of the reactor material. As a result, the conversion of
methane proves to be insufficiently high. This shortcoming is eliminated by means of steamoxygen
reforming performed in a shaft reactor at the second stage, and almost all the methane unconverted at the
first stage is converted into a mixture of hydrogen and carbon monoxide. As a result, this method of two
stage steam and steamoxygen reforming is optimal at a methanol production capacity of up to 6500 t/day,
limited by the unit capacity of a tubular steam conversion reactor according to the data of foreign and Rus
sian researchers.
When it is necessary to create a methanol production plant with a higher capacity of up to 10000 t/day,
it is preferable to use onestage steamoxygen autothermal reforming in a shaft reactor, whose unit capacity
has no similar limitations. This requires a unit for the separation of CO2 from the obtained syngas.
Some typical parameters and performance characteristics for the main types of natural gas reforming
are given in Table 2 according to the Haldor Topsøe data [8, 29].
The data of Table 2 confirm the correctness of selection for twostage (steam and steamoxygen auto
thermal) reforming, characterized by the lowest consumption of natural gas as a main feedstock, fuel, and
energy source.
A variant of the technology for the twostage steamoxygen conversion of natural gas is the Tandem pro
cess developed on the basis of experience in the longterm operation of the industrial plant of the AZOT
Grodno Production Association (Belarus). Flue gases obtained via the combustion of fuel serve as a heat
source in the processes with the use of tubular steam conversion, whereas the Tandem process uses the
process flow of converted gas after the shaft oxygen converter as such a source.
In the Tandem process, a tubular furnace is replaced by a tubular reactor, in which the heating gas is
under a pressure close to the process gas pressure, i.e., the reactor tubes are operated under less stressed
conditions. For this reason, the conversion process pressure can be increased to ~90 atm. To reflect the
importance of all the components participating in the synthesis of methanol for this process, the ratio
(H2 – CO2) : (CO + CO2), called a functional or factorial, is used. The Tandem process provides a value
f = 2.02–2.05. The developer of this technology is M.Kh. Sosna [30].

100 TREGER, ROZANOV
Reaction gas of Initial natural

steam conversion gassteam mixture
Steamair mixture
Syngas
Gas outlet
tube
Catalys
Shell
Catalystfilled
reaction tubes
Shaft reactor Reaction gas of

oxygen conversion Tubular reactor
Fig. 12. Sketch of the reaction units of the pilot plant for the production of syngas by the Tandem method.
The tubular converter incorporated into the pilot syngas production unit (Fig. 12) of the ammonia
plant of the AZOT Grodno Production Association has the following parameters:
Shell diameter, 3600 mm;
Shell height, 24 240 mm;
Reaction tube diameter, 133 × 10 mm;
Reaction tube length, 13 200 mm;
Number of reaction tubes, 180.
The reactor has 19 gas outlet tubes 133×10 mm in size per 180 reaction tubes of the same steel.
Each reaction tube is inserted into a shell with a diameter of 168 × 8 mm and a length of 12 m to form
an annular 9.5mm gap, through which the converted gas from the shaft reactor passes in countercurrent
to the reaction mixture, transferring heat to it. Displacing shells are fixed to the second lower tube grid
welded to the shell of the tubular converter in its top section. Both tube grids form the chamber collecting
the converted gas, which has passed through the shaft afterconverter and transferred its heat to the reac
tion tubes. The outlet converted gas temperature is 570–600°C.
The tubular baffle as a whole is divided into 19 bundles consisting of 3–12 reaction tubes, the converted
gas from which with a temperature of up to 750°C and a methane concentration of ∼28% is collected into
the lifting tubes and withdrawn into the collector placed above the upper tube grid inside the tubular con
verter.
To compensate thermal elongations, the end of the reactor is equipped with a system of pigtails linking
reaction tubes with lifting tubes.
Work [31] presents the gas heated reformer (GHR) which was developed by Synetix and, in the
authors’ opinion, decreases the energy consumption by 10% and the oxygen consumption by 25%, and
also reduces the capital expenditures on the process.
In the 1990s, the company developed the advanced gas heated reformer (AGHR) technology, which
was characterized by a simple and cheaper design and could be scaled. Paper [31] describes different GHR
designs, the best of which, in the developers’ opinion, is the variant with slip gaskets (Fig. 13).
Despite good engineering and economic characteristics and the attainment of a required ratio between
hydrogen and carbon oxides, we should also mention some shortcomings which are inherent in the Tan
dem process and could be revealed only upon its detailed study. First is a rather rigid connection between
the steam and oxygen conversion stages. In this case, it is necessary to have a rather low methane conver
sion (less than 40%) at the steam conversion stage and to inject an additional amount of steam and/or
methane at the steamoxygen conversion stage in order to increase the heat capacity of the obtained syngas

To intratubular space
From intertubular Catalystfilled tube

space
Protective tube
Tube To intertubular space
From intertubular space

Gasket
Fig. 13. Synetix advanced gas heated reforming (AGHR) reactor.
to such a level that the heat would be sufficient for the heating of the initial steam conversion gas and the
extremely endothermic reaction between methane and steam.
Another shortcoming is the need for a simple and efficient solution of the thermal tube elongation
problem, which is solved in a tubular furnace by hanging the reaction tubes on springs together with the
gas inlet and outlet collectors.
In our case, the upper end of the tubes is fastened in the tube grid, and their lower end is free. The gas
is withdrawn through the gas outlet tubes, which occupy a certain volume in the intertubular space and
decrease the number of tubes which could be installed in it (according to our estimate, 581 tubes are
installed instead of 953 tubes).
9. DIRECT SYNTHESIS OF LOWER OLEFINS FROM SYNGAS

One of the methods for the processing of natural gas is its conversion into syngas and further into valu
able products by the Fischer–Tropsch process:
2CO + 4H2 → C2H4 + 2H2O + 210.5 kJ/mol.
In the opinion of R.A. Sheldon [32], the synthesis of lower olefins by the Fischer–Tropsch method is
thermodynamically less probable than the formation of highmolecular saturated compounds, but the
equilibrium of these reactions is attained slowly, thus enabling the kinetic monitoring of product yields.
The yield can be increased by modifying a catalyst.
The performed studies show that, if necessary, it is possible to develop a process oriented to the pre
dominant synthesis of light olefins, i.e., a Fischer–Tropsch synthesis catalyst with increased cracking
activity toward C5+ hydrocarbons. For example, there are some known ironmanganese catalysts for the
synthesis of narrow fractions of hydrocarbons, predominantly C2–C4 olefins [33, 34].
Thus, the hydrocarbon product fraction obtained on the Ruhrchemie iron catalyst (Germany) pro
moted with manganese, zinc, and potassium oxides had the following composition (wt %): C2H4, 30;
C3H6, 20; C4H8, 15; C2–C4 alkanes, 15; C5+ hydrocarbons, 20. To increase the yield of lower olefins, C2–C4
alkanes and some liquid hydrocarbons can be subjected to pyrolysis.

102 TREGER, ROZANOV
CO2
Steam, P = 10 atm
Com2 C4
Com1 S1
C1 C2
P1 E1
Com3
Syngas
E1 C5
Separation of
sour products
from H2O Copper ammonium
T3 solution
Steam, P = 40110 atm C3
T3 Ethanolamine
S2 T4
Liquid pyrolysis CH4 + 20% H2

products C4H8 C3H6 C2H4
C6
E5
C2H6
Р1 C3H8 Separa
SU2 SU1 tion of
C4H10
ΣC5+ H2
H2
Fig. 14. Production of olefins from syngas: (Com) compressors, (R) reactor, (E) heat exchangers, (S) separators, (C)
absorption and distillation columns, (SU) separation units, (F) pyrolysis furnace.
The recent variant of the Synsol process (hightemperature Fischer–Tropsch process) predominately
for the production of olefins from syngas with a selectivity to olefins of 70% was presented at the Fisher–
Tropsch Catalysis Symposium in the report from the Sasol [35].
The flowchart for the Fischer–Tropsch synthesis of lower olefins looks as follows (Fig. 14). Syngas
under a pressure of 10 atm is delivered with compressor Com1 into reactor unit R1, where the synthesis
of hydrocarbons occurs in the presence of a catalyst at a pressure of 10 atm and a temperature of 380°C.
The reaction products are fed to heat utilization unit E1 and S1, where the temperature of the reaction
flow decreases to 200°C to generate steam with a pressure of 10 atm.
The reaction mixture is further cooled in heat exchanger E2, separated from sour products in column
C1 and the unit for the separation of sour products from water, compressed to the pressure of 40 atm
(Com2), and delivered to column C2 for ethanolamine washing from carbon dioxide. The regeneration
of ethanolamine is performed in column C3 with boiler E3. Unconverted carbon monoxide is separated
from the reaction products via the absorption purification of the reaction mixture with a copper ammo
nium solution (columns C4 and C5). The separated carbon monoxide is delivered for mixing with fresh
syngas.
The hydrogen and methane fractions are further separated from the reaction products in separation
unit SU1. The hydrogen fraction is mixed with the initial syngas, and the methane fraction is used as a
fuel.
The hydrocarbon mixture is fed to separation unit SU2, where it is separated into ethylene, propylene,
and butylenes as commercial products and the other C2, C3, C4, and C5+ hydrocarbons. Olefins, such as
ethylene, propylene, and butylenes, are commercial products.
To increase the yield of target olefins, the paraffins obtained by means of gas separation are fed to pyrol
ysis furnace F1 for processing. The thermal pyrolysis products are subjected to quenching in heat
exchanger E5 with the generation of highpressure steam in separator S2 and separated in column C6
with heat exchanger E4 into liquid hydrocarbons returned into the recycle through heatexchanger E2
and gaseous hydrocarbons delivered for mixing with the reaction mixture from reactor unit R1.

