(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2017/121980 Al
20 July 2017 (20.07.2017) PO PCT

(51) International Patent Classification: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
C07C 29/152 (2006.01) C07C 31/04 (2006.01) HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KH, KN,
KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA,
(21) International Application Number: MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG,
PCT/GB2016/053959 NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS,
(22) International Filing Date: RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY,
16 December 2016 (16. 12.2016) TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN,
ZA, ZM, ZW.
(25) Filing Language: English
(84) Designated States (unless otherwise indicated, for every
(26) Publication Language: English kind of regional protection available): ARIPO (BW, GH,
(30) Priority Data: GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ,
1600793.2 15 January 2016 (15.01.2016) GB TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,
TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,
(71) Applicant: JOHNSON MATTHEY DAVY TECHNO¬ DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
LOGIES LIMITED [GB/GB]; 5th Floor, 25 Farringdon LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
Street, 25 Farringdon Street, London EC4A 4AB (GB). SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
GW, KM, ML, MR, NE, SN, TD, TG).
(72) Inventor: YIU, Kar Chi; Johnson Matthey Davy Techno
logies Limited, 10 Eastbourne Terrace, London W2 6LG Declarations under Rule 4.17 :
(GB).
— as to applicant's entitlement to apply for and be granted a
(74) Agent: RD3LAND, John; Johnson Matthey Process Tech patent (Rule 4.1 7(H))
nologies, PO Box 1, Belasis Avenue, Billingham Cleveland — of inventorship (Rule 4. 1 7(iv))
TS23 1LB (GB).
Published:
(81) Designated States (unless otherwise indicated, for every
kind of national protection available): AE, AG, AL, AM, — with international search report (Art. 21(3))
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM,

(54) Title: METHANOL PROCESS

o
00 (57) Abstract: A process is described for the synthesis of methanol comprising the steps of: (i) passing a first synthesis gas mixture
comprising a make-up gas and a first loop recycle gas stream through a first synthesis reactor containing a cooled methanol synthesis
catalyst to form a first product gas stream, (ii) recovering methanol from the first product gas stream thereby forming a first methan
ol- depleted gas mixture, (iii) combining the first methanol-depleted gas mixture with a second loop recycle gas stream to form a
second synthesis gas mixture, (iv) passing the second synthesis gas mixture through a second synthesis reactor containing a cooled
methanol synthesis catalyst to form a second product gas stream, (v) recovering methanol from the second product gas stream
o thereby forming a second methanol-depleted gas mixture, and (vi) forming the first and second loop recycle gas streams from the
second methanol-depleted gas mixture, wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst than
the second synthesis reactor and the recycle ratio of the first loop recycle gas stream to form the first synthesis gas mixture is in the
o range 0. 1 to 1 :1, and the recycle ratio of the second loop recycle gas stream to form the second synthesis gas mixture is in the range
1. 1 :1 to 6 : 1.
Methanol process

This invention relates to a process for synthesising methanol.

Methanol synthesis is generally performed by passing a synthesis gas comprising hydrogen ,

carbon oxides and any inert gases at an elevated temperature and pressure through one or
more beds of a methanol synthesis catalyst, which is often a copper-containing composition.
Methanol is generally recovered by cooling the product gas stream to below the dew point of
the methanol and separating off the product as a liquid. The crude methanol is typically
purified by distillation. The process is often operated in a loop: thus the remaining unreacted
gas stream is usually recycled to the synthesis reactor as part of the synthesis gas via a
circulator. Fresh synthesis gas, termed make-up gas, is added to the recycled unreacted gas
to form the synthesis gas stream. A purge stream is often taken from the circulating gas
stream to avoid the build-up of inert gasses.

The process may be operated using two synthesis reactors each containing a bed of methanol
synthesis catalyst.

US 7,790,775 discloses a process for use in equilibrium exothermic gas phase reactions
comprising the steps of (a) providing a recycle stream with the addition of make-up gas, to form
a feed gas stream; (b) heating the feed gas stream; (c) passing the heated feed gas stream to
a first reactor containing a catalyst for the exothermic gas phase reactions at conditions
suitable for the reaction; (d) removing a product stream comprising product and unreacted
gases from the first reactor; (e) cooling and partially condensing the product stream to form a
gas phase and a liquid phase; (f) separating the liquid phase containing the desired product
from the product stream and removing said liquid phase; (g) separating the gas phase from the
product stream to form a gas stream; (h) optionally mixing the gas stream from the product
stream with additional make-up gas; (i) heating the gas stream; (j) passing the heated gas
stream to a final reactor containing a catalyst for the exothermic gas phase reactions at
conditions suitable for the reaction; (k) removing a final product stream comprising product and
unreacted gases from the final reactor; (I) cooling and partially condensing the final product
stream to form a final gas phase and a final liquid phase; (m) separating the final liquid phase
containing the desired product from the final product stream and removing said final liquid
phase; and (n) separating the gas phase from the final product stream and recycling the gas to
step (a); and in which the gas stream from step (g) is compressed prior to heating in step (i).

US 8,536,235 discloses a process for the synthesis of methanol comprising the steps of: (a)
passing a synthesis gas mixture comprising a loop gas and a make-up gas through a first
synthesis reactor containing a methanol synthesis catalyst, said reactor cooled by boiling water
under pressure, to form a mixed gas containing methanol, (b) cooling the mixed gas containing
methanol, (c) passing said cooled mixed gas containing methanol through a second synthesis
reactor containing a methanol synthesis catalyst in which further methanol is synthesised to
form a product gas stream, (d) cooling said product gas to condense methanol, (e) recovering
said methanol and returning unreacted gas as the loop gas to said first synthesis reactor,
wherein the mixed gas containing methanol from the first synthesis reactor is cooled in heat
exchange with either said loop gas or said make-up gas.

