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USOO5216034A

United States Patent [191

[11]
[451

Sie
[54] PROCESS FOR THE PRODUCTION OF
METl-IANOL

Patent Number:

5,216,034

Date of Patent:

Jun. 1, 1993

OTHER PUBLICATIONS

Westerterp et a1, Ind. Eng. Chem. Res, 1989, 28,

[75] Inventor:

Swan T. Sie, Amsterdam,

Netherlands

[73] Assignee:

Shell Oil Company, Houston, Tex.

[21] Appl. No.: 783,187

763-771.
Post et al, Chemeca 88, Australias Bicentennial Inter
national Conference for the Process Industries, Sidney,

Aug. 28-31, 1988.

Saito et a1, AICI-IE Symposium No. 262, vol. 84, pp.
l02ll3, 1988.

[22] Filed:

[30]

Oct. 28, 1991

Foreign Application Priority Data

Oct. 29, 1990 [GB]

[51]

United Kingdom ............... .. 9023465

Int. Cl.5 ..................... .. C07C 27/06; C07C 27/08

[52]

vs. C]. .................................................. .. 518/706

[58]

Field of Search ....................................... .. 518/706

[56]

References Cited
U.S. PATENT DOCUMENTS
3,598,527 8/1971
4,235,799 11/1980

Quartulli et a1. .................. .. 518/706

Wentworth et a1. ............. .. 518/706

'

Primary Examiner-Howard T. Mars

Attorney, Agent, or Firm-Y. Grace Tsang

{57]

ABSTRACT

A process for the production of methanol by reacting a

gaseous mixture comprising hydrogen and carbon mon
oxide in the presence of a catalyst composition in a
?uidized bed while cooling, characterized in that the
reaction is carried out in a plurality of ?uidized catalyst
bed reactors in series with interstage removal of metha
nol from the reaction mixture.

6 Claims, 1 Drawing Sheet

US. Patent

June 1, 1993

5,216,034

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5,216,034

PROCESS FOR THE PRODUCTION OF

METHANOL
FIELD OF THE INVENTION
The invention relates to a process for the production

of methanol by reacting a gaseous mixture comprising

hydrogen and carbon monoxide in the presence of a

catalyst composition in a ?uidized bed while cooling.

BACKGROUND OF THE INVENTION

sion percentage is therefore difficult. Effective control

of the reaction temperature across the catalyst bed

proved to be especially important.

In industrially applied processes, in which the cata
lyst is present in the form of a ?xed bed of particles,
high gas velocities are applied to promote effective
removal of reaction heat and to allow good control of
the reaction temperature. Due to these high velocities
and the thermodynamic limitations low conversions per
pass (i.e. less than 30%) are obtained. To achieve ac

ceptable yields of methanol from synthesis gas it is cus

Processes for the production of methanol by reacting

tomary to recompress unconverted synthesis gas and

a gaseous mixture comprising hydrogen and carbon

monoxide in the presence of a catalyst composition in a
?uidized bed have been disclosed in the prior art. Also
it is known in the art to use a slurry of a heterogeneous
catalyst in an inert liquid for this reaction.

recycle it to the reactor inlet. This requires recycle

compressors of large capacities, which are costly and

have high power consumptions.

An object of the present invention is the development
of an industrial process for methanol manufacture with

A lecture reporting work by Y. Saito, M. Kuwa and

satisfactory conversion percentages in relatively simple
O. Hashimoto during the 1987 Annual Meeting of the
equipment.
American Institute of Chemical Engineers, New York, 20
Nov. 15-20, 1978, entitled Development of a ?uidized
SUMMARY OF THE INVENTION
bed methanol synthesis process discloses a process
The present invention provides a process for the
using a reactor with the catalyst in a ?uidized bed,
production of methanol by reacting a gaseous mixture
cooled by means of a cooling jacket covering the sur
rounding wall of the bed. The temperature was adjusted 25 comprising hydrogen and carbon monoxide in the pres
ence of a catalyst in a plurality of ?uidized catalyst bed
by the temperature of the coolant (water being con
reactors in series with interstage removal of methanol
verted into high pressure steam). This process requires
from the reaction mixture.
high space velocities and causes a considerable drop in
pressure over the reactor, the conversion per pass was

about 16%. Unconverted carbon monoxide and hydro 30

gen were recompressed and recycled through the reac
101'.