Hence, a possible process flowsheet for the synthesis of lower olefins from syngas consists of the main
reactor unit, the reaction mixture purification unit, the unit for the separation of unconverted hydrogen
and carbon monoxide, the gas separation unit, and the unit for the pyrolysis of hydrocarbons obtained in
the process of synthesis.
The yield of products from syngas at a molar ratio CO : H2 = 1 : 2 can be the following (% per total
feedstocks): C2H4, 9.6; C4H8, 5.2; methane fraction, 14.3; C3H6, 4.9; liquid products, 0.9; CO2, 63.8;
losses, 1.3.
A rough estimate shows that the cost of C2–C4 olefins in this process must be 2–3 times higher than
for the pyrolysis of hydrocarbons.
Some compensation can be gained by the utilization of the fairly large heat of the reaction.
The capital expenditures on the process of the Fischer–Tropsch synthesis of lower olefins from syngas
are distributed as follows (%): syngas production, 60; Fischer–Tropsch process, 25–30; separation and
upgrading of products, 10–15.
10. MTO PROCESS: METHANOL TO OLEFINS

The methanoltoolefins process consists of three reaction stages: conversion of natural gas into syn
gas, conversion of syngas into methanol, and catalytic pyrolysis of methanol to olefins. The first stage has
already been described above. The two other stages will be considered below. The ICI methanol synthesis
process is illustrated in Fig. 15 [36].
Adiabatic methanol synthesis reactors with catalyst beds in a single reactor and cooling with cold
bypasses have certain advantages and are most often used in industry and installed in many world coun
tries, including the two largest plants of Russia in Gubakh and Tomsk. Syngas is compressed by a com
pressor to ~10 MPa to be fed to the methanol synthesis reactor. The compressed syngas is mixed with the
recycled gas, and the resulting mixture is separated into two flows. The main flow is fed to a recuperative
heat exchanger, where it is heated with the outlet reaction gas from the synthesis of methanol and then
passed to the inlet of the synthesis column.
The other flow of the recycled gas and syngas mixture is slightly heated in the secondstage reaction gas
cooling heat exchanger and used as cold bypasses introduced between the catalyst beds of the reactor to
withdraw reaction heat and maintain a specified temperature.
The reaction gas cooled in the recuperative heat exchangers is subjected to further cooling in air and
water coolers.
The methanol condensate is separated from uncondensed gases in a separator. The main fraction of
uncondensed gases is additionally compressed by a compressor and passed into the recycle to the metha
nol synthesis reactor. A small fraction of uncondensed gases is withdrawn in the form of blowdown to
remove inert gases and fed to the combustion furnace and is also used to add hydrogen to the initial meth
ane.
The methanol condensate is collected in a tank, where pressure is relieved, and socalled tank gases are
removed at the top. The crude methanol from this tank is passed to the first column, where lightboiling
socalled ether gases are stripped from methanol.
The residue of the first column is fed to the second column, where finished methanol is withdrawn at
the top, and bottom distillation residues containing predominantly water are separated at the bottom.
In the opinion of Academician I. I. Moiseev [25], the synthesis of methanol is one of the most perfect
processes classified among the best examples of contemporary chemical engineering and is characterized
by a high degree of energy recuperation.
For this reason, the advertisement of methanol processes cites only the total consumption of natural gas
as a feedstock and fuels in gigajoules per tonne of methanol (including the power generation oxygen units).
For example, this consumption in the advertising materials [36] is 30 GJ/t, which is 882 Nm3/(t methanol)
at a natural gas caloricity of 34 GJ/1000 Nm3. The advertisement of another company in the same journal
[37] gives the natural gas consumption range of 29–33 GJ/t.
The material balance calculated by us for the production of methanol gives the consumption of natural
gas as feedstocks and fuel of 902 Nm3/(t methanol). The consumption of natural gas per kilomole of meth
anol is essential for the further estimation and comparison of olefin synthesis processes and is 28.9 Nm3.
Different technical and engineering and economic characteristics of methanol production are consid
ered in [9]. The engineering and economic characteristics of a methanol production process depend first
of all on the natural gas cost.
The methanol production flowsheet of Haldor Topsøe is shown in Fig. 16.

104 TREGER, ROZANOV
N2
Air Air
Steam separation
Natural
gas H2O O2 H2O
Purifica Steam Steam

Steam Cooling
tion from oxygen generation
conversion
sulfur conversion
Combus
tion
Air furnace
Syngas to methanol production
Methanol
synthesis
reactor
Circulation Blowdown Methanol
compressor gases to
combustion
Compression
Cooler
Recuperative heat Separator Tank Distillation
exchangers columns
Fig. 15. ICI methanol production process.
This process also incorporates an adiabatic reactor, the heat from which is withdrawn due owing the
heating of the reaction gas, which is intermediately cooled between reactor stages. In this variant, three
catalyst beds are applied, which requires the temperature drop between the inlet and outlet of a catalyst
bed (ΔT) or the recycled gas volume to be increased.
The design of this reactor is maximally simplified, since each catalyst bed is placed into an individual
vessel. The reaction gas is cooled in external heat exchangers.
The methanol synthesis flowsheet of Lurgi, another wellknown company engaged in the production
of methanol, is shown in Fig. 17.
The Lurgi isothermic reactor represents an apparatus with catalystfilled tubes cooled with boiling
water.
The heated gas is fed to the catalystfilled tubes installed inside the reactor. The boiling water temper
ature is maintained at a level of 250°C with a pressure controller. The greatest volume of the catalyst
located in the lower part of tubes has a low temperature, which provides high activity of the catalyst for a
long time.
The gases at the outlet from the reactor have a temperature only 3°C higher than the boiling water tem
perature. The gases at the outlet from the reactor contain from 5.5 to 10 mol % of methanol.
The maximum capacity of one branch in the system of Lurgi reactors, when two reactors are used in
the same process line, is 3000 (t methanol)/day.
The development by Lurgi of the MegaMethanol process of high unit capacity (more than 1 million
tonnes) with the production of inexpensive methanol was reported in [40].