US 5,827,901 describes a process in which methanol is produced from a synthesis gas

containing hydrogen and carbon oxides on copper-containing catalysts at pressures in the
range 20 to 120 bar and temperatures in the range 130 DEG to 350 DEG C . The synthesis gas
is first of all passed through a first synthesis reactor, in which the catalyst is provided in tubes
surrounded by water as a coolant, which is boiling at an elevated pressure. From the first
reactor a first mixture containing gases and methanol vapour is withdrawn and passed without
cooling through a second synthesis reactor. In the second reactor the catalyst is cooled with
synthesis gas to which a make-up gas has been added.

US 8,629, 19 1 describes a process for producing methanol from a synthesis gas containing
hydrogen and carbon oxides wherein the synthesis gas is passed through a first, water-cooled
reactor in which a part of the carbon oxides is catalytically converted to methanol. The resulting
mixture containing synthesis gas and methanol vapour is supplied to a second , gas-cooled
reactor in which a further part of the carbon oxides is converted to methanol. Subsequently,
methanol is separated from the synthesis gas, and synthesis gas is recirculated to the first
reactor. The cooling gas flows through the second reactor co-current to the mixture withdrawn
from the first reactor.

US 5,631 ,302 describes a process in which methanol is catalytically produced from a synthesis
gas containing hydrogen and carbon oxides on copper-containing catalysts under pressures in
the range from 20 to 20 bars and at temperatures in the range from 200 to 350 DEG C . The
synthesis gas is passed through a first synthesis reactor, which consists of a shaft reactor and
contains a fixed bed of a copper-containing catalyst. The reaction in the shaft reactor is carried
out adiabatically and without a recycling of synthesis gas. Together with recycle gas, the gas
mixture which has not been reacted in the first synthesis reactor is passed through a second
synthesis reactor, which contains a copper-containing catalyst, which is disposed in tubes and
is indirectly cooled through boiling water.

US 201 4/0031 438 A 1 describes a method for producing methanol from inert-rich syngas by
installing a catalytic pre-reactor upstream of a single or multi-stage synthesis loop, a first part of
the syngas being converted to methanol in the catalytic pre-reactor. In addition, an inert gas
separation stage, for example a pressure swing adsorption system or a membrane system, is
connected downstream of the synthesis loop, whereby a hydrogen-enriched syngas stream can
be returned to the synthesis loop. In the processing of methane-rich syngas, the inert gas
separation stage may also comprise an autothermal reformer in which methane is converted to
carbon oxides and hydrogen, which are also returned into the synthesis loop.

W O 201 4/01 2601 A 1 describes a process for producing methanol comprising the steps of (a)
providing a fresh methanol synthesis gas containing hydrogen, carbon monoxide and carbon
dioxide; (b) providing a recycle gas stream containing unconverted methanol synthesis gas and
mixing a part of the recycle stream with the fresh synthesis gas to form a process gas stream;
(c) introducing and reacting the process gas stream in a first methanol reaction unit in presence
of a methanol catalyst and obtaining a first effluent stream containing methanol and a part of
the unconverted synthesis gas contained in the recycle stream; and (d) introducing and
reacting at least another part of the recycle gas stream in a second methanol reaction unit in
presence of a methanol catalyst and obtaining a second effluent stream containing methanol
and another part of the unconverted synthesis gas contained in the recycle stream, wherein the
recycle stream is pressurised by a common circulator.

WO201 4/206635 A 1 describes a process for the preparation of methanol in parallel reactors,
comprising the steps of (a) reacting carbon oxides and hydrogen in the presence of a methanol
catalyst in a first methanol reactor to obtain a first methanol-containing effluent, (b) introducing
and reacting unconverted synthesis gas in a second methanol reactor in the presence of a
methanol catalyst to obtain a second methanol-containing effluent, the first methanol reactor
and the second methanol reactor being connected in parallel, (c) combining the first and
second effluent, and (d) cooling and separating the combined and cooled effluent into a
methanol-containing liquid phase and unconverted synthesis gas, wherein the methanol
catalyst in the first methanol reactor is indirectly cooled by boiling water and the methanol
catalyst in the second methanol reactor is either directly or indirectly cooled by the unconverted
synthesis gas prior to conversion into the second effluent.

DE 351 8362 A 1 describes a process for producing methanol where, starting from a
conventional methanol synthesis process in which unreacted synthesis gas is recycled to the
inlet of the reactor, a methanol synthesis reactor which operates without recycling is arranged
upstream of the recycling process.

W e have realised that the efficiency of multiple-stage methanol synthesis may be improved by
using different recycle ratios for different types of reaction reactor.
Accordingly the invention provides a process for the synthesis of methanol comprising the
steps of:
(i) passing a first synthesis gas mixture comprising a make-up gas and a first loop recycle
gas stream through a first synthesis reactor containing a cooled methanol synthesis
catalyst to form a first product gas stream,
(ii) recovering methanol from the first product gas stream thereby forming a first methanol-
depleted gas mixture,
(iii) combining the first methanol-depleted gas mixture with a second loop recycle gas
stream to form a second synthesis gas mixture,
(iv) passing the second synthesis gas mixture through a second synthesis reactor
containing a cooled methanol synthesis catalyst to form a second product gas stream,
(v) recovering methanol from the second product gas stream thereby forming a second
methanol-depleted gas mixture, and
(vi) forming the first and second loop recycle gas streams from the second methanol-
depleted gas mixture,
wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst
than the second synthesis reactor and the recycle ratio of the first loop recycle gas stream
to form the first synthesis gas mixture is in the range 0 . 1 to 1:1, and the recycle ratio of the
second loop recycle gas stream to form the second synthesis gas mixture is in the range
1.1:1 to 6 : 1.

Using different recycle ratio enables dilution of the loop gases to the preferred inlet
compositions for the different reactors. The present invention reaps the benefit of using the
different types of reactor because the synthesis gas is first reacted in a reactor that favours
high reactant concentration, taking advantage of the high rate of reaction at high concentration .
The penalty of using such reactor is then removed by passing the synthesis gas to the second
reactor that favours lower reaction rate, while reaping the benefit of higher feed efficiency.
Importantly, the dilution stream for the first reactor has the least rate-determining reactant,
which means the required recycle flow to achieve the required dilution is minimised.

