US 2012O1161.

37A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2012/0116137 A1
Fang et al. (43) Pub. Date: May 10, 2012
(54) SINGLE LOOP MULTISTAGE FUEL requisite thermal capacity to moderate the high heat release of
PRODUCTION the reactions and to provide the reactants and reaction envi
ronments for the efficient operation of the process. The first
(75) Inventors: Howard L. Fang, Bridgewater, NJ stage converts a portion of the synthesis gas to methanol, the
(US); Moshe BEN-REUVEN, second stage converts the methanol to dimethylether, the third
Princeton, NJ (US); Richard E. stage converts the methanol and dimethylether to fuel and the
BOYLE, Philadelphia, PA (US);
Robert M. KOROS, Westfield, NJ fourth stage converts the high melting point component,
(US) durene, and other low volatility aromatic components such as
tri- and tetra-methylbenzenes to high octane branched paraf
(73) Assignee: PRIMUS GREEN ENERGY fins. The four-stage catalyst used for hydrotreating is resistant
INC., HILLSBOROUGH, NJ (US) to CO poisoning. The reactions i produce water as a side
product that is carried through to a high pressure separator
(21) Appl. No.: 12/942,680 after the fourth stage. The streams from the separator are a
(22) Filed: Nov. 9, 2010 liquid fuel stream, a water stream and a gaseous stream that
contains light hydrocarbon gases and the unreacted synthesis
Publication Classification gas. The larger part of this gas stream is recycled to the inlet
of the first stage and mixed with the fresh synthesis gas
(51) Int. Cl. stream. Alternatively, the fresh synthetic gas stream is mixed
C07C I/02 (2006.01) with the product of the second stage. The smaller part of the
BOI. 8/00 (2006.01) gas stream from the separator is sent to hydrocarbon recovery
(52) U.S. Cl. .......... 585/317:585/310; 422/187; 585/322 and to fuel gas used for providing preheat of various streams.
The liquid fuel is sent for blending into fuel products, such as
(57) ABSTRACT gasoline, jet fuel, or diesel, and the water stream can be sent,
Synthetic fuels are produced from Synthesis gas in a four for example, to the synthesis gas producing plant for steam
stage reactor System with a single recycle loop providing the generation.
Patent Application Publication May 10, 2012 Sheet 1 of 5 US 2012/01161.37 A1
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US 2012/011 6 137 A1 May 10, 2012

SINGLE LOOP MULTISTAGE FUEL the durene content close to equilibrium, which would give a
PRODUCTION satisfactory product (FIG. 9 of the article). The article does
not show that it was demonstrated. The olefinic content of the
FIELD OF THE INVENTION product was reduced as the pressure of hydrogen was
increased and was overall lower than in the Mobil MTG
0001. This invention relates to a new process to directly product thereby producing lowered Research and Motor
produce transportation fuels, such as gasoline, jet fuel and Octanes.
diesel from synthesis gas containing principally carbon mon 0007. In Skovetal (U.S. Pat. No. 4,520,216), three stages
oxide, carbon dioxide, and hydrogen. are sequenced with no intermediate separation using a single
BACKGROUND OF THE INVENTION
recycle loop with interstage heat exchange. This scheme pro
duces an undesirable high durene content fuel. Jornet al (U.S.
0002 The prior art describes several alternatives to pro Pat. No. 4,481,305) proposes a very complex set of recycles
duce gasoline and distillate from synthesis gas that do not for a three-reaction stage configuration.
anticipate the present invention of four reaction stages with an 0008. In still another configuration, catalytic activities of
overall recycle loop to produce commercial quality fuels. the first three stages were integrated into one catalyst for a one
Chang etal (U.S. Pat. No. 3,894,102) and Zahner et al (U.S. stage process (F. Simard, U. A. Sedran, J. Sepulveda, N. S.
Pat. No. 4,011,275) propose that synthesis gas be passed over Figoli, H. I. de Lasa, Applied Catalysis A: General 125
methanol producing catalyst with an acid component activity (1995):81-98). The one-stage conversion process used a com
to convert methanol to dimethylether and then feeding this bined synthesis gas/methanol and methanol-to-gasoline cata
intermediate mixed product to a fuel producing stage with lyst, a ZnO CrO+ZSM-5 catalyst, that produced gasoline
recycle of light components to mix with the intermediate compounds from Synthesis gas feed, however, the selectivity
mixed product feed. to carbon dioxide was extremely high, ca 70%, making the
0003. In another example, Chang et al (U.S. Pat. No. process impractical. The overall reaction is described by
4,076.761) use synthesis gas produced from coal, shale and/ 2nCO+nH->(CH)-nCO, with a minor amount of water
or residua that is conveyed to a carbon oxide converter and (Javier Erena et al. Chemical Engineering Science 55 (2000)
thence to a fuel producing stage with recycle of light gases 1845-1855).
back to the synthesis gas stage, the carbon oxide conversion 0009. The complexity of the demonstrated and commer
stage or the fuel producing stage. cialized fixed bed Mobil Methanol-to-Gasoline (MTG) pro
0004 Garwoodletal (U.S. Pat. No. 4,304,951) disclose the cess can be appreciated from the description of the commer
advantage of hydrotreating only the heavy fraction of product cialized MTG process by Yurchak in D. M. Bibby, C. D.
from a fuel producing stage using ZSM-5 catalyst. The Chang, R. W. Howe, S. Yurchak (Eds.), Methane Conversion,
hydrotreating step is carried out using essentially pure hydro 1988, Elsevier Science Publishers, B. V., Amsterdam, 251
gen and isolated from the prior three stages to produce liquid 272. In this process, synthesis gas is first converted to a
fuel from Synthesis gas. methanol/water (CHOH/HO) mixture in a stand-alone
0005. Thereby, the referenced patents proceed with four plant. The methanol/water mixture is recovered and sent to
sequential stages with separation of liquid intermediates and intermediate tankage. Recycle is used to provide a heat sink
product concentration steps after the first, third and fourth for the highly exothermic reaction and to enhance synthesis
stages, resulting in a complex and low efficiency process. In gas conversion for this equilibrium limited reaction. The
addition, due to the production of high melting point (-79° recycle gases are cooled to remove the methanol/water pro
C.) durene, the cooling condenserahead of the separator after duced and must be reheated before returning to the reactor.
the ZSM-5 stage needs a light gasoline recycle wash to keep The product methanol/water mixture from tankage is fed to a
it clean from durene deposition. two stage reactor system containing a lead reactor with a
0006 Haldor Topsoe (J. Topp-Jorgensen, “Topsoe Inte catalyst that partially converts the methanol to dimethylether
grated Gasoline Synthesis—the TIGAS Process', in D. M. (DME) and then to another reactor with a recycle loop, the
Bibby, C. D. Chang, R. W. Howe, S.Yurchak (Eds.), Methane methanol-to-gasoline (MTG) reactor that converts the metha
Conversion, 1988, Elsevier Science Publishers, B. V., nol/DME mixture to a heavy gasoline containing large
Amsterdam, 293–305) simplified the Mobil Methanol-to amounts of durene, 1,2,4,5-tetramethyl benzene molecule
gasoline (MTG) scheme by combining the first three stages that has a high freezing point (79.3°C.) and must be removed
within one synthesis gas recycle loop without intermediate to make a viable gasoline product. The removal is effected by
separation utilizing a proprietary catalyst for the first step to a hydrotreating step performed on a heavy fraction of the
enable it to operate effectively at the lower pressures required intermediate product from the fuel producing reactor stage
by the ZSM-5 step. Methanol production is equilibrium lim and the hydrotreated fraction is combined with the light gaso
ited and conversion would be enhanced by operation at high line fraction to produce the gasoline product. The
pressure. However, at high pressures, ZSM-5 produces hydrotreater is operated at elevated pressure and is Supplied
increasing amounts of the undesirable component, durene. with a hydrogen rich stream, which is produced from a por
The proprietary catalyst produced DME in addition to metha tion of the synthesis gas by a separation step Such as Pressure
nol to increase the conversion to oxygenates. At elevated Swing Adsorption (PSA). The hydrotreating catalyst is pre
pressure, however, ZSM-5 produces a gasoline with a very Sulfided and operated with a hydrogen rich gas recycle (Yur
high heavy aromatic content, in particular with high concen chak, 1985) and Garwood et al. (U.S. Pat. No. 4.304,951).
trations of durene that then would require hydrotreating as in One of the catalysts tested but rejected due to low activity is
the MTG New Zealand plant. Operating at about 20 atmo a presulfided commercial cobalt molybdate on alumina (Co
spheres, the durene level was more than about three times a MoO/Al2O) catalyst.
satisfactory level and it was stated, though not shown, that an 0010. The commercial plant built and operated in New
isomerization step could be introduced into the loop to bring Zealand using this scheme has the complexity of three recycle
US 2012/011 6 137 A1 May 10, 2012

