United States Patent (19) 11) Patent Number: 4,628,066

Bonnell et al. (45. Date of Patent: Dec. 9, 1986

(54) PROCESS FOR THE PRODUCTION OF 4,235,799 11/1980 Wentworth et al. ............ 260/449.5
METHANOL 4,346,179 8/1982 Sugier et al. ........................ 518/707
(75) Inventors: Leo W. Bonnell, Macungie; Joseph FOREIGN PATENT DOCUMENTS
M. Pietrantonio, Allentown, both of 1157053 1 1/1983 Canada ................................ 260/638
Pa.
(73) Assignee: Air Products and Chemicals, Inc., Primary Examiner-Howard T. Mars
Allentown, Pa. Attorney, Agent, or Firm-Mark L. Rodgers; E. Eugene
Innis; James C. Simmons
21) Appl. No.: 828,920 57 ABSTRACT
22) Filed: Feb. 12, 1986
The present invention is a process for increasing the
(51) Int. Cl.' ....................... C07C27/06; C07C31/04 capacity of a gas phase synthesis loop for the produc
52) U.S. C. .................................... 518/700; 518/704; tion of methanol from a syngas feed. The syngas feed is
518/706; 518/707 initially passed to a liquid phase methanol reactor to
58) Field of Search ................ 518/700, 706, 707, 704 convert a portion of the syngas to methanol or metha
(56) References Cited nol and higher aliphatic alcohols. The mixture is subse
U.S. PATENT DOCUMENTS quently cooled to condense and recover the methanol
and/or higher alcohols. The unreacted syngas is passed
1,868,096 7/1932 Dreyfus. to a gas phase synthesis loop for further conversion and
3,326,956 6/1967 Davies et al. .................... 260/449.5 recovery of methanol.
3,888,896 6/1975 Espino et al. .................... 260/449.5
3,923,694 12/1975 Cornthwaite ....................... 252/463
4,031,123 6/1977 Espino et al. .................... 260/449.5 13 Claims, 1 Drawing Figure
U.S. Patent Dec. 9, 1986 4,628,066
 4,628,066
1. 2
the steam reforming of natural gas, is passed to a liquid
PROCESS FOR THE PRODUCTION OF phase methanol reactor to convert a portion of the
METHANOL syngas to methanol. The resultant methanol-containing
syngas reactor effluent is cooled to condense the metha
TECHNICAL FIELD OF THE INVENTION 5 nol, thereby producing a first methanol stream and an
The present invention relates to the production of unreacted syngas stream. The unreacted syngas stream
methanol or methanol and higher aliphatic alcohols is passed to a conventional gas-phase methanol synthe
from a syngas feed comprising carbon monoxide and sis loop to convert at least a portion of the unreacted
hydrogen. syngas stream to methanol, thereby forming a second
O methanol stream. Both the first and second methanol
BACKGROUND OF THE INVENTION streams are recovered as product or for further process
Various methods have been developed for the pro Ing.
duction of methanol from gas mixtures containing car The present invention allows the syngas feed to be
bon oxides and hydrogen. U.S. Pat. No. 1,868,096 dis 15
passed at an increased flow rate, and at a single pass,
closes a process for producing methanol by passing a through the liquid-phase methanol reactor for partial
reaction gas mixture under the requisite conditions of conversion to methanol, with the unconverted syngas
temperature and pressure initially over one or more being used as a substitute feed to the gas-phase synthesis
catalyst masses composed of zinc oxide or zinc oxide loop. This provides a method for increasing the capac
and chromium oxide and subsequently passing said mix ity of an existing gas-phase methanol synthesis loop
ture over one or more methanol catalysts sensitive to without the extensive equipment modification and cost
sulfur poisoning such as catalysts comprising copper, involved in expanding the gas-phase loop itself. The
manganese or compounds of copper or manganese. The liquid phase reactor does not contain a recycle loop and
reaction gases are passed successively through a num therefore can efficiently "debottleneck' an existing
ber of reaction vessels arranged in series as an open system without incurring costly recycle compression
system. 25
requirements. Consequently, the amount of syngas
U.S. Pat. No. 4,235,799 discloses a process for pro which can be processed in a given period of time can be
ducing methanol by passing a mixture of hydrogen and significantly increased in a manner more economical
one or more carbon oxides into contact with at least two and efficient than previously thought possible.
