LPDME Overview

Progress in Petrochemical Science
CRIMSON PUBLISHERS
C Wings to the Research
ISSN 2637-8035 Review Article
The Direct Dimethyl Ether (DME) Synthesis

Process from Syngas: Current Status and Future
prospects I. Process Feasibility and Chemical
Synergy in LPDMEtm Process
Makarand R Gogate*
Jawaharlal Nehru College of Engineering, India
*Corresponding author: Makarand R Gogate, Jawaharlal Nehru College of Engineering, 259 Samarthnagar, Opp SBI Branch, Aurangabad, India, Tel:
+1-573-529-3214; Email:
Submission: May 11, 2018; Published: August 06, 2018
Abstract
A novel one-step process for co-production of dimethyl ether (DME) and methanol, in the liquid phase was first conceived by the UA researchers,
as an advance over the liquid phase methanol synthesis process (LPMeOHtm). The one-step, direct DME process (LPDMEtm) is based on the application
of “dual catalysis”, where 2 functionally different yet compatible catalysts are used as a physical mixture, well-dispersed in the inert liquid phase. Three
different reactions, methanol synthesis (via CO and CO2), water-gas shift, and methanol dehydration (to form DME) take place over the 2 catalysts,
Cu/ZnO/Al2O3 and typically γ-Al2O3. The favorable thermodynamic and kinetic coupling of methanol dehydration reaction (very rapid and at/near
thermodynamic equilibrium) with the methanol synthesis reaction (slower kinetics and highly thermodynamic) leads the beneficial “chemical synergy”.
This synergy helps to overcome the limitation on thermodynamic equilibrium conversion, and increases the per-pass syngas conversionand reactor
productivity. The catalyst deactivation phenomena in LPDMEtm processes also greatly alleviated compared to methanol alone; the increase in syngas
conversion and methyl equivalent productivity (MEP) are sustained over a longer on-stream time.
Here, we review the salient developments in the LPDMEtm process since its inception, first at UA research laboratories and elsewhere including Air
Products and Chemicals, Inc. First, we demonstrate the rationale of the LPDMEtm process, and outline briefly the research studies in the two processes,
that illustrate the chemical synergy in the LPDMEtm process. This successful example of “cooperative catalysis” can be adapted in principle to many other
organic reactions. We then briefly discern the intrinsic kinetics of the LPMeOHtm and LPDMEtm systems, and also shed light of the catalyst deactivation
phenomena in these processes. In closing, we outline the reactor design/scale-up and plant operational experience of the 3 commercial technologies, as
currently practiced by JFE holdings, BP-AMOCO, and Halder-Topsoe.
Keywords: Natural gas; Steam reforming; Coal; Syngas; Methanol; DME, Bi-functional catalysts; Cu/ZnO/Al2O3; γ-Al2O3, Slurry reactors; Bubble column
reactors; Chemical synergy; Methyl equivalent productivity (MEP); Intrinsic kinetics; Phase equilibrium; Chemical reaction equilibrium; Catalyst
deactivation
Introduction
Figure 1: Commercial technologies that are currently available for conversion of syngas conversion to value-added chemicals.
The direct DME process is the one covered in this report.