The flowsheet of this process incorporates two serially arranged tubular reactors (Fig. 18). In the first
tubular reactor cooled with boiling water, the partial conversion of syngas is performed on the Cu/ZnO
catalyst at high temperature and large volume rate. In the second reactor, the feedstock gas is fed into
empty tubes, and the hot gas from the first reactor is passed in countercurrent through the catalyst in the
intertubular space. Hence, the temperature of the reacting gas outside the tubes continuously decreases,
thus shifting the equilibrium in the desired direction.
However, such a considerable decrease attained in the methanol prime cost by this technique
from $108–$113/t for competitors to $79/t at close natural gas consumption coefficients of 850–
900 Nm3/t methanol looks quite surprising. Many companies strive to create methanol plants in countries
with very cheap natural gas.
The technology developed by companies in the United States (UOP) and Norway (Norsk Hydro) [41]
with the use of the SAPO34 silicoaluminophosphate catalyst provides an 80% ethylene and propylene
yield at a nearly complete methanol conversion and enables an increase in the selectivity to carbon up to
85–89% in the case of recycled C4–C6 olefins. The MTO (methanoltoolefins) technology was subjected
to pilot testing at a large plant of Norsk Hydro (Norway).
This plant had a capacity of 500 kg of methanol per day and was in operation for more than a year. Since
the methanol decomposition catalyst requires periodic regeneration from coke deposits, it had passed 450
operationregeneration cycles by that moment. Continuous operation lasted for 3 months. The
UOP/Hydro MTO unit incorporated a fluidizedbed reactor in combination with a fluidizedbed regen
erator. The catalyst is continuously fed into the regenerator, where coke is annealed. It has been reported
that the SAPO catalyst is resistant to abrasion.
Some works on the creation of an industrial plant for the production of polyethylene and polypropy
lene from natural gas through the intermediate synthesis of methanol and conversion into olefins were
performed according to the UOP/Hydro technology. The plant capacity was up to 400 000 t of polyethyl
ene and polypropylene per year.
The reactions occurring in the synthesis of olefins from methanol are
CH3OH ← → CO + 2H2 – 90.8 kJ/mol (endothermic reaction),
CH3OH + H2O ←
→ CO2 + 3H2 – 49.6 kJ/mol,
CH3OH + H2 → CH4 + H2O – 71.6 kJ/mol,
2CH3OH → C2H4 + 2H2O + 30.0 kJ/mol (exothermic reaction),
2CH3OH + H2 → C2H6 + 2H2O – 75.4 kJ/mol,
3CH3OH → C3H6 + 3H2O + 102.6 kJ/mol,
3CH3OH + H2 → C3H8 + 3H2O – 14.4 kJ/mol,
4CH3OH → C4H8 + 4H2O – 164.1 kJ/mol,
4CH3OH + H2 → C4H10 + 4H2O + 37.7 kJ/mol,
4CH3OH → C4H6 + 4H2O + H2 + 274.2 kJ/mol,
5CH3OH → C5H10 + 5H2O + 226.0 kJ/mol,
5CH3OH + H2 → C5H12 + 5H2O + 351.3 kJ/mol,
2CH3OH ←
→ (CH3)2O + H2O + 24.0 kJ/mol,
2CH3OH → C2H5OH + H2O + 74.9 kJ/mol,
3CH3OH → (CH3)2CO + 2H2O + H2 + 98.0 kJ/mol,
CH3OH → C + H2O + H2 + 41.0 kJ/mol.
The reactions occurring in the pyrolysis of C2–C4 fractions to olefins are
C2H6 → C2H4 + H2 – 137.3 kJ/mol,
C3H8 → C3H6 + H2 – 124.3 kJ/mol,
C4H10 → 2C2H4 + H2 – 231.1 kJ/mol,
C4H8 → 2C2H4 – 105.0 kJ/mol,
C4H8 + H2 → C3H6 + CH4 + 54.0 kJ/mol,

106 TREGER, ROZANOV
DESULFURIZATION REFORMING
Distillation column
boilers
steam
Heat
utilization
cooling
Heat Heat water
utilization utilization
air to
combustion
Start hydrocarbon Heating of

circulation blowdown gases
Methanol synthesis reactor compressor steam
Blow
Expander down
gases
Separator
Commercial
methanol
Heat
utilization cooling
water
Pressure Wastewater
relief vessel
Higher alcohols
DISTILLATION
Fig. 16. Haldor Topsøe methanol production plant [38].
C4H8 → 4C + 4H2 – 1.2 kJ/mol,

3C4H8 → 2C6H6 + 6H2 – 83.3 kJ/mol,
C4H6 + H2 → 2C2H4 + 5.4 kJ/mol,
C4H6 → 2C2H2 + H2 – 595.8 kJ/mol,
C5H10 → C2H4 + C3H6 – 93.8 kJ/mol,
(CH3)2O → C2H4 + H2O + 5.6 kJ/mol.
The selective acetylene hydrogenation reaction is
C2H2 + H2 → C2H4 + 190.5 kJ/mol.
The reaction of CO2 elimination from the reaction gas is
2NaOH + CO2 → Na2CO3 + H2O – 117.2 kJ/mol.
The possibilities of varying the ratio between the synthesized products (ethylene and propylene) are
considered in [42]. The process was patented in Russia [43]. A pilot MTO process plant with a capacity of
10 t of methanol per day was created by Total in Belgium. Some industrial plants for the production of ole
fins by the pyrolysis of methanol were created in China, but coal is predominantly used as a feedstock
instead of natural gas [44].

Highpressure
steam
Boiler
Boiler feedwater
feedwater Waste REACTOR
Heavy 58 atm heat 53 atm 50 atm
residues recovery
boiler Gas puri
Start
Partial
fication and
oxidation
condensation Heat exchanger
Highpressure GAS RECYCLE

steam COMPRESSOR Cooler
STEAM
SUPERHEATER
Lowpressure
SEPARATOR steam
TURBINE
Methanol Methanol
distillation
Lowpressure
condensate
Fig. 17. Lurgi methanol production process [39].
The coaltoolefins process (coal → syngas → methanol → olefins) was implemented in China on a
large scale and under the name DMTO, where “D” means Dalian (Dailan Institute of Chemical Physics
of the China Academy of Sciences). According to the available information, six methanol processing
plants with a total olefin capacity of 3.4 million tonnes were in operation in China by 2014, and the total
capacity with respect to olefins synthesized by the coaltoolefins method should exceed 9 million tonnes
in the two next years.
The processes for the production of olefins from natural gas through methanol and its derivatives are
reviewed in [45].
In the initial flowsheet, the reaction gas of methanol conversion was first purified from water and then
from CO2 by means of alkali washing and, finally, subjected to drying [41].
In a more recent variant of this process flowsheet, the water and CO2 removal stages are spaced apart
by the stages of compression and dimethyl ether (DME) separation via the absorption by methanol fed to
the MTO process.
This flowsheet was refined in [46] owing to the fact that only some methanol is fed for DME absorp
tion, and the remaining methanol is passed immediately into the process. During DME absorption by
methanol, a certain amount of it will be entrained by the reaction gas, so this stage is also supplied with
water for the absorption of methanol by water.
It is recommended to feed water into an MTO reactor as a diluent to increase the process selectivity to
olefins and reduce catalyst carbonization.
The subsequent flowsheet for the distillation and separation of reaction products in its more recent
variant has also been improved. The earlier flowsheet implied the consecutive separation of products in
the order of increasing boiling temperature: methane was first, the C2 hydrocarbon fraction (separated
into ethylene and ethane in a special column) was second, propylene was the following product, and pro
pane was finally stripped from the C4+ fraction in the last column. As a result, all the highboiling frac

108 TREGER, ROZANOV
Gascooled Watercooled
reactor reactor
Steam
Circulation
compressor
CO + H2 Water
Gas
blowdown
Crude methanol
Fig. 18. Lurgi twostage MegaMethanol process.
tions, which are most prone to resinification, passed throughout the entire sequence of the distillation sys
tem.
In the more recent variant (Fig. 19), the reaction gas is separated immediately in the first column into
a “light” C1–C2 fraction and a “heavy” C3–C5 fraction, which are further separated in the conventional
direct sequence. Moreover, taking into account the severe requirements on polymerizationgrade ethyl
ene, this flowsheet was complemented with the stage of selective acetylene hydrogenation to ethylene on
a palladium catalyst. Most of the earlier descriptions of the MTO process developed by UOP and Norsk
Hydro did not report the presence of acetylene in the reaction gas and the stage of its removal in the pro
cess flowsheet.
Methanol conversion gases can be separated using the widely known commercialized technologies for
the separation of gasoline pyrolysis gases and different hydrocarbons.
According to the principal flowsheet shown in Fig. 19, the methanol containing a certain amount of
DME and water is vaporized in an evaporator, heated in a recuperative heat exchanger by the reaction gas
of pyrolysis, and fed to a reactor to synthesize lower olefins. The process is performed in a fluidized bed of
the silicoaluminophosphate SAPO34 catalyst. The reaction heat is removed by means of steam genera
tion in an integrated heat exchanger.
The permanent activity of the catalyst is maintained with a regenerator, into which some coked catalyst
is continuously poured to anneal carbon deposits from its surface with air. The regenerated catalyst is con
tinuously returned back into the reactor. The regeneration heat is withdrawn in an integrated heat
exchanger to generate steam. The air fed to regeneration is heated in a recuperative heat exchanger by the
waste air after regeneration.
After the condenser and the separator, the reaction gas from methanol conversion is compressed by a
compressor for the removal of water and fed for DME recovery. After this stage, the reaction gas is fed to
the carbon dioxide removal column. The column is irrigated with a sodium hydroxide solution at the top,
and a soda solution with residual sodium hydroxide is withdrawn at the bottom. This column performs the
additional condensation of steam. After this stage, the reaction gas is delivered for terminal afterdrying in
a KA zeolite column.
The mixture of reaction gases is dried in alternatively operated zeolite absorbers. When one adsorber
operates in the regime of adsorption of water from the reaction gases (about a day), the other adsorber is
subjected to regeneration. The moisture is removed from the zeolite by the heated methane, which is fur
ther passed for combustion. After regeneration, the adsorbent is cooled with cold methane.
The ethane, propane, and C4 fractions separated in the distillation system are passed for processing
into light olefins (predominantly, ethylene and propylene) into the reactor with the catalyst, which was
specially developed by the ATOFINA/UOP companies for this purpose. The reactors are operated in an
alternating regime: one of them is operated in the hydrocarbon conversion regime, and the other is oper

