United States Patent
Hack et al.
(51) METHOD FOR PRODUCING PROPYLENE
FROM METHANOL,
(75) Inventors: Markus Hack, Karen (DE); Ulrich
Koss, Darmstat (DE); Peter Konig,
Hombueg (DE); Martin Rothaemel,
Frankfuet am Main (DE); Hans-Dieter
Holtmann, Boenen (DE)
MG Technologies AG, Frankfurt am
Main (DE)
Subject to any dislaimer, the term ofthis
patent is extended or adjusted under 33
(73) Assignee:
(9) Notice:
USC. 154{b) by 472 days
(21) Appl Nos 107296356
(22) PCT Filed: May 22, 2001
(85) PCTNo: — PET/EPOLOs8ss
§ 371 XA),
(2). (4) Date: Now. 25, 2002
(57) PCE Pub, Nos WOOU2190
PCT Pub, Date: Dee. 6, 2001
(3) Prior Publication Data
US 2005)0139635 AL Jul. 24, 2003,
(1) mc.
076 1}00 2006.01)
co7e 6100 (2006.01)
USON
(10) Patent No.
(5) Date of Patent
US 7,015,369 B2
Mar. 21, 2006
62) US. 585/640, 585/302; 585/32.
585/638; 585/639)
carch 58568,
585/639, 640, 302, 324, 327
‘See application file for complete search hisiory.
(8). Fleld of Classification
60) References Cited
US. PATENT DOCUMENTS.
Si7a4580 8 * 4/1998 Mulvaney et Sas
S817 A * LNI908 Marker ta SH5.640
FOREIGN PATENT DOCUMENTS
ep 44 8000,
ee (0882192
111998
* cited by examiner
Primary Esaminer—Waltee D. Grin
“Assistant Exaniner—In Suk Bullock
(74) Attorney, Agent, or Firm—Norris McLaughlin. &
Marcus PA
6 ABSTRACT
A process for producing propylene from methanol, wherein
methanol vapor is reacted on first catalyst obtain ist
‘vapor mixture containing dimethyl ether (DME), which is
reacted on a form-sclective zeolite catalyst disposed as bed
in at least two series-connected shaft reactors to produce 2
product mixture containing propylene.
9 Claims, 2 Drawing Sheets U.S. Patent Mar. 21,2006 Sheet 1 of 2 US 7,015,369 B2
18
16
117 U.S. Patent Mar. 21,2006 Sheet 2 of 2 US 7,015,369 B2
Fig.2 US 7,015,369 B2
1
METHOD FOR PRODUCING PROPYLENE
FROM METHANOL,
‘This invention relates to a process of producing propylene
from methanol, wherein methanol vapo is reacted on 8 fist
catalyst o obtain a first vapor mixture containing dimethyl
‘ether (DME), and from the frst vapor mixture a product
mixture containing propylene is produced on 2 form-sclee-
tive zeolite catalyst, which prodket mixture is cooled
‘Such processes ar known and described for instance in
EP 04448 000 BI and DE 197 23 363.1, The formselective
zooite catalyst is disposed in a tbula rector and is cooled
indirectly, in order to dissipate heat produced
isthe object undying the invention to achieve a rather
high content of propylene in the product mixture. At the
lime, it should be possible to omit the expensive
Tubular resetor, in order to obtain a rather inexpensive
process
In accordance with the invention, tis object is solved in
the above-mentioned process in that the form-selective
zeolite catalyst is disposed as bed in at least two series-
‘connceted shaft reactors, that & first partial stream of the
DM-contaning frst vapor mixture together with seam is
introduced into the firs shalt reacion, a fist intermediate
product mixtuc is withdrawn from the first shat reactor and
8 charged into the second shaft reactor, a second partial
stream of the DME-containing fist vapor mixture also being
‘supplied to the second shaft reactor that rom the lst one of
the series-connected shaft rectors product mixture is ith-
‘drawn, cooled, a fration rich in propane is separated and
residual substances are obtained, which are in par gascous
tnd contain C,, hydrocarbons, and that at least part of the
residual substances are recirculated into atleast one of the
Shaft reactors. Usually, the form-selective zeolite catalyst
will be disposed as bed in a maximum of four or five
seriesconpected shaft reactors. The separation of the fae
tion rich in propane may be effected in 8 manner known per
‘efor Instance by disillation or by adsorption,
"The frst catalyst on which the methanol is at frst con
‘verted i part usally is likewise contained as bed ina shaft
reactor, and this frst catalyst may be an ALLO, catalyst in a
‘manner known per se. Details of the fist eaalyst are knowa
from EP 01 448 000 BI and DE 197 23 363 AL. These
publications aso describe the form-selectve zeolite catalyst
Which can be used in the process ia accordance with the
invention. This catalyst isa pentasi-type catalyst containing
protons with an alkali content of less than 380 ppm and
preferably Tess than 200 ppm. This catalyst has a. Zo0
‘Content of less than 0.1 wife, 4 C&O content of les than 0.1
‘wh, a BET surface area of 300 to 600 mig, and 8 pore
volume (determined by mercury porosimetry) of 0.3 to 08
img. Usually, the pressure inthe vicinity ofthis catalyst is
‘ot more than about 0.9 bae aad preferably lies in tbe range
from 0.2 10.0.7 bar,
‘To the first shalt reactor, which contains the zeolite
catalyst, a mixture is charged which usually comprises 110
40 vol% DME (calculated dry). At the same time, a
‘sufficient steam content of the mixture is ensured, the H
‘content of the mixture Iying in the range from 40 to 80)
vol-. For subsequent shaft actors the same conditions are
applicable as regard the HO coatent of the mixture enter-
ing the respective reactor. Usually, atleast 10¥% ofthe frst
‘vapor mixture coming from the frst catalyst are supplied to
‘each shaft reactor.