Volume - 2 Issue - 4
Copyright © All rights are reserved by Makarand R Gogate. 1/9
Progress Petrochem Sci Copyright © Makarand R Gogate
Coal and natural gas as fossil fuels continue to be at the nation’s these solvents include a high solubility for syngas components,
forefront of energy conversion and power generation processes. H2, CO, CO2, and CH4, and a very minimal interaction between the
In the United States, abundant and plentiful supply of natural gas solvent and catalyst.Some of the key advantages of the LPMeOHtm
coupled with its very low costs (~$2MM/BTU and projected to process include better heat transfer characteristics and isothermal
even descend further) has made it an ideal feedstock for conversion operation, use of the CO-rich syngas (from low-cost coal sources),
to syngas (a mixture of CO and H2, via the highly endotherm steam and a very high chemical selectivity to methanol. In the United
reforming or auto-thermal steam reforming). Syngas is a very States, the process feasibility and development studies on the new
versatile carbon source that is the primary feedstock for further LPMeOHtm process were initially undertaken by Universities of
conversion to value-added chemicals (Figure 1). The recent Akron and Pittsburgh, and Air Products and Chemicals, Inc. (APCI),
emphasis on biomass (now primarily lignocellulosic woody sponsored by Electric Power Research Institute (based in Palo Alto,
feedstocks), considered to be a “renewable” and “sustainable” Calif.) and Dept. of Energy (a United States Federal agency, with
energy source, has made also this an appealing source of our energy headquarters in Washington, D.C). The UA researchers, since 1985,
needs. carried out process development studies in various fundamental
and applied aspects, i.e., demonstration of process feasibility,
Syngas generation is the first key step in further conversion
intrinsic kinetics, process chemistry, thermodynamic analysis and
to methanol and dimethyl ether (DME). The stoichiometric
development of a software package for combined phase and chemical
composition of the syngas is a strong function of the type of C
reaction equilibria for this multiphase and multicomponent system
source; coal (lignite, peat, or bituminous/subbituminous), natural
(which enables one to compute the concentrations of dissolved
gas, or biomass, and gasifier type. The low rank carbon sources
syngas components in the liquid solvent phase, at given reaction
such as coal (with low H/C ratios) result in a CO-rich syngas (H2/
conditions), external mass transfer analysis, thermal stability, and
CO <1), while the high CV fuels such as natural gas (with high H/C
scale-up [4-8]. The UA researchers’ also first conceived the direct
ratios) lead to stoichiometric or balanced syngas, or, a composition
one-step DME synthesis process, termed as LPDMEtm process [9-12]
which reflects the stoichiometry of methanol synthesis reaction via
and later, the DME-to-olefins and DME-to-hydrocarbons processes
CO hydrogenation (which requires 2 moles of H2 per mole of CO).
[13-16], both enhancements over Mobil Oil’s original methanol-
The syngas compositions also contain small proportions of CO2
to-gasoline and methanol-to-olefins process [17-20]. The APCI
(from total combustion of C) and CH4 (both typically <5%). The
component has been more focused on catalyst deactivation studies
controlling mechanism of methanol synthesis reaction and vapor
and feasibility/demonstration studies on the pilot scale (5 TPD
or liquid phase mode of operation governs the choice of feedstock
& 10 TPD scale), of the LPMeOHtm and LPDMEtm processes, at its
and the H2/CO ratio.
Alternative Fuels Development Unit (AFDU) in LaPorte, Texas [21-
The introduction of a liquid phase process, in 1975, termed as 24]. Later, in 1996 Eastman Chemical Company (based in Kingsport,
“liquid phase methanol synthesis process (LPMeOHtm) by Chem Tennessee) assumed a major role in the process development
Systems, Inc., has been seen as trendsetting in syngas conversion and pilot scale/commercial scale operation (in partnership with
processes [1-3]. In the LPMeOHtm process, a finely powdered APCI), and formed a separate corporate entity, the Air Products
methanol catalyst (of the order of 100µm or less) is dispersed Liquid Phase Conversion Company, L.P. – with support from U.S.
or slurried in high-boiling hydrocarbon solvent inert oil). Apart Department of Energy [25,26].
from the high boiling point, other key desirous characteristics of
Figure 2: A schematic diagram of the LPMeOHtm process in operation at Eastman’s Coal-to-Chemicals complex at Kingsport,
Tennessee.
How to cite this article: Makarand R G. The Direct Dimethyl Ether (DME) Synthesis Process from Syngas: Current Status and Future prospects I. Process
2/9
Feasibility and Chemical Synergy in LPDMEtm Process. Progress Petrochem Sci .2(4). PPS.000542.2018. DOI: 10.31031/PPS.2018.02.000542
Figure 3: A schematic of the commercial bubble column slurry reactor (LPMeOHtm reactor) design.