ated in the regime of regeneration via the annealing of carbon deposits with oxygen in the air. The initial
mixture is heated in a recuperative heat exchanger by the reaction gas from the reactor.
The catalyst is placed in the reactor tubes. The heat required for the conversion of hydrocarbons is sup
plied to the intertubular space with flue gases obtained in the combustion of the methane fraction sepa
rated in the distillation system. The flue gases leaving the intertubular space of the reactor with a relatively
high temperature are used to generate steam in a waste heat recovery boiler.
The catalyst is regenerated with the air heated in a recuperative heat exchanger with the waste air after
regeneration. To remove the regeneration heat, the intertubular space is supplied with air for cooling
instead of combustion gases. The hot air leaving the intertubular space is passed into the recuperative heat
exchanger for heating the inlet air.
The reaction gas from the conversion of C2–C4 paraffins is cooled in a recuperative heat exchanger,
compressed by a compressor to the pressure of 30 atm, and delivered for mixing with the reaction gas of
methanol conversion. According to communication [47], the presence of the stage called by the authors
the olefin cracking process (OCP) increases the yield of olefins by 20%.
The mixture of reaction gases is fed to column 1, where all the products are separated into C1–C2
(“light”) and C3–C5+ (“heavy”) fractions.
The ethaneethylene fraction containing acetylene, which must be removed to a content of 1–10 ppm
as required by the GOST (State Standard) for ethylene, is withdrawn at the top of this column. Acetylene
is removed by its hydrogenation in the presence of a palladium catalyst. The ethaneethylene fraction is
additionally compressed, heated in a recuperative heat exchanger, and fed to an adiabatic hydrogenation
reactor.
The hydrogenated ethaneethylene fraction is cooled and fed to column 2. In this column, hydrogen
and methane are separated from the ethaneethylene fraction. The methane fraction is partially passed for
combustion to heat the paraffin pyrolysis reactor and partially directed into the fuel system. The liquid res
idue of column 2 is delivered to ethylene column 3 as a feed. Commercial ethylene is separated at the top
of this column, and its bottom residue is the ethane fraction, which is partially recycled for pyrolysis into
the paraffin pyrolysis reactor or can partially be delivered to the fuel system.
The C3–C5+ hydrocarbons from the bottom of column 1 are fed to column 4, where the propanepro
pylene fraction is separated at the top, and C4–C5+ hydrocarbons are withdrawn at the bottom. The pro
panepropylene fraction is fed to propylene column 5. To obtain propylene with a concentration of 99.8%
(polymerizationgrade quality), this column must have nearly 200 trays. It usually consists of two parts
(splittype column): the liquid from the stripping section is pumped as a reflux to the enriching section,
and the vapor from the enriching section is fed to the bottom of the stripping section (omitted in the flow
sheet). The propane fraction, which is partially recycled to the paraffin pyrolysis reactor or can partially
be used in a mixture with the butanebutylene fraction as liquefied household gas, is withdrawn at the bot
tom of column 5.
The bottom residue of column 4 is fed to column 6. The fraction of C4 hydrocarbons (butanebutylene
divinyl fraction), which is partially recycled for pyrolysis into the paraffin pyrolysis reactor or can partially
be used as liquefied household gas, is withdrawn at the top of this column. The butenebutylenedivinyl
fraction can also be used at synthetic rubber plants for the separation of divinyl. The C5+ fraction repre
senting pyrogasoline is withdrawn at the bottom of column 6.
10.1. Lurgi MethanoltoPropylene (MTP) Process

The flowsheet of the reaction unit of the MTP process is shown in Fig. 20 [48].
The MTP process incorporates the reaction unit consisting of two serially arranged reaction units (1)
and (2). Reaction (2) incorporates fixedbed reactors based on ZSM5, which has a more prolonged
period of active service in contrast to the SAPO catalyst. Both methanol of A grade and less pure methanol
can be used as an initial feedstock in the MTP process. The methanol fed for processing is preliminarily
dehydrated with the formation of DME and water. The process is performed in reactor (1) on an Al2O3
based catalyst.
The obtained methanol/DME/water mixture is further fed to methanol conversion reactor unit (2)
consisting of several adiabatic fixedbed reactors with a catalyst providing the selective formation of pro
pylene in the presence of steam. The MTP process is performed in a multideck reactor, in which the cat
alyst is placed in several sections. Modified ZSM5 zeolite produced by SüdChemie is used as a catalyst.
Byproducts are a fraction of gasoline hydrocarbons, a propanebutane fraction, and a blowdown gas,
and, if necessary, ethylene can be separated as a commercial product.

110 TREGER, ROZANOV
Flue Drying H2 + CH4 Ethylene Propylene

gases C3 fraction
NaOH
solution
1 2 3 4 5 6
(CH3)2O
C2H2
Na2CO3 removal C2 fraction
C5+
solution
Water fraction
С3С5+ fraction Ethane
Air Propane
Methane C4
Methanol homologues
Pyrolysis
Water
of C2C4
paraffins
Methanol Alkali Pyrolysis products
pyrolysis Quenching washing
Fig. 19. Production of lower olefins from methanol: (1–6) distillation columns.
The process is performed at a pressure of 1.28–1.58 atm and moderate temperatures of 420–490°C.
These MTP process conditions provide a 99% methanol/DME conversion with a selectivity to propylene
of 60–65%. The specified conversion and selectivity level is controlled and maintained by introducing a
certain amount of fresh initial feedstocks between the reactors.
The selected process conditions reduce the formation of coke on the catalyst surface. The active service
period of the catalyst under operating conditions is 500–600 h, after which the catalyst is regenerated via
the annealing of coke in a nitrogenair mixture flow. The regeneration temperature is the same as the MTP
process temperature, thus enabling the catalyst to be regenerated immediately in the reactor. Since the
catalyst regeneration and conversion process temperatures are the same, the possible effect of temperature
drop on the structure, activity, and selectivity of the catalyst is eliminated.
The methanol conversion process is performed in three parallel arranged reactors, among which two
reactors are alternatively operated under working conditions, and the third reactor is operated under
regeneration conditions.
The gaseous mixture of products leaving reaction unit (2) is passed to cooling and separation stage (3).
The separated C5 fraction is recycled to reaction unit (2).
Hence, in contrast to the MTO process, the conversion of methanol is performed in the MTP processes
stage by stage first with the formation of an equilibrium methanol/DME/water mixture and then with the
predominant synthesis of propylene in combination with the pyrolysis of a C5 fraction. It is also notewor
thy that the formed byproducts, i.e., C4–C5 fractions, are subjected to pyrolysis in both processes to
increase the yield of C2–C3 olefins. However, the pyrolysis of a C4+ fraction in the MTO process is per
formed in a special reactor, whereas the pyrolysis of a C5 fraction in the MTP process is performed imme
diately in the reactor for the pyrolysis of an initial methanol/DME/water mixture.
The separation of a blowdown gas used as a fuel gas for internal consumption is also provided. Ethylene
can also be separated, if necessary. A propanebutane mixture and a fraction of gasoline hydrocarbons are
separated as byproducts. Some data on the MTP process capacity are given in Table 3.
11. PROCESS FOR THE SYNTHESIS OF OLEFINS FROM DIMETHYL ETHER

The synthesis of dimethyl ether (DME) is one of the new promising trends in the processing of natural
gas and is frequently considered as an alternative to the methanol synthesis method. An increased interest
in DME is dictated by the fact that it is an intermediate product in the conversion of methanol into hydro
carbons and can also be used as an energy source. The process for the synthesis of olefins from DME is
reported in [49–51]. In [51], this process is called SDTO (Sintez gas via Dimethyl ether To Olefins).
In recent years, intensive work on the creation of a method for the synthesis of DME from syngas in a
single stage without intermediate separation of methanol has been performed. The process is performed
on bifunctional catalysts, which can catalyze the synthesis of methanol and its dehydration [52].

