(19)

& 
(11) EP 1 871 732 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C07C 29/149 (2006.01) C07C 31/04 (2006.01)
18.07.2012 Bulletin 2012/29 C07C 29/48 (2006.01)

(21) Application number: 06749945.9 (86) International application number:

PCT/US2006/013743
(22) Date of filing: 12.04.2006
(87) International publication number:
WO 2006/113294 (26.10.2006 Gazette 2006/43)

(54) SELECTIVE OXIDATIVE CONVERSION OF METHANE TO METHANOL, DIMETHYL ETHER AND

DERIVED PRODUCTS
SELEKTIVE, OXIDATIVE UMWANDLUNG VON METHAN IN METHANOL, DIMETHYLETHER UND
ABGELEITETE PRODUKTE
CONVERSION OXYDATIVE SELECTIVE DE METHANE EN METHANOL, DIMETHYL ETHER ET
PRODUITS DERIVES

(84) Designated Contracting States: • PRAKASH, Surya, G., K.

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Hacienda Heights, CA 91745 (US)
HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI
SK TR (74) Representative: Holme Patent A/S
Vesterbrogade 20
(30) Priority: 15.04.2005 US 671650 P 1620 Copenhagen V (DK)
30.01.2006 US 763678 P
(56) References cited:
(43) Date of publication of application: WO-A-2005/037746 FR-A- 2 543 946
02.01.2008 Bulletin 2008/01 US-A- 4 243 613 US-A- 5 364 887

(73) Proprietor: UNIVERSITY OF SOUTHERN • PATENT ABSTRACTS OF JAPAN vol. 009, no. 082
CALIFORNIA (C-275), 11 April 1985 (1985-04-11) -& JP 59
Los Angeles, CA 90007-4344 (US) 216839 A (KOUEI KAGAKU KOGYO KK), 6
December 1984 (1984-12-06)
(72) Inventors:
• OLAH, George, A.
Beverly Hills, CA 90210 (US)
EP 1 871 732 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 871 732 B1

Description

BACKGROUND

5 [0001] Hydrocarbons are essential in modem life. Hydrocarbons are used as fuel and raw material in various fields,
including the chemical, petrochemical, plastics, and rubber industries. Fossil fuels, such as coal, oil and gas, are com-
posed of hydrocarbons with varying ratios of carbon and hydrogen, and is non-renewably used when combusted, forming
carbon dioxide and water. Despite their wide application and high demand, fossil fuels present a number of disadvantages,
including the finite reserve, irreversible combustion and contribution to air pollution and global warming. Considering
10 these disadvantages, and the increasing demand for energy, alternative sources of energy are needed.
[0002] One such alternative frequently mentioned is hydrogen, and the so-called "hydrogen economy." Hydrogen is
beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however, is not a natural energy
source, and its generation from hydrocarbons or water is a highly energy-consuming process. Further, when hydrogen
is produced from hydrocarbons, any claimed benefit of hydrogen as a clean fuel is outweighed by the fact that generation
15 of hydrogen itself, mainly by reforming of natural gas, oil or coal to synthesis gas ("syn-gas") a mixture of CO and H2,
is far from clean. It consumes fossil fuels, with a quarter of the energy of the fuel being lost as heat. Hydrogen is also
not a convenient energy storage medium because it is difficult and costly to handle, store, transport and distribute. As
it is extremely volatile and potentially explosive, hydrogen gas requires high-pressure equipment, costly and non-existent
infrastructure, special materials to minimize diffusion and leakage, and extensive safety precautions to prevent explo-
20 sions.
[0003] It was suggested that a more practical alternative is methanol. Methanol, CH3OH, is the simplest liquid oxy-
genated hydrocarbon, differing from methane (CH4) by a single additional oxygen atom. Methanol, also called methyl
alcohol or wood alcohol, is a colorless, water-soluble liquid with a mild alcoholic odor, and is easy to store and transport.
It freezes at -97.6°C, boils at 64.6°C, and has a density of 0.791 at 20°C.
25 [0004] Methanol is not only a convenient and safe way to store energy, but, together with its derived dimethyl ether
(DME), is an excellent fuel. Dimethyl ether is easily obtained from methanol by dehydration and is an effective fuel
particularly in diesel engines because of its high cetane number and favorable properties. Methanol and dimethyl ether
can be blended with gasoline or diesel and used as fuels, for example in internal combustion engines or electricity
generators. One of the most efficient use of methanol is in fuel cells, particularly in direct methanol fuel cell (DMFC), in
30 which methanol is directly oxidized with air to carbon dioxide and water while producing electricity.
[0005] Contrary to gasoline, which is a complex mixture of many different hydrocarbons and additives, methanol is a
single chemical compound. It contains about half the energy density of gasoline, meaning that two liters of methanol
provides the same energy as a liter of gasoline. Even though methanol’s energy content is lower, it has a higher octane
rating of 100 (average of the research octane number (RON) of 107 and motor octane number (MON) of 92), which
35 means that the fuel/air mixture can be compressed to a smaller volume before being ignited. This allows the engine to
run at a higher compression ratio (10-11 to 1 against 8-9 to 1 of a gasoline engine), more efficiently than a gasoline-
powered engine. Efficiency is also increased by methanol’s higher "flame speed," which enables faster, more complete
fuel combustion in the engines. These factors explain the high efficiency of methanol despite its lower energy density
than gasoline. Further, to render methanol more ignitable even under the most frigid conditions, methanol can be mixed
40 with gasoline, with volatile compounds (e.g., dimethyl ether), with other components or with a device to vaporize or
atomize methanol. For example, an automotive fuel can be prepared by adding methanol to gasoline with the fuel having
a minimum gasoline content of at least 15% by volume (M85 fuel) so that it can readily start even in low temperature
environments. Of course, any replacement of gasoline in such fuels will conserve oil resources, and the amount of
methanol to add can be determined depending upon the specific engine design.
45 [0006] Methanol has a latent heat of vaporization of about 3.7 times higher than gasoline, and can absorb a significantly
larger amount of heat when passing from liquid to gas state. This helps remove heat away from the engine and enables
the use of an air-cooled radiator instead of a heavier water-cooled system. Thus, compared to a gasoline-powered car,
a methanol-powered engine provides a smaller, lighter engine block, reduced cooling requirements, and better accel-
eration and mileage capabilities. Methanol is also more environment-friendly than gasoline, and produces low overall
50 emissions of air pollutants such as hydrocarbons, NOx, SO2 and particulates.
[0007] Methanol is also one of the safest fuels available. Compared to gasoline, methanol’s physical and chemical
properties significantly reduce the risk of fire. Methanol has lower volatility, and methanol vapor must be four times more
concentrated than gasoline for ignition to occur. Even when ignited, methanol burns about four times slower than gasoline,
releases heat only at one-eighth the rate of gasoline fire, and is far less likely to spread to surrounding ignitable materials
55 because of the low radiant heat output. It has been estimated by the EPA that switching from gasoline to methanol would
reduce incidence of fuel-related fire by 90%. Methanol burns with a colorless flame, but additives can solve this problem.
[0008] Methanol also provides an attractive and more environment-friendly alternative to diesel fuel. Methanol does
not produce smoke, soot, or particulates when combusted, in contrast to diesel fuel, which generally produces polluting

2
 EP 1 871 732 B1

particles during combustion. Methanol also produces very low emissions of NOx because it burns at a lower temperature
than diesel. Furthermore, methanol has a significantly higher vapor pressure compared to diesel fuel, and the higher
volatility allows easy start even in cold weather, without producing white smoke typical of cold start with a conventional
diesel engine. If desired, additives or ignition improvers, such as octyl nitrate, tetrahydrofurfuryl nitrate, peroxides or
5 higher alkyl ethers, can be added to bring methanol’s cetane rating to the level closer to diesel. Methanol can also be
used in the manufacture of biodiesel fuels by esterification of fatty acids.
[0009] Closely related and derived from methanol, and also a desirable alternative fuel is dimethyl ether. Dimethyl
ether (DME, GH3OCH3), the simplest of all ethers, is a colorless, nontoxic, non-corrosive, non-carcinogenic and envi-
ronmentally friendly chemical that is mainly used today as an aerosol propellant in spray cans, in place of the banned
10 CFC gases. DME has a boiling point of-25°C, and is a gas under ambient conditions. DME is, however, easily handled
as liquid and stored in pressurized tanks, much like liquefied petroleum gas (LPG). The interest in dimethyl ether as
alternative fuel lies in its high cetane rating of 55 to 60, which is much higher than that of methanol and is also higher
than the cetane rating of 40 to 55 of conventional diesel fuels. The cetane rating indicates that DME can be effectively
used in diesel engines. Advantageously, DME, like methanol, is clean burning, and produces no soot particulates, black
15 smoke or SO2, and only very low amounts of NOx and other emissions even without after-treatment of its exhaust gas.
Some of the physical and chemical properties DME, in comparison to diesel fuel, are shown in Table 1.