The present invention utilises the advantages of each type of reaction reactor, hence it has a
low recycle ratio section for the first synthesis reactor and a high recycle ratio section for the
second synthesis reactor.

By the term "recycle ratio", w e mean the molar flow ratio of the recycled loop gas to the make¬
up gas that form the synthesis gas mixtures fed to the first and second synthesis reactors.
Accordingly the recycle ratio for the first synthesis gas arises from the proportion of the loop
recycle gas combined with a make-up gas, and the recycle ratio for the second synthesis gas
arises from the proportion of the loop gas combined with the first methanol-depleted gas
mixture, both expressed relative to the make-up gas.

The recycle ratio to form the first synthesis gas mixture fed to the first synthesis reactor is in the
range 0 . 1:1 to 1:1. Whereas the recycle ratio to form the second synthesis gas mixture fed to
the second synthesis reactor may be 1 . 1 :1 to 6 : 1, it is preferably in the range 1 .5: 1 to 6 : 1, more
preferably 2 : 1 to 6 : 1.

The prior art processes having recycle of a loop gas to multiple reactors either do not have the
ability to operate multiple reactors with different recycle ratios or do not disclose operating with
different recycle ratios.

The first synthesis gas comprises a make-up gas. Make-up gas typically comprises hydrogen,
carbon monoxide, and/or carbon dioxide. The make-up gas may be generated by the steam
reforming of methane or naphtha using established steam reforming processes, including pre-
reforming. However the present invention is of particular effectiveness in utilising reactive
synthesis gases generated by processes including a step of partial oxidation of a hydrocarbon,
biomass or carbonaceous feedstock. By "reactive synthesis gases" we mean a synthesis gas
comprising hydrogen, carbon monoxide and carbon dioxide in which the ratio (by volume) of
hydrogen to the total carbon oxides is >2: 1. Such processes include combined reforming in
which a first portion of a hydrocarbon feedstock is subjected to steam reforming and a second
portion is subjected to autothermal reforming; and from coal or biomass gasification .
Alternatively, off-gases from refineries or other chemical processes comprising principally
hydrogen and carbon oxides (mainly as carbon monoxide) may also be used. In the present
invention, the make-up gas preferably contains carbon monoxide in the range 20-35% vol,
more preferably 25-35% vol.

The use of more reactive synthesis gas leads to smaller catalyst volumes being used, and the
greater net heat of reaction gives a heat release per unit volume of catalyst which can be more
than double that in a process based on steam reforming alone. Therefore providing effective
cooling of the catalyst becomes more important as the carbon monoxide to carbon dioxide ratio
in the synthesis gas increases.

The make-up gas may be combined with the first loop recycle gas stream to form the first
synthesis gas mixture. The recycle loop stream contains hydrogen and therefore may enhance
the methanol formation in the first synthesis reactor where the higher CO-content synthesis
gases are used.
The composition of first synthesis gas at the first synthesis reactor inlet is preferably as follows;
15-30 mol% carbon monoxide, 0.5-1 0 mol% carbon dioxide, 55-85 mol% hydrogen and the
balance one or more inert gases. The pressure of the first synthesis gas at the first synthesis
reactor inlet is preferably 50-1 00 bar abs. The temperature of the first synthesis gas at the first
synthesis reactor inlet is preferably 200-250°C and at the outlet preferably 230-280°C.

The composition of second synthesis gas at the second synthesis reactor inlet is preferably as
follows; 3-1 0 mol% carbon monoxide, 0.5-1 0 mol% carbon dioxide, 65-95 mol% hydrogen and
the balance one or more inert gases. The pressure of the second synthesis gas at the second
synthesis reactor inlet is preferably 50-1 00 bar abs. The temperature of the second synthesis
gas at the second synthesis reactor inlet is preferably 2 1 5-250°C and at the outlet preferably
250-300°C.

The loop recycle gas streams may be circulated by means of a two-stage circulator or
alternatively by two separate circulators. By "two-stage circulator" w e include a circulator that
has two inlets and/or two outlets, for example as may be provided by a single casing containing
two impellers with an offtake at an intermediate pressure between the first and second
impellors and another offtake after the second impeller. Thus the loop recycle gas streams
may be circulated by means of two circulators, which may be arranged either in a single casing
having one inlet and two outlets at different pressures, a single casing having two inlets at
different pressures and one outlet, or in two separate casings. Accordingly, in one
embodiment, the circulator may comprise a first stage and a second stage where the first stage
is fed with the first methanol-depleted gas mixture and the second stage is fed with the second
recycle loop gas stream. The first methanol-depleted gas mixture and the second recycle loop
gas stream are combined in the circulator which then provides the second synthesis gas, which
may be heated and fed to the second synthesis reactor. The methanol-depleted gases fed to
the circulator may be enriched if desired by a portion of the make-up gas. In an alternative
embodiment, the first stage of a two-stage circulator may be fed with the second methanol-
depleted gas stream (minus any purge gas) and produce two separate loop recycle gas
streams; one, from the circulator first stage, which is fed to the second synthesis reactor and
one from the circulator second stage, which is fed to the first synthesis reactor. In this case,
the recycle loop gas fed to the second synthesis reactor may be diluted by the first methanol-
depleted gas mixture, which may also contain a portion of the make-up gas. This arrangement
provides the flexibility of switching the pressure of the first and second synthesis reactors. In
an alternative embodiment, two circulators may be provided. A first circulator is fed with the
first methanol-depleted gas mixture and a second circulator with the second methanol-depleted
gas stream, minus any purge stream. The product of the second circulator is divided and
portions fed to the first and second synthesis reactors. The portion fed to the second synthesis
reactor is mixed with the first methanol-depleted gas stream coming from the first circulator. In
this case, the product of the first circulator may if desired be diluted with a portion of the make¬
up gas. This arrangement provides the possibility of operating at the same pressure in the first
and second synthesis reactors.