catalyst loops and three separation steps involving cooling the SUMMARY OF THE INVENTION
intermediate products to liquefy them to enable conventional
separation and distillation steps and stepping down of pres 0014. This invention relates to a new process to directly
Sures and recompression, one for making methanol one for produce transportation fuels, such as gasoline, jet fuel and
making the raw gasoline and the third for removing the diesel from synthesis gas containing principally carbon mon
durene. Typical catalysts and conditions used in each step in oxide, carbon dioxide, and hydrogen. The synthesis gas may
the Mobil MTG plant built in New Zealand are shown in Table be produced from Such raw materials as natural gas, coal,
5 below. It is clear from this abbreviated description that this wood and other biological materials. The process entails four
prior art process is quite complex and inefficient in its han sequential catalytic stages with intermediate heat exchange to
dling of intermediate products and the recycles and it requires provide the requisite temperature in each stage, but with no
several high cost high pressure feed and recycle compressors, interstage separation. The unreacted gases from the fourth
and high pressure pumps. stage are recycled to the first stage. The recycle enhances the

TABLE 5(a)
Prior Art MTG Reaction Sequence
Typical Reactor Typical Reactor
Temperature, C. Pressure, Atm
Principal Reactions Feed Catalysts Note (1) Note (2)
CO + H2 (P CH-OH + H2O CO, H., Reduced 230-290 SO-100
CuOZnOf
Al2O3
CH-OH (9 (CH)O + H2O CHOH, HO Y-Al2O3 31O-320 18-22 pressure
CH-OH P (CH), + n H2O CHOH, (CH)O, ZSM-5 3SO-366 18-22
n/2(CH3)2O > (CH2) + n/2H2O HO
Durene () iso-Durene (CH2), H2 Sulfided 220-270 30-40
Ni Won
SiO2/Al2O3/
faujasite
Notes
(1) (CH2) with 4 < n < 10 denotes on the average the composition of the gasoline product which is a mixture of paraffins,
iso-paraffins, olefins, cyclics and methyl substituted aromatics,
Note
(2) Reactor conditions from K.G. Allum and A.R. Williams, “Operation of the World's First Gas-to-Gasoline Plant, in D.M.
Bibby, et al (Editors), Methane Conversion, 1988, Elsevier Science Publishers, B.V., Amsterdam, p691-711.