Table 1: Comparison of the physical properties of DME and diesel fuel

DME Diesel fuel
20
Boiling point °C -24.9 180-360
Vapor pressure at 20°C (bar) 5.1 -
Liquid density at 20°C (kg / m3) 668 840 - 890
Heating value (kcal / kg) 6,880 10,150
25 Cetane number 55 - 60 40 - 55
Autoignition temperature (°C) 235 200 - 300
Flammability limits in air (vol %) 3.4 - 17 0.6 - 6.5

30 [0010] Currently, DME is exclusively produced by dehydration of methanol. A method for synthesizing DME directly
from synthesis gas by combining the methanol synthesis and dehydration steps in a single process has also been
developed.
[0011] Another methanol derivative is dimethyl carbonate (DMC), which can be obtained by converting methanol with
phosgene or by oxidative carbonylation of the methanol. DMC has a high cetane rating, and can be blended into diesel
35 fuel in a concentration up to 10%, reducing fuel viscosity and improving emissions.
[0012] Methanol and its derivatives, e.g., DME, DMC, and biodiesel, have many existing and potential uses. They can
be used, for example, as a substitute for gasoline and diesel fuel in ICE-powered cars with only minor modifications to
the existing engines and fuel systems. Methanol can also be used in fuel cells, for fuel cell vehicles (FCVs), which are
considered to be the best alternative to ICEs in the transportation field. DME is also a potential substitute for LNG and
40 LPG for heating homes and in industrial uses.
[0013] Methanol is also useful in reforming to hydrogen. In an effort to address the problems associated with hydrogen
storage and distribution, suggestions have been made to use liquids rich in hydrogen such as gasoline or methanol as
a source of hydrogen in vehicles via an on-board reformer. It is also considered that methanol is the safest of all materials
available for such hydrogen production. Further, because of the high hydrogen content of liquid methanol, even compared
45 to pure cryogenic hydrogen (98.8 g of hydrogen in a liter of methanol at room temperature compared to 70.8 g in liquid
hydrogen at -253°C), methanol is an excellent carrier of hydrogen fuel. The absence of C-C bonds in methanol, which
are difficult to break, facilitates its transformation to pure hydrogen in 80 to 90% efficiency.
[0014] In contrast to a pure hydrogen-based storage system, a reformer system is compact, containing on a volume
basis more hydrogen than even liquid hydrogen, and is easy to store and handle without pressurization. A methanol
50 steam reformer is also advantageous in allowing operation at a much lower temperature (250-350°C) and for being
better adapted to on-board applications. Furthermore, methanol contains no sulfur, a contaminant for fuel cells, and no
nitrogen oxides are formed from a methanol reformer because of the low operating temperature. Particulate matter and
NOx emissions are virtually eliminated, and other emissions are minimal. Moreover, methanol allows refueling to be as
quick and easy as with diesel fuel. Thus, an on-board methanol reformer enables rapid and efficient delivery of hydrogen
55 from liquid fuel that can be easily distributed and stored in the vehicle. To date, methanol is the only liquid fuel that has
been processed and demonstrated on a practical scale as suitable for use in a fuel cell for transportation applications.
[0015] In addition to on-board reforming, methanol also enables convenient production of hydrogen in fueling stations
for refueling hydrogen fuel cell vehicles. A fuel cell, an electrochemical device that converts free chemical energy of fuel

3
 EP 1 871 732 B1

directly into electrical energy, provides a highly efficient way of producing electricity via catalytic electrochemical oxidation.
For example, hydrogen and oxygen (air) are combined in an electrochemical cell-like device to produce water and
electricity. The process is clean, with water being the only byproduct. However, because hydrogen itself must first be
produced in an energy-consuming process, by electrolysis or from a hydrocarbon source (fossil fuel) with a reformer,
5 hydrogen fuel cells are still necessarily limited in utility.
[0016] A system for producing high purity hydrogen has been developed by steam reforming of methanol with a highly
active catalyst, which allows operation at a relatively low temperature (240-290°C) and enables flexibility in operation
as well as rapid start-up and stop. These methanol-to-hydrogen (MTH) units, ranging in production capacity from 50 to
4000 m3 H2 per hour, are already used in various industries, including the electronic, glass, ceramic, and food processing
10 industries, and provide excellent reliability, prolonged life span, and minimal maintenance. Operating at a relatively low
temperature, the MTH process has a clear advantage over reforming of natural gas and other hydrocarbons which must
be conducted at above 600°C, because less energy is needed to heat methanol to the appropriate reaction temperature.
[0017] The usefulness of methanol has led to development of other reforming processes, for example, a process
known as oxidative steam reforming, which combines steam reforming, partial oxidation of methanol, and novel catalyst
15 systems. Oxidative steam reforming produces high purity hydrogen with zero or trace amounts of CO, at high methanol
conversion and temperatures as low as 230°C. It has the advantage of being, contrary to steam reforming, an exothermic
reaction, therefore minimizing energy consumption. There is also autothermal reforming of methanol, which combines
steam reforming and partial oxidation of methanol in a specific ratio and addresses any drawback of an exothermic
reaction by producing only enough energy to sustain itself. Autothermal reforming is neither exothermic nor endothermic,
20 and does not require any external heating once the reaction temperature is reached. Despite the aforementioned pos-
sibilities, hydrogen fuel cells must use highly volatile and flammable hydrogen or reformer systems.
[0018] U.S. patent no. 5,599,638 discloses a simple direct methanol fuel cell (DMFC) to address the disadvantages
of hydrogen fuel cells. In contrast to a hydrogen fuel cell, the DMFC is not dependent on generation of hydrogen by
processes such as electrolysis of water or reformation of natural gas or hydrocarbon. The DMFC is also more cost
25 effective because methanol, as a liquid fuel, does not require cooling at ambient temperatures or costly high pressure
infrastructure and can be used with existing storage and dispensing units, unlike hydrogen fuel, whose storage and
distribution requires new infrastructure. Further, methanol has a relatively high theoretical volumetric energy density
compared to other systems such as conventional batteries and the H2-PEM fuel cell. This is of great importance for
small portable applications (cellular phones, laptop computers, etc.), for which small size and weight of energy unit is
30 desired.
[0019] The DMFC offers numerous benefits in various areas, including the transportation sector. By eliminating the
need for a methanol steam reformer, the DMFC significantly reduces the cost, complexity and weight of the vehicle, and
improves fuel economy. A DMFC system is also comparable in its simplicity to a direct hydrogen fuel cell, without the
cumbersome problems of on-board hydrogen storage or hydrogen producing reformers. Because only water and CO2
35 are emitted, emissions of other pollutants (e.g., NOx, PM, SO2, etc.) are eliminated. Direct methanol fuel cell vehicles
are expected to be virtually zero emission vehicles (ZEV), and use of methanol fuel cell vehicles offers to nearly eliminate
air pollutants from vehicles in the long term. Further, unlike ICE vehicles, the emission profile is expected to remain
nearly unchanged over time. New membranes based on hydrocarbon or hydrofluorocarbon materials with reduced cost
and crossover characteristics have been developed that allow room temperature efficiency of 34%.
40 [0020] Methanol as indicated provides a number of important advantages as transportation fuel. Contrary to hydrogen,
methanol does not require any energy intensive procedures for pressurization or liquefaction. Because it is a liquid at
room temperature, it can be easily handled, stored, distributed and carried in vehicles. It can act as an ideal hydrogen
carrier for fuel cell vehicles through on-board methanol reformers, and can be used directly in DMFC vehicles.
[0021] Methanol is also an attractive source of fuel for static applications. For example, methanol can be used directly
45 as fuel in gas turbines to generate electric power. Gas turbines typically use natural gas or light petroleum distillate
fractions as fuel. Compared to such fuelsz, methanol can achieve higher power output and lower NOx emissions because
of its lower flame temperature. Since methanol does not contain sulfur, SO2 emissions are also eliminated. Operation
on methanol offers the same flexibility as on natural gas and distillate fuels, and can be performed with existing turbines,
originally designed for natural gas or other fossil fuels, after relatively easy modification. Methanol is also an attractive
50 fuel since fuel-grade methanol, with lower production cost than higher purity chemical-grade methanol, can be used in
turbines. Because the size and weight of a fuel cell is of less importance in static applications than mobile applications,
various fuel cells other than PEM fuel cells and DMFC, such as phosphoric acid, molten carbonate and solid oxide fuel
cells (PAFC, MCFC, and SOFC, respectively), can also be used.
[0022] In addition to use as fuels, methanol and methanol-derived chemicals have other significant applications in the
55 chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. Most of the 32
million tons of annually produced methanol is used to manufacture a large variety of chemical products and materials,
including basic chemicals such as formaldehyde, acetic acid, MTBE (although it is increasingly phased out for environ-
mental reasons), as well as various polymers, paints, adhesives, construction materials, and others. Worldwide, almost