The LPMeOHtm Demonstration Project at the Kingsport site is a phase reactor system. The 2 functionally different yet compatible
$213.7 million cooperative agreement between the U.S. Department catalysts catalyze three parallel reactions: Methanol synthesis
of Energy (DOE) and Air Products Liquid Phase Conversion (from hydrogenation of CO/CO2), water gas shift, and methanol
Company, L.P, a partnership between APCI and Eastman Chemical dehydration to produce DME. The process is based on application of
Company. The commercial scale reactor systems at Eastman’s dual catalysis in a single reactor stage, and based on a combination
coal-to-chemicals complex, in Kingsport, Tennessee, are based of an equilibrium-limited reaction (methanol synthesis) and an
on the bubble column slurry reactor (BCSR) designsand are one equilibrium unlimited reaction (methanol dehydration). The
of the largest; the reactor main is 7.5ft (or, 2.286m) in diameter process chemistry is represented by the following 3 equations:
and 70ft (21.34m) tall, the design capacity is 260 short tons/day,
CO2 + 3H2=CH3OH + H2O…… (1)
at nominal conditions of 1000psig (or, 70atm) and 60 oF (or, 315
ᵒC). It is interesting to note that this represents a very significant CO + H2O= CO2 + H2……… (2)
scale-up from APCI’s prior experience at the AFDU (in LaPorte,
2 CH3OH = CH3OCH3 + H2O…… (3)
TX), where the nominal diameters were 1.5-2ft (0.457-0.609m).
The LPMeOHtm technology, in operation at the Eastman’s coal-to- The first two reactions take place over the co-precipitated
chemicals complex, is illustrated in Figure 2. The basic reactor Cu/ZnO/Al2O3 catalyst and the third one takes place over γ-Al2O3
design of the commercial bubble column slurry reactor is given catalyst. The selective chemical removal of product methanol, from
in Figure 3. The new corporate entity, Air Products Liquid Phase Reaction (1), via its dehydration, via Reaction (3), overcomes the
Conversion Company, L.P., formed for this purpose (to demonstrate chemical equilibrium barrier on methanol synthesis alone, and
LPMeOHtm/LPDMEtm process on commercial scale) has successfully improves the per-pass syngas conversion and reactor productivity.
carried out demonstration runsof these processes at this complex.
The process chemistry and dynamics of the LPDMEtm process,
Discussion i.e., synthesis of methanol and DME from CO/CO2/H2 mixtures,
is very interesting and can be complicated at times.The chemical
From LPMEOHTMto LPDMETM – the direct DME synthesis
synergy in this process was first noted by researchers at Mobil Oil
process
Company [27] and given as comparisons in a series of curve-pairs
Since its discovery in 1975, the LPMeOHtm and LPDMEtm that relate the overall conversion of syngas (plotted as ordinate) to
processes have been illustrative examples of how a mature the proportion of H2 in the feed syngas (plotted as abscissa), each
technology on a commercial scale (ICI low temperature methanol at a specific T and P conditions. In these comparisons, the lower
synthesis process) can be successfully adapted to a liquid phase curve represents a methanol synthesis process over a standard Cu/
operation. The LPMeOHtm process is a highly flexible process that is ZnO/Al2O3 catalyst, with a nominal molar ratio of 60%:25%:15%.
well-suited to process low-value CO-rich syngas feeds, uses milder The upper curves represent the operation under a DME+ MeOH
reactor design conditions (of temperature and pressure), and a co-production mode with an identical Cu/ZnO/Al2O3 catalyst for
simpler one from a process engineering standpoint. The direct, one- methanol synthesis, but which also has a methanol dehydration
step DME synthesis process is based on the concept and application component, γ-alumina, incorporated therein (10% by weight). The
of so-called “dual catalysis” where 2 functionally different catalysts illustrative comparison is given in Figure 4a-4d. It is clear that the
in a physically admixed form are finely dispersed in a slurry three reactions in the LPDMEtm process chemistry give rise to a
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very interesting interplay, based on a dual thermodynamic–kinetic As stated above, this interplay and thermodynamic-kinetic coupling
coupling, which results in higher syngas conversion and per-pass is often referred to as “chemical synergy”.
volumetric reactor productivity, than in the LPMeOHtm mode alone.
Figure 4(a): Overall syngas conversion as a function of % H2 in the feed syngas, as a comparison for DME+MEOH operation and
MeOH alone (T=260 0C, P=50 atm) (Adapted from Zahner (1977).
Figure 4(b): Overall syngas conversion as a function of % H2 in the feed syngas, as a comparison for DME+MEOH operation and
MeOH alone (T=290 0C, P=50atm).
Figure 4(c): Overall syngas conversion as a function of % H2 in the feed syngas, as a comparison for DME+MEOH operation and
MeOH alone (T=260 0C, P=20atm).