0011. In the Mobil MTG process, durene is produced in conversion of the synthesis gas to the desired products and
enough quantities to result in undesirable cold temperature also serves as a heat sink for the highly exothermic reactions
performance of the gasoline and must consequently be involved in each stage. This invention is distinct from the
reduced. It is shown in Sergei et al. (“Process Aging Studies prior art in that it operates at elevated pressure, preferably
in the Conversion of Methanol to Gasoline in a Fixed Bed about 50-100 atmospheres in all four stages, to yield high
Reactor, Ind. Eng. Chem. Process Des. Dev. Vol. 18, No. 3, reactor utilization efficiencies to produces a hydrocarbon
1979) that ZSM-5 produces durene in much larger quantities mixture ready for market as transportation fuels after the
than expected from equilibrium. This is shown in Table 5(b), usual additives used in the industry are added. To the contrary,
which is an abstract of Table V of the reference. the prior art teaches that low pressures of 1 to 20 atmospheres
in the third stage are required to produce acceptable transpor
tation fuels.
TABLE 5(b) 0015 This invention also provides a unique multistage
time on stream in cycle, h 11 645 process operating at essentially uniform pressure that con
maximum temperature, F. 745 745 779 779 verts synthesis gas to hydrocarbon fuels. Furthermore, the
tetramethylbenzenes, mol % equil exptl equil exptl multistage process uses a single recycle loop connecting the
durene (1,2,4,5-)
isodurene (1,2,3,5-)
33.0
SO.4
67.6
24.0
32.8
S.O.3
97.3
1.1
last to the first stage. Cooling is preferably accomplished
prehnitine (1,2,3,4-) 16.6 8.4 16.9 1.6 within and/or in-between stages to remove the exothermic
heat of reaction produced in all stages.
0016. The process contains four reactor stages in series,
0012 Halving the amount of durene during an average preferably interconnected with heat exchangers to adjust the
cycle has been shown to produce a satisfactory fuel, therefore temperature of the outflow of one stage to correspond to the
isomerizing the tetra-methyl-benzenes to an equilibrium mix desired inlet temperature of the next stage. Each stage may
ture would be satisfactory to eliminate part of the problem. have one or more reactors in series or in parallel, loaded with
However, a certain amount of dealkylation of tetra-methyl the same catalyst. No separation or removal of intermediate
benzene is also provided by the catalyst used in the New product is made. The first stage converts synthesis gas to
Zealand plant (Garwood et al.). methanol and water; the second stage converts a portion of the
0013 Therefore, there remains a need for an efficient pro methanol to dimethylether; the third stage converts methanol
cess to produce fuel from Synthesis gas, whereby the fuel and dimethylether to gasoline and heavy gasoline; and the
contains low amounts of durene and highly Substituted ben fourth stage converts the heavy gasoline via hydrotreating
Zenes for better viscometric properties in cold temperature reactions to gasoline (C. to Cs), jet fuel, diesel or a combina
performance. tion thereof, as desired.
US 2012/011 6 137 A1 May 10, 2012