The direct synthesis of dimethyl ether from syngas occurs according to the following total reactions:
3CO + 3H2 → CH3OCH3 + CO2 + 245.7 kJ/mol, (I)
2CO + 4H2 → CH3OCH3 + H2O + 204.8 kJ/mol. (II)
Here, reaction Ι includes three stages, i.e., the formation of methanol, its dehydration (reaction III),
and the conversion of water gas (reaction IV):
2CH3OH ⇔ (CH3)2O + H2O + 23.4 kJ/mol, (III)
CO + H2O ⇔ CO2 + H2 + 40.9 kJ/mol. (IV)
In the absence of the conversion reaction, the process follows Eq. (II).
The technology is nearly the same as for the synthesis of methanol, but only 15–20% of carbon oxides
are converted in the synthesis of methanol after passing through the reactor with a catalyst versus 60–80%
in the synthesis of DME under close conditions. Correspondingly, the reactor capacity per unit volume
abruptly grows. According to different estimates, the direct synthesis of DME from syngas is 5–20% less
expensive than the synthesis of an equivalent amount of methanol [53].
Since the DMEtoolefins reaction is similar to the methanoltoolefins reaction, the conversion of
dimethyl ether into light olefins is performed using the same conditions as for the synthesis of olefins from
methanol.
The same catalysts, namely, on the basis of SAPO and zeolites, are used for both reactions. The pre
dominant synthesis of light C2–C4 olefins up to 80 mol % is observed at a temperature of 300–500°C and
a pressure of 1.4–6.8 atm [54]. To maintain the selectivities to ethylene and propylene at a certain level,
it is recommended to use dilution with inert compounds.
In [55], an aluminophosphate catalyst similar to the SAPO34 catalyst was tested at a laboratory DME
conversion plant. A fluidizedbed reactor (∅ 20 mm) was used for experiments. The reaction temperature
was 550°C, and the linear velocity of the initial reagent flow was varied within a range of 11.0–16.0 cm/s.
For comparative analysis, methanol was also used as an initial feedstock. The experimental data are listed
in Table 4.
During the experiment, the formation of cokeforming deposits on the catalyst surface was observed
and, as a result, it was deactivated. It was shown that the catalyst was easily regenerated by annealing in an
air flow at a temperature of 600°C for 10 min. The proposed catalyst used at the laboratory plant endured
more than 100 regeneration cycles, and its activity remained nearly unchanged.
The parameters of the three processes which can occur in the unit for the synthesis of products are
given in Table 5 [55].
The flowsheet of an industrial process for the synthesis of methanol and dimethyl ether from natural
gas is illustrated in Fig. 21. The methanol and DME production processes have much in common, but
separation and purification conditions slightly differ from each other owing to the difference between the
boiling temperatures of these components.
12. MCTO PROCESS: METHYL CHLORIDE TO OLEFINS

The reactions occurring during the synthesis of methyl chloride via the oxidative chlorination of meth
ane are
CH4 + HCl + 0.5O2 → CH3Cl + H2O,
CH4 + 2HCl + O2 → CH2Cl2 + 2H2O,
CH4 + 3HCl + 1.5O2 → CHCl3 + 3H2O,
CH4 + 4HCl + 2O2 → CCl4 + 4H2O.
The heat liberated in all the substitutive oxidative chlorination reactions is 157 kJ per mole of converted
hydrogen chloride:
CH4 + 1.5O2 → CO + 2H2O +519.6 kJ/mol,
CH4 + 2O2 → CO2 + 2H2O +803.0 kJ/mol.
The reactions occurring in the catalytic conversion of methyl chloride into olefins are
2CH3Cl → C2H4 + 2HCl – 31.7 kJ/mol,
3CH3Cl → C3H6 + 3HCl + 10.5 kJ/mol,

112 TREGER, ROZANOV
Steam H2O
Gaseous
products
MeO
C5−
3
2
1 C6−
Water
condensate
Fig. 20. Flowchart of the reaction unit in the MTP process: (1) preliminary methanol conversion reactor, (2) metha
nol/DME conversion unit, (3) cooling and separation unit.
4CH3Cl → C4H8 + 4HCl + 41.4 kJ/mol,

5CH3Cl → C5H10 + 5HCl + 72.5 kJ/mol,
CH3Cl → C + H2 +HCl + 10.3 kJ/mol,
CH3Cl + H2 → CH4 + HCl + 85.3 kJ/mol,
2CH3Cl + H2 → C2H6 + 2HCl + 105.4 kJ/mol,
4CH3Cl → C4H6 + 4HCl + H2 + 151.4 kJ/mol.
The reactions occurring in the hydrogenation of chlororganic compounds are
CH3Cl + H2 → CH4 + HCl,
CH2Cl2 + H2 → CH3Cl + HCl,
CHCl3 + H2 → CH2Cl2 + HCl,
CCl4 + H2 → CHCl3 + HCl.
The heat liberated in all the reactions of hydrodechlorination of methyl chlorides is 85.8 kJ per mole
of converted hydrogen.
The selectivity of methane conversion into methyl chlorides is 94%, and the selectivity to a methyl
chloride in total methyl chlorides is 92%.
Table 3. Characteristics of the MTP process developed by Lurgi [46]

Product Capacity, kt/yr Yield, %
Methanol 1700
Ethylene 20 2.7
Propylene 474 65.0
C3/C4 fraction 41 5.7
Gasoline 185 25.3

Table 4. Conversion of different oxygenate feedstocks in the presence of an aluminophosphate catalyst

Selectivity, wt %, to
Initial reagent Conversion = = = =
C2H4 C3H6 C2 – C3 C2 – C4
Methanol 100.00 62.79 22.34 85.13 89.57
DME + H2O 100.00 62.80 22.65 85.45 90.23
DME 100.00 59.35 24.22 83.57 88.32
The MCTO process consists of two main reaction stages: synthesis of methyl chloride via the oxychlo
rination of methane and pyrolysis of methyl chloride to olefins. The methyl chloride production flowchart
is shown in Fig. 22 [56].
The methane oxychlorination process was studied in reactors of different types, such as fluidizedbed,
tubular, and adiabatic reactors [57], and tested at a pilot plant [58], and there also exist some patents on a
methane oxychlorination catalyst [59] and the process for the production of olefins from methane through
methyl chloride as a whole [60].
Natural gas is first subjected to purification form sulfurcontaining compounds and drying as described
in section 2 and then used to separate methane homologues (predominantly, from ethane to pentane),
which are further converted into an additional amount of C2–C4 olefins at a special stage together with
the methane homologues obtained in the catalytic pyrolysis of methyl chloride. These stages are described
in section 3.
Methane separated from homologues is mixed with hydrogen chloride and oxygen and fed to the meth
ane oxychlorination reactor.
The methane oxychlorination process is performed in excess methane to increase the methyl chloride
yield, reducing the formation of other methyl chlorides (methylene chloride, chloroform, and carbon tet
rachloride), and to use a fourstage adiabatic reactor in which excess methane serves to remove most of
the reaction heat. At a methane conversion of ∼15%, the process is performed with an unconverted meth
ane recycle. The content of methyl chloride in total synthesized methyl chlorides is 90–92 mol %. The
development of a singlestage adiabatic methane oxychlorination process instead of a fourstage reactor
has also been published [61].
The catalyst is a mixture which consists of copper, potassium, and lanthanum chlorides at a molar ratio
of 1 : 1 : 0.15 and is deposited onto GIAP8 porous corundum by impregnation from an aqueous solution.
The inlet reactor temperature of 300–320°C is controlled by heating the recycled gashydrogen chlo
ride mixture in a recuperative heat exchanger. The temperature at the inlet to catalyst beds ΙΙ, ΙΙΙ, and ΙV
is controlled by injecting ∼16% of hydrogen chloride. This technique is used to return the unconverted
hydrogen chloride back into the reactor for its complete utilization.
The temperature at the outlet from each catalyst bed of 400–420°C is controlled by oxygen injection.
A low oxygen concentration decreases the formation of carbon oxides, and a nearly complete conversion
of oxygen in a catalyst bed eliminates the possibility of excess over the specified temperature.
The pressure in the reactor of 10 ata was selected for the case of using graphite heat exchangers
designed for the pressure of 10 ata at the following stage.
The reaction gas of methane oxychlorination is passed through a recuperative heat exchanger into a
condensing and stripping column, where the condensation of hydrochloric acid from the reaction gas is
performed simultaneously with its distillation aimed at stripping the reaction water. In this case, the heat
produced by the condensation of water from the reaction gas and the dissolution of unconverted hydrogen
chloride in it is used for distillation.
Weak hydrochloric acid with a concentration below the azeotropic point (~16%) is accumulated at the
bottom of this column and passed to the recycle to the methane oxychlorination reactor. According to cal
culations, the boiler of this column has a backup function.
The reflux condenser of this column condenses pure water. The gas washed from hydrogen chloride is
compressed to the pressure of 30 ata by a compressor to facilitate the removal of water from the reaction
gas and provide the maximum condensation of methyl chloride by conventional cooling.
The condensation of water from the compressed reaction gas is performed via its stagewise cooling first
with recycled water and then with a salt solution at a temperature of 0°C in heat exchangers. A salt solution
with a temperature of 0°C was selected to provide the maximum cooling of the reaction gas and the con
densation of water without its freezing.