beds of catalyst arranged in series. The catalyst beds are The liquid phase methanol reactor can be retrofitted
operated at increasing temperature levels in the direc 30
into any typical gas-phase loop which is capable of
tion of flow of the mixture. The mixture is subsequently synthesizing methanol from the syngas feed. The liquid
cooled by indirect heat exchange and passed into phase reactor typically has a pressure drop of less than
contact with at least one further bed of catalyst. about 5 psi, thereby requiring minimal additional com
U.S. Pat. No. 4,346,179 discloses a process for pro pression for the gas-phase synthesis loop feed. An addi
ducing methanol and its higher homologs from a syn 35 tional advantage of the present process is that, by using
thesis gas containing essentially carbon dioxide, carbon various catalysts in the liquid phase reactor, the process
monoxide and hydrogen. A synthesis gas is treated in a can be designed to produce higher aliphatic alcohols as
first catalytic reaction zone at 230-350° C. The effluent
from the first catalytic reaction zone is cooled and con well as methanol as products.
densed and a gas fraction is separated from the liquid BRIEF DESCRIPTION OF THE OR AWINGS
condensate. The gas fraction is subsequently treated at
240-300 C. and a second catalytic reaction zone to The single FIGURE is a schematic flow diagram of
produce a liquid methanol fraction. The liquid methanol one embodiment of the present invention.
fraction is subsequently admixed with the liquid con DETAILED DESCRIPTION OF THE
densate to form a gasoline constituent product. 45 INVENTION
U.S. Pat. No. 3,888,896 discloses a process for pro
ducing methanol from carbon monoxide and hydrogen The present invention is a process for increasing the
saturating an inert organic liquid medium, such as production of methanol from a syngas feed. Typically,
pseudocumene, with carbon monoxide and hydrogen methanol is produced from a syngas feed, such as the
and contacting the saturated liquid medium with a me SO feed produced from the reforming of natural gas, using
thanol-forming catalyst such as those containing zinc a gas-phase methanol synthesis loop. Increasing the
and chromium. capacity of a standard gas-phase methanol loop itself, is
U.S. Pat. No. 4,031,123 discloses a similar method for difficult and costly due to the high recycle ratios em
preparing methanol with the improvement that paraf ployed; e.g. 8-1 is common, and the high reactor pres
finics and cycloparaffinics are used as the inert hydro 55 sure drops. Due to the strong exothermic nature of the
carbon liquid in which the catalyst bed is in contact. methanol synthesis reaction, high recycle ratios are
Canadian Pat. No. 1,157,053 discloses a liquid phase necessary to keep reactor temperatures at acceptable
methanol synthesis process wherein methanol is pro levels. As a result, a proportionate addition of recycle
duced by contacting a synthesis gas comprising hydro compression capacity, catalysts, reactor volume and
gen and carbon monoxide with a catalyst in the pres 60 heat exchanger surface is necessary to increase the ca
ence of an inert liquid. The catalyst in contact with the pacity of the synthesis loop, with corresponding high
inert liquid is in the form of particles of a size less than capital costs. Even a small increase in the syngas capac
about 125 microns. ity of the gas-phase loop requires a significant increase
in cost.