0017. An additional uniqueness of this scheme is that the product coming out of the fourth reactor has a freezing point
requisite hydrotreating reactions in the fourth stage are car of less than about -5°C., preferably about -15 to about -20°
ried out in the presence of high concentrations of carbon C., while the product coming out of the third reactor has a
monoxide, which are present in the recycle synthesis gas and freezing point of about 30-50° C.
is, in effect, used as the treat gas. We have discovered that 0020. The fourth stage catalysts that we have found to
there are a large variety of catalysts that may be used in the selectively accomplish this task are Group IX or X metal
fourth stage to achieve the requisite reactions under these oxide (e.g. nickel oxide) catalyst on alumina reduced in the
unique and unusual conditions of high partial pressure of presence of hydrogen and carbon monoxide in the absence of
carbon monoxide (carbon monoxide molar fraction in the sulfur. In certain embodiments, the catalyst can be Group IX
fourth stage is about 20-25%). It is commonly taught in the art or X metal oxide (e.g. cobalt oxide) catalyst combined with a
that the hydrotreating step should be carried out in the Group VI metal oxide (molybdenum oxide) catalyst on alu
absence of Substantial amounts of carbon monoxide to avoid
poisoning of the catalyst. mina reduced in the presence of hydrogen and carbon mon
0018. The total flow exiting from the fourth stage is cooled oxide and in the absence of sulfur. A specific example of the
to condense the product liquid hydrocarbon and water. These catalyst include unsulfided cobalt molybdate on alumina or
are removed from the recycle gases in a high pressure sepa atomic nickel on alumina, the reduction, if any, being carried
out in the presence of synthesis gas. Sulfiding the catalyst
rator. The vapor from the high-pressure separator is split into Surface is not necessary but catalytic reduction using either a
two streams: a stream that is sent to fuel gas and LPG recovery He flow or a mixture of H and CO under operating tempera
and another larger stream that is sent to the recycle compres ture is desirable. Temperature of the fourth stage ranges from
sor for return to the feed of the first reaction stage. The recycle 120 to 23.0°C. (248 to 446°F) depending on the catalyst used,
gas is composed of unreacted synthesis gas and Small with the preferred temperature being about 150-180° C. (302
amounts of by-product light gases. The overall process yield to 356°F). These temperatures are surprisingly lower than
is greater than about 25%, preferably about 15 to about 45% 232 to 427°C. (450 to 800 F) disclosed by Garwood (U.S.
(based on weight of the converted synthesis gas). The fuel Pat. No. 4,304,951) for treating a 200-400°F. bottoms frac
produced from the process preferably contains about 30 to tion. We ascribe this valuable difference in temperature and
about 40% straight and/or branched paraffins, more prefer the more desirable product mix to treating the whole product
ably C4 to C8, most preferably C5 to C7; about 15 to about from the fuel forming step in the presence of synthesis gas
25% cyclic paraffins, preferably C6 to C8 hydrocarbons; instead of a bottoms fraction with principally hydrogen. We
about 2 to about 5% toluene; about 6 to about 10% xylenes; also ascribe this surprising result to using unsulfided cata
about 10 to about 15% trimethylbenzenes (TMB), and about lysts, unlike Garwood that teaches by example that mixed
15 to about 20% durene and other tetra- or higher methyl oxide catalysts need to be sulfided. Han et al. (U.S. Pat. No.
substituted benzenes.
4,973,784) teaches the use of Zeolites for treating the durene
0019. The entire reactor system is operated at elevated containing product in the presence of substantial partial pres
pressure, 50 to 100 atmospheres, with modest pressure Sure of hydrogen producing undesirable benzene. Our novel
decreases due to pressure drop as a result of flow through the process does not produce benzene. Still in another variation,
catalysts, pipes, and heat exchangers. This pressure drop is Chester et al. (U.S. Pat. No. 4,387,261) propose treating the
maintained at modest values to economize on the size and entire product from the fuel forming stage, but preferably a
cost of the recycle compressor. The high pressure enhances heavy fraction thereof, using ZSM-12, preferably impreg
the conversion of synthesis gas to the methanol intermediate nated with platinum, an expensive metal, at elevated tempera
in the first stage, has no effect in the conversion of methanol tures and pressures to dealkylate durene to form Xylene, tolu
to the intermediate dimethylether. However, it is known in the ene, benzene and undesirable light gases such as C and C.
art (Yurchak) that the conversion of ethanol/dimethylether to hydrocarbon. The present process is clearly Superior in that it
gasoline in the third stage also produces heavy gasoline, does not produce light gases in the treating stage (stage 4).
principally 2Cs aromatics, such as tri-methylbenzenes, tet Still in another example, Dwyer et al. (U.S. Pat. No. 4,347,
ramethylbenzenes, and durene. In particular, highly undesir 397), showed that treating the whole or bottoms product from
able tetra-methyl benzene and durene are produced which the fuel producing stage with Zeolites principally isomerizes
have high melting points (79° C. or greater) and limited the durene to other tetramethylbenzenes, thereby, producing
solubility in the hydrocarbon mixture even at room tempera less desirable heavy product than the present process.
ture. Their viscometric behavior cannot be tolerated in an 0021 Examples of catalysts and temperature ranges that
all-weather commercial fuel. In the present process, however, can be used for the first three stages are as follows: in the first
this intermediate product, containing heavy gasoline, is con stage, R-1, CuO/ZnO/Al2O in the range of 190 to 300° C.,
verted to desirable hydrocarbon products in the fourth stage with the preferred range of 220 to 260°C.; in the second stage,
by significantly reducing the trimethylbenzene and tetram R-2, gamma-alumina in the range of 300 to 450° C. with the
ethylbenzene and durene isomer groups via hydrotreating and preferred range of 400 to 420°C.; and in the third stage, R-3,
producing desirable fuel compounds Such as toluene, Xylenes ZSM-5 in the range of 300 to 500° C. with preferred range of
and C to Cs hydrobarbons, principally Cs to C, hydrocar 343 to 420° C.
bons. This conversion is obtained by the proper choice of
catalyst, space Velocity and temperature of the reactor. The
presence of heavy gasoline in the product produced from the BRIEF DESCRIPTION OF THE DRAWINGS
third reaction is undesirable because it increases the freezing
temperature of the fuel which renders the fuel unusable in old 0022 FIG. 1 is a schematic of a process of the present
weather. The fourth reactor converts the heavy gasoline to invention.
toluene, Xylenes, and/or C to Cs hydrobarbons, which lowers 0023 FIG. 2 is a schematic of an embodiment of the
the freezing point of the fuel product. Preferably, the fuel present process that includes four reactors in Stage I.
US 2012/011 6 137 A1 May 10, 2012