4
 EP 1 871 732 B1

70% of methanol is used to produce formaldehyde (38%), methyl-tert-butyl ether (MTBE, 20%) and acetic acid (11%).
Methanol is also a feedstock for chloromethanes, methylamines, methyl methacrylate, and dimethyl terephthalate, among
others. These chemical intermediates are then processed to manufacture products such as paints, resins, silicones,
adhesives, antifreeze, and plastics. Formaldehyde, produced in large quantities from methanol, is mainly used to prepare
5 phenol-, urea- and melamine-formaldehyde and polyacetal resins as well as butanediol and methylene bis(4-phenyl
isocyanate) (MDI; MDI foam is used as insulation in refrigerators, doors, and in car dashboards and bumpers). Formal-
dehyde resins are predominantly employed as an adhesive in a wide variety of applications, e.g., manufacture of particle
boards, plywood and other wood panels. Examples of methanol-derived chemical products and materials are shown in
FIG. 1.
10 [0023] In producing basic chemicals, raw material feedstock constitutes typically up to 60-70% of the manufacturing
costs. The cost of feedstock therefore plays a significant economic role. Because of its lower cost, methanol is considered
a potential feedstock for processes currently utilizing more expensive feedstocks such as ethylene and propylene, to
produce chemicals including acetic acid, acetaldehyde, ethanol, ethylene glycol, styrene, and ethylbenzene, and various
synthetic hydrocarbon products. For example, direct conversion of methanol to ethanol can be achieved using a rhodium-
15 based catalyst, which has been found to promote the reductive carbonylation of methanol to acetaldehyde with selectivity
close to 90%, and a ruthenium catalyst, which further reduces acetaldehyde to ethanol. The possibility of producing
ethylene glycol via methanol oxidative coupling instead of the usual process using ethylene as feedstock is also pursued,
and significant advances for synthesizing ethylene glycol from dimethyl ether, obtained by methanol dehydration, have
also been made.
20 [0024] Conversion of methanol to olefins such as ethylene and propylene, also known as methanol to olefin (MTO)
technology, is particularly promising considering the high demand for olefin materials, especially in polyolefin production.
The MTO technology is presently a two-step process, in which natural gas is converted to methanol via syn-gas and
methanol is then transformed to olefin. It is considered that methanol is first dehydrated to dimethyl ether (DME), which
then reacts to form ethylene and/or propylene. Small amounts of butenes, higher olefins, alkanes, and aromatics are
25 also formed.

30

[0025] Various catalysts, e.g., synthetic aluminosilicate zeolite catalysts, such as ZSM-5 (a zeolite developed by Mobil),
silicoaluminophosphate (SAPO) molecular sieves such as SAPO-34 and SAPO-17 (UOP), as well as bi-functional
supported acid-base catalysts such as tungsten oxide over alumina (WO3/Al2O3), have been found to be active in
35 converting methanol to ethylene and propylene at a temperature between 250 and 350°C. The type and amount of the
end product depend on the type of the catalyst and the MTO process used. Depending on the operating conditions, the
weight ratio of propylene to ethylene can be modified between about 0.77 and 1.33, allowing considerable flexibility. For
example, when using SAPO-34 according to an MTO process developed by UOP and Norsk Hydro, methanol is converted
to ethylene and propylene at more than 80% selectivity, and also to butene, a valuable starting material for a number
40 of products, at about 10%. When using an MTO process developed by Lurgi with ZSM-5 catalysts, mostly propylene is
produced at yields above 70%. A process developed by ExxonMobil, with ZSM-5 catalyst, produces hydrocarbons in
the gasoline and/or distillate range at selectivity greater than 95%.
[0026] There is also a methanol to gasoline (MTG) process, in which medium-pore zeolites with considerable acidity,
e.g., ZSM-5, are used as catalysts. In this process, methanol is first dehydrated to an equilibrium mixture of dimethyl
45 ether, methanol and water over a catalyst, and this mixture is then converted to light olefins, primarily ethylene and
propylene. The light olefins can undergo further transformations to higher olefins, C3-C6 alkanes, and C6-C10 aromatics
such as toluene, xylenes, and trimethylbenzene.
[0027] With decreasing oil and gas reserves, it is inevitable that synthetic hydrocarbons would play a major role. Thus,
methanol-based synthetic hydrocarbons and chemicals available through MTG and MTO processes will assume in-
50 creasing importance in replacing oil and gas-based materials. The listed uses of methanol is only illustrative and not
limiting.
[0028] Methanol can also be used as a source of single cell proteins. A single cell protein (SCP) refers to a protein
produced by a microorganism which degrades hydrocarbon substrates while gaining energy. The protein content depends
on the type of microorganism, e.g., bacteria, yeast, mold, etc. The SCP has many uses, including uses as food and
55 animal feed.
[0029] Considering the numerous uses of methanol, it is clearly desirable to have improved and efficient methods of
producing methanol. Currently, methanol is almost exclusively made from synthesis gas obtained from incomplete
combustion (or catalytic reforming) of fossil fuel, mainly natural gas (methane) and coal.

5
 EP 1 871 732 B1

[0030] Methanol can also be made from renewable biomass, but such methanol production also involves syn-gas and
may not be energetically favorable and limited in terms of scale. As used herein, the term "biomass" includes any type
of plant or animal material, i.e., materials produced by a life form, including wood and wood wastes, agricultural crops
and their waste byproducts, municipal solid waste, animal waste, aquatic plants, and algae. The method of transforming
5 biomass to methanol is similar to the method of producing methanol from coal, and requires gasification of biomass to
syn-gas, followed by methanol synthesis by the same processes used with fossil fuel. Use of biomass also presents
other disadvantages, such as low energy density and high cost of collecting and transporting bulky biomass. Although
recent improvements involving the use of "biocrude," black liquid obtained from fast pyrolysis of biomass, is somewhat
promising, more development is needed for commercial application of biocrude.
10 [0031] The presently existing method of producing methanol involves syn-gas. Syn-gas is a mixture of hydrogen,
carbon monoxide and carbon dioxide, and produces methanol over a heterogeneous catalyst according to the following
equations:

15

20

[0032] The first two reactions are exothermic with heat of reaction equal to - 21.7 kcal.mol-1 and - 9.8 kcal.mol-1,
respectively, and result in a decrease in volume. Conversion to methanol is favored by increasing the pressure and
25
decreasing the temperature according to Le Chatelier’s principle. The third equation describes the endothermic reverse
water gas shift reaction (RWGSR). Carbon monoxide produced in the third reaction can further react with hydrogen to
produce methanol. The second reaction is simply the sum of the first and the third reactions. Each of these reactions is
reversible, and is therefore limited by thermodynamic equilibrium under the reaction conditions, e.g., temperature, pres-
sure and composition of the syn-gas.
30
[0033] Synthesis gas for methanol production can be obtained by reforming or partial oxidation of any carbonaceous
material, such as coal, coke, natural gas, petroleum, heavy oil, and asphalt. The composition of syn-gas is generally
characterized by the stoichiometric number S, corresponding to the equation shown below.