The present invention is able to minimise the recycle gas going back to the first synthesis
reactor in order to minimise pressure drop and maximise reaction rate, while achieving the
required dilution. In the process described in W O 201 401 2601 A 1 , the recycle stream back to
first reactor has to be significantly larger because it is a mixture of unreacted gases from the
first and second reactors, whereas by using the second methanol-depleted gas stream as the
source of the recycle loop gas, the gas with the least carbon monoxide (CO) is used to dilute
the first synthesis gas, which also has other advantages.

In the present invention, at least part of the second methanol-depleted gas mixture is used to

form the first and second loop recycle gas streams. Thus, the second methanol-depleted gas
may be divided into a first loop recycle gas stream, which is combined with make-up gas, and
optionally other gas streams to form the first synthesis gas mixture, and a second loop recycle
gas stream, which may optionally be combined with make-up gas and/or other gas streams to
form the second synthesis gas mixture. A purge stream may be recovered from the second
methanol-depleted gas and/or the first loop recycle gas stream and/or the second loop recycle
gas stream.

If desired, for example, if shipping diameter is a limitation, in order to adjust the duty and so
relative size of the first and second synthesis reactors, a proportion of the make-up gas may
bypass the first synthesis reactor and enter the high recycle ratio loop as a secondary feed.
Thus a portion of the make-up gas in the range 0-70% vol may be fed to the second synthesis
reactor. However, for efficiency reasons, preferably the portion is < 1 0% vol of the make-up gas
and more preferably 0% vol, i.e. there is no by-pass, so that the process is operated in series.

The first synthesis reactor is preferably a design with a higher heat transfer relative to the
cooled catalyst volume. The heat transfer can be conveniently characterised by the Volumetric
UA. The Volumetric UA may be defined as the multiple of the overall heat transfer coefficient,
U , times the total heat transfer area A , per cubic metre of cooled catalyst in the reactor.
Although any converter could be used in this position, desirably the first synthesis reactor has a
Volumetric UA of > 50 kW/m /K and more preferably > 90 kW/m /K. Such converters include
those where the catalyst is disposed in a plurality of tubes that are cooled by a heat exchange
medium.

The second synthesis reactor has a lower heat transfer relative to the cooled catalyst volume
than the first synthesis reactor. For example, the Volumetric UA may be < 40 kW/m /K. The
second synthesis reactor can be of any type, but high overall conversion of carbon oxides into
methanol is associated with high recycle flows or low converter exit temperature. There are
several converter types that may be used and these include: (i) converters featuring one or
more adiabatic beds and with no heat transfer surface in contact with the catalyst (ii) converters
with gas cooling, such as a tube cooled converter, an isothermal methanol converter and a
gas-cooled converter, and (iii) water-cooled converters with radial flow.

The first and second synthesis reactors may comprise one or more reactors.

In a preferred arrangement, the first synthesis reactor comprises a methanol synthesis catalyst

disposed in tubes that are cooled by water under pressure, and the second synthesis reactor
comprises a fixed bed of a methanol synthesis catalyst that is cooled in heat exchange with
either water under pressure or a synthesis gas mixture selected from the first synthesis gas
mixture and the second synthesis gas mixture.

Preferably the first synthesis reactor is an axial-flow, steam-raising converter (aSRC). In such
reactors the synthesis gas typically passes axially through vertical, catalyst-containing tubes
that are cooled in heat exchange with boiling water under pressure. The catalyst may be
provided in pelleted form directly in the tubes or may be provided in one or more cylindrical
containers that direct the flow of synthesis gas both radially and axially to enhance heat
transfer. Such contained catalysts and their use in methanol synthesis are described in
WO201 2 146904 (A1 ) . A n aSRC typically has a Volumetric UA > 100kW/m /K. Steam raising
converters in which the catalyst is present in tubes cooled by boiling water under pressure offer
a useful means to remove heat from the catalyst. However, while the aSRC offers the highest
cooling factor, it makes poorer use of the reactor volume so the reactor shell is relatively large
for the quantity of catalyst that it holds. Furthermore, aSRC's can suffer from a high pressure
drop. By having a low recycle ratio to the first synthesis reactor the advantages of the aSRC
are maximised while the disadvantages are minimised.

The second synthesis reactor may be a radial-flow steam raising converter, a gas-cooled
converter or a tube cooled converter. In each of these, a bed of particulate catalyst is cooled
by tubes or plates through which a coolant heat exchange medium passes. Alternatively the
second synthesis reactor may be a quench reactor in which one or more beds of particulate
catalyst are cooled by a synthesis gas mixture injected into the reactor within or between the
beds.

In a radial-flow steam raising converter (rSRC) the synthesis gas typically passes radially

(inwards or outwards) through a bed of particulate catalyst which is cooled by a plurality of

tubes or plates through boiling water under pressure is fed as coolant. Such reactors are
known and are described for example in US4321 234. A rSRC has poorer heat transfer than an
aSRC but has very low pressure drop, hence it favours operation with high recycle ratio. A
rSRC typically has a Volumetric UA in the range 12-24 kw/m /K.

In a tube-cooled converter (TCC), the catalyst bed is cooled by feed synthesis gas passing

through open-ended tubes disposed within the bed that discharge the heated gas to the
catalyst. TCC's therefore can provide sufficient cooling area for a more reactive synthesis gas
e.g. from combined reforming or coal gasification, but the increased heat of reaction would
mean that the circulating loop gas flow would be insufficient to carry away the reaction heat
unless the recycle ratio is high. A TCC typically has a Volumetric UA in the range 6-1 5
kW/m /K. As an alternative to a TCC, a gas cooled converter (GCC), may be used to cool the
catalyst bed by passing the synthesis gas though tubes in a heat exchanger-type arrangement.
A GCC is described for example in the aforesaid US 5827901 . The use of a TCC is preferred
over the GCC in that it is simpler and cheaper to fabricate due to the use of open topped tubes
and the elimination of the upper header and all of the differential expansion problems that the
gas cooled converter raises. A TCC therefore has the advantage of low equipment cost and
lower outlet temperature, which favours the synthesis reaction equilibrium, but it has a lower
heat transfer than aSRC and higher pressure drop than rSRC.