A lecture reporting work by M. F. M. Post; S. T. Sie

and J. M. Oelderik during the Chemeca 88 (Australias
Bicentennial International Conference for the process 35

industries), Sydney Aug. 28-31, 1988, entitled Synthe

sis of Methanol in A Fluidized Bed of Catalyst dis
closes ?uidized bed methanol synthesis at bench scale

BRIEF DESCRIPTION OF THE DRAWING

The sole drawing is a ?owsheet of an installation
comprising three reactors in series which is suitable for
carrying out the process of the present invention.

DETAILED DESCRIPTION OF THE

INVENTION

with conversions up to 60% at 8.1 MPa and 250 C.

The gaseous mixture fed into the reactors comprises

hydrogen and carbon monoxide in a molar ratio
H2:CO=l to 3:1, preferably between 1.5 to 25:1, more

(523 K.) and good catalyst stability. For commercial

preferably around 2:1. Synthesis gas obtained by partial

operations the conversions were too low however.

oxidation of methane with oxygen (H2:CO=2:l), is a

Also there is Chemical Week, 36 Apr. 16, 1980) dis

closing a process known as Chem Systems three-phase
process in which an inert liquid was used to ?uidize the
catalyst and to remove the heat of reaction. Good con 45

recommended starting material, synthesis gas obtained

by reforming of methane and/or carbon dioxide
(H2:CO=3:1) can also be used.

The reaction temperature depends on the activity of

versions per pass are claimed, however, the inert liquid
the catalyst composition employed. In the case of an
caused transport problems and affected the reaction
active catalyst the temperature may be as low as 100
rate. The process also required separation of methanol
C., but may be as high as 350 C.
from the entrained inert liquid.
The pressure in the reaction zone is usually in the
Cheap methanol in very large quantities is valuable 50 range of from 5 to 35 MPa and again this is dependent
product as a fuel and a starting material for further
on the activity of the catalyst composition employed
chemical processing. Therefore there is a need for an

economically attractive industrial bulk manufacturing

process, using cheap starting materials and operating

and with active catalysts pressures below 10 MPa can

be used. According to the present process conditions

under attractive economical, environmental and safe 55 are chosen so as to achieve per pass conversions of at
least 50%.
conditions, i.e. using rather simple equipment and re
The catalyst compositions employed in the practice
sulting in a signi?cant reduction of the methanol cost
of this invention may suitably comprise e.g. copper/~
price. Therefore, considerable research and develop
zinc optionally promoted with another element such as
ment efforts have been made for a further improved
aluminum or chromium, on a carrier such as e.g. car
methanol manufacturing process.
bon, silica and/or alumina. Catalyst materials compris
The formation of methanol from hydrogen and car
ing copper and zinc optionally promoted with another
bon monoxide is a strongly exothermic equilibrium
element are preferred. Particle size and distribution of
reaction so that relatively high operating pressures and
the catalyst material must be suitable for ?uidized bed
temperatures are required for reasonable reaction rates,
but under such reaction conditions the attainable con 65 or made so e.g. by grinding and sieving. A particle size
below 0.4 millimeter is generally suitable. Also ade
version is strongly limited by the thermodynamic equi
quate resistance of the catalyst towards attrition is im
librium. Finding a satisfactory compromise as to the
portant.
reaction conditions between reaction rate and conver

5,216,034

Interstage removal of methanol can e.g. be effected

by cooling and condensation or by adsorption/absorp

tion to a solvent. Cooling and condensation are pre

ferred and are conveniently effected in a heat exchanger

connected to a gas/liquid separator. The gaseous phase
from which methanol has been removed can then be
directly fed into the next reactor (without reheating or

recompressing).
On a practical scale it is recommended to use a series

version percentage in the upper section and conse

quently also of the ef?uent.