114 TREGER, ROZANOV
Table 5. Parameters of the methanol, methanol + dimethyl ether, and dimethyl ether synthesis processes
Parameter Methanol Methanol + dimethyl ether Dimethyl ether
Recycle ratio 5 5 2
Gas emissions, % 23 15 5
Singlepass conversion, % 14 18 50
Total conversion, % 77 85 95
The reaction gas is further cooled in heat exchangers to a temperature of 35 to 40°C to condense most
of methyl chloride (more than 80%). In this case, residual moisture will be frozen on the heattransfer sur
face. For this reason, the heat exchangers must periodically be stopped to thaw the moisture while engag
ing reserve heat exchangers.
The reaction gas is further passed for the recovery of residual methyl chloride using the absorption with
cooled carbon tetrachloride in an absorption column. The reaction gas purified from methyl chloride is
recycled for the oxidative chlorination of methane. The reaction gas is partially blown down to remove
inerts (N2, CO2). Since the blowdown gas contains nearly 55% of methane, 9.5% of CO, and 7.5% of H2,
it is delivered for combustion with steam generation.
The carbon tetrachloride from the bottom of the absorption column is fed to the desorption column to
strip dissolved methyl chloride. The pressure in the column is decreased to 9 ata to reduce the bottom tem
perature and prevent resinification. The regenerated carbon tetrachloride is fed by a pump to the top tray
of the absorber through a recuperative heat exchanger.
Methyl chloride stripped in the desorption column, chloromethanes condensed by deep cooling, and
the recycle of unconverted chloromethanes from the hydrodechlorination process are fed to the column
for the stripping of dissolved gases. Chloromethanes from the bottom of this column are fed to the next
column, where methyl chloride delivered for pyrolysis is withdrawn at the top, and methylene chloride,
Natural gas CO2
1. Syngas production 2. Product synthesis 3. Purification
Desulfu CO2 Distillation

Reformer Reactor Separator
rization removal column
Oxygen
Gas emission Product
Fig. 21. Industrial synthesis of methanol and dimethyl ether from natural gas.
chloroform, and carbon tetrachloride, which are mixed with hydrogen and fed to the hydrodechlorination
reactor, are withdrawn at the bottom.
The hydrodechlorination of polychloromethanes is performed in the presence of a nickelmolybdenum
catalyst at an incomplete conversion of chloromethanes for a single pass (of nearly 30%), but at a low
selectivity to methane (of nearly 35%), and the others are 40% of methyl chloride and 25% of olefins (eth
ylene and propylene) [62]. The MCTO with total utilization of polychloromethanes has been patented
[63]. The process is performed at a pressure of 9 ata and a temperature of 300°C. The reaction heat is used
to generate hightemperature steam. The production of chlorine for the synthesis of vinyl chloride gener
ates hydrogen in an amount sufficient to perform the hydrodechlorination of polychloromethanes.
The reaction gas of hydrodechlorination is fed to the condensing and stripping column, where low
boiling gases (hydrogen, methane, ethane, hydrogen chloride, and some methyl chloride) mixed with the

reaction gas from the pyrolysis of methyl chloride are separated at the top, and methyl chloride and
unconverted chlororganics mixed with the methyl chloride and chlororganics from the oxychlorination of
methane are withdrawn at the bottom.
The material balance calculated by us for a methyl chloride plant gave the consumption of natural gas
as a feedstock of 531 Nm3 per tonne of methyl chloride or 26.8 Nm3 per kilomole of CH3Cl.
The comparison of technologies for the production of methanol and methyl chloride from methane for
their further conversion into lower olefins [56] shows that the methanol synthesis process is characterized
by ~25% higher capital expenditures and a ~10% higher methane consumption because of the presence
of the energy and materialconsuming stage of syngas production from methane.
The process flowchart for the production of lower olefins from methyl chloride is shown in Fig. 23.
Methyl chloride obtained from natural gas is heated in a recuperative heat exchanger and fed to the
reactor for the catalytic conversion of methyl chloride into light olefins together with the unconverted
methyl chloride recycle from distillation column 5. The process is performed in a fluidized bed of the
SAPO34 silicoaluminophosphate catalyst at a pressure of 3 ata and a temperature of 425–450°C. The
reaction heat is very small and can be both positive and negative depending on the process selectivity to
ethylene and methane produced as a byproduct. The kinetics of the catalytic pyrolysis of methyl chloride
was studied in [64].
On the basis of kinetic studies, the order and activation energy of this reaction were determined. The
kinetic equation derived for the methyl chloride conversion reaction rate is
6.13
–
T mol
W = 5.51e P CH3 Cl , .
l kat h
A constant catalyst activity is maintained using a regenerator, into which some coked catalyst is con
tinuously poured to anneal the carbon deposits formed on the catalyst surface with air. The regenerated
catalyst is continuously returned back into the reactor. The regeneration heat is withdrawn in an integrated
heat exchanger to generate steam. The air delivered for regeneration is heated in a recuperative heat
exchanger with the waste air after regeneration. To increase the pyrolysis process selectivity to ethylene
and propylene, it was proposed to use an incompletely regenerated catalyst with residual carbon [65].
The reaction gas from the conversion of methyl chloride after the recuperative heat exchanger is mixed
with the lowboiling gases from the hydrogenation of polychloromethanes, compressed to the pressure of
30 ata by a compressor, and passed into column 1, where the products are separated into the C1–C2 + HCl
(“light”) and C3–C5+ + CH3Cl (“heavy”) fractions.
The “light” fraction is fed to column 2, where hydrogen and methane are separated from the ethane
ethylene fraction and hydrogen chloride. The hydrogenmethane fraction can be returned to the process
as a source of methane and hydrogen. The liquid residue of column 2 enters ethylene column 3 as a feed.
In this column, commercial ethylene is separated at the top, and hydrogen chloride and ethane, whose
boiling temperatures differ from each other by ~3.5°C, are withdrawn at the bottom.
There is no need for the complete separation of hydrogen chloride from ethylene, because the sepa
rated ethylene is further passed to the stages of dichloroethane synthesis via the direct and oxidative chlo
rination of ethylene in the production of vinyl chloride. Hydrogen chloride containing up to 1% of ethane
is delivered to the stage of methyl chloride synthesis via the oxidative chlorination of methane. Thus syn
thesized chloromethanes, as well as methyl chloride, give predominantly olefins upon pyrolysis.
The C3–C5 hydrocarbons and methyl chloride from the bottom of column 1 are fed to column 4, where
the propanepropylene fraction is separated at the top, and C4–C5+ hydrocarbons with methyl chloride are
withdrawn at the bottom.
The liquid residue of column 4 is fed to column 5, where unconverted methyl chloride returned from
the top of column 5 to the reactor and the C4–C5 fraction are separated. The propanepropylene fraction
from the reflux vessel of column 4 is fed by a pump to propylene column 6.
Commercial propylene is withdrawn at the top of column 6, and the propane fraction, which is deliv
ered for conversion into an additional amount of lower olefins or can be used in a mixture with the butane
butylene fraction as liquefied household gas, is separated at the bottom of this column. The C4–C5+ frac
tion separated in column 7 into the C4 fraction as a distillate and the C5+ fraction as a liquid residue is with
drawn at the bottom of column 5. The C5+ fraction can be used as a liquid fuel, and the C4 fraction can be
passed for conversion into lower olefins or used as liquefied household gas.
The comparison of technologies for the production of lower olefins from methanol and methyl chlo
ride [56] shows that both processes have close technologies for the synthesis of olefins and the separation

116 TREGER, ROZANOV
Dissolved gases CH3Cl to

CH4 recycle pyrolysis
Blowdown gases
Natural
gas
CH4 + H2 H2O
from
Compression
distillation
and condensation CH3Cl
Purification of chloromethanes absorption
from sulfur
Light gases CH3Cl

Water quenching to separation
and stripping desorption
Methane
oxychlori Weak hydrochloric
nation acid
N2 reactor
O2
Air Air
H2 from chlorine
separation
production
CH2Cl2, CHCl3, Condensing and
and CCl4 hydrogenation stripping column
reactor
Fig. 22. Methyl chloride production process.
of target products and similar attained process selectivities. An experimental comparison of the catalytic
pyrolysis of methanol and methyl chloride is available in [66].
13. PRODUCTION OF LIQUID FUEL FROM SYNGAS