0024 FIG. 3 is a schematic of an embodiment of the of cooled recycle gas for each stage or a combination of these
present invention that introduces the synthesis gas feed at the two methods oftemperature control may be used. FIGS. 2 and
entrance of the third reactor (R-3). 3 show examples of these renditions, which are familiar to
0025 FIG. 4 is a GC-MS spectrum of a typical fuel those skilled in the art. These examples do not limit the
obtained when the Reactor Stage 4 is not used. variations possible in the detailed design of this process.
0026 FIG. 5 is a GC-MS spectrum of the fuel product 0030 FIG. 2 is a schematic of a further embodiment of the
using the hydrotreating reactor (Reactor Stage 4) containing present process where the first reactor 1 contains four inter
Catalyst A and Catalyst B. cooled reactors (1a, 1b, 1C, and 1d) with heat exchangers
0027 FIG. 6 is a comparison of fuel samples with and (21a, 21b, 21c, and 21d) cooling the outlets of each of the
without Reactor Stage 4 with Catalyst A. reactors (la, 1b, lc, or 1d), respectively. Additionally, heat
exchangers 22 and 23 are used to moderate the temperature of
DETAILED DESCRIPTION OF THE PREFERRED the exit flows of the second reactor 2 and the third reactor 3,
EMBODIMENTS respectively. An extra heat exchanger 24 is mounted between
0028. The invention will be readily understood from the the fourth reactor 4 and the gas-liquid separator 5, to cool the
Figures. Referring to FIG. 1, synthesis gas enters the process outlet from the fourth reactor 4. The output from gas-liquid
through conduit 19 at low pressure, and preferably is com separator 5 is further divided into two parts: (1) the unreacted
pressed by compressor 7 to 20 to 100 atmospheres, preferably gas stream which will be fed into a control valve 40 to further
50 atmospheres, and is passed to the first reactor 1 via con separate into the recycled and the bleeding gas; and (2) the
duits 17 and 18. The first reactor 1 (R-1) converts synthesis condensed liquid stream which can be fed into a fuel-water
gas to principally methanol and some water. The product separator. Due to the difference in density between water and
from the first reactor 1, a vapor mixture of essentially metha synfuel, the water accumulates at the bottom of the separator
nol, water and unreacted synthesis gas, flows through conduit and can be drained out periodically.
10 to a second reactor 2 (R-2). The second reactor 2 converts 0031 FIG. 3 is a schematic of a further embodiment of the
a portion of the methanol to dimethylether. The product from present process wherein the synthesis gas feed is introduced
second reactor 2, which essentially contains methanol, dim into the loop ahead of the third reactor 3 (R-3). Synthesis gas
ethylether, water and unreacted synthesis gas, flows via con enters the process through conduit 19 at low pressure and is
duit 11 to a third reactor 3 (R-3). The third reactor 3 converts compressed by a compressor 7 to match the pressure of the
methanol and dimethylether to fuel product (gasoline, jet fuel flow passing out of the second reactor 2 (R-2) in conduit 11.
and/or diesel) and heavy gasoline. The product from the third The compressed synthesis gas in conduit 17 is mixed into the
reactor 3 contains essentially fuel product (C4-C8 hydrocar flow in conduit 11 to produce the flow in conduit 9 which is
bons, toluene, and Xylene), heavy gasoline (>C8 aromatics) led into R-3. The flow in conduit 11 is the product from the
and water, with minor amounts of unreacted methanol and second reactor 2 (R-2), which contains essentially methanol,
dimethylether and unreacted synthesis gas. This product dimethylether, water, and unreacted synthesis gas. R-3 con
flows via conduit 12 to a fourth reactor 4 (R-4) to convert the verts the synthesis gas and olefins and other hydrocarbon
heavy gasoline to fuel product. The product from the fourth contaminants in the synthesis gas feed passing in conduit 9 to
reactor 4 contains essentially fuel product with low heavy a product which is essentially fuel product (principally C4-C8
gasoline content, water, minor amounts of unreacted metha hydrocarbons, toluene, and Xylene), heavy gasoline (2C8
nol and dimethylether and unreacted synthesis gas, which aromatics) and water, with minor amounts of unreacted
pass via conduit 13 to a separator 5. The separator 5 separates methanol and dimethylether and unreacted synthesis gas. The
the flow 13 into three streams: (a) conduit 22 carries out R-3 effluent passes through conduit 12 to the fourth reactor 4
essentially water with Some impurities for cleaning and reuse (R-4) which converts the heavy gasoline to fuel product. The
to make steam for the synthesis gas generating step not shown effluent from R-4, which is essentially fuel product with low
in the diagram; (b) conduit 20 carries out essentially fuel durene content, water, minor amounts of unreacted methanol
product that can be commercially marketed after addition of and dimethylether and unreacted synthesis gas, passes via
proper additives as required by commerce; and (c) conduit 14 conduit 13 to the separator 5. The separator 5 separates the
carrying essentially light gases (including light paraffins flow 13 into three streams: (a) conduit 22 carries essentially
below C4) and unreacted synthesis gas. The flow in conduit water with some impurities for reuse. Such as to make steam
14 is split into two streams: (a) flow through conduit 21 for the synthesis gas generating step not shown in the dia
directed to further processing to recover LPG and excess gas gram; (b) conduit 20 carries essentially a fuel product which
for use as fuel for process heating needs; and (b) flow through can be sold on the market after proper additives are added as
conduit 15 is directed to a recycle compressor 6. The recycle required by commerce; and (c) conduit 14 carries essentially
compressor steps up the pressure of the recycle gas from light gases and unreacted synthesis gas. The flow in conduit
losses through flow from conduit 18 to conduit 15 to match 14 is split into two streams with (a) flow through conduit 21
the inlet pressure of R-1 so that it can be mixed with the directed to further processing to recover LPG and excess gas
synthesis gas feed stream from conduit 17. The flow in con for use as fuel for process heating needs; and (b) flow through
duits 15 and 16 is the greaterpart of the flow from conduit 14, conduit 15 directed to a recycle compressor 6. The recycle
being about 5 to 20 times larger than the flow in conduit 17, compressor steps up the pressure of the recycle gas from
preferably 9 times larger. losses through flow from conduit 16 to conduit 15 to match
0029 Reactors 1 through 4 are preferably fixed bed reac the inlet pressure of R-3. The flow in conduits 15 and 16 is the
tors containing catalysts for effecting the desired reaction in greater part of the flow from conduit 14, being about 5 to 20
each of the reactors. Due to the exothermicity of the reactions times larger than the flow in conduit 17, preferably 9 times or
occurring in each stage, the reactors stages maybe sectioned larger.
with intermediate heat transfer to remove excess heat or the 0032. In FIG. 3, the feed synthesis gas is introduced and
temperatures may be controlled via “cold-shot' side streams mixed into the recycle loop in the line between R2 and R3
US 2012/011 6 137 A1 May 10, 2012