‘The temperatures at the inlet ofthe shal reactors in which
the zeolite catalyst is disposed lie in the range from 350 to
500" C. ad mstly 380 to 480° C, Expedivally, the shaft
%
o
2
reactors are operated without means for indirect cooling,
Te production and the operation of these shaft rectors are
thus simpliied considerably. Its ensured thatthe tempera-
ture atthe outlet of one or more of the shaft reactors is by
50 to 100° C, higher than at tbe inlet ofthe respective shaft
‘An advantageous embodiment of the process consists ia
that the team-contaning produet mixture withdrawn from
the last shal eeactor is cooled to temperatures in the range
from 100 to 250° C, is compressed toa presse inthe range
from 3 10 15 bag, and a compressed product mixture is
pradced, whose 11,0 content is liquefied for not more than
30 wis. The compressed product mixture is passed throug
at least one indirect heat exchanger and is cooled therein
against a water phase. From the heat exchanger, a conden-
sate-contining cooled product mixture is withdrawn, whose
‘content is Tiquefied for at least 80 wi-% and whose
femperature is by 20 10 150° C. lower than at the inlet ofthe
heat exchanger, In this way, heat of condensation is trans-
{ered tothe water phase. From the cooled progct mixture
containing condensate a water phase is separated, and this
water phase is ecirculated to the indirect heat exchanger,
‘where the water phase wholly or lagely evaporates. The
steam produced is at least parly inoduced into the first
shaft reactor,
Embodiments of the process will be explained with ref
ereace to the drawings, in which
FIG. 1 shows te flow diagram ofthe fest process variant,
and
FIG. 2 shows the flow diagram of a second process
‘As shown in FIG. 1, the methanol vapor to be reacted,
‘which usually has temperatures in the range from 200 10
50° Cis supplied va line (1) and passed through the bed
of the fist eaalyst (2) On the fist catalyst, which consists
Jor instance of granular AL.O,, a first exotbermal conversion
takes place, and inline (3) first vapor mixture is obtained,
‘whieh usually contains. at lest 50 vol-% DME and in
dition methanol and steam, The temperature of line (3)
lies in the range from 350 to 450° C, The vapor mixture of|
line 3) is divided into Hines 32), (34), and (3c). The partial
siream in line (3b) is also referred to as “first arial stream",
and the one in line (a) is referred to as “Second partial
Together with residual substances from lines (4) and (8),
whieh are supplied inthe cooled condition, the mixture of
Tine (38) is introduced into the first shaft reactor (6), whieh
‘contains 2 bed ofthe form-selective zeolite catalyst. Steam
is supplied via line (1) Its ensured thatthe temperature of
the mixture entering the catalyst bed in the reactor (6) les ia
the range from 350 10 300" Cand preferably 380 to 480° C,
On the eatalyst in the reactor (6), exothermal conversion
reactions take place, and in line (9) a frst intermediate
product mixture i obtained with temperatures in he range
rom 400 to 6" C. IE necessary, this mixture ean be passed
through an indirect cooler (10), which isnot required in all
eases and in the dav is indicated in broken lines
To the mixture of line (8) the patil Seam from line (3a)
is added, which here is also relerred to as “second partial
siwam’ The fuether reaction is effected inthe second shaft
reactor (12), which likewise contains a bed of the form-
slective zeolite catalyst. The prooess conditions in the
reactor (12) are about the same as inthe reactor (6, and this
fs also teue forthe tied shaft reactor (18) From the reactor
(12) second intermediate product mixture is obtained via
line (13), to which seonnd intermediate proclict mixture the US 7,015,369 B2
-
thie partial stream from line (3c) is added. Here 28 wel, the
mixture in Line (13) can be passed through an indzeet cooler
10), if necessary.