BY THE FISCHER–TROPSCH METHOD WITH FURTHER PYROLYSIS
OF FUEL TO LOWER OLEFINS
Since most of ethylene is produced in the world via the pyrolysis of naphtha [67], and the Fischer–
Tropsch method is used in world practice predominantly for the synthesis of liquid fuel, it also was of inter
est to consider the variant of the synthesis of lower olefins via the pyrolysis of liquid fuel obtained from
syngas by the Fischer–Tropsch method. The sequence of reactions is actually the same as in the MTO pro
cess, but methanol is replaced by gasoline, i.e., methane → syngas → gasoline → lower olefins:
nCO + (2n + 1)H2 → CnH2n + 2 + nH2O + n146.5 kJ/mol.
The Fischer–Tropsch reaction is highly exothermic, and the liberated heat is nearly 35 kcal (146.5 kJ)
per carbon atom of a “structural unit” –CH2– [68]. The main problem requiring solution in the design of
reactors is heat withdrawal. An increase in the catalyst bed temperature must be reduced to a minimum.
To accomplish this, it is necessary to quickly withdraw the heat from catalyst particles. An undesired
increase in the Fischer–Tropsch reaction temperature reduces the process selectivity owing to the
increased formation of methane. The increase in temperature also leads to an increase in the coking rate
of the catalyst and its deactivation and sintering.
A large heattransfer rate is attained upon feeding syngas at a high linear velocity to create a turbulent
flow through long narrow tubes packed with catalyst particles or during the operation in a fluidizedbed
reactor. The catalyst is loaded into narrow tubes, through which syngas is passed. The intertubular space
is filled with a heattransfer fluid, as a rule, water, which is converted into steam at the outlet from the reac
tor.
To avoid overheating, the first industrial Fischer–Tropsch reactors were manufactured in the form of
plates spaced apart by 7mm gaps [69]. At present, reaction tubes with an inner diameter of 18 or even
12 mm are also sometimes recommended.
Five multitubular reactors designed by Lurgi and Ruhrchemie were installed for the production of wax
at the Sasolburg Fischer–Tropsch plant built in 1955. These reactors were still in operation at the time of
publication [70]. Each reactor contains 2050 tubes with an inner diameter of 50 mm and a length of 12 m.

Flue
gases
H2 + CH4 Ethylene Propylene
C3 fraction
CH3Cl
С1С2
fraction
2 3 4 6 7
С3С5+ C2 + HCl
fraction fraction C5+
Air
HCl + ethane to fraction
CH3Cl pyrolysis oxychlorination
CH3Cl recycle Propane
Light hydro
genation gases 5 С4
Methane
homologues
Pyrolysis of
Pyrolysis products С4С5+ fraction С2С4 paraffins
Fig. 23. Production of lower olefins from methyl chloride: (17) distillation columns.
They are operated at a pressure of 2.7 MPa and a temperature of 230°C. The capacity of each reactor is
nearly 21 000 t/year.
To provide efficient heat withdrawal at such a large diameter of tubes, it is necessary to create a high
linear velocity of gases, and the length of reaction tubes should be increased to retain the desired contact
time.
Advantages of multitubular fixedbed reactors consist in that their operation is simple and possible
within a wide range of temperatures independently of whether the Fischer–Tropsch products are gaseous
or liquid under reaction conditions.
However, fixedbed reactors are difficult to manufacture, and the replacement of the catalyst in them
is a complicated and timeconsuming process. The Fischer–Tropsch reaction rate is controlled by diffu
sion, so it is necessary to apply a catalyst with small grains. However, the application of such a catalyst
leads to an increase in the gradient of pressures in a reactor.
An alternative way for more efficient process performance is the use of fluidizedbed reactors.
The pressure drop in a fluidizedbed reactor does not grow with increasing gas velocity. The pressure drop
in a fluidizedbed reactor is proportional to the fluidized catalyst mass. The linear velocity of the gas in
industrial reactors with a fluidized catalyst bed is such that a turbulent regime with fast circulation and stir
ring is created in a reactor. As a result, the reaction zone is nearly isothermal with a bed temperature drop
of no more than 2°C.
However, a fluidizedbed reactor has some shortcomings. Such reactors are difficult to operate, espe
cially a catalyst circulation reactor. The efficient separation of catalyst particles from the outlet gas is dif
O2 H2O
Ethylene
Syngas FischerTropsch Liquid Fuel Separation
CH4 production synthesis fuel pyrolysis of products
Propylene
Fig. 24. Production of lower olefins via the Fischer–Tropsch synthesis.

118 TREGER, ROZANOV
O2 H2O CO
Syngas Methanol Methanol Ethanol Ethylene

CH4 production synthesis homologyzation Ethanol dehydration
Fig. 25. Production of ethylene via the homologyzation of methanol to ethanol.
ficult owing to their very small size (<100 μm). To separate catalyst particles from the outlet gas after flu
idizedbed reactors, the twophase system is equipped with cyclones. However, the catalyst loss in
cyclones is significant even at a degree of separation more than 99%. For this reason, additional oil scrub
bers for the trapping of catalyst dust are installed at the outlet from the reactor, and this increases capital
expenditures. To improve the stage of separating the catalyst and the outlet gas, it was proposed to use
porous metallic filters.
A catalyst circulation fluidizedbed reactor (lift reactor) has a zone with a very high linear velocity,
which causes erosion owing to the abrasive effect of the iron catalyst, so it is necessary to line this zone
with a protective layer of ceramic.
Another version of a fluidizedbed reactor is a slurry reactor. Small catalyst particles are suspended in
a liquid phase, through which a gas is bubbled; i.e., it represents a reactor with a fluidized catalyst bed in
a threephase system. Such a variant of implementation for the Fischer–Tropsch process is applied in the
production of highmolecular waxes, which are liquid under synthesis conditions. One of the shortcom
ings of a slurry reactor is the need for the separation of synthesized highmolecular hydrocarbons from the
catalyst.
The Fischer–Tropsch process has been implemented in industry predominantly in the fuel variant.
The distribution of expenditures on its creation is the following: syngas production, 60%; Fischer–Trop
sch synthesis, 25–30%; separation and upgrading, 10–15%.
The process flowchart for the production of liquid fuel from syngas by the Fischer–Tropsch method
with further pyrolysis of fuel to lower olefins is shown in Fig. 24.
14. SEQUENCE OF REACTIONS:

METHANE → SYNGAS → METHANOL → ETHANOL → ETHYLENE
The sequence of reactions methane → syngas → methanol has already been described above, so only
the two remaining reactions, the homologyzation of methanol to ethanol and the dehydration of ethanol
to ethylene, will be considered below (Fig. 25).
Ethylene can selectively be obtained via the catalytic dehydration of ethanol, but the possibilities of its
practical application are restricted by the cost of ethanol.
A set of industrial methods for the production of ethylene from traditional feedstocks of different com
panies is presented in [71]. HalconSD Group proposes ethylene production based on the dehydration of
ethanol over the Syndol catalyst developed by the company.
Another method consists in the abovementioned process for the dehydration of ethanol obtained via
the homologyzation of methanol, and the latter reaction proceeds with a selectivity of 90% according to
the data [72] as
CH3OH + CO + 2H2 → C2H5OH + H2O + 15.9 kJ/mol.
The catalytic dehydration of ethanol proceeds readily and selectively as
C2H5OH → C2H4 + H2O + 103.8 kJ/mol.
The flowchart of ethylene production by the abovedescribed pattern is shown in Fig. 25.
Table 6. Approximate relative cost of olefins synthesized by different methods (expert estimates)
Method Ethane pyrolysis Pyrolysis of broad fractions MCTO process MTO process
Relative cost 1 1.07–1.09 1.10–1.15 1.15–1.20

Capital expenditures
Offsites
800 Onsites
Millions of dollars
600
400
200 MTO Cracking
0
Methanol Ethane Naphtha
Process
Fig. 26. Capital expenditures on the MTO process and the cracking of ethane and naphtha.
Production cost
Payback of investments
800
Constant expenditures
Variable expenditures
Millions of dollars
600
400
MTO Cracking
200
0.25 $/gal 0.4 $/gal
0
Methanol Methanol Ethane Naphtha
Process
Fig. 27. Cost of the MTO process and the cracking of ethane and naphtha.
15. CONCLUSIONS
According to expert estimates, the approximate relative cost of olefins obtained by different methods
has proven to be minimal for the lower olefins synthesized from ethane (Table 6).
Expert estimates cannot always be true, as it is difficult to take into account all the expenditures and
complexities of technologies. For example, the separation of ethane requires laborious natural gas
purification and drying stages and then the separation of ethane under pressure and a temperature
below –100°C. A high ethylene yield is usually observed in the pyrolysis of ethane. However, other prod
ucts, including such a valuable component as propylene, are hardly formed in this case. From this view
point, the conclusion made at the end of book [11] is of interest and cited below.
At nearly equal prices on straightrun gasoline, ethane, and liquefied gases, a decrease in the unit con
sumption of feedstocks and a number of other items of expenditures upon the transition from gasoline
fractions to gaseous fractions is accompanied by a nearly equal decrease in the value of byproducts. For
this reason, there is almost no decrease in the prime cost in comparison with the use of gasoline.
Moreover, ethane separated from all the natural gas produced in the world under the assumption that
its content is 3% on average will provide only onethird of the world demand for ethylene.
The competitiveness of the MTO process in comparison with the existing industrial methods for the
production of lower olefins [73] is illustrated in Figs. 26 and 27. According to the estimates of Nexant spe
cialists, the MTO process becomes competitive with the use of methanol whose cost does not exceed
$0.25/gal ($83/t). Such cost of methanol is possible only under the condition of its production at a capac