BRIEF SUMMARY OF THE INVENTION 65 The present invention increases the capacity of a
The present invention is a process for increasing the typical gas-phase methanol loop without many of the
capacity; i.e. debottlenecking, a typical gas-phase meth drawbacks involved with increasing the loop size itself.
anol synthesis loop. A syngas feed, such as a feed from Referring to the accompanying FIGURE, a syngas feed
 3
4,628,066
4.
stream 2, containing carbon dioxide and hydrogen, is pressed to a pressure between 750 and 3000 psia in com
compressed, if necessary, in compressor 4 to form a pressor 18, to form a compressed syngas stream 20. The
compressed syngas feed 6 which is passed to a liquid compressed syngas stream 20 is combined with a recy
phase methanol reactor 8. The composition of the syn cle stream 32 to form a combined syngas stream 22
gas feed 2 to the liquid phase methanol reactor can be which is passed to a gas-phase synthesis loop facility 24
any composition that is an acceptable feed to a conven to convert at least a portion of the syngas to methanol.
tional gas-phase methanol facility. A typical composi The gas phase synthesis loop can be any typical gas
tion would be 73% H2, 15% CO, 8% CO2, and 4% phase facility common in the art, such as that disclosed
methane and other inerts, with a preferred stoichiomet in U.S. Pat. Nos. 3,326,956; 3,923,694 and 4,235,799.
ric ratio H2/(CO -- 1.5 CO2) between 2-3. Feeds with a 10 The methanol synthesized in the gas-phase synthesis
stoichiometric ratio outside of this range can be pro loop is removed from the facility as a second methanol
cessed, but the efficiency of the system will decrease. product stream 26, and is optionally combined with the
For example, if the stoichiometric ratio falls below 2, first methanol product stream 14 from separator 12 to
the unconverted syngas would be difficult to process in form a single methanol product stream 34. The unre
the downstream loop because of the hydrogen defi 15 acted syngas from the gas-phase synthesis loop 24 is
ciency. removed as stream 28 and compressed to a pressure
Typically, the liquid phase methanol reactor operates between 750 and 3000 in compressor 30 to form a com
at a pressure between 400 to 1200 psia, and the syngas pressed syngas stream 32. This compressed syngas
feed 2, if not within this pressure range, is compressed in stream 32 is recycled and combined with compressed
compressor 4. The liquid phase methanol reactor 8 can 20 syngas stream 30 entering the gas-phase synthesis loop
be any suitable reactor which is capable of converting a 24 for further processing. A purge stream 36 is also
portion of the feed gas to methanol. Such reactors are taken from the synthesis loop.
described in U.S. Pat, Nos. 3,888,896 and 4,031,123 and
Canadian Pat. No. 1,157,053, all assigned to Chen Sys ure,In the the embodiment shown in the accompanying fig
liquid phase methanol reactor and associated
tems, Inc. The reactor consists of an active methanol 25 methanol recovery equipment is located intermediate to
synthesis catalyst suspended in an inert hydrocarbon the two stages of feed gas compression (compressors 4
liquid, usually a mineral oil. The synthesis gas is bubbled and 18) for the gas phase synthesis loop. Placing the
through the catalyst-oil mixture where a portion of the liquid phase reactor at this point of the process reduces
H2, CO and CO2 are converted to methanol. Two oper
ating modes can be used: the catalyst can be pellet-sized 30 the number of moles of gas that must be fed to the sec
and fluidized by the inert liquid, or a powdered catalyst ond comprssion stage. Since high single pass conver
can be entrained in the liquid, forming a slurry. sions are achievable in the liquid phase methanol reac
The catalyst used in the liquid phase reactor can be tor, the amount of syngas fed to the system can be in
any known methanol-forming catalyst, such as those creased significantly, and hence methanol production
listed in Column 4 of U.S. Pat. No. 4,031,123. The parti 35 increased, without the large cost and equipment in
cle sizes of the catalyst employed are known by those crease necessary to reach such capacity with the gas
skilled in the art. Average particle sizes may range from phase loop alone. Depending upon the circumstances of
0.00002 to 0.25 inches, depending on the bed type the application, it may be preferable to place the liquid
(fixed, fluidized, or slurry) and liquid flow rate. By phase reactor after the second stage of compression, i.e.
