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RANDHAVA et al.
(54) DIMETHYL ETHER (DME) PRODUCTION
(22) Filed:
Dec. 11,2014
PROCESS
Publication Classi?cation
(51)
(52)
Int. Cl.
C07C 41/09
U.S. Cl.
Prospect, IL (US)
USPC
(2006.01)
(57)
........................................................ ..
568/698
ABSTRACT
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US 2014/0364654 A1
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PROCESS
FIELD OF INVENTION
[0001]
KJ/mol
(3)
BACKGROUND OF INVENTION
as the optimum energy vector for the 21st century. Its high
DME and some methanol (REF. 1). The DME and methanol
produced are used here as the CO2 absorption solvent. While
the DME synthesis temperatures are 536 to 572 F. (260 to
300 C.), this causes a huge energy loss in heating and cool
fuels.
[0003] DMEs overall physical properties are similar to
those of LPG. DME lique?es at 59 psia (6.1 bar) or 13 F.
(25 C.). Its vapor pressure at 122 F. (50 C.) is 170 psig
(12.7 bar), While that ofpropane is 250 psig (18.3 bar). Since
DME can readily exist in a liquid form, it is easily transport
able in terms of international trade.
Feed Gas
Phase
Temperature, C. ( F.)
Pressure, bar (psig)
Vapor
205 (401)
71 (1,015)
Exxon
UNITEL
Vapor
110 (230)
82 (1,175)
ICI
Vapor
80 (176)
84 (1,204)
Mobil
Vapor
77 (170)
85 (1,218)
Johns on
TEC
Vapor
Matthey
Vapor
240 (464)
100 (1,436)
230 (446)
85 (1,218)
10.68
5.74
9.33
12.05
135*
10.10
CO
15.75
9.08
8.70
10.31
7.90
4.89
C02
H2
H20
N2
CH4O
9.50
61.16
0.22
2.27
0.42
10.60
64.00
0.24
9.76
0.58
10.45
69.37
0.11
1.66
0.38
4.14
69.03
0.10
3.84
0.53
5.80
83.20
0.10
135*
0.30
3.27
81.24
0.12
0.00
0.38
100.00
100.00
100.00
100.00
TOTAL
100.00
100.00
US 2014/0364654 A1
TABLE 1-continued
FEED SYNGAS COMPARISON WITH LITERATURE DATA IN METHANOL SYNTHESIS
Feed Gas
Present
Invention
1
UNITEL
ICI
Exxon
Mobil
TEC
Johnson
Matthey
3.88
7.05
7.97
6 70
10.53
16.62
Feed Gas H2 to CO
Molar Ratio
Feed Gas Module
Number
C02 in Feed Gas, wt%
2.05
2.71
3.08
4.49
5.65
9.56
33.85
37.67
43.65
19.59
35.69
23.64
Methanol Synthesis
12.65
12.56
9.52
8.83
5.10
1.24
2.35
1.99
4.00
3 00
29.65
15.00
5.64
1.48
8.85
No
No
Yes
No
Yes
Yes
No
No
Yes
i
Yes
No
Yes
Yes
Yes
No
No
ofMethanol Synthesis
Loop
Recovery from H2
generation;
[0020]
[0013]
vided;
US 2014/0364654 A1
TABLE 2
STEAM REFORMER COMPARISON
CONVENTIONAL
PRESSURIZED
[0031]
Nontransportable
pander-turbocompressor system.
[0032] FIG. 5 is a simpli?ed process ?ow diagram for the
natural gas to DME via the methanol dehydration route using
a single MRF methanol synthesis reactor.
DETAILED DESCRIPTION OF THE INVENTION
[0033]
(871 C.)
Reformer ?ue gas exit
convective
Reformer process gas exit temperature:
about 1,020 to 1,050 F. (549 to
5 66 C.)
Reformer ?ue gas exit temperatures:
1,060 to 1,100 F. (571 to 593 C.)