In a quench reactor, the one or more beds of particulate catalyst are cooled by a synthesis gas

mixture injected into the reactor within or between the beds. Accordingly, a quench reactor has
a Volumetric UA of 0 kW/m /K. Such reactors are described, for example, in US3458289,
US34751 36 and US441 1877.

Alternative converter designs, such as the Linde Variobar converter comprising a bed of
methanol synthesis catalyst cooled in heat exchange with boiling water passing through a
spiral-wound heat exchanger within the bed, typically have an intermediate Volumetric UA of
30-40 kW/m /K. Such converters may be used as the second synthesis reactor in combination ,
for example, with an axial-flow steam-raising converter, or may be used as the first synthesis
reactor in combination with a quench reactor, a tube-cooled converter or even a radial-flow
steam-raising converter.

The methanol synthesis catalysts are preferably copper-containing methanol synthesis

catalysts, in particular the methanol synthesis catalyst in the first and second synthesis reactors
is a particulate copper/zinc oxide/alumina catalyst. Particularly suitable catalysts are Mg-doped

copper/zinc oxide/alumina catalysts as described in US 47881 75. The same or different

methanol synthesis catalysts may be used in the first and second synthesis reactors.
Methanol synthesis may be effected in the first and second synthesis reactors at elevated
temperature and pressure, for example pressures in the range 20 to 120 bar abs and
temperatures in the range 130°C to 350°C. Where two-stage or separate circulation is effected
for the recycle loop gas streams to the first and second synthesis reactors, they may be
operated at the same or different pressures. Thus the first reactor may be operated at a higher
pressure, the same pressure or a lower pressure than the second reactor. This may provide
advantages in methanol recovery. In a preferred embodiment, the pressure in the second

synthesis reactor is higher than the pressure in the first synthesis reactor. The difference in
pressure between the reactors may be >4 bar. The circulators may be conventional
compressors suitably adapted for processing the recycle loop gas at the desired pressures.

The product gas stream withdrawn from the second synthesis reactor typically has a
temperature in the range from 180 to 250°C, preferably 200-300°C.

The proportion of the methanol made in the first and second reactors may be in the range
30:70 to 70:30, for example 40:60 to 60:40 or 50:50.

The gas mixtures fed to the first and second synthesis reactors may be heated before being fed
to the reactors. The heating may be effected by conventional heat exchange using a suitable
heat exchange apparatus. If a gas-cooled converter (GCC) is used, at least part of the first or
second synthesis gas mixture may be heated by passing it through heat exchange tubes or
plates disposed within a catalyst bed disposed in the second synthesis reactor. Preferably, the
first and/or second synthesis gases are heated in gas-gas heat exchangers using the product
gases from the reactors. Other temperature adjustment of the feed or product gases may be
performed using conventional heat exchange apparatus. Thus the product gas streams from
the first and second synthesis reactors may be cooled in one or more stages of heat exchange,
e.g. with water or air cooling, to condense methanol therefrom, which may suitably be
recovered using gas-liquid separators. The cooling may be performed to fully or partially
condense the methanol from the first and second product gas streams. Preferably essentially
all of the methanol is condensed from the second product gas stream. The recovered liquid
methanol streams may be processed separately but are preferably combined and passed for
further processing , such as one or more, preferably two or three, stages of distillation to
produce a purified methanol product.

A purge gas stream is preferably recovered from the loop to avoid the build-up of inert gases,
such as nitrogen, methane and argon. The purge gas typically comprises hydrogen and
carbon oxides and may be used for hydrogen recovery, for example by pressure-swing
absorption or by using suitable membranes, or may be subjected to one or more further
processing stages including autothermal reforming, water-gas shift and methanol synthesis.
The purge may be recovered from the first methanol-depleted gas or the second methanol
depleted gas depending on whether the stoichiometry of the make-up gas is hydrogen-rich or
carbon-rich. Preferably the purge is recovered from the second methanol depleted gas mixture
and the remaining methanol depleted gas mixture used as the recycle loop gas mixture.

The invention will be further described by reference to the figures in which;

Figure 1 depicts a process according to an embodiment of the present invention utilising an
aSRC and rSRC where the second reactor is at a higher pressure than the first reactor;
Figure 2 depicts a process according to an embodiment of the present invention utilising an
aSRC and rSRC where the second reactor is at a lower pressure than the first reactor; and
Figure 3 depicts a process according to an embodiment of the present invention utilising an
aSRC and rSRC where both reactors are at a similar pressure.

It will be understood by those skilled in the art that the drawings are diagrammatic and that

further items of equipment such as feedstock drums, pumps, vacuum pumps, compressors,
gas recycling compressors, temperature sensors, pressure sensors, pressure relief valves,
control valves, flow controllers, level controllers, holding tanks, storage tanks and the like may
be required in a commercial plant. Provision of such ancillary equipment forms no part of the
present invention and is in accordance with conventional chemical engineering practice.

