United