35

Ideally, S should be equal to or slightly above 2. A value above 2 indicates excess hydrogen, while a value below 2
40
indicates relative hydrogen deficiency. Reforming of feedstock having a higher H/C ratio, such as propane, butane or
naphthas, leads to S values in the vicinity of 2, ideal for conversion to methanol. When coal or methane is used, however,
additional treatment is required to obtain an optimal S value. Synthesis gas from coal requires treatment to avoid formation
of undesired byproducts. Steam reforming of methane yields syn-gas with a stoichiometric number of 2.8 to 3.0, and
requires lowering the S value closer to 2 by adding CO2 or using excess hydrogen in some other process such as
45
ammonia synthesis. However, natural gas is still the preferred feedstock for methanol production because it offers high
hydrogen content and, additionally, the lowest energy consumption, capital investment and operating costs. Natural gas
also contains fewer impurities such as sulfur, halogenated compounds, and metals which may poison the catalysts used
in the process.
[0034] The existing processes invariably employ extremely active and selective copper-based catalysts, differing only
50
in the reactor design and catalyst arrangement. Because only part of syn-gas is converted to methanol after passing
over the catalyst, the remaining syn-gas is recycled after separation of methanol and water. There is also a more recently
developed liquid phase process for methanol production, during which syn-gas is bubbled into liquid. Although the
existing processes have methanol selectivity greater than 99% and energy efficiency above 70%, crude methanol leaving
the reactor still contains water and other impurities, such as dissolved gas (e.g., methane, CO, and CO2) dimethyl ether,
55
methyl formate, acetone, higher alcohols (ethanol, propanol, butanol), and long-chain hydrocarbons. Commercially,
methanol is available in three grades of purity: fuel grade, "A" grade, generally used as a solvent, and "AA" or chemical
grade. Chemical grade has the highest purity with a methanol content exceeding 99.85% and is the standard generally

6
 EP 1 871 732 B1

observed in the industry for methanol production. The syn-gas generation and purification steps are critical in the existing
processes, and the end result would largely depend on the nature and purity of the feedstock. To achieve the desired
level of purity, methanol produced by the existing processes is usually purified by sufficient distillation. Another major
disadvantage of the existing process for producing methanol through syn-gas is the energy requirement of the first highly
5 endothermic steam reforming step. The process is also inefficient because it involves transformation of methane in an
oxidative reaction to carbon monoxide (and some CO2) which in turn must be reduced to methanol.
[0035] The selective conversion of methane (natural gas) to methanol without first producing a mixture of carbon
monoxide and hydrogen (syn-gas) is a long standing challenge and a much desired practical goal. Although various C-
H activations of converting methane to methyl derivatives have been reported, such chemistry is still far from being
10 practical. Whereas claims of selective and direct oxidation of methane to methanol were made using a variety of oxidizing
agents and metal oxide catalysts, any claimed high selectivity conversion was achieved only in very low yields of methanol.
At higher conversions, selectivity is rapidly lost and only mixtures of oxidation products (formaldehyde, formic acid and
carbon dioxide) are obtained. For further overview of the background can be mentioned: US 4,243,613, which mentions
a continuous process for the partial oxidation of methane to produce mixtures of formaldehyde and methanol. WO
15 2005/037746 which provides a gas-phase process for catalytic conversion of a lower alkane comprising at most 5 carbon
atoms to at least one produce selected from the group consisting of alcohols, aldehydes and mixtures thereof. JP
59216839, which discloses a catalytic process for decomposition of formaldehyde into methanol and an alkali formate.
FR 2 543 946, which presents a way of producing methanol by hydrogenolysis of methyl formate, under hydrogen
pressure in the presence of a catalyst, and finally US 5,364,887, which provides a way producing methanol in a catalytical
20 process from a synthesis gas which contains H2, CO and CO2.
[0036] Thus, although various, detailed reaction conditions have been explored to achieve high methanol conversion
rate without complete oxidation, it has not yet been possible to achieve the combination of high yield, selectivity and
catalyst stability that would render direct oxidative conversion competitive with the conventional syn-gas-based methanol
production. There is a need for improved processes that effectively produce methanol from methane by high selectivity
25 good yield oxidative conversion, and these are now provided by the present invention.

SUMMARY OF THE INVENTION

[0037] The invention relates to a method of preparing methanol from a methane source without first producing syn-
30 gas. This method comprises oxidizing methane under conditions sufficient to produce a mixture of methanol and for-
maldehyde with smaller amounts of formic acid and carbon dioxide; converting the formaldehyde under conditions
sufficient to form methanol and formic acid or methyl formate; and subsequently hydrogenatively converting the methyl
formate under conditions sufficient to form methanol. Advantageously, the methanol oxidation mixture is treated without
separation of its components to convert substantially all the formaldehyde therein to methyl alcohol without any by-
35 products. Preferably, unreacted methane is recovered and recycled to the oxidizing step.
[0038] The formaldehyde can be converted via solid base catalysis into methanol and formic acid, which are then
subsequently converted under conditions sufficient to form methyl formate. The formic acid can be reacted with the
formaldehyde under conditions sufficient to produce methanol. It is also possible to subject the formaldehyde to catalytic
dimerization under conditions sufficient to form methyl formate which then is converted to methanol. The methyl formate
40 can be converted to methanol by catalytic hydrogenation, or by electrochemical reduction.
[0039] The methane source may be natural gas, coal gas, or a methane hydrate. The methane source may be oxidized
by contact with an oxidizing agent under conditions sufficient to substantially form methanol and formaldehyde. Useful
oxidizing agents include molecular oxygen or air and a suitable catalyst, or hydrogen peroxide and an oxide catalyst.
The oxide catalyst may be a single or mixed catalyst based on V, Ti, Ga, Mg, Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn
45 and that is optionally provided on a silica or alumina support.
[0040] To form other products, the methanol can be dehydrated under conditions sufficient to produce dimethyl ether.
The dimethyl ether can be heated in the presence of an acidic-basic or zeolitic catalysts to form ethylene or propylene.
The latter can be converted either to higher olefins, synthetic hydrocarbons or aromatics and their products for use as
feedstocks for chemicals or as transportation fuels. Ethanol or propanol can be prepared by hydration of the ethylene
50 or propylene, respecively. Alternatively, the dimethyl ether can be used as a substitute for natural gas and LPG for
heating purposes for households or industrial use.
[0041] In the area of synthetic fuels, an improved diesel fuel can be prepared by mixing sufficient amounts of dimethyl
ether with conventional diesel fuel. Also, dimethyl carbonate can be formed by reaction of the methanol with phosgene
or by the oxidative carbonylation of the methanol, and an improved diesel fuel can be prepared by mixing sufficient
55 amounts of dimethyl carbonate with conventional diesel fuel. A transportation fuel can be prepared by adding methanol
to gasoline with the fuel having a minimum gasoline content of at least 15% by volume.
[0042] As to other uses, the methanol or dimethyl ether can act as convenient energy storage and transportation
materials in order to minimize or eliminate the disadvantages or dangers inherent in the use and transportation of LNG

7
 EP 1 871 732 B1

or LPG. It is also possible to use the methanol for preparing single cell proteins for human or animal alimentation.

BRIEF DESCRIPTION OF THE DRAWINGS

5 [0043] The features and benefits of the invention will become more evident from review of the following detailed
description of illustrative embodiments and the accompanying drawings, wherein:

FIG. 1 shows known examples of methanol-derived chemical products and materials; and
FIG. 2 schematically illustrates the present inventive process termed the METHANOL ECONOMY™ process by
10 inventor George Olah.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0044] The invention relates to new, efficient, oxidative conversions of a methane source such as natural gas to
15 methanol or dimethyl ether. This method comprises oxidizing methane under conditions sufficient to obtain a mixture of
methanol and formaldehyde, but substantially excluding formic acid and carbon dioxide. Formaldehyde is subsequently
converted under conditions sufficient to form methanol and formic acid or methyl formate; and subsequently the methyl
formate is hydrogenatively converted under conditions sufficient to form methanol without any by-products. Preferably,
the methane oxidation mixture is treated directly without separation of its components to produce methanol. This process
20 achieves high selectivity in methanol with practically applicable yields.
[0045] In one embodiment, the formaldehyde formed in the methane oxidation step is catalytically converted via a
modified Cannizzarro reaction to methanol and formic acid, which are subsequently reacted under conditions sufficient
to form methyl formate. Alternatively, the formaldehyde is converted to methyl formate by its catalytic dimerization. Methyl
formate by itself has a high octane number of 115 (RON) and can serve as a fuel for internal combustion engines. In
25 another embodiment, the formic acid that is obtained is used to reduce formaldehyde to produce methanol.
[0046] Advantageously, methane available from any of its natural sources (natural gas, coal field methane, methane
hydrates, etc.) is oxidized by contact with an oxidizing agent. The oxidizing agent may be molecular oxygen, or can
comprise hydrogen peroxide and an oxide catalyst. The oxide (mixed oxide) catalysts may be based on V, Ti, Ga, Mg,
Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn and is optionally provided on a silica or alumina support. Any unreacted methane
30 may be recovered and then recycled to the oxidizing step.
[0047] Methyl formate can be converted without any by-product to methanol by its catalytic hydrogenation or by
electrochemical reduction. If desired, methanol can subsequently be dehydrated under conditions sufficient to produce
dimethyl ether.
[0048] The resulting methanol product can be used in a variety of ways. It is a convenient and safe material for energy
35 storage and transportation. It is an excellent fuel for internal combustion engines and fuel cells. Methanol can be dehy-
drated under conditions sufficient to produce dimethyl ether. Dimethyl ether is an excellent substitute for diesel fuel.
Methanol and/or dimethyl ether can be catalytically converted to ethylene or propylene (as well as other olefins). These
light olefins can be converted into synthetic hydrocarbon mixtures and their products including for example ethanol (by
hydration of ethylene), higher carbon olefins or aromatics and be used as feedstock for derived varied chemicals and
40 transportation fuels. Methanol is also useful as a source of single cell proteins.
[0049] The invention relates to new, efficient, oxidative conversions of a methane source such as natural gas to
methanol or dimethyl ether. This method comprises oxidizing methane under conditions sufficient to obtain a mixture of
methanol and formaldehyde, but substantially excluding formic acid and carbon dioxide. Formaldehyde is subsequently
converted under conditions sufficient to form methanol and formic acid or methyl formate; and subsequently the methyl
45 formate is hydrogenatively converted under conditions sufficient to form methanol without any by-products. Preferably,
the methane oxidation mixture is treated directly without separation of its components to produce methanol. This process
achieves high selectivity in methanol with practically applicable yields.
[0050] In one embodiment, the formaldehyde formed in the methane oxidation step is catalytically converted via a
modified Cannizarro reaction to methanol and formic acid, which are subsequently reacted under conditions sufficient
50 to form methyl formate. Alternatively, the formaldehyde is converted to methyl formate by its catalytic dimerization. Methyl
formate by itself has a high octane number of 115 (RON) and can serve as a fuel for internal combustion engines. In
another embodiment, the formic acid that is obtained is used to reduce formaldehyde to produce methanol.
[0051] Advantageously, methane available from any of its natural sources (natural gas, coal field methane, methane
hydrates, etc.) is oxidized by contact with an oxidizing agent. The oxidizing agent may be molecular oxygen, or can
55 comprise hydrogen peroxide and an oxide catalyst. The oxide (mixed oxide) catalysts may be based on V, Ti, Ga, Mg,
Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn and is optionally provided on a silica or alumina support. Any unreacted methane
may be recovered and then recycled to the oxidizing step.
[0052] Methyl formate can be converted without any by-product to methanol by its catalytic hydrogenation or by

8
 EP 1 871 732 B1

electrochemical reduction. If desired, methanol can subsequently be dehydrated under conditions sufficient to produce
dimethyl ether.
[0053] The resulting methanol product can be used in a variety of ways. It is a convenient and safe material for energy
storage and transportation. It is an excellent fuel for internal combustion engines and fuel cells. Methanol can be dehy-
5 drated under conditions sufficient to produce dimethyl ether. Dimethyl ether is an excellent substitute for diesel fuel.
Methanol and/or dimethyl ether can be catalytically converted to ethylene or propylene (as well as other olefins). These
light olefins can be converted into synthetic hydrocarbon mixtures and their products including for example ethanol (by
hydration of ethylene), higher carbon olefins or aromatics and be used as feedstock for derived varied chemicals and
transportation fuels. Methanol is also useful as a source of single cell proteins.
10 [0054] The invention relates to a method of synthesizing methanol by oxidative conversion of methane (natural gas)
which avoids initial production of syn-gas. It has now been discovered that methane can be selectively, and at the same
time with high conversion, converted to methanol by using an initial oxidation step, which produces a mixture of methanol
with formaldehyde as the major products. This oxidation step is followed by a treatment step, during which the mixture
is treated without any separation, resulting in significantly increasing the yield of methanol. This makes the overall process
15 practical for the production of methanol without the necessity of converting methane first to syn-gas and producing
methanol subsequently by presently used Fischer-Tropsch type chemistry.
[0055] The initial oxidation of methane to a mixture of methanol and formaldehyde can utilize any of the known catalytic
oxidation procedures in a flow system between temperatures of about 150 - 700°C, with the formation of formic acid
and carbon dioxide to be kept to a minimum. The skilled person is well aware of general wide and feasible conditions
20 to conduct this oxidation in this manner. Such oxidations can utilize different oxidizing agents preferably oxygen (or air).
Oxidation with hydrogen peroxide or its equivalents are also effective over a variety of catalysts. Varied oxide (mixed
oxide) catalysts based on V, Ti, Ga, Mg, Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn and the like are used preferably on
supports such as silica or alumina. The overall amount of oxygenate formation in a single pass though is generally kept
at less than about 20-30% with the unreacted methane being recycled.
25 [0056] It was reported that in the homogeneous gas phase oxidation of methane, methane is reacted with oxygen at
a high pressure (about 30-200 atm) and a high temperature (about 200-500°C). Optimum conditions for selective oxidation
to methanol have been extensively investigated. It was observed that selectivity to methanol increases with decreasing
oxygen concentration in the system. At best, 75-80% selectivity in methanol formation at 8-10% conversion, was achieved
under cold flame conditions (450°C, 65 atm, less than 5% O2 content), using a glass-lined reactor, which seemed to
30 suppress secondary reactions. Most other studies obtained under their best reaction conditions (temperatures of
450-500°C and pressures of 30-60 atm) reported selectivities of 30-40% methanol with 5-10% methane conversion. At
high pressure, gas phase radical reactions are predominant, limiting the expected favorable effects of solid catalysts.
Selectivity to methanol can only be moderately influenced by controlling the factors that affect radical reactions such as
reactor design and shape and residence time of the reactants.
35 [0057] At about ambient pressure (1 atm), catalysts can play a crucial role in partial oxidation of methane with O2. A
large number of catalysts, primarily metal oxides and mixed oxides, have been studied. Metals have also been tested
but they tend to favor complete oxidation. In most cases, the reactions were performed at temperatures from about 600
to 800°C, and formaldehyde (HCHO) was obtained as the predominant, and often the only, oxidation product. Silica
itself exhibits a unique activity in oxidation of methane to formaldehyde. Higher methane conversions were, however,
40 obtained with silica-supported molybdenum (MoO3) and vanadium (V2O5) oxide catalysts. The yield of formaldehyde
remained nevertheless in the range of 1 to 5%. An iron molybdate catalyst, Fe2O3(MoO3)2.25, was found to be the most
active catalyst for partial oxidation of methane, with a reported formaldehyde yield of 23%. Reaction over a silica supported
PCl3-MoCl5-R4Sn catalyst gave a 16% yield. A silica-supported MoO3 catalyst has been observed to show a high
selectivity of 90% to oxygenated compounds (CH3OH and HCHO) at methane conversion of 20-25% in excess steam.
45 At the high temperatures used for partial oxidation of methane, methanol formed on the catalyst’s surface is rapidly
decomposed or oxidized to formaldehyde and/or carbon oxides, explaining its absence in the obtained product mixture.
[0058] In order to minimize formation of byproducts and increase selectivity to methanol, use of lower reaction tem-
peratures (< 250°C) is preferable. Currently used catalysts for methane oxidation are, however, not sufficiently active
at lower temperatures. Since gas phase reactions generally require higher temperatures (> 400°C), liquid phase reactions
50 operating at more moderate temperatures can be used. For example, methanol can be obtained through electrophilic
oxygenation (i.e., oxygen functionalization) of methane in superacids (Olah et. al. Angew. Chem. Int. Ed. Engl. 1978,
17, 909). When methane is reacted in superacids (Bronsted acids that are many million times stronger than concentrated
sulfuric acid) at room temperature with hydrogen peroxide (H2O2), methane produces methanol in high selectivity. The
reaction proceeds in strong acids through the insertion of protonated hydrogen peroxide, H3O2+, into the methane C-H
55 bond. The methanol formed in the strong acid system is in protonated form, CH3OH2+, and is protected from further
oxidation, resulting in the high selectivity observed. Considering the generally high cost of liquid superacids, cheaper
peroxides and strong acid systems can be used.
[0059] Methanol formed from oxidation of methane can be thus chemically protected in strong acids systems inhibiting