In Figure 1, a make-up gas in line 10 comprising hydrogen, carbon monoxide and carbon

dioxide is combined with a first recycle loop gas stream 70 and the resulting first synthesis gas
mixture passed via line 14 to a gas-gas interchanger 16 where it is heated in indirect heat
exchange with a first product gas stream 24. The heated first synthesis gas mixture is fed by
line 18 to the inlet of an axial steam-raising converter 20, containing catalyst-filled tubes 22
through which the synthesis gas mixture is passed. The tubes are cooled by boiling water
under pressure. The catalyst is a particulate copper/zinc oxide/alumina catalyst. The boiling
water under pressure is fed to the shell side of the reactor and a mixture of boiling water and
steam is withdrawn and supplied to a steam drum (not shown). The methanol synthesis
reaction takes place as the synthesis gas passes axially through the catalyst-filled tubes 22 to
form a first product gas stream containing methanol vapour. The first product gas stream is
recovered from the outlet of the first synthesis reactor 20 and fed via line 24 to the interchanger
16 where it is partially cooled . The partially cooled gas is fed via line 26 to one or more further
stages of heat exchange 28 to condense methanol therefrom. The resulting gas-liquid mixture
is passed to a gas-liquid separator 30 and liquid methanol is recovered via line 32. A first
methanol-depleted gas mixture comprising unreacted hydrogen and carbon oxides is recovered
from the separator 30 and fed by line 34 to the first stage of a two-stage circulator 72. The
second stage of the two-stage circulator 72 is fed with a second recycle loop gas fed by line 74.
The first methanol-depleted gas 34 and the second recycle loop gas 74 are combined in the
circulator 72 to form a second synthesis gas mixture. The circulator compresses the second
synthesis gas mixture which is fed from the circulator by line 42 to a gas-gas interchanger 44
where it is heated in indirect heat exchange with a second product gas stream 52. The heated
second synthesis gas is fed by line 46 to the inlet of a radial steam-raising converter 48
containing a bed of methanol synthesis catalyst 50, containing a plurality of heat exchange
tubes though which boiling water under pressure is passed as coolant. Whereas tubes are
depicted, alternative heat exchange devices such as plates through which the coolant may be
passed, may also be used. The catalyst is a particulate copper/zinc oxide/alumina catalyst.
The boiling water under pressure is fed to the tube side of the reactor and a mixture of boiling
water and steam is withdrawn and supplied to a steam drum (not shown). The methanol
synthesis reaction takes place as the synthesis gas passes radially through the bed of catalyst
50 to form a second product gas stream containing methanol vapour. The second product gas
stream is recovered from the outlet of the second synthesis reactor 48 and fed via line 52 to the
interchanger 44 where it is partially cooled . The partially cooled gas is fed via line 54 to one or
more further stages of heat exchange 56 to condense methanol therefrom. The resulting gas
liquid mixture is passed to a gas-liquid separator 58 and liquid methanol is recovered via line
64. A second methanol-depleted gas mixture is recovered in the separator 58 and fed by line
60 to a purge off-take line 62, which removes a portion of the gas to reduce the build-up of inert
gases. The remaining second methanol-depleted gas mixture in line 36 is divided to form the
first recycle loop gas 70 and the second recycle loop gas 74. The crude methanol streams 32
and 64 are combined and send by line 66 for further processing such as one or more stages of
distillation to produce a purified methanol product.

A portion of the make-up gas may be diverted from line 10 by dotted-line 76 to line 34 and/or
line 74 fed to the circulator 72. This may be done in order to adjust the duty and so the relative
sizes of the first and second synthesis reactors, or may also be used to enrich the second
synthesis gas. Where the portion of make-up gas 76 is fed to line 74, a suitable control valve
on line 10 may be used to control the flow.

In Figure 2 , the two-stage circulator is configured to produce separate recycle loop gas

streams. Such an arrangement provides the flexibility of switching the pressure of first and
second synthesis reactors. Thus in Figure 2 a make-up gas fed via line 10 is mixed with a first
recycle loop gas containing hydrogen , fed by line 80, to form the first synthesis gas mixture 14 .
The first synthesis gas mixture is converted in the first synthesis reactor 20 in the same manner
as depicted in Figure 1. The first methanol depleted gas mixture 34 is mixed with a second
recycle loop gas 82 to form the second synthesis gas mixture 42. The second synthesis gas
mixture is converted in the second synthesis reactor in the same manner as depicted in Figure
1. The second methanol-depleted gas recovered from the gas-liquid separator 58 is fed by line
60 to a purge off-take line 62, which removes a portion of the gas to reduce the build-up of inert
gases. The remaining second methanol-depleted gas mixture is fed to the first stage of the
circulator 72 by line 36. The first stage of the circulator provides the second recycle loop gas 82
used to form the second synthesis gas mixture 42. The second stage of the circulator 72
provides the first recycle loop gas stream 80. The crude methanol streams 32 and 64 are
again combined and send by line 66 for further processing such as one or more stages of
distillation to produce a purified methanol product.

A portion of the make-up gas may be diverted from line 10 by dotted-line 76 to line 34 used to
prepare the second synthesis gas mixture 42. This may be done in order to adjust the duty and
so the relative sizes of the first and second synthesis reactors, and/or may also be used to
enrich the second synthesis gas to enhance overall process efficiency.

In Figure 3 , two separate circulators are used to produce separate recycle loop gas streams.

Such an arrangement provides the ability to operate the first and second synthesis reactors at
the same pressure. Thus in Figure 3 a make-up gas fed via line 10 is mixed with a first recycle
loop gas containing hydrogen , fed by line 90, to form the first synthesis gas mixture 14 . The
first synthesis gas mixture is converted in the first synthesis reactor 20 in the same manner as
depicted in Figure 1. The first methanol-depleted gas mixture is passed by line 34 to a first
circulator 92 where it is compressed and passed by line 94 to be mixed with a second recycle
loop gas in line 96 to form the second synthesis gas mixture 42. The second synthesis gas
mixture is converted in the second synthesis reactor in the same manner as depicted in Figure
1. The second methanol-depleted gas recovered from the gas-liquid separator 58 is fed by line
60 to a purge off-take line 62, which removes a portion of the gas to reduce the build-up of inert
gases. The remaining second methanol-depleted gas mixture is fed by line 36 to a second
circulator 98. The second circulator provides a compressed recycle loop gas stream 100 which
is divided to provide the first recycle loop gas 90 use to prepare the first synthesis gas mixture

14 , and the second recycle loop gas 96 use to prepare the second synthesis gas mixture 42.
The crude methanol streams 32 and 64 are again combined and send by line 66 for further
processing such as one or more stages of distillation to produce a purified methanol product.