instead of in the line to RI, as shown in FIG.1. The principal 0035. A micro syringe with a fixed volume of 1 Jul was used
advantage of this alternative over introducing the feed syn to inject the liquid fuel into the GC-MS system (HP7890).
thesis into R-1 is obtained in the case in which the synthesis The reproducibility of the Syringe is reasonably accurate and
gas contains alkane and/or olefin hydrocarbons molecules the Volume fluctuation cannot exceed an uncertainty of more
with two or more carbon atoms and/or larger cyclic and aro than 10%. Therefore, if a significant variation is observed for
matic molecules. Although some olefin species may be in a specific species in the mass count from the GC-MS signal,
trace amounts, the catalysts residing in R-3 and R-4 convert the sampling fluctuation caused by the Syringe sampling can
the olefins directly into fuel product thus increasing the yield, not account for Such signal change. The signal variation must
prior to the reactions in R-1 and R-2. An additional advantage then come from compositional differences between the
is that if this type offeed were to be fed into R-1, it would have samples. Thus traces and quantitative mass counts or abun
to be first purified by a process. Such as for example, extrac dance of quadrupole detection can be used to compare pro
cess performance.
tion or steam reforming, to render the feed devoid of potential 0036 Being that the pilot plant was once-through and
catalyst poisons for the R1 catalyst, Such as olefins and aro contained no recycle, the synthesis gas flow was set to repre
matic molecules. In effect, in this rendition of the invention, sent the recycle case by restricting the conversion in R-1 to
third and fourth reactors 3 and 4 (R3 and R4) act as purifiers that calculated for a recycle case. Thus, for a once-through
of the fresh feed synthesis gas for R-1, as it receives synthesis case of 10% conversion of synthesis gas to methanol in R-1,
gas via the recycle loop. the once-through system would be simulating a 10:1 recycle
0033. Without further description, it is believed that one of rate for 100% conversion.
ordinary skill in the art can, using the preceding description EXAMPLE 1.
and the following illustrative examples, make and utilize the
compounds of the present invention and practice the claimed 0037. In this example, R-1, R-2 and R-3 were used in-line
methods. The following examples are given to illustrate the with R-4 off-line to provide a base case for comparison to the
present invention. It should be understood that the invention is beneficial effect of R-4 hydrotreating. R-1 contained 400g of
not to be limited to the specific conditions or details described copper/zinc oxide/alumina (Katalco 51-9) catalyst, R-2 con
in the examples. tained 200g of gamma-alumina (SAS250) and R-3 contained
200 g of the Zeolite ZSM-5. The synthesis gas was composed
Reactor Configuration and Methods Used for the Examples of the following flows: 6130 scm H.2200 scm CO, and 500
scm. Ar. Temperatures were as follows: R-1, 280° C.; R-2,
0034. The invention can be best described by giving 385°C.; and R-3, 410° C. The pressure was 50 atmospheres
examples from laboratory tests of the concept. A once at the outlet with minor pressure drop through the reactors.
through pilot plant utilizing three “Berty-design' (Berty) Liquid was collected in the separator at the rate of 6-7 g/h
internally recycled autoclave reactors were used in series for hydrocarbon together with by-product water. The hydrocar
R-1 (the first reactor), R-2 (the second reactor), and R-3 (the bon was analyzed by IR and GC-MS. The IR was used to
third reactor) followed by an upflow 1.5"x12" long fixed bed confirm the identity of the components in the sample. The
GC-MS results are shown in FIG. 4.
reactor for R-4 (the fourth reactor). Each of these reactors EXAMPLE 2
simulates a reaction stage and it is clear to those familiar with
the art that this process concept extends to the use offixedbed 0038. In this example, R-1, R-2, R-3 line up, flows, tem
reactors instead of one or more of the internally recycled peratures and pressure were the same as in Example 1 and R-4
reactors. The catalysts in the Berty reactors were loaded into was added containing 50 g of catalyst-A (Criterion KL6515,
a catalyst basket and the temperature of the bed was measured a 60% Ni on alumina catalyst) held at 130° C. Liquid was
by a thermocouple inserted into the catalyst in each basket. collected in the separator at the rate of 7.04 g/h hydrocarbon
The catalyst in R-4 was loaded in two layers separated by a and by-product water. The hydrocarbon was analyzed by IR
metal screen Support and alumina beads. The temperature and GC-MS. The GC-MS results in FIG. 5(a) show that the
was measured between the two beds. A by-pass system durene content was significantly reduced compared to
around R-4 permitted introducing or removing R-4 from the Example 1, which did not utilize R-4.
flow from R-3 to the product separator to demonstrate the EXAMPLE 3
beneficial effects of the fourth reaction stage. The tubing 0039. In this example the reactor line-up and pressure
connections between reactors were heated with heating tape were the same as in Example 2, however, the catalyst in R-4
to prevent condensation of liquid intermediate and final prod was 50 g of catalyst-B (Alfa Aesar 45579, a cobalt molybdate
ucts. The synthesis gas feed was Supplied to R-1 as a mixture on alumina) held at 140° C. Liquid was collected in the
of CO. H. and an Artracer Supplied in pressurized cylinders, separator at the rate of 7.24 g/h hydrocarbon and by-product
metered using mass flow meters to give the desired compo water. The hydrocarbon was analyzed by IR and GC-MS. The
sition. The pressure of the system was held constant by a GC-MS results in FIG. 5(b) show that the durene content was
backpressure regulator. The depressured gas was cooled by a significantly reduced compared to Example 1, which did not
water cooled condenser and a Jorgensen glass tube was used utilize R-4.
as a separator to separate the product liquid hydrocarbon, EXAMPLE 4
water and the synthesis gas containing light hydrocarbon 0040. In this example, the GC-MS traces from Example 1
gases not collected in the separator. The collected hydrocar and Example 3 are Superimposed for comparison and shown
bon liquid was analyzed by IR and GC-MS and the total hot in FIG. 6 and quantified in Table 1. Table 1 lists the data of
gases after each reactor were sampled and analyzed using a integrated area of all major bands for the liquid fuel Samples
GC-MS. Material balance was achieved by using the Artracer with and without R-4. The catalyst used in R-4 is either cat-A
and a massflow meter. The density of the collected liquid (CRI-Critetrion KL6515) or cat-B (Alfa Aesar 45579). The
hydrocarbon was measured. The temperature inside each retention times of individual band (in minutes) and the per
reactor was controlled via outer heater elements to tempera centage changes derived from differences in band areas are
tures set and measured in the inside of the catalyst beds. also listed in Table 1 for comparison.
US 2012/011 6 137 A1 May 10, 2012