9
 EP 1 871 732 B1

subsequent oxidation using predominantly metals and metal complex catalysts dissolved in sulfuric acid or oleums
(Periana et al. Science, 1993, 259, 340). Several homogeneous catalytic systems activate under these conditions the
otherwise very unreactive C-H bonds of methane at lower temperatures and with surprisingly high selectivity. At a
temperature around 200°C, the conversion of methane to methanol by concentrated sulfuric acid using an HgSO4 catalyst
5 is efficient. Oxidation of methane produces methyl hydrogen sulfate (CH3OSO3H), which can be hydrolyzed to methanol
in a separate step. At a conversion of 50%, 85% selectivity to methyl hydrogen sulfate is achieved. To complete the
catalytic cycle, Hg+ is reoxidized to Hg2+ by H2SO4. Overall, the process uses one molecule of sulfuric acid for each
molecule of methanol produced. SO2 generated during the process can be easily oxidized to SO3, which upon reaction
with H2O will produce H2SO4 that can be recycled.
10 [0060] The cleavage of methyl hydrogen sulfate to methanol and its separation from sulfuric acid media is, however,
an energy consuming cumbersome process requiring regeneration of sulfuric acid. The use of poisonous mercury also
makes the process also somewhat unattractive. However, non- toxic metals such as platinum, iridium, rhodium, palladium,
ruthenium, and gold, can also be used in methane oxidation, the best results are obtained with a platinum complex in
H2SO4.
15 [0061] As water formed during the oxidation reaction progressively dilutes the sulfuric acid, decreasing its acidity.
Because the activity of platinum, as well as those of mercury and most metal systems, decrease rapidly at lower acidity,
the oxidative conversion is conducted in oleum (a mixture of H2SO4 and SO3). SO3 reacts with the water formed during
the reaction to give H2SO4, thereby avoiding a decrease in acidity.
[0062] As methanol is formed in small mounts mostly with formaldehyde (and formic acid) in direct methane oxidation
20 with air or oxygen, it has now been found that this mixture can be further processed in a second treatment step without
prior separation, resulting in a substantial increase in methanol content and making the overall process selective and
practical for commercial production of methanol. This subsequent treatment of formaldehyde and formic acid, formed
in the oxidation step, can be carried out in different ways.
[0063] According to one embodiment, formaldehyde is treated over a solid base catalyst such as CaO and MgO,
25 deposited on a suitable carrier, in a variation of the so-called Cannizarro reaction, producing methanol and formic acid.
These products readily react with each other to form methyl formate.

2 HCHO → CH3 OH + HCOOH

30 CH3 OH + HCOOH → HCOOCH3 +H2O

[0064] An alternative way to carry out the conversion of formaldehyde into methyl formate involves a modification of
the Tischenko reaction, i.e., catalytic dimerization of formaldehyde with an aluminum alkoxide catalyst or with Cu, PbO,
SnO2-V2O5, Fe2O3-V2O5, SnO2-MoO3, SnO2-Sb2O5 or ZrO2 catalysts converting formaldehyde into methyl formate
35 over a temperature range of about 120 to 180°C. The skilled chemist is again familiar with the general wide practical
and feasible conditions for carrying out these reactions in high conversions and yields.

40

[0065] Methyl formate obtained via the Cannizzarro or Tischenko reaction is subsequently catalytically hydrogenated
over copper chromite catalyst giving 2 moles of methanol with no by product. Methyl formate can also be electrochemically
reduced using Cu, Sn, Pb electrodes.
45
HCOOCH3 + H2 → 2 CH3OH

[0066] Thus the overall reaction is:

50

[0067] Formic acid formed in the Cannizarro type reaction can itself serve as reducing agent (as a source of hydrogen)
55 when reacted thermally or catalytically with formaldehyde to produce methanol.

CH2O + HCO2H → CH3OH + CO2

10
 EP 1 871 732 B1

[0068] Suitable combinations of these reactions allow oxidative conversion of methane to methanol with overall high
selectivity and yield. Combining with the Cannizarro type reaction step gives two moles of methanol for three moles of
formaldehyde with one mole of carbon dioxide available to be recycled to produce additional methanol according to the
method described in copending U.S. Patent Application US 2006/0235091 of G. Olah et al. entitled Efficient And Selective
5 Conversion Of Carbon Dioxide To Methanol, Dimethyl Ether And Derived Products filed of even date herewith.

10

15 [0069] As methanol is readily dehydrated to dimethyl ether, the present oxidative conversion of methane to methanol
is also well suited to produce dimethyl ether for use as a fuel or in chemical applications. To the extent that any preferred
reaction conditions are desired, routine testing can be conducted to find such preferred or optimized conditions.
[0070] Any suitable source of natural gas or methane can be used for methanol production according to the present
invention. Other than the conventional natural gas sources, methanol can be produced, for instance, from "biogas," a
20 result of anaerobic bacteria’s breaking down organic material in the absence of oxygen. Biogas is produced in the
digestive tracks of most mammals, organisms such as termites, and microorganisms during digestion, as well as in
wetlands, swamps and bogs, where large amounts of rotting vegetation may accumulate. Biogas is composed mainly
of methane and carbon dioxide in varying proportions, and contains trace levels of other elements such as hydrogen
sulfide (H2S), hydrogen, and/or carbon monoxide.
25 [0071] The present method of selectively converting methane to methanol is particularly advantageous in view of the
numerous applications of methanol as fuel and for other chemical applications. The safety and versatility of methanol
makes the present direct conversion especially desirable.
[0072] As known in the art, methanol can be blended with gasoline as an oxygenated additive and used in internal
combustion engines with only minor modifications. Methanol can also be used to generate electricity in a fuel cell, by
30 catalytically reforming methanol to H2 and CO or by allowing methanol to directly react with air in a direct methanol fuel
cell (DMFC). DMFC greatly simplifies the fuel cell technology and makes it readily available to a wide range of applications,
including portable mobile electronic devices and electricity generators.
[0073] Another significant benefit of direct conversion of natural gas (methane) to methanol or dimethyl ether is ready
and safe transportation of fuel when pipelines are not feasible or available. LNG (liquefied natural gas), which is currently
35 widely transported across the seas under cryogenic conditions using very large tankers (>200,000 tonnes), unloaded
at LNG terminals, and fed into pipelines to satisfy increasing needs and substitute for diminishing local natural gas
sources, presents potential hazards for devastating accidents. The direct conversion of natural gas to methanol (dimethyl
ether) according to the present invention provides a safe alternative to transporting natural gas.
[0074] In addition to being a conveniently storable energy source and fuel, methanol is also the starting material for
40 various chemicals such as formaldehyde, acetic acid, and a number of other products including polymers, paints, ad-
hesives, construction materials, synthetic chemicals, pharmaceuticals, and single cell proteins. Significantly, methanol
can be conveniently converted in a simple catalytic step to ethylene and/or propylene (e.g., in a methanol to olefin or
MTO process), the building blocks for producing synthetic hydrocarbons and their products. This means that hydrocarbon
fuel and products currently derived from fossil fuel can be obtained from methanol, which can advantageously be obtained
45 in a simple selective conversion of methane.
[0075] The improved and efficient direct production of methanol from methane (natural gas) according to the present
invention also provides the needed raw material for the newly termed METHANOL ECONOMY™ process , allowing
convenient storage of energy in a liquid product that can be used as fuel in the direct oxidation methanol fuel cell and
as starting materials for synthetic hydrocarbons for fuel and varied products. METHANOL ECONOMY™ process is based
50 on efficient direct conversion of natural gas resources to methanol or dimethyl ether, and production of these substances
by chemical recycling of carbon dioxide, which can be atmospheric or industrial exhaust gas. The concept of the METH-
ANOL ECONOMY™ process presents significant advantages and possibilities. In this process, methanol is used as (1)
a convenient energy storage medium as itself or in the form of a derived product; (2) a readily transportable and dispen-
sable fuel, including for methanol fuel cells; and (3) a feedstock for synthetic hydrocarbons and their products currently
55 obtained from oil and gas resources, including polymers and even single cell proteins, which can be used for animal
feed or human consumption. Methanol and/or dimethyl ether can be produced by the disclosed process using any
method of dehydration such as treatment of methanol over a solid acidic catalyst such as Nafion-H or the like. These
products are of great practical use as transportation fuels in internal combustion engines or fuel cells. Dimethyl ether

11
 EP 1 871 732 B1

can also be used as a substitute for natural gas. Both are also raw materials for olefins (such as ethylene and propylene)
and for subsequent production of synthetic hydrocarbons and derived products.

EXAMPLES
5
[0076] The following examples illustrate but not limit the utility of the present process. They are based on the use of
known suitable or modified chemical reactions that are applied to the processes of the invention.