A portion of the make-up gas may be diverted from line 10 by dotted-line 76 to line 94 used to
prepare the second synthesis gas mixture 42. This may be done in order to adjust the duty and
so the relative sizes of the first and second synthesis reactors, and/or may also be used to
enrich the second synthesis gas to enhance overall process efficiency.

The same processes as depicted in Figures 1-3 may be performed replacing the radial steam
raising converter 48 with a tube-cooled converter in which the catalyst bed is cooled in direct
heat exchange with the second synthesis gas. Thus in each case, the second synthesis gas
may be fed from heat exchanger 44 via line 46 to the bottom of a tube cooled converter and
passed upwards through a plurality of tubes disposed within the catalyst bed . The gas is
heated as it passes upwards through tubes. The heated gas exits the tubes within the reactor
above the bed and then passes down through the bed where it reacts to form a gas mixture
containing methanol vapour. The product gas may be collected and fed via line 52 to heat
exchanger 44 where it is cooled.

The Invention is further illustrated by reference to the following Example.

Example 1
A computer model of a process according to the present invention was developed and
compared against a process where there is a single common circulator operating at either a
high or low recycle ratio. The benefits of operating the process in which the recycle ratios are
different for the different reactors are as follow:

1. When compared to the process operating at a high recycle ratio, the present invention
achieves the same catalyst and feed efficiency and benefits from higher energy efficiency
and smaller piping and loop equipment.

2 . When compared to the process operating at a low recycle ratio, the present invention
achieves higher catalyst and feed efficiency. It also benefits from operating at lower
pressure to achieve the same feed efficiency.

If the process of US 7,790,775, operating with two radial-flow steam-raising converters at a

molar recycle ratio of 3.38, is compared with the process of Figure 1 operating with a molar
recycle ratio of 0.55 for the axial-flow steam raising converter and 2.50 for the radial-flow
steam-raising converter, the following figures are obtained;

Configuration Comparative Example Figure 1

Capacity, MTPD 5500 5500
Methanol production 50% rSRC and 50% rSRC 60% aSRC and 40% rSRC
Total catalyst, m3 182.8 159.6
Reactor pressure, bara 76.0 / 80.0 76.0 / 80.0
Total Converter heat
148.05 167.53
removed as steam, MW
Circulator Power, MW 10.05 5.61 (2 stage total)

Syngas Comp Power, MW 9.21 9.21

Total Compressor Power,

19.26 14.82
MW
The benefit of the present invention is that a lower catalyst volume is required, higher steam
production is achieved and lower compression power is required. Accordingly, the present
invention is also able to provide significant equipment cost and energy savings.

The compositions, temperatures and pressures of for the streams depicted in Figure 1 are set
out in the following tables.

Stream 10 14 18 24 32 34 42 46
Pressure 7.7 7.7 7.6 7.4 7 .1 7 .1 8.2 8 .1

MPa(abs)
Temperature 120 93 225 255 45 45 55 240
°C
Flow 520 8 11 8 11 6 13 5 12 1521 1521
kNm /hr
(vapour)
Flow 142.8
Tonne/hr
(liquid)
Composition
Mole%
H20 0.5 0.3 0.3 0.3 1.8 0.0 0.0 0.0
H2 67.6 73.4 73.4 65.0 0.4 77.7 8 1 .8 8 1 .8

CO 29.4 19.7 19.7 9.7 0.3 11.6 5.5 5.5

CO2 1.9 1.6 1.6 2.3 0.8 2.6 1.5 1.5
CH3OH 0.0 0.2 0.2 16.4 96.4 0.7 0.6 0.6
Inerts 0.7 4.8 4.8 6.3 0.2 7.5 10.5 10.5
Stream 52 60 62 64 70 74 76
Pressure 8.0 7.7 7.7 7.7 7.7 7.7 7.7
MPa(abs)
Temperature 270 45 45 45 45 45 120
°C
Flow 1399 1326 26 291 1009 0
kNm /hr
(vapour)
Flow 98.0
Tonne/hr
(liquid)
Composition
Mole%
H2O 0.7 0.0 0.0 13 . 1 0.0 0.0 0.5
H2 79.5 83.9 83.9 0.4 83.9 83.9 67.6
CO 2.3 2.5 2.5 0 .1 2.5 2.5 29.4
CO2 1.0 1.0 1.0 0.3 1.0 1.0 1.9
CH3OH 5.0 0.6 0.6 85.9 0.6 0.6 0.0
Inerts 11.4 12.0 12.0 0.3 12.0 12.0 0.7
Claims.

1. A process for the synthesis of methanol comprising the steps of:

(i) passing a first synthesis gas mixture comprising a make-up gas and a first loop recycle
gas stream through a first synthesis reactor containing a cooled methanol synthesis
catalyst to form a first product gas stream,
(ii) recovering methanol from the first product gas stream thereby forming a first methanol-
depleted gas mixture,
(iii) combining the first methanol-depleted gas mixture with a second loop recycle gas
stream to form a second synthesis gas mixture,
(iv) passing the second synthesis gas mixture through a second synthesis reactor
containing a cooled methanol synthesis catalyst to form a second product gas stream,
(v) recovering methanol from the second product gas stream thereby forming a second
methanol-depleted gas mixture, and
(vi) forming the first and second loop recycle gas streams from the second methanol-
depleted gas mixture,
wherein the first synthesis reactor has a higher heat transfer per cubic metre of catalyst
than the second synthesis reactor and the recycle ratio of the first loop recycle gas stream
to form the first synthesis gas mixture is in the range 0 . 1 to 1:1, and the recycle ratio of the
second loop recycle gas stream to form the second synthesis gas mixture is in the range
1.1:1 to 6 : 1.