TABLE 1.
Retention time Band area of the base Band area of the fuel using R4 with Band area of the fuel using R4 with
Species (minutes) fuel without R4 (x1002) ) (2)(2)(x10(2)) (% change from base) CRI (x10(2)) (% change from base)
i-C4 5.64 9.66 32.21 (+23.3%) 26.40 (+1.73%)
C4 6.28 7.04 23.91 (+239%) 19.86 (+182%)
i-CS 8.91 107.04 264.96 (+147%) 201.05 (+87.8%)
C5 9.25 21.88 60.77 (+1.78%) 45.12 (+106.2%)
i-C6 10.83 - 10.91 261.82 561.69 (+11.4%) 408.61 (+56.1%)
C6 11.15 19.95 53.81 (+170%) 39.54 (+98.2%)
Dimethyl- 12.16 19.74 41.54 (+11.0%) 21.67 (+9.8%)
cyclo-C5
i-C7 12.41 101.96 232.91 (+128%) 165.83 (+62.6%)
C7 12.63 1949 14.78 (-24%) 13.12 (-32.7%)
Dimethyl- 13.53 48.13 89.48 (+86%) (2) 0.52 (+46.5%)
cyclo-C6
Toluene 15.22 60.68 48.62 (-19.8%) 53.39 (–12%)
Xylene 18.1 - 18.9 270.5 245.50 (-9.2%) 256.63 (-5.1%)
TMB 23.3 +24.1 + 763.55 646.47 (-15.4%) 660.11 (-13.5%)
25.8
Durene 36-40 2238.70 1551.3 (-30.7%) 1456.48 (-34.9%)
(2) indicates text missing or illegible when filed

0041. It is interesting to note that all but the n-C, aliphatic 0043. The beneficial effect of the hydrotreatment is evi
portions, including C, Cs, C and i-C7, significantly dent in that all desirable fuel components increased at the
increased for the fuels after R-4 hydrotreatment. All changes expense of significant decreases of the undesirable trimeth
are significant, much more than 100% of the original values. ylbenzenes and durene.
Also, dimethylcyclopentane, dimethylcyclohexane, and
other alkyl-substituted cyclic components increased. On the
other hand, the areas under the curve for tri- and tetra-meth
ylbenzene as well as toluene and xylenes are lowerfor the R-4 EXAMPLE 5
product, Suggesting conversion from heavy aromatics to par
affins, naphthenes and less Substituted aromatics.
0042. We can simplify the data by grouping them with 0044) Further test were carried out at various R-4 tempera
similar molecular size. For example, i-C and C can be tures and we found Surprisingly that an optimum tempera
grouped as C. total. The grouped data are listed in Table 2. As tures for R-4 exist to produce the highest rate of hydrocar
we group the data following molecular sizes, the increase bons. These results are shown in Table 3. It is clear that
using cat-A is 23.6% for C, 152% for Cs, 118% for C and Catalyst-Bexhibits a maximum fuel production rate at about
103% for C, with larger increases for the smaller molecules, 140°C., whereas Catalyst-A would appear to have an optimal
but on the basis of smaller amounts in the feed to R-4. The
increase of cyclic components is relatively lower. For temperature of about 130°C. The measurements suggest that
example, the increase for dimethylcyclohexane is 86% for the beneficial reactions that reduce the trimethyl- and tetram
cat-A and 46.5% for cat-B. All the substituted aromatics ethybenzene including durene require a certain minimum
decreased across R-4 and most significantly because of their temperature but as the temperature is further increased crack
larger amount, trimethylbenzene and durene. ing reactions reduce the fuel yield.
TABLE 2

Band area of the base fuel Band area of the fuel using R4 with Band area of the fuel using R4 with
Species without R4(x10(2)) (2)(2)(x100) ) (% change from base) CRI (x10(2)) (% change from base)
C4O2) 16.7 56.12 (+23.6%) 46.26 (+177%)
C5(2) 128.92 325.73 (+152%) 246.17 (+90.9%)
C6(2) 281.77 651.5 (+11.8%) 448.15 (+59%)
Dimethyl-cyclo-C5 19.74 41.54 (+11.0%) 21.67 (+9.8%)
C7(2) 121.45 247.69 (+1.03%) 178.95 (+47.3%)
Dimethyl-cyclo-C6 48.13 89.48 (+86%) 70.52 (+46.5%)
Toluene 60.68 48.62 (-19.5%) 53.39 (–12%)
Xylene 270.5 245.50 (-9.2%) 256.63 (-5.1%)
TMB 763.55 646.47 (-15.4%) 660.11 (-13.5%)
Durene 2238.70 1551.3 (-30.7%) 1456.48 (-34.9%)