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Figure 4(d): Overall syngas conversion as a function of % H2 in the feed syngas, as a comparison for DME+MEOH operation and
MeOH alone (T=260 0C, P = 20 atm, 10vol% H2O vapor in syngas.
The chemical synergy in LPDMEtm process CO: CO2: CH4 = 37.4:46.3:8.6:7.7 was used for all experiments. This
composition is typical of syngas from Koppers-Totzek or Texaco
As noted above, the chemical synergy in the direct, one-step
gasifiers, corresponding to CO-rich syngas, with a H2:CO ratio of
DME process was perhaps first noted by the researchers’ at Mobil
0.8. The nominal feed flowrate was 1 SLPM which corresponded to
Oil Corporation [27]. The researchers’ at University of Akron and
2.678mol/h.
Air Products and Chemicals, Inc., were pioneering in the LPDMEtm
studies, including process chemistry, process feasibility, roles of The chemical synergy in the LPDMEtm process system was
CO/CO2/H2, thermodynamic analysis, and intrinsic kinetics of illustrated with 3 different catalyst slurry ratios, as follows:
LPMeOHtm and LPDMEtm systems. We now consider the research
A. 15g Cu/ZnO/Al2O3 catalyst (labeled as EPJ-19, UCI/BASF)
portfolios of the University of Akron and Air Products, Inc.
+ 0.5g γ-Al2O3 catalyst (overall slurry ratio = 4.5%)
Experimental studies at university of Akron
B. 80g Cu/ZnO/Al2O3 catalyst + 5g γ-Al2O3 catalyst (overall
We first highlight the author’s own experimental studies on slurry ratio =20%)
the LPDMEtm process, carried out during his doctoral studies at
University of Akron. We will next discuss the APCI work on process C. 150g Cu/ZnO/Al2O3catalyst + 10g γ-Al2O3 catalyst (overall
feasibility and chemical synergy. It is clear from the foregoing slurry ratio =33%)
discussion that the forward water-gas shift, in which all primary The starting volume of the catalyst slurry was 550mL Witco-40
reactants, CO, CO2, H2O, and H2, participate, plays a very crucial role mineral oil (under ambient conditions). The density of Witco-40 oil
in the overall chemistry. is a strong function of T and compared to a R.T. value 0.773 g/cm3,
At the UA research component, the experiments were carried its value at 250 oC is only 0.613g/cm3. It is interesting to note that
out in a 1-liter stirred autoclave fitted with a 6-blade turbine these slurry ratios cover the entire range of practical conditions of
impeller, within a high-temperature, high-pressure slurry reactor interest, from gas-to-liquid mass transfer free to gas-to-liquid mass
system. The nominal temperature and pressure conditions were transfer limited regions. Of course, the chemical synergy and the
250 oC and 70atm. A feed syngas with nominal composition of H2: % increase in MEP productivity is expected to be higher for higher
slurry ratios.
Table 1: The chemical synergy in the LPDMEtm process as function of catalyst slurry ratio (at nominal reactor conditions
of T=250 0C, P=70atm, syngas flow=2.678mol/h, impeller speed=1500rpm, 1liter stirred autoclave).