An advantage that can be secured according to a

preferred embodiment of the present invention is that

the temperature and quality of the high pressure steam
generated in the lower section(s) of the catalyst bed is
increased.
A further advantage of the process according to the
present invention is that it is possible to replenish the

of reactors with interstage removal of methanol in 10 catalyst while the reaction is operated, catalyst stability
requirements can be sacri?ced in favor of higher activ
which each next reactor has a smaller capacity than the
ity so that it is possible to carry out the reaction at an
previous one, alternatively it is feasible to use e.g.
unusually high temperature in the lower (main) sec
groups of parallel reactors in series wherein the number
tion(s) of the catalyst bed providing additional room to
of parallel reactors in each next group (and conse
improve space-time-yield. Consequently there is addi
quently their total capacity) is smaller than in the previ
tional room to increase the temperature (quality) of the
ous group and where interstage removal of methanol is
high pressure steam generated.
effected between the groups of reactors.
The invention is further elucidated by the attached
More in particular it is preferred to use a plurality of
drawing (FIG. 1), which represents a ?owsheet of an
reactors in series of which at least one (but preferably
installation suitable for carrying out the process of the
all of them) comprises a plurality of interconnected
invention and comprises a number of reactors (R1, R2,
?uidized bed sections whereby each section is cooled by
R3) in series with a catalyst in a fluidized bed, which
at least one heat exchanger and whereby the tempera
reactors are equipped with at least one heat exchanger,
ture in the highest section is reduced to below the (high
an inlet for synthesis gas and an outlet for reaction mix
est) temperature in a lower section. More preferably the
highest section of the catalyst bed is cooled by at least 25 ture, which outlet is connected to a heat exchanger (E1,
E2, or E3), which in turn is connected to a gas/liquid
one heat exchanger cooled with a mixture containing
(methanol) separator (S1, S2, or S3), having an outlet for
hydrogen and carbon monoxide such as cold feed gas.
unconverted synthesis gas, which in turn is connected
The temperature in at least one lower section of the
to a next fluidized bed reactor and so on.
catalyst bed can be controlled by adjusting the tempera
By selecting suitable reaction conditions and an ac
ture of a heat exchanger converting water into high
tive catalyst, such as H2:CO=67:32, T=250-200 C.,
pressure steam. Preferably the heat exchangers of the
P=8 MPa and a reduced CuZnO-Cr2O3-catalyst
feedgas/reaction mixture ?ow in countercurrent with
having a particle size below 0.1 millimeter, it is possible
each other. The various sections of the ?uidized cata
to obtain a degree of conversion of more than 60% per
lyst bed can be in one reactor, or each ?uidized catalyst
bed section can be present in a separate reactor of a 35 pass through the reactor, this is followed by interstage

series of interconnected reactors. The terms highest

and lower' refer obviously to the one reactor embodi
ment, but have a corresponding meaning with respect to
the incoming gas feed and effluent when more than one
reactor are employed.

removal of methanol formed, preferably by cooling and

condensation and the remaining gaseous phase is then
passed through another reactor, which reactor could be
smaller than the ?rst reactor, the procedure of inter
stage removal of methanol formed and using the gase
ous phase as the feed gas for another reactor is repeated
a number of times. After multiple stages an overall yield

Usually the highest temperature in the lower sec

tion(s) of the fluidized catalyst bed is between 200 C.
of at least 90% of the feed gas of the first reactor can
and 350 C., often between 250 C. and 320 C., and it is
thus be obtained and methanol formed separated by
preferred to employ reactors wherein the temperature
in the highest section of the fluidized catalyst bed is 10 45 interstage removal between the reactors. A methanol
purity of over 98% can be obtained.
to 100 centigrades, preferably at least 25 centigrades,
It is clear that in case the incoming feed gas of the
lower than the highest temperature in a lower section of
?rst reactor is e.g. synthesis gas containing more than 2
the catalyst bed. Any ?uidized bed sections in between
moles of hydrogen per mole of carbon monoxide that
the lowest and highest section should preferably be
cooled to a temperature above the temperature of the 50 after three or more passes through a reactor and inter