‘The mixture of line (13) is passed theough the thet shaft
reactor (18), which in the present ease is the lst one of the
seriesconnécted shaft reactors, which contain a zeolite
‘catalyst as bed. The product mixture withdrawn via line (1S)
usually has a propylene conten, calculated dry, of 40 16 60
vol- and in tddliion contains other substances which here
are also referred to as residual substances
‘he mixture of line (18) is first subjected toa cooing (16),
and there is obtained a condensate rich in water, Which
‘condensae is discharged via line (17). Gaseous and vapor-
‘ous substances are withdrawn via line (20), and a liquid
mixture is discharged via line (21). The gases and vapors
which also contain the desired propylene are charged into a
first column (22), gases are separaed and ate recirculated
via line (4), s described, The botiom preduc of column 22)
ows through line (28) into a second column (24), from the
top of which fraction rich in propylene with a propylene
‘content of usually at least 80 vol- is withdrawn through
Tine (28). The bottom product (mostly C,,,hydrocatboas)
Jeaving column 24) vi line (26) i tecitulated via line (8).
‘The residual substances of lies (4) and (8) may also patly
be added to the mixtures of line (3a) andjor line’ (3c).
Excesses are removed through lines (4a) and (84).
The liquid mixtuee of line (2) flows into the third col
(28), from whieh a light Cy, traction is separated and is
Fecitculated via line (29) and through line (8). The heavy
‘consituens, usually petcoleum hydrocarbons, ate withe
‘drawn through line (M0) and are removed from the process
In the process of FIG, 2 there is utilized the heat content
‘of the product mixture which comes from the Iss shaft
reactor (18) via ine (18) and usually has temperatures in the
range from 400 to 604 C. First of al, the proget mixture
feleases part of its heat in the heat exchanger (16) and then
in the preheater (38), 10 which liguid andior vaporous
‘methanol is supplied through line (36). From the prebeater
(35), methanol vapor with temperatures inthe range from
200 10. 350° C, & withdrawo via line (1) and is passed
through the bed ofthe fst eatalyst (2). With temperatures of
100 to 250° C., the product mixture which also contains
steam flows though line (37) to» compressor (38) and at the
‘outlet thereof inline 29) fas a pressure of 3 to 15 bar and
for economic reasons mosily ot more than 10 bar; the
temperature lies inthe range from 130 10 250° C. The steam
‘of the mixture in Tne (39) isnot yetor hardly condensed, nd
rot more than 30 wt-% and preferably not more than 10
‘wie of the HO content ae liquefied already.
Inthe indirect heat exchanger (40), the product mixture of
line (39) i further cooled, a Water phase Serving as cooing
medium, which water phase is supplied via line (41). The
water phase wholly of largely evaporates and the steam
produced is discharged via line (7), the temperature lies
between 100 and 200° C., and the pressure les between O.1
and 10 bar. This line 7) opens into line (36), which for a
better clarity has not been represented completely.
‘he product mixture coming from the heat exchanger 40)
via line (2) is partly condensed, and at least 80 wie ofthe
‘content ae liguelied, Tre temperatures inline (42) are
by 20 t0 150°C. and mostly 30 to 120° C. lower than inline
(39), and the pressure has also decreased by 0.1 t0 10 bar
For being separated, the product mixture of line (42) is
‘charged into a separator (44), from which a water phase is,
‘withdrawn via line (48) anda liguid mixture containing
Petroleum hydroeursons is withdrawn via line (21). Gases
find vapors which also contain the desired propylene escape
via line 20). The water phase of line (48) can be recirculated
to the beat exchanger (40) through line (41) Inthe present
‘ease, iis charged ito the stripper (46), 0 that by means of
%
4
stripping, g2s (eg. nitrogen) from line (47) low-boiling
hhydrocarbons (e.g. C; hydrocarbons) can be removed
through line (48). The stipped water phase llows back tothe
het exchanger (40) via line (41, fresh water is supplied via
Tine (49), Moreover, te explanations given in conjunction
with FIG. Lare applicable
EXAMPLE I
‘There is employed a plant corresponding to FIG. ofthe
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