100%
rate: 100%
[0036]
100 to 250 psig (7.9 to 18.3 bar) and preferably about 150 to
200 psig (11.4 to 14.8 bar). The saturated natural gas and the
majority of the recycle gas B mixture is brought to the requi
site elevated temperature and supplied the endothermic heat
for the steam reforming reactions by transfer of heat from the
hot burner ef?uent gas through the metal walls of catalyst
tubes. The pressurized reformer 4 is different to a conven
high capacity for sulfur uptake and metal carbonyls and can in
most cases, completely guard itself against residual poisons.
US 2014/0364654 A1
Thus, the costly acid gas removal step before the methanol
the synthesis gas are the CO to CO2 molar ratio and the
concentration of inerts. A high CO to CO2 molar ratio will
make-up boiler feed water and heat exchanged with the inter
nal methanol synthesis reactor e?Iuents before it is fed to the
top of the saturator 2 (FIG. 3).
[0044] Although the invention has been described with ref
erence to its various embodiments, from this description,
those skilled in the art may appreciate changes and modi?ca
tions thereto, which do not depart from the scope and spirit of
increase the reaction rate and the achievable per pass conver
Example 1
[0045] A combined gaseous mixture of 804.78 lbmol/hr of
natural gas and 762.92 lbmol/hr of recycle gas B are fed to the
bottom of a saturator, while a stream of hot water is fed at the
top of the saturator (FIG. 2). The rising gaseous stream evapo
rates the hot water as it travels down the saturator. The ?ow
(4)
(5)
(6)
[0041]
reforming reactors.
[0046] The saturated natural gas and the remaining recycle
gas B mixture is then preheated by the HP burner ?ue gas
before entering the tubular steam reformer operated at 1,600
E. (871 C.) and 300 psig (21.7 bar). A syngas with the
Temp., F. ( C.)
Composition
CH4
C02
N2
H20
VAPOR
1,021.0 (544.4)
295 (21.4)
5,030.10
3.0395
Mol %
5.69
5.90
1.20
20.91
CO
16.41
H2
49.88
power/steam generation.
(21.0 bar) and 220 F. (104.4 C.) to 671 F. (355.0 C.) which
then generates an additional 682 hp electric power. The syn
gas is then further cooled to knockout most of its moisture
content, 1,032.97 lbmol/hr before it is compressed to the
US 2014/0364654 A1
the pressure to 10 psig (1.7 bar) instead of 120 psig (9.3 bar),
synthesis feed gas. The methanol synthesis loop feed gas has
reboiler heat duty for the light end distillation column (Table
6).
TABLE 6
LIGHT END DISTILLATION COLUMN COMPARISON
Cases
Case 1
3.8847
2.05
Composition
10.68
9.50
2.27
0.22
CO
15.75
H2
01140
61.16
0.42
248,659
1,477,999
VAPOR
Temp., F. ( C.)
Mol %
CH4
co2
N2
H20
1,370,906
4,264,289
TABLE 7
8,971.74
15
1,018.5 (71.2)
Module
10 (1.7)
15
401.0 (205.0)
Flowrate, lbmol/hr
120 (9.3)
Stages
VAPOR
Temp., 0 F. (O c.)
Case 2
177.2 (80.7)
11.0 (1.8)
Flowrate, lbmol/hr
637.88
Composition
Mol %
CH4
CO2
N2
H20
0.00
0.00
0.00
7.95
CO
0.00
H2
CH4O
0.00
92.05
Acetic Acid
Acetone
Ethanol
14.73 ppm
13.09 ppm
31.33 ppm
(Table 5):
[0052]
CRUDE METHANOL PRODUCT
PHASE
TABLE 5
VAPOR
TABLE 8
Temp., F. ( C.)
105.0 (40.6)
974.5 (68.2)
Flowrate, lbmol/hr
680.46
Composition
Mol %
Feed Stream
Phase
CH4
CO2
N2
H20
0.46
4.42
0.02
7.47
CO
0.07
H2
CH4O
Acetic Acid
Acetone
Ethanol
[0050]
0.22
87.34
13.81 ppm
13.28 ppm
29.56 ppm
Liquid
Temp., F. ( C.)