2. A process according to claim 1 wherein the recycle ratio of the loop recycle gas stream to
form the second synthesis gas mixture is in the range 1.5: 1 to 6 : 1, preferably 2 : 1 to 6 : 1.

3. A process according to claim 1 or claim 2 wherein the make-up gas contains carbon
monoxide in the range 20-35% vol.

4. A process according to any one of claims 1 to 3 wherein the loop recycle gas streams are
circulated by means of a two-stage circulator comprising a first stage and a second stage,
or alternatively by two separate circulators, preferably wherein the loop recycle gas
streams are circulated by means of two circulators arranged either in a single casing
having one inlet and two outlets at different pressures, a single casing having two inlets at
different pressures and one outlet, or in two separate casings.

5. A process according to claim 4 wherein a circulator comprises a first stage and a second
stage, the first stage is fed with the first methanol-depleted gas mixture and the second
stage is fed with the second recycle loop gas stream, and the first methanol-depleted gas
 mixture and the second recycle loop gas stream are combined in the circulator to provide
the second synthesis gas.

6. A process according to claim 5 wherein the methanol-depleted gases fed to the circulator
are enriched by a portion of the make-up gas.

7. A process according to claim 4 wherein a circulator comprises a first stage and a second
stage, the first stage is fed with the second methanol-depleted gas stream minus any
purge gas and produces two separate loop recycle gas streams; one from the circulator
first stage, which is combined with the first methanol-depleted gas mixture and fed to the
second synthesis reactor, and one from the circulator second stage, which is fed to the
first synthesis reactor.

8. A process according to claim 7 wherein the first methanol-depleted gas mixture contains a
portion of the make-up gas.

9. A process according to claim 4 wherein two separate circulators are used, a first circulator
is fed with the first methanol-depleted gas mixture and a second circulator is fed with the
second methanol-depleted gas stream, minus any purge stream, the second circulator
product is divided into the first and second recycle loop gas streams, and the second
recycle loop gas stream is mixed with the first methanol-depleted gas stream product of
the first circulator.

10 . A process according to claim 9 where the first methanol-depleted gas stream product of
the first circulator is diluted with a portion of the make-up gas.

11. A process according to any one of claims 1 to 10 wherein the first synthesis reactor
comprises a methanol synthesis catalyst disposed in tubes that are cooled by water under
pressure, and the second synthesis reactor comprises a fixed bed of a methanol synthesis
catalyst that is cooled in heat exchange with either water under pressure or a synthesis
gas mixture selected from the first synthesis gas mixture and the second synthesis gas
mixture.

12 . A process according to any one of claims 1 to 11 wherein the first synthesis reactor is an
axial flow steam-raising converter.

13 . A process according to any one of claims 1 to 12 wherein the second synthesis reactor is
selected from a radial flow steam-raising converter, a tube-cooled converter, a gas-cooled
converter or a quench reactor.
14 . A process according to any one of claims 1 to 13 wherein the methanol synthesis catalysts
are copper-containing methanol synthesis catalysts, preferably compositions comprising
copper, zinc oxide and alumina.

15 . A process according to any one of claims 1 to 14 wherein methanol synthesis in the first
and second reactors is performed at pressures in the range 20 to 120 bar abs and
temperatures in the range 130°C to 350°C.

16 . A process according to claim 15 wherein the pressure in the second synthesis reactor is
higher than the pressure in the first synthesis reactor.

17 . A process according to any one of claims 1 to 16 wherein the gas mixtures fed to the first
and/or second synthesis reactors are heated in gas-gas heat exchangers using the
product gases from the reactors.

18 . A process according to any one of claims 1 to 17 wherein the product gas streams from the
first and second synthesis reactors are cooled in one or more stages of heat exchange to
condense methanol therefrom.

19 . A process according to any one of claims 1 to 18 wherein a purge gas stream is recovered
from the second methanol depleted gas mixture and is used for hydrogen recovery, or is
subjected to one or more further processing stages including autothermal reforming,
water-gas shift and methanol synthesis.
A . CLASSIFICATION O F SUBJECT MATTER
INV. C07C29/152 C07C31/04
ADD.

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

WO 2014/012601 Al (T0PS0E HALDOR AS [DK] ) 1-19

23 January 2014 (2014-01-23)
ci ted i n the appl i cati on
cl aims 1-9
f i gure 1

W0 2014/206635 Al (HALDOR TOPS0E AS [DK] ) 1-19

3 1 December 2014 (2014-12-31)
ci ted i n the appl i cati on
cl aims 1-6
f i gure 1

US 2011/065966 Al (MUEELLER DI ERK [DE] ET 1-19

AL) 17 March 2011 (2011-03-17)
cl aims 1-13

□ Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :

"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to be of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot be
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot be
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

3 March 2017 04/04/2017

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Del anghe, Patri ck
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cited in search report date member(s) date

WO 2014012601 Al 23-01-2014 AU 2012385744 Al 05-02-2015

CA 2878964 Al 23-01-2014
CN 104470630 A 25-03-2015
EA 201590225 Al 30-06-2015
EP 2874738 Al 27-05-2015
KR 20150036365 A 07-04-2015
US 2015175509 Al 25-06-2015
O 2014012601 Al 23-01-2014

WO 2014206635 Al 3 1 -12 -2014 CA 2911306 Al 31-12-2014

CN 105392762 A 09-03-2016
EA 201690088 Al 29-07-2016
EP 2818458 Al 31-12-2014
US 2016107961 Al 21-04-2016
WO 2014206635 Al 31-12-2014

US 2011065966 Al 17 -03 -2011 AT 528274 T 15-10-2011

BR PI0816071 A2 24-02-2015
CN 101790501 A 28-07-2010
DE 102007040707 Al 05-03-2009
EG 25675 A 14-05-2012
EP 2181083 Al 05-05-2010
US 2011065966 Al 17-03-2011
WO 2009030353 Al 12-03-2009