EXAMPLE 1
10
[0077] A gaseous mixture of methane (20 mol%), O2 (10 mol%), diluted with nitrogen, was passed over preheated
SiO2 at 650°C in a quartz tube continuous flow reactor to obtain 17% of formaldehyde in a single passover. The conversion
of methane was 30 %. Similar reactions over other oxide and mixed oxide catalysts are expected to provide yields of
formaldehyde in the range of 10 - 20% with about 20 to 50 % methane conversion. Unreacted methane is recycled.
15 Smaller amounts of CO as well as CO2 that are produced can be used in the additional preparation of methanol. Air can
be substituted for oxygen in the oxidation step.
[0078] In a subsequent second step, the product mixture formed in the first step without any separation of the reaction
products under basic catalytic conditions (CaO, MgO and the like) either under the gas phase flow conditions (100 -
180°C) or under batch conditions (at 150°C) provides methanol and formic acid. The conversion and selectivity in the
20 Cannizzaro reaction is > 90%. Methanol and formic acid can be separated or reacted further to produce methyl formate
in high yield to be converted to methanol as shown below in Examples 3 and 4.

EXAMPLE 2

25 [0079] Over a ZrO2 catalyst, the gaseous formaldehyde obtained in Example 1 was reacted at 150°C to obtain methyl
formate in 99% selectivity with 85 % conversion. The other aforementioned catalysts are expected to provide similar
selectivity and conversions.

EXAMPLE 3
30
[0080] The methyl formate obtained by the processes of Examples 1 and 2 is catalytically reduced with molecular
hydrogen in the gas phase over copper chromite catalysts at atmospheric pressure in the temperature range of 100 -
230°C. Selectivity to methanol is > 90 % and methyl formate conversion is about 85 to 90 %.

35 EXAMPLE 4

[0081] A 1: 1 mixture of formic acid and formaldehyde obtained from the corresponding products of Example 1 was
passed over WO3/Al2O3 in a quartz tube reactor at 190°C. Methanol and methyl formate were obtained in overall 40 %
yield and a 2:1 ratio. The conversion of formic acid was 70 %. When the reaction of 1:1 formaldehyde and formic acid
40 ((2 to 10 M solution) in water was carried out at 250°C in a glass lined reactor, clean conversion gave methanol in 60 % yield.
[0082] These examples illustrate the general utility of the present process but skilled practitioners can utilize the
disclosure and teachings provided herein to generate a wide variety of other chemicals and products as disclosed.

45 Claims

1. A method of preparing methanol from a methane source without first producing syn-gas which comprises oxidizing
methane under conditions sufficient to produce a mixture of methanol and formaldehyde with smaller amounts of
formic acid and carbon dioxide; converting the formaldehyde under conditions sufficient to form methanol and formic
50 acid or methyl formate; and subsequently hydrogenatively converting the methyl formate under conditions sufficient
to form methanol.

2. The method of claim 1, wherein the methanol oxidation mixture is treated without separation of its components to
convert substantially all the formaldehyde therein to methyl alcohol without any by-products.
55
3. The method of claim 2, wherein the formaldehyde is converted via solid base catalysis into methanol and formic
acid, which are then subsequently converted under conditions sufficient to form methyl formate.

12
 EP 1 871 732 B1

4. The method of claim 3, which further comprises reacting the formic acid with the formaldehyde under conditions
sufficient to produce methanol.

5. The method of claim 1, which further comprises subjecting the formaldehyde to catalytic dimerization under conditions
5 sufficient to form methyl formate.

6. The method of claim 1, wherein the methane source is natural gas, coal gas, or methane hydrates.

7. The method of claim 1, wherein the methane source is oxidized by contact with an oxidizing agent under conditions
10 sufficient to substantially form methanol and formaldehyde.

8. The method of claim 7, wherein the oxidizing agent is molecular oxygen or air and a suitable catalyst.

9. The method of claim 7, wherein the oxidizing agent comprises hydrogen peroxide and an oxide catalyst.
15
10. The method of claim 9, wherein the oxide catalyst includes single or mixed catalysts based on V, Ti, Ga, Mg, Cu,
Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn and are optionally provided on a silica or alumina support.

11. The method of claim 1, wherein unreacted methane is recovered and recycled to the oxidizing step.
20
12. The method of claim 1, wherein the methyl formate is converted to methanol by catalytic hydrogenation.

13. The method of claim 1, wherein the methyl formate is converted to methanol by electrochemical reduction.

25 14. The method of claim 1 which further comprises dehydrating methanol under conditions sufficient to produce dimethyl
ether.

15. The method of claim 14 which further comprises heating dimethyl ether in the presence of an acidic-basic or zeolitic
catalysts to form ethylene or propylene.
30
16. The method of claim 15 which further comprises converting ethylene or propylene either to higher olefins, synthetic
hydrocarbons or aromatics and their products for use as feedstocks for chemicals or as transportation fuels.

17. The method of claim 15 which further comprises hydrating ethylene or propylene to form ethanol or propanol.
35
18. The method of claim 14 wherein the dimethyl ether is used as a substitute for natural gas and LPG for heating
purposes for households or industrial use.

19. The method of claim 14 which further comprises preparing an improved diesel fuel by mixing sufficient amounts of
40 dimethyl ether with conventional diesel fuel.

20. The method of claim 1 which further comprises forming dimethyl carbonate by reaction of the methanol with phosgene
or by oxidative carbonylation of the methanol.

45 21. The method of claim 20 which further comprises preparing an improved diesel fuel by mixing sufficient amounts of
dimethyl carbonate with conventional diesel fuel.

22. The method of claim 1 which further comprises preparing transportation fuel by adding methanol to gasoline with
the fuel having a minimum gasoline content of at least 15% by volume.
50
23. The method of claim 14 which further comprises utilizing the methanol or dimethyl ether as convenient energy
storage and transportation materials in order to minimize or eliminate the disadvantages or dangers inherent in the
use and transportation of LNG or LPG.

55 24. The method of claim 14 which further comprises utilizing the methanol for preparing single cell proteins for human
or animal alimentation.

13
 EP 1 871 732 B1

Patentansprüche

1. Verfahren zum Herstellen von Methanol aus einer Methanquelle ohne zunächst Synthesegas herzustellen, welches
aufweist: Oxidieren von Methan unter Bedingungen, die zum Erzeugen einer Mischung aus Methanol und Formal-
5 dehyd mit geringen Mengen an Formylsäure und Kohlendioxid ausreichend sind; Umwandeln des Formaldehyds
unter Bedingungen, die zum Bilden von Methanol und Ameisensäure oder Methylformiat ausreichend sind; und
darauffolgendes Umwandeln des Methylformiats durch Hydrierung unter Bedingungen, die zum Bilden von Methanol
ausreichend sind.

10 2. Verfahren nach Anspruch 1, wobei die Methanoloxidationsmischung ohne Trennung von deren Komponenten be-
handelt wird, um im Wesentlichen sämtliches darin enthaltenes Formaldehyd zu Methylalkohol ohne jegliche Ne-
benprodukte umzuwandeln.

3. Verfahren nach Anspruch 2, wobei das Formaldehyd mittels einer Festbettkatalyse in Methanol und Formylsäure
15 umgewandelt wird, die dann im Folgenden unter Bedingungen umgewandelt werden, die zum Bilden von Methyl-
formiat ausreichend sind.

4. Verfahren nach Anspruch 3, welches weiter das Reagieren von Formylsäure mit dem Formaldehyd unter Bedin-
gungen, die zum Herstellen von Methanol ausreichend sind, aufweist.
20
5. Verfahren nach Anspruch 1, welches weiter das Unterwerfen des Formaldehyds einer katalytischen Dimerisierung
unter Bedingungen, die zum Bilden von Methylformiat ausreichend sind, aufweist.

6. Verfahren nach Anspruch 1, wobei die Methanquelle natürliches Gas, Kohlegas oder Methanhydrate ist.
25
7. Verfahren nach Anspruch 1, wobei die Methanquelle durch Kontakt mit einem Oxidationsmittel unter Bedingungen,
die ausreichend sind, um im Wesentlichen Methanol und Formaldehyd zu bilden, oxidiert wird.

8. Verfahren nach Anspruch 7, wobei das Oxidationsmittel molekularer Sauerstoff oder Luft und ein geeigneter Kata-
30 lysator ist.

9. Verfahren nach Anspruch 7, wobei das Oxidationsmittel Wasserstoffperoxid und einen Oxidkatalysator umfasst.

10. Verfahren nach Anspruch 9, wobei der Oxidkatalysator einzelne oder gemischte Katalysatoren baiserend auf V, Ti,
35 Ga, Mg, Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La oder Sn umfasst und optional auf einem Siliziumdioxid- oder Alumini-
umträger bereitgestellt wird.