177.4 (80.8)
116.4 (9)
Flowrate, lbmol/hr
637.88
Composition
Mol %
CH4O
H20
Acetic Acid
Acetone
Ethanol
92.05
7.95
14.73 ppm
13.09 ppm
31.33 ppm
US 2014/0364654 A1
TABLE 8-continued
Feed Stream
Phase
Liquid
21 to 30
30
TABLE 9
1 to 7
8 to 20
Feed Stage
116 (9)
Composition,
Inlet
Outlet
Simulated Out
mol %
Gas
Gas
let Gas
77.3
9
0.5
99.9834 mol %
99.9884 Wt %
[0053]
H2
83.2
77.3
CO
7.9
2.1
2.2
CO2
5.8
4.4
4.4
CH4 +N2
2.7
3.2
3.2
H20
CH4O
0.1
0.3
2.8
10.2
2.7
10.2
Total
100.0
100.0
100.0
Temperature, 0 c. (O F.)
Pressure, bar (psig)
240 (464)
100 (1,436)
260 (500)
99 (1,421)
260 (500)
99 (1,421)
Example 3
[0058]
(FIG. 3).
Example 2
[0055] The pressurized fumace ef?uent leaving the inter
changer at 467 F. (241 .70 C.) and 140 psig (10.7 bar) is
thesis loop.
presented. In this example, the feed gas ?ow rate to the metha
to 178.95 tons/day.
US 2014/0364654 A1
TABLE 13
TABLE 11
Phase
Vapor
VAPOR
300 (21.7)
1,600 (871)
97.09
Temp., F. ( C.)
125.0 (51.7)
42-00 (30-0)
Component
Natural
Remaining
Syngas
FlOWT?t?, lmel/hf
1,164-35
Molar Flow,
lbmol/hr
Gas to
Separator
Recycle Gas B
to Saturator
Recycle Gas B to
Reformer
from
Reformer
Composition
Mol %
Saturated Natural
766.15
5.63
10.46
0.00
261.98
168.48
136.33
0.01
1,026.64
171.23
146.75
2,003.23
1,084.81
0.00
0.00
0.00
20.12
2.42
173.85
116.18
12.10
0.00
0.00
173.81
116.12
0.06
20.07
2.41
834.87
2,589.21
0.00
0.02
0.00
804.78
868.93
3,660.32
5,239.85
CH4
002
0.29
4-62
CH4
co2
N2
N2
0-23
HZO
H20
CO
H2
CH40
[0061]
002
0-27
94-54
0.03
co
H2
CH4O
02116
C3H8
TOTAL
284.25
299.94
146.75
[0064]
with the remaining recycle gas B, then all the CH4 slip in the
steam reformer ef?uent will come from the natural gas feed
stream and the CH4 conversion of the natural feed stream to
Phase
Vapor
300 (21.7)
TABLE 12
COMPARISON OF INLET GASES TO THE H2 MEMBRANE
SYSTEM BETWEEN EXAMPLES 1 AND 3
EXAMPLE
EXAMPLE 1
EXAMPLE 3
30
80
15
Synthesis Loop
Purge Rate for Recycle Gas B
Inlet Gas Comp., mol %
1,600 (871)
CH4
CO2
13 .51
1 1 .17
13 .43
1 1 .12
N2
H2O
2.88
0.02
7.03
0.01
CO
11.80
8.95
H2
CH4O
59.87
0.75
58.83
0.63
73.02
Component Molar
Flow, lbmol/hr
Natural Gas to
Separator
766.15
5.63
10.46
0.00
765.43
4.25
10.44
1,516.31
CO
0.00
0.00
457.10
H2
0.00
0.00
1,943.21
0.00
20.12
2.42
0.00
20.10
2.41
0.00
0.01
0.00
804.78
2,318.94
3,531.54
CH4
C02
N2
HZO
CH4O
C2H6
03118
TOTAL
Syngas from
Reformer
206.53
153.45
10.44
760.80
compression power.