stage removal of methanol a hydrogen rich ef?uent gas

is obtained. By applying membrane separation to this
According to a preferred embodiment of the inven
hydrogen rich gas it is possible to obtain chemically
tion high pressure steam generated in the lowest section
pure hydrogen.
of the ?uidized catalyst bed is used for purposes outside
the present process, whereas the coolant gas of the 55
EXAMPLE
highest section is the incoming gas feed which is pre
Synthesis gas having the molecular composition of
heated, preferably by means of a feed gas pre-heater
67% H2, 32% CO and 1% CO2 is converted to metha
located in the reactor.
nol in three reactors in series, each containing a fluid
This embodiment of the invention has the advantage
ized bed of catalyst in which cooling tubes are present
of high conversions in relatively simple equipment, also
to remove the reaction heat. Boiler feed water passing
it offers the possibility of a high throughput. Further
through the tubes is partly converted to saturated steam
advantages which can be achieved by this embodiment
of high pressure and the mixture of water and steam is
are that the temperature of the highest section of the
separated in a steam drum. The steam produced is used
?uidized bed and consequently the temperature of the

highest section.

effluent of the reactor can be lower than the mean tem 65 as process steam, whereas the water is recycled to the

perature of the reactor which results in a higher temper

ature and consequently a higher reaction rate in the
lower section(s) of the ?uidized bed and a higher con

inlet of the cooling tubes. The pressure of the steam

generation circuit is set according to the desired tem
perature in the ?uidized bed.

5,216,034

position comprising copper and zinc in a ?uidized bed

Each of the reactors is ?lled with a ?uidizable cata

while cooling, wherein:

lyst containing copper, zinc and chromium in the

atomic ratio of 25/48/27 in the form of microspheres of

a. the reaction is carried out in a plurality of fluidized

catalyst bed reactors in series with interstage re

an average diameter of 50 microns. The catalyst is pre

moval of methanol from the reaction mixture by

cooling and condensation or by absorption/absorp

pared according to the procedure disclosed in US. Pat.

No. 4,522,938, issued Jun. 11, 1985, which is herein
incorporated by reference, for catalyst 5 described

tion to a solvent;
b. at least one of said ?uidized bed(s) in said ?uidized

therein. The amounts of catalysts in the first, second and

third reactor correspond to the weight ratio of

catalyst bed reactors from (a) is divided in a plural

ity of interconnected ?uidized bed sections ar
ranged in sequence in the direction of ?ow of the
gaseous mixture whereby each section is cooled by

100:45:20 respectively. Before use, the catalyst in each

reactor is activated by reduction in a ?ow of hydrogen
gas at a pressure of 100-500 kPa and 220 C.

at least one heat exchanger and whereby the tem

perature in the last section in sequence is reduced

The synthesis gas used as feed is preheated to 230 C.

and fed to the bottom of the ?rst reactor. The space
velocity in the ?rst reactor amounts to 3500 Nm3 per

from 10 to 100 centigrades below the highest tem

m3 of settled catalyst per hour. The inlet pressure of the

perature in the preceding section(s);

c. the conversion per pass through the reactors is at

?rst reactor is 8 MPa, and the average bed temperature

amounts to 250 C. The reactor ef?uent from the top of

least 50 %; and
d. the operating conditions of the reactors are within
the temperature range from 200 to 350 C. and the
pressure is within the range from 5 to 35 Mpa.

the reactor having a molar composition of 45.1% Hz,

21.3% CO, 0.8% COZand 32.8% CH3OH is cooled to
about 30 C. and led to a gas-liquid separator where the
major part of the methanol formed is separated off as
liquid methanol. The gaseous stream leaving the separa

2. The process according to claim 1, wherein the

molar ratio of carbon monoxide and hydrogen in the

tor having the molar composition 66.4% 11;, 31.4% CO,

and fed to the bottom of the second reactor. This reac
tor is operated at an inlet pressure of 7.5 MPa, an aver

gaseous mixture is in a molar ratio H2:CO= 1.5 to 2.5:1.

3. The process according to claim 1, wherein the last
section in sequence of the catalyst bed is cooled by at
least one heat exchanger cooled with a gas mixture

age temperature of 250 C. and a space velocity of 3200

comprising hydrogen and carbon monoxide.

1.2% CO3 and 1% CH3OH, is heated to about 230 C. 25

Nm3 per in3 of settled catalyst per hour.