LPMeOHtm Process LPDMEtm Process

Catalyst Syngas con- (CH3-) (CH3-) equivalent
Slurry Syngas conversionc
Syngas versionc (%, equivalent Syngas productivity, MEP
ratio %) H2(%) CO(%) H2(%) CO(%) (%, at chemical
(%) at chemical productivity, (%) (mol/h), (Increase
equilibria)
equilibria) MEP (mol/h) in MEP, %)
4.5 55.6 21.4 36.9 37.5 0.266 61.4 29.2 43.3 85 0.281 (5.48)
20 68.1 28.6 45.3 37.5 0.321 84.8 58.5 70.1 85 0.401 (24.8)
33 72.4 29.9 48.4 37.5 0.342 87.6 62.4 73.4 85 0.534 (56.1)
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The experimental data for the LPMeOHt and LPDMEtm process produce bulk chemicals/fuels/fuel additives from synthesis gas
systems is given in Table 1. At the outset, it is very interesting to (syngas) generated from coal and natural gas. In APCI research
note that the chemical synergy “exists” in LPMeOHtm system, even studies, all kinetic experiments on one-step syngas to DME process
alone. For the three catalyst slurry ratios, 4.5%, 20%, and 33%, (LPDMEtm) were carried out in 300cm3 stirred autoclave reactor
the syngas conversion is at 36.9, 45.3, and 48.3%, for LPMeOHtm systems. For the LPDMEtm process, a γ-Al2O3 based methanol
case. The overall syngas conversion is actually higher than the dehydration catalyst was used in a physically admixed form, with
syngas conversion at chemical equilibrium, 37.5%, at these Cu/ZnO/Al2O3 methanol catalyst, in an 80:20 weight ratio. The
conditions, T=250 ᵒC, P=70atm, and % H2 in feed syngas=37%. experimental conditions used for all experiments were 250 ᵒC,
This is a reflection of very facile kinetics of forward water gas shift 5.2MPa (or, 52atm), and a gas hourly space velocity of 6,000lit/kg
reaction, which also takes place at or near chemical equilibrium. At cat.h. Under these conditions, the experiments were free from all
these reaction conditions, the K-value for forward WGS reaction is internal and external transport gradients, and thus under kinetic
about 1000 times higher than either the CO or CO2 hydrogenation control.
reactions [28,29].
A first important element of the APCI one-step DME process
It is worth noting that, from a scientific standpoint, the shift in research is the influence of H2: CO ratio in the feed syngas on
chemical equilibrium which results in higher syngas conversions the LPDMEtm reactor productivity and comparison to LPMeOHtm
and methanol space-time yields, can be thought to work on the productivity. A new term, called “methanol equivalent productivity”,
basis of “phase equilibrium” or partitioning of methanol in vapor abbreviated as MEP, was defined for the LPDMEtm process, which
phase and liquid phase, or net condensation of methanol, even in was simply defined as the methanol productivity plus 2 times the
a purely vapor phase gas-solid reaction. There are other reports DME productivity. The comparison of MEP productivity for LPDMEtm
that validate this working principle of phase partitioning [30]. The and LPMEOHtm processes, as a function of H2: CO ratio in syngas, is
experimental observations indicate that methanol exhibits a rather illustrated in Figure 5. The chemical synergy is immediately seen
unusual phase behavior around its critical point, 510K and 81atm. from Figure 5. The MEP of LPDMEtm (upper curve) is always greater
than that of LPMeOHtm process (lower curve). However, it is clearly
Research portfolio of APCI, Inc.
seen that the magnitude of the synergy varies with H2:CO ratio. For
We now consider the research portfolio of Air Products and a H2:CO above 1.5, the percentage increase in MEP is only around
Chemicals on the single-step syngas to DME process. Over the 20%. However, this increase becomes 45% at a H2:CO of 1.0 and
past 15 years, Air Products &Chemicals, Inc., with Department of >90% at a H2:CO of 0.5. In other words, the chemical synergy is
Energy (DOE) sponsorship, has been actively engaged in research the highest at the CO-rich end (highly non-stoichiometric) of the
and development for LPMeOHtm and LPDMEtm processes, with the syngas compositions. The LPDMEtm process is also uniquely flexible
overall objective to produce methanol, DME, and other chemicals and can be adapted to IGCC power production combined with once-
based on methanol/DME as feedstocks, with the ultimate goal to through methanol/DME option.
Figure 5: The methanol equivalent productivity (MEP) from LPDMEtm (▲), the MEP from LPMeOHtm (Δ), and the % increase in
the MEP from LPMeOHtm to LPDMEtm (•) as a function of H2:CO ratio in the feed syngas.
To further understand the dependence of the chemical synergy regimes of kinetic control. (Figure 6) depicts the MEP for the 4
on the H2:CO ratio in feed syngas, it is instructive to examine if the cases, as follows: (a) the base catalyst system (at km, kd and kw), (b)
system is under kinetic control: The change in MEP was assessed the system with km increased by a factor of 4 (4 km, kd, kw), (c) the
by numerical simulations for 4 independent cases under different system with kd increased by a factor of 4 (km, 4 kd, kw) and (d) the
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system with kw increased by a factor of 4 (km, kd, 4 kw). Figure 6 methanol dehydration reaction and water gas shift reaction, does
also shows the MEP curve for the system of 3 chemical reactions not exert any appreciable influence at all, on the MEP productivity.