TOTAL
100.00
[0063]
2,097
100.00
2,079
the CH4 slip in the steam reformer ef?uent (S9 in FIG. 5) and
US 2014/0364654 A1
10
Example 4
[0066] Keeping the same operating conditions as shown in
Table 9, the MRF reactor is simulated by Aspen Plus Basic
Engineering V7.3 using all the feed syngases in Table 1. The
simulated results are summarized in Table 15 (Example 3 data
are also included in the table for comparison purposes).
TABLE 15
SIMULATED MRF METHANOL REACTOR RESULTS USING
ALL THE FEED SYNGASES IN TABLE 1 UNDER THE SAME
OPERATING CONDITIONS AS SHOWN IN TABLE 9
Methanol
Synthesis
Processes
Present
Invention
2
Present
Invention
1
UNITEL
ICI
Exxon
Mobil
TEC
Johns on
Matthey
1.35*
7.90
5.80
83.20
0.10
1.35*
0.30
10.10
4.89
3.27
81.24
0.12
0.00
0.38
7.49
18.76
7.65
61.70
0.42
3.91
0.07
TOTAL
100.00
10.68
15.75
9.50
61.16
0.22
2.27
0.42
5.74
9.08
10.60
64.00
0.24
9.76
0.58
9.33
8.70
10.45
69.37
0.11
1.66
0.38
12.05
10.31
4.14
69.03
0.10
3.84
0.53
100.00
100.00
100.00
100.00
100.00
100.00
45.7
6.9
10.0
16.0
1.3
20.1
47.1
5.9
11.2
17.2
1.7
16.9
54.6
3.7
10.2
18.5
2.7
10.3
60.1
3.3
9.6
13.2
3.2
10.6
61.0
3.0
3.7
19.4
1.4
11.5
77.3
2.2
4.4
3.2
2.7
10.2
77.3
1.4
1.9
11.3
1.9
6.2
100.0
2.05
100.0
2.05
100.0
2.71
100.0
3.08
100.0
4.49
100.0
5.65
100.0
9.56
3.28
3.88
7.05
7.97
6.70
10.53
16.62
2.46
1.66
0.86
0.83
2.49
1.36
1.50
14.36
12.32
10.31
8.44
8.94
8.23
5.21
1.26
1.05
2.08
2.52
1.06
2 18
1 57
Gas, lbmol/hr
CO Conversion, %
C02 Conversion, %
74
6
72
11
66
20
68
24
76
26
77
38
75
48
[0067]
Example 5
[0068] Same as Example 3 except that the pressurized
burner in the reformer is replaced by an atmospheric pressure
burner. The primary heat transfer mechanism is radiation now
rather than convection. A comparison of reformer process gas
e?1uent temperatures, reformer ?ue gas ef?uent tempera
TABLE 16
A COMPARISON OF REFORMER PROCESS GAS EFFLUENT
EXAMPLE 3
EXAMPLE 5
150 (11.4)
2 (1.2)
Convective
Radiative
1,021 (549)
1,600 (871)
1,080 (5 82)
1,825 (996)
284.05 (46%)
615.40 (100%)
79.17 (75%)
105.71 (100%)
F. ( C.)
US 2014/0364654 A1
Dec.11, 2014
brane and the purge rate from the H2 membrane to the pres
required to keep the inert gases (CH4 and N2) and CO2 at
appropriate concentrations.
and equivalents.
this way, all the high pressure steam required for the
downstream steam reforming reactions is provided;
Steam reforming the saturated natural gas and the remain
ing recycle gas to produce a syngas;
Recovering the heat from the reformer ef?uent by super
heating the saturated high pressure steam to generate
generation;
Directing the e?luent from the medium pressure heat
recovery boiler into a cooler where bulk of the water
sis;
Subj ecting the combined gas mixture to the methanol syn
thesis loop in the presence of Haldor Topsoe MK-121
methanol synthesis catalyst to obtain a reaction product
gas mixture including methanol, carbon dioxide, water
vapor, inerts like methane and nitrogen, and unconverted
loop.
9. The process as set forth in claim 1, wherein the steam
reformer HP burner can be replaced by a conventional low or
US 2014/0364654 A1
Dec. 11,2014
12
at high steam reformer operation pres sure (300 psig) and mild