varying the catalyst composition as well as the reaction at a point along stream 16. As the amount of required
conditions in the reactor, higher aliphatic alcohols may methanol production for the liquid phase reactor in
be produced along with the methanol. The higher ali creases, higher pressure requirements become necessary
phatic alcohols may be condensed and recovered with for high conversions due to equilibrium constraints.
the methanol as a combined product, or may be sepa The present process scheme allows for an increase in
rated and recovered as an additional product. 45 the production of methanol over a traditional methanol
The reactor pressure at the exit can be between 200 synthesis facility, and also provides for an efficient and
psia and 2,000 psia with a preferred range being be economical method of increasing the capacity of a con
tween 400 psia and 1,000 psia. Below about 400 psia ventional gas-phase methanol synthesis loop. Prior at
methanol synthesis equilibrium becomes increasingly tempts to increase the capacity of existing gas-phase
unfavorable, and condensation of methanol requires 50 loops included frequent replacement of catalyst, build
costly refrigeration. The reactor temperature can be ing a new, separate loop, and enlarging the existing
between 150° C. and 400° C. with best performance loop. All of these methods proved unattractive, as the
between 230 C. and 250° C. Normally, the contents of cost associated with each is high when compared to the
the reactor vary by only a few degrees C. from top to corresponding increase in capacity achieved.
bottom, or edge to center. The reactor space velocity in 55 The liquid phase reactor operates with a high single
units of standard liters (0° C. 1 atm) offeed per hour, per pass conversion. The inert liquid in the liquid phase
kilogram of catalyst, is preferably between 4000 and reactor functions as an excellent heat-transfer medium
10,000 for the slurry mode of reactor operation with and heat sink, thereby allowing the exothermic metha
powdered catalyst, and between 2,000 and 6,000 for the nol synthesis reaction to proceed to a much higher level
fluidized mode with pelletized catalyst. 60 of conversion of carbon dioxides to methanol without
After partial conversion to methanol, the resultant significant temperature rise of the gas and catalyst mass.
methanol-containing syngas is removed from contact Such a temperature rise is detrimental to catalyst life
with the catalyst as stream 10 and the methanol fraction and thermodynamic equilibrium, and therefore a limit
is condensed and separated from the remaining syngas ing factor in a stand alone gas phase system. The high
in separator 12. The condensed methanol fraction is 65 heat capacity of the inert oil relative to the feed gas
removed from the separator as a methanol product provides for direct and rapid heating of the gas to syn
stream 14 and the unreacted syngas is removed as thesis temperatures without the need for feed-product
stream 16. The unreacted syngas stream 16 is com heat exchangers.
 4,628,066
S 6
Additionally, because a typical liquid phase reactor phase synthesis loop to produce a second methanol
has a AP of less than 5 psi it can be incorporated directly stream; and
into an existing synthesis gas compression system with (d) recovering both the first and second methanol
out the need for a significant increase in compressor size Streams.
or power. 5 2. The process in accordance with claim 1 wherein
The following example illustrates one embodiment of said syngas feed is passed to a liquid phase methanol
the present invention and is not meant to be limiting. reactor to convert a portion of the syngas to methanol
EXAMPLE 1
and higher aliphatic alcohols.
3. The process in accordance with claim 1 wherein
A computer simulation was developed to establish 10 said syngas feed is compressed to between 400 and 1200
the effect of retrofitting a liquid phase methanol reactor psi prior to being passed to the liquid phase methanol
at the front end of a conventional gas phase synthesis reactor.
loop. The gas phase loop was designed to produce 2100 4. The process in accordance with claim 1 wherein
metric tons per day (MT/D) of methanol from natural said unreacted syngas stream is compressed to between
gas without supplemental CO2 addition. The feed is 15 750 and 3000 psi prior to being passed to the gas phase
compressed to 490 psi and fed to the liquid phase reac synthesis loop.