The reactor effluent from the top of the second reac

4. The process according to claim 3, wherein ef?uent

from said heat exchanger comprising said gas mixture

tor having a molar composition of 44.6% Hz, 20.7%

CO, 1.0% CO; and 33.7% CH3OH, is cooled to about
30 C. and led to a second gas-liquid separator where
the major part of the methanol is separated off as liquid

comprising hydrogen and carbon monoxide is used as

feed gas for said process.
5. The process according to claim 1, wherein the

methanol. The gaseous stream from the second separa

section in sequence of the catalyst bed is controlled by

adjusting the temperature of a heat exchanger convert
ing water into steam.
6. A process for the production of methanol by react
ing a feed gas mixture comprising carbon monoxide and
40 hydrogen in a molar ratio HzzCO=l to 3:1 hydrogen

tor having a molecular composition of 66.5% H2, 30.8%

CO, 1.5% CO; and 1.2% CH3OH, is heated to about
230 C. and fed to the bottom of the third reactor. This
reactor is operated at an inlet pressure of 7 MPa, an

average temperature of 250 C. and a space velocity of

2900 Nm3 per in3 settled catalyst per hour. The reactor
ef?uent withdrawn from the top of the third reactor

having a molar composition of 49.9% Hz, 22.2% CO,

temperature in a least one section other than the last

and carbon monoxide in the presence of a catalyst com

position comprising copper and zinc optionally pro

moted with an element selected from the group consist
ing of aluminum and chromium in a fluidized bed reac

1.3% CO; and 26.5% CH3OH, is cooled to about 30 C.

and led to a third gas-liquid separator where the major 45 tor while cooling, wherein:
a. the reaction is carried out in a plurality of ?uidized
part of methanol is withdrawn as liquid methanol.
catalyst bed reactors in series with interstage re
The conversion of CO in the ?rst, second and third
moval of methanol from the reaction mixture or by
reactor amounts to 60, 60 and 58%, respectively. The
total conversion of CO amounts to 93%. The amounts
adsorption/absorption to a solvent;
b. at least one of said ?uidized bed(s) in said ?uidized
of methanol withdrawn from the ?rst, second and third
catalyst bed reactors from (a) is divided in a plural
separator are 19.3, 8.1 and 2.4 moles per 100 moles of
ity of interconnected ?uidized bed sections ar
original synthesis gas feed. The total amount of metha-_
ranged vertically in sequence in the direction of
nol is 29.8 moles per 100 moles of synthesis gas, which
?ow of the gaseous mixture;
represents 90.3% of the theoretical yield.
c. each section of said ?uidized bed from (b) is cooled
The ranges and limitations provided in the instant
by at least one heat exchanger, wherein the lowest
speci?cation and claims are those which are believed to
section of the ?uidized bed is cooled by a heat
particularly point out and distinctly claim the instant
exchanger which converts water into high pressure
invention. It is, however, understood that other ranges
steam, and said feed gas mixture comprising carbon
and limitation that perform substantially the same func
monoxide and hydrogen is ?rst introduced as cool
tion in substantially the same manner to obtain the same
ant to a heat exchanger designed to cool the high
or substantially the same result are intended to be within
est section of the ?uidized bed, whereby the tem
the scope of the instant invention as de?ned by the
perature in the highest section is reduced from 10
instant speci?cation and claims.
to 100 centigrades to below the highest tempera
What is claimed is:
ture in a lower section and whereby the said feed
1. A process for the production of methanol by react 65
gas mixture is warmed to a higher temperature;
ing a gaseous mixture comprising carbon monoxide and
. the effluent which comprises said warmed feed gas
hydrogen in a molar ratio H2:CO=1 to 3:1 hydrogen
and carbon monoxide in the presence of a catalyst com

mixture exiting from the heat exchanger of the

5,216,034

e. the conversion per pass through the reactors is at

highest section of the ?uidized bed from (c) is

least 50%; and

passed to the lowest section of the fluidized bed to

5
be used as feed gas for making methanol;

f. the operating conditions of the reactors are within

the temperature range from 200 to 350 C. and the
pressure is within the range from 5 to 35 Mpa.
*

10

25

45

55

65