at chemical equilibrium (solid line). The cases, (●) km, 4kd and The only kinetic rate constant that profoundly influences the MEP
4kw; (○) km, kd, 4kw, appear as 2 curves immediately up top on the productivity is km, the rate constant for methanol synthesis. From
(x) km, kd, kw, i.e., the base catalyst system case. In fact, the curve the (▲) 4km, kd and kw case, it is seen that increasing the kinetic
symbols for the base catalyst case and the 4kw case almost overlap. rate constant for the methanol synthesis reaction raises the MEP
It is clearly seen that quadrupling the rate constant kd and kw, for productivity from about 40% to 55%.
Figure 6: The methanol equivalent productivity (MEP) as a function of H2:CO ratio in the syngas feed. Symbol legend: (x), km,
kd, kw, i.e., base catalyst system; (●), km, 4kd, kw; (▲), 4km, kd, kw; (Δ), km, kd, 4kw. The solid line over a H2: CO ratio of 0.5-2.0 is
represents MEP at equilibrium.
From Figure 6, it is clear that the overall LPDMEtm system is source for methanol (perhaps quite naively because CO was in large
still under “thermodynamic control”. It is thus possible to increase excess in typical feed syngas streams, compared to CO2), for typical
the MEP productivity (and % syngas conversion for LPDMEtm case) process conditions of H2<70%, CO+CO2=25-30%, CO/CO2=15-20%,
if we are able to increase the kinetic rate constants of the three CH4<5%, 70-100 bar, and 500-650K. The prevailing (but erroneous)
component reactions (with, say, design of more active and selective viewpoint of CO hydrogenation was pushed forward further by Klier
catalysts that are effective at low temperatures, compared to Cu/ and his team at Lehigh University [30-34]. However, this viewpoint
ZnO/Al2O3 system, which requires 230-270 ᵒC). These cases are was countered by the early Russian reports from Rozowski & Kagan
denoted by 4km, 4kd, and 4kw, respectively. [35], who clearly showed that over Cu based catalysts under low
temperature conditions, CO2 is the primary source of methanol,
Role of the water gas shift reaction
i.e., methanol is produced primarily via hydrogenation of carbon
We now make a few brief remarks on one of the long-standing dioxide, a reaction which is accompanied by the reverse water
controversial topics in methanol synthesis chemistry, the principal gas shift reaction, i.e., hydrogenation of CO2. More recent isotopic
source of C in CH3OH, i.e., CO vs. CO2, and the role of water gas labeling experiments (using labeled reactants, 14C/12C) have
shift reaction. We again point to the interested reader a few provided further evidence for CO2being the primary source, based
very important and pertinent contributions by UA researchers’ on analysis of surface elementary reactions and rate controlling
to provide unequivocal explanations to this controversial area steps [35,36]. This theory is now confirmed by several researchers
[4,5,9]. The works of Lee & Parameswaran [5] are the most including Skryzpek [37,38] and other recent works from Korean
instructive in this regard. Based on extensive experimental studies research groups [39,40].
and detailed thermodynamic and kinetic analysis of the overall
reaction mechanisms, it has been conclusively proven that, under To further underscore the very important role of water gas
a variety of syngas types (or H2/CO ratios) – from no-CO2 to no- shift reaction in the overall LPMeOHtm and LPDMEtm process
CO, and balanced (or, stoichiometric, with H2/CO=2-2.5) to CO-rich, chemistry, we briefly invoke the kinetic rate models of Graaf et al.
and experimental conditions, the primary dominant pathway for [41,42]. We refer to the interested reader to those original works
methanol synthesis and the principal source of C in CH3OH is the for details of the kinetic model development and kinetic analysis,
hydrogenation of CO2. and some additional details are included in Part 2 of this Series on
“Kinetic Studies and Catalyst Deactivation”. Here, we summarize
From a historical standpoint, the early proposals on the the key findings from their work on a semi-quantitative basis.
reaction mechanisms and roles of CO/CO2 in the vapor phase From the kinetic analysis, it is clear that the primary source of C
methanol process implicitly assumed that CO was the primary in CH3OH is CO2, i.e., methanol synthesis occurs primarily via CO2
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