120 TREGER, ROZANOV
O2
Methane Methane C2H4 Methyl
Natural gas Chloro
partial oxidative C2H2 chloride
O2 Cl2 pyrolysis
oxidation dimerization C2H3Cl synthesis
O2 H2O O2 CH3Cl O2
Methanol
CO C2H4 HCl
Syngas Methane Methyl
production thermo chloride
oxidative pyrolysis
Homolyzation Methanol Gasoline pyrolysis
to ethanol synthesis production
C2H4
Synthesis C2H4
C3H6
of olefins C2H2
C4H8
Gasoline
Ethanol Catalytic thermal
dehydration cracking pyrolysis
C2H4 C2H4 C2H4 C2H4

C3H6 C3H6 C3H6
C4H8 C4H8 C4H8
Fig. 28. Different variants for the production of olefins from natural gas.
ity of no less than 10000 t/day. The possibility of attaining such a capacity is provided by the MegaMeth
anol technology developed by Lurgi.
The engineering and economic evaluation performed by us for the MTO process with a capacity of
350000 t of ethylene per year shows that this method for the production of lower olefins becomes compet
itive with the other processes of their synthesis in the case of the selling of propylene and other byprod
ucts. It is interesting that the implementation of the pyrolysis stage only for methanol bought at a com
mercial price makes the production of ethylene unprofitable. Hence, the difference between the prime
cost and commercial price of methanol is of great importance at a high methanol consumption coefficient
close to 5 t per tonne of ethylene owing to the fact that the greater part of the methanol molecule is con
verted into water during pyrolysis.
According to [74], the method of producing liquid fuel through the oxychlorination of methane was
more profitable than others. Table 7 presents the results of comparative analysis of the capital cost for pro
cessing natural gas to liquid hydrocarbons, reported in [74].
Based on this comparison, it is concluded that, despite the need for special construction materials, the
technology of oxychlorination proved to be the best among the technologies of direct conversion of natural
gas due to its high selectivity. The authors argue that the global replacement of special construction mate
rials in the facility of the methane oxichlorination by carbon steel would save up to 15% of capital costs.
It is noted that the stage of conversion of methyl chloride is mastered well enough, while the stage of syn
thesizing methyl chloride by the oxychlorination of methane raises some questions.
Table 7. A comparative analysis of capital costs of the processing of natural gas into liquid hydrocarbons (million
U.S. dollars at a capacity of 14 500 bar/d)
Fischer–
Oxidative Partial Oxychlorination MTG*, MTG,
Tropsch
condensation oxidation of methane fixed bed fluidized bed
process
Processing equipment 273.2 346.9 218.4 261.1 220.5 240.0
Utilities, infrastructure, 208.2 273.5 204.8 208.3 203.6 216.9
and offsites
Miscellaneous expenses 202.1 223.6 173.8 213.3 197.4 189.9
Total 683.5 844.0 597.0 682.7 621.5 646.8
*MTG, methanoltogasoline conversion.

The fact that in foreign countries, a simpler method of utilization of offgas hydrogen chloride from
the direct chlorination of methane was selected, that is, interaction with methanol to produce methyl
chloride, while in the Soviet Union, the process for oxychlorination of methane was developed and
brought to the beginning of construction at the TajikKhimProm industrial group at the end of 1990s.
Therefore, almost all the difficult issues in this process have been solved [75].
The engineering and economic evaluation performed by us for the MCTO process for the production
of lower olefins via the pyrolysis of methyl chloride synthesized by the oxychlorination of methane shows
that such a process is also profitable, though the capacity of 100 000 t of ethylene per year selected by us
is minimal for satisfactory profitability.
The engineering and economic analysis of the rapidly developing trend in China with the use of coal
as an initial feedstock for the synthesis of olefins was performed in [76]. The process in short is called CTO
(Coal to Olefins). As well as the process with the use of natural gas as an initial feedstock, this process is
characterized by a lower prime cost of synthesized olefins in comparison with the processes for the pro
duction of olefins from oil feedstocks. The authors conclude that this process can be competitive with the
processes for the production of olefins from oil feedstocks despite higher capital expenditures and the tax
on CO2 emissions into the atmosphere.
Different aspects of the production of lower olefins from coal and natural gas are considered in [50].
Data are cited that the demand of China for methanol in 2013 was 26–28 million tonnes, 19% (~5 million
tonnes) of which were used in the MTO process, and the demand of China for methanol by 2020 is pre
dicted at a level of >70 million tonnes, including 64% (~45 million tonnes) of methanol for the MTO pro
cess. Two plants for the processing of methanol into propylene and four plants for the production of eth
ylene and propylene were created in the period of 2010–2014. In this case, coal is used as an initial feed
stock. It is planned to create nine plants for the production of olefins by CTO technology, seven MTO
process plants, and one MTP process plant in the period of 2014–2015. Some enterprises intend to use
imported methanol.
Some information that the coal price in the period of 2000–2014 exceeded the cost of natural gas only
once (from the second half of 2012 to the first half of 2013) is also given. The authors believe that natural
gas can prove to be a more preferable and inexpensive feedstock than coal in other regions. All the consid
ered variants for the processing of natural gas into ethylene and propylene are shown in Fig. 28.
It was reported in the presentation of the PLATTS editor, M. Tsay, made at the III Moscow Interna
tional Chemical Forum held on October 28–29, 2015, in Ekspocentr central exhibition complex, in Sec
tion “Petrochemical Production,” that due to the significant reduction in the cost of naphtha, the pro
duction cost of 1 ton of olefins derived from naphtha or coal (CTO process), appeared in 2015 at the same
level.
The report of the Linde AG project manager, D. Efremov, “Technology of production of ethylene using
the oxidative dimerization of methane (ODM)” at the same forum, informed on the use of the heat of the
reaction ODM gas for obtaining additional ethylene by pyrolysis of ethane both contained in the reaction
gas and input thereto from the outside.
No details about the process of ODM are given, except that the catalyst developed by Siluria (United
States) has worked in a pilot plant for 2 years and continue to be tested.
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Translated by E. Glushachenkova

Technologies For The Synthesis of Ethylene and Propylene From Natural Gas

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ISSN 20799780, Review Journal of Chemistry, 2016, Vol. 6, No. 1, pp. 83–123. © Pleiades Publishing, Ltd.

Technologies for the Synthesis of Ethylene

Keywords: natural gas, methane, ethylene, propylene.

2. NATURAL GAS PURIFICATION

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E11 To initial gas

E4 E5 C H C2H6

E8 Stable gasoline

3. SEPARATION OF METHANE HOMOLOGUES AND THEIR PROCESSING INTO

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3.1 Synthesis of Ethane via the Pyrolysis of an Ethane Fraction

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3.2. Pyrolysis of Ethane and C3–C4 (and Higher) Hydrocarbon Fractions

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4. OXIDATIVE CONDENSATION (DIMERIZATION) OF METHANE TO ETHYLENE

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Pyrogas compression, Purification Ethylene Propylene

Fig. 4. Flowchart for the pyrolysis of C2–C4 methane homologues.

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5. PYROLYSIS OF METHANE AND ITS HOMOLOGUES

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7. PARTIAL OXIDATION OF METHANE TO METHANOL

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8. CONVERSION OF METHANE INTO SYNGAS

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(CO + H2)/CH4, mol/mol

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Reaction gas of Initial natural

Shaft reactor Reaction gas of

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From intertubular Catalystfilled tube

Tube To intertubular space

From intertubular space

Fig. 13. Synetix advanced gas heated reforming (AGHR) reactor.

9. DIRECT SYNTHESIS OF LOWER OLEFINS FROM SYNGAS

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Liquid pyrolysis CH4 + 20% H2

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10. MTO PROCESS: METHANOL TO OLEFINS

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Purifica Steam Steam

Syngas to methanol production

Fig. 15. ICI methanol production process.

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Start hydrocarbon Heating of

Fig. 16. Haldor Topsøe methanol production plant [38].

C4H8 → 4C + 4H2 – 1.2 kJ/mol,

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Highpressure GAS RECYCLE

Fig. 17. Lurgi methanol production process [39].

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Fig. 18. Lurgi twostage MegaMethanol process.

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10.1. Lurgi MethanoltoPropylene (MTP) Process

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Flue Drying H2 + CH4 Ethylene Propylene