(2) indicates text missing or illegible when filed

US 2012/011 6 137 A1 May 10, 2012

d) passing the third exit stream through a fourth reactor to

TABLE 3 convert the heavy gasoline to isoparaffins, naphthenes,
R-4Temperature, Liquid Fuel
and less Substituted aromatics, which produces a fourth
Catalyst o C. Collected, gh exit stream; and
e) recycling the unreacted synthesis gas in the fourth exit
Catalyst-A 130 7.04 stream to the first reactor;
170 6.11
190 5.39 wherein no removal or separation of the first, second or third
220 5.15 exit streams are effected during the process.
Catalyst-B 120 6.03
140 7.24
2. The process of claim 1, wherein the first, second, third,
160 5.83 and fourth reactors operate at about 50-100 atmospheres.
18O 4.83 3. The process of claim 1, wherein the fuel contains essen
tially C4-C8 hydrocabons, toluene, and xylene.
4. The process of claim 1, wherein the heavy gasoline
EXAMPLE 6 contains 2C8 aromatics.
5. The process of claim 1, the first reactor operates at about
0045. The product from R-4 has significantly improved in 190 to 300° C.
viscometric properties over that obtained from R-3. The 6. The process of claim 1, wherein the second reactor
freezing point of the fuel was decreased and the viscosity was operates at about 300 to 450° C.
decreased. The fuel color is also changed from yellow to 7. The process of claim 1, wherein the third reactor oper
colorless. However the density of the fuel was not signifi ates at about 300 to 500° C.
cantly changed indicating that the aromatic content was not
changed significantly. The fuel density at room temperature 8. The process of claim 1, wherein the fourth reactor oper
ates at about 100 to 220° C.
from R-3 was 0.83 g/ml and from R-4, 0.82 g/ml.
9. The process of claim 1, wherein the first reactor contains
EXAMPLE 7 CuO/ZnO/Al2O catalysts.
10. The process of claim 1, wherein the second reactor
0046. This example compares the fuel product rate with contains gamma-alumina catalysts.
and without R-4 as given in Examples I, without R-4 and 11. The process of claim 1, wherein the third reactor con
Example 5 with R-4. Table 4 below shows the comparison: tains ZSM-5 catalysts.
12. The process of claim 1, wherein the fourth reactor
TABLE 4 contains Group IX or X metal oxide catalyst on alumina
R-4Temperature, reduced in the presence of hydrogen and carbon monoxide
o C. Fuel Rate, gh and in the absence of sulfur.
Without R-4 S-6
13. The process of claim 12, wherein the Group IX or X
With R-4 Catalyst-A 130 7.0 metal oxide is nickel oxide.
With R-4 Catalyst-B 140 7.2 14. The process of claim 1, wherein the fourth reactor
contains Group IX or X metal oxide catalyst combined with a
The comparison shows that, by producing a more advanta Group VI metal oxide catalyst on alumina reduced in the
geous mix of hydrocarbons, R-4 enhanced the recovery of presence of hydrogen and carbon monoxide and in the
absence of sulfur.
fuel.
0047 Although certain presently preferred embodiments 15. The process of claim 14, wherein the Group IX or X
of the invention have been specifically described herein, it metal oxide is cobalt oxide and the Group VI metal is molyb
will be apparent to those skilled in the art to which the inven denum oxide forming cobalt molybdate.
tion pertains that variations and modifications of the various 16. The process of claim 1, wherein prior to step e), the
embodiments shown and described herein may be made with fourth exit stream is separated into a first stream containing
out departing from the spirit and scope of the invention. water, a second stream containing unreacted synthesis gas,
Accordingly, it is intended that the invention be limited only and a third stream containing fuel.
to the extent required by the appended claims and the appli 17. The process of claim 1, wherein the first, second, and
cable rules of law. third exit streams are heated or cooled prior to being passed
through the second, third, and fourth reactors, respectively.
What is claimed is: 18. The process of claim 1, wherein the heavy gasoline
1. A process for making fuel from Synthesis gas comprising contains trimethylbenzene, tetramethylbenzene, and durene.
the steps of 19. The process of claim 1, wherein the less substituted
a) passing the synthesis gas through a first reactor to con aromatics are toluene and Xylene.
Vert synthesis gas to methanol and water, which pro 20. The process of claim 1, wherein the freezing point of
duces a first exit stream; the third exit stream is about 30 to about 50° C.
b) passing the first exit stream through a second reactor to 21. The process of claim 1, wherein the freezing point of
convert methanol to dimethylether, which produce a the fuel is less than about -5°C.
second exit stream; 22. The process of claim 1, wherein the yield is greater than
c) passing the second exit stream through a third reactor to about 25% by weight based on the synthesis gas.
convert methanol and dimethylether to fuel and heavy 23. The process of claim 1, wherein the synthesis gas is
gasoline, which produces a third exit stream; initially passed directly into the third reactor.
US 2012/011 6 137 A1 May 10, 2012

24. The process of claim 23, wherein the synthesis gas 26. The system of claim 25, wherein the first catalyst is
contains alkane and/or olefin hydrocarbons molecules with CuO/ZnO/Al2O.
two or more carbon atoms and/or larger cyclic and aromatic 27. The system of claim 25, wherein the second catalyst is
molecules. gamma-alumina.
25. A system for making fuel product comprising 28. The system of claim 25, wherein the third catalyst is
ZSM-5.
a. a first reactor containing a first catalyst for converting
synthesis gas to methanol and water; 29. The system of claim 25, wherein the fourth catalyst is
b. a second reactor containing a second catalyst for con Group IX or X metal oxide catalyst on alumina reduced in the
verting methanol to dimethylether; presence of hydrogen and carbon monoxide and in the
absence of sulfur.
c. a third reactor to containing a third catalyst for convert 30. The system of claim 29, wherein the Group IX or X
ing methanol and dimethylether to fuel and heavy gaso metal oxide is nickel oxide.
line; 31. The system of claim 25, wherein the fourth reactor
d. a fourth reactor containing a fourth catalyst for convert contains Group IX or X metal oxide catalyst combined with a
ing the heavy gasoline to isoparaffins, naphthenes, and Group VI metal oxide catalyst on alumina reduced in the
less Substituted aromatics; presence of hydrogen and carbon monoxide and in the
e. a separator for separating a product exiting the fourth absence of sulfur.
reactor into a first stream containing fuel product, a 32. The system of claim 31, wherein the Group IX or X
second stream containing water, and a third stream con metal oxide is cobalt oxide and the Group VI metal is molyb
taining unreacted synthesis gas; and denum oxide forming cobalt molybdate.
f, a recycle stream to recycle a portion of the third stream to c c c c c
the first reactor.