tor where about 33% of the CO and 7% of the CO2 is 5. The process in accordance with claim 1 wherein
converted to methanol at a 10,000 l/hr-kg space veloc the syngas feed has a stoichiometric ratio H2/(CO -- 1.5
ity. The reactor effluent is cooled to condense the meth CO2) between 2 and 3.
anol and the remaining feed is compressed to about 1000 20 6. The process in accordance with claim 1 wherein
psi and fed to the gas phase synthesis loop for further said liquid phase methanol reactor comprises an active
methanol synthesis. methanol synthesis catalyst having average particle
A heat and material balance for key streams in this sizes ranging from 0.00002 to 0.25 inches suspended in
process are reported in Table 1 below. an inert hydrocarbon liquid.
TABLE 1
Stream Number 2 6 14 20 26 32 36
Pressure 240 490 460 1000 862 1000 90
(psia)
Temperature 100 279 92 222 100 130 70
(F)
Ave. Mol. Wit. 9.74. 9.74 30.84 9.52. 27.80 5.29 5.22
Flow Rates
Moles/Hr.
Hydrogen 25,470 25,470 - 21,420 30 21 1,710 7,820
Carbon 5, 180 5,180 - 3,440 - 4,770 180
Monoxide
Carbon 2,710 2,710 20 2,500 10 3,760 140
Dioxide
Methane 1,290 1,290 - 1,290 20 34,030 1,270
Nitrogen 70 70 m 70 - 1,760 70
Water - - 20 - 2,350 30 10
Methanol - - 1,830 60 5,660 1,180 -
Ethanol - 20 - 5 --
Total Flow
Mole/Hr. 34,720 34,720 2,080 28,780 8,075 257,350 9,490
1b/Hr. 338,170 338,170 64,150 273,990 224,290 1,361,380 49,540
Phase Vapor Vapor Liquid Vapor Liquid Vapor Vapor

From the above results, it was calculated that the 45 7. The process in accordance with claim 1 wherein
overall production of pure methanol was increased to the liquid phase methanol reactor is positioned interme
2613 MT/ED, of which 1974 MT/D came from the gas diate to two stages of feed compression for the gas
phase loop and 629 MT/D from the liquid phase reac- phase loop. o
tor. This represents a 24.5% increase in methanol pro- 8. The process in accordance with claim 1 wherein
duction over the previous rate of 2100 MT/D for the 50 the liquid phase methanol reactor is located subsequent
stand-above gas phase loop. In addition, 11 MT/D of to the last stage of feed compression for the gas phase
ethanol and higher alcohols would be produced. synthesis loop. o
Having thus described the present invention, what is 9. The process in accordance with claim 1 wherein
now deemed appropriate for Letters Patent is set out in methanol production is increased by over 24% of the
the following appended claims. 55 production rate of a stand-alone gas phase synthesis
What is claimed is: loop.
1. In a gas phase synthesis loop for the production of 10. The process in accordance with claim 1 wherein
methanol from a syngas feed containing carbon dioxide the liquid phase methanol reactor has a AP for the syn
and hydrogen, the improvement for increasing the ca- gas of less than 5 psi.
pacity of methanol production which comprises: 60 11. The process in accordance with claim 1 wherein
(a) passing said syngas feed, in a single pass, to a liquid the liquid phase methanol reactor temperature is be
phase methanol reactor to convert a portion of the tween 150 C. and 400 C. w
syngas to methanol, thereby forming a methanol- 12. The process in accordance with claim 11 wherein
containing syngas reactor effluent; the liquid phase methanol reactor temperature is be
(b) cooling said methanol-containing syngas reactor 65 tween 230 C, and 250' C.
effluent to condense the methanol, thereby produc 13. The process in accordance with claim 1 wherein
ing a first methanol stream and an unreacted syngas the syngas feed is produced from the reforming of natu
stream; ral gas. k x 2k x sk
(c) passing said unreacted syngas stream to a gas