11. Verfahren nach Anspruch 1, wobei nichtumgesetztes Methan wiedergewonnen und im Oxidierungsschritt wieder-
verwendet wird.
40
12. Verfahren nach Anspruch 1, wobei das Methylformiat durch katalytische Hydrierung zu Methanol umgewandelt wird.

13. Verfahren nach Anspruch 1, wobei das Methylformiat durch elektrochemische Reduktion zu Methanol umgewandelt
wird.
45
14. Verfahren nach Anspruch 1, welches weiter das Dehydrieren von Methanol unter Bedingungen, die zum Herstellen
von Dimethylether ausreichend sind, aufweist.

15. Verfahren nach Anspruch 14, welches weiter das Erwärmen des Diemthylethers in der Anwesenheit von einem
50 Säure-Base- oder einem zeolithischen Katalysator zum Bilden von Ethylen oder Propylen aufweist.

16. Verfahren nach Anspruch 15, welches weiter das Umwandeln von Ethylen oder Propylen entweder in höhere Olefine,
synthetische Kohlenwasserstoffe oder Aromaten und deren Produkte zur Verwendung als Rohstoff für Chemikalien
oder als Kraftstoffe für Transportmittel aufweist.
55
17. Verfahren nach Anspruch 15, welches weiter das Hydrieren von Ethylen oder Propylen zum Erzeugen von Ethanol
oder Propanol aufweist.

14
 EP 1 871 732 B1

18. Verfahren nach Anspruch 14, wobei der Dimethylether entweder als Ersatz für natürliches Gas und LPG für Heiz-
zwecke für den Haushalt oder für industrielle Zwecke verwendet wird.

19. Verfahren nach Anspruch 14, welches weiter das Herstellen eines verbesserten Dieselkraftstoffs durch Mischen
5 ausreichender Mengen von Dimethylether mit konventionellem Dieselkraftstoff aufweist.

20. Verfahren nach Anspruch 1, welches weiter das Bilden von Kohlensäuredimethylester durch Reaktion des Methanols
mit Phosgen oder durch oxidative Carbonylierung des Methanols aufweist.

10 21. Verfahren nach Anspruch 20, welches weiter das Herstellen eines verbesserten Dieselkraftstoffs durch Mischen
ausreichender Mengen von Kohlensäuredimethylester mit konventionellem Dieselkraftstoff aufweist.

22. Verfahren nach Anspruch 1, welches weiter das Herstellen von Kraftstoff für Transportmittel durch Hinzufügen von
Methanol zu Benzin aufweist, wobei der Kraftstoff minimal einen Benzingehalt von wenigstens 15 Volumenprozent
15 hat.

23. Verfahren nach Anspruch 14, welches weiter das Verwenden des Methanols oder Dimethylethers als vorteilhaften
Energiespeicher und Transportmaterial zum Verringern oder Beseitigen der Nachteile oder inhärenten Gefahren
bei der Verwendung und dem Transport von LNG oder LPG aufweist.
20
24. Verfahren nach Anspruch 14, welches weiter das Verwenden des Methanols zum Herstellen von Einzellerprotein
für die menschliche oder tierische Ernährung aufweist.

25 Revendications

1. Procédé de préparation de méthanol à partir d’une source de méthane, sans produire préalablement du gaz de
synthèse, qui consiste à oxyder du méthane dans des conditions suffisantes pour produire un mélange de méthanol
et de formaldéhyde avec de plus faibles quantités d’acide formique et de dioxyde de carbone ; convertir le formal-
30 déhyde dans des conditions suffisantes pour former du méthanol et de l’acide formique ou du formiate de méthyle ;
et convertir ultérieurement par hydrogénation le formiate de méthyle dans des conditions suffisantes pour former
du méthanol.

2. Procédé selon la revendication 1, dans lequel le mélange d’oxydation du méthanol est traité sans séparation de
35 ses composants pour convertir sensiblement la totalité du formaldéhyde contenu dans celui-ci en alcool méthylique,
sans aucun produit secondaire.

3. Procédé selon la revendication 2, dans lequel le formaldéhyde est converti par catalyse basique solide en méthanol
et acide formique, qui sont ensuite convertis ultérieurement dans des conditions suffisantes pour former du formiate
40 de méthyle.

4. Procédé selon la revendication 3, qui consiste en outre à faire réagir l’acide formique avec du formaldéhyde dans
des conditions suffisantes pour produire du méthanol.

45 5. Procédé selon la revendication 1, qui consiste en outre à soumettre le formaldéhyde à une dimérisation catalytique
dans des conditions suffisantes pour former du formiate de méthyle.

6. Procédé selon la revendication 1, dans lequel la source de méthane est du gaz naturel, du gaz de houille ou des
hydrates de méthane.
50
7. Procédé selon la revendication 1, dans lequel la source de méthane est oxydée par contact avec un agent oxydant
dans des conditions suffisantes pour former sensiblement du méthanol et du formaldéhyde.

8. Procédé selon la revendication 7, dans lequel l’agent oxydant est de l’oxygène moléculaire ou de l’air, et un catalyseur
55 approprié.

9. Procédé selon la revendication 7, dans lequel l’agent oxydant comprend du peroxyde d’hydrogène et un catalyseur
d’oxydation.

15
 EP 1 871 732 B1

10. Procédé selon la revendication 9, dans lequel le catalyseur d’oxydation comprend des catalyseurs simples ou mixtes
à base de V, Ti, Ga, Mg, Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La ou Sn, et sont éventuellement fournis sur un support
de silice ou d’alumine.

5 11. Procédé selon la revendication 1, dans lequel le méthane n’ayant pas réagi est récupéré et recyclé à l’étape d’oxy-
dation.

12. Procédé selon la revendication 1, dans lequel le formiate de méthyle est converti en méthanol par hydrogénation
catalytique.
10
13. Procédé selon la revendication 1, dans lequel le formiate de méthyle est converti en méthanol par réduction élec-
trochimique.

14. Procédé selon la revendication 1, qui consiste en outre à déshydrater du méthanol dans des conditions suffisantes
15 pour produire de l’oxyde de diméthyle.

15. Procédé selon la revendication 14, qui consiste en outre à chauffer de l’oxyde de diméthyle en présence d’un
catalyseur acido-basique ou zéolithique pour former de l’éthylène ou du propylène.

20 16. Procédé selon la revendication 15, qui consiste en outre à convertir de l’éthylène ou du propylène soit en oléfines
supérieures, hydrocarbures synthétiques ou composés aromatiques, et leurs produits destinés à être utilisés en
tant que matières premières pour produits chimiques ou en tant que carburants de transport.

17. Procédé selon la revendication 15, qui consiste en outre à hydrater de l’éthylène ou du propylène pour former de
25 l’éthanol ou du propanol.

18. Procédé selon la revendication 14, dans lequel l’oxyde de diméthyle est utilisé en tant que substitut pour le gaz
naturel et le gaz de pétrole liquéfié, à des fins de chauffage de logements ou pour un usage industriel.

30 19. Procédé selon la revendication 14, qui consiste en outre à préparer un carburant diesel amélioré en mélangeant
des quantités suffisantes d’oxyde de diméthyle avec un carburant diesel classique.

20. Procédé selon la revendication 1, qui consiste en outre à former du carbonate de diméthyle par réaction du méthanol
avec du phosgène ou par carbonylation oxydante du méthanol.
35
21. Procédé selon la revendication 20, qui consiste en outre à préparer un carburant diesel amélioré en mélangeant
des quantités suffisantes de carbonate de diméthyle avec un carburant diesel classique.

22. Procédé selon la revendication 1, qui consiste en outre à préparer un carburant de transport en ajoutant du méthanol
40 à de l’essence, le carburant ayant une teneur minimum en essence d’au moins 15 % en volume.

23. Procédé selon la revendication 14, qui consiste en outre à utiliser le méthanol ou l’oxyde de diméthyle en tant que
matériaux pratiques de stockage d’énergie et de transport, afin de réduire ou d’éliminer les inconvénients ou dangers
inhérents à l’utilisation et au transport de gaz naturel liquéfié ou de gaz de pétrole liquéfié.
45
24. Procédé selon la revendication 14, qui consiste en outre à utiliser le méthanol pour préparer des protéines d’orga-
nismes unicellulaires destinées à l’alimentation humaine ou animale.

50

55

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 5599638 A [0018] • FR 2543946 [0035]

• US 4243613 A [0035] • US 5364887 A [0035]
• WO 2005037746 A [0035] • US 20060235091 A, G. Olah [0068]
• JP 59216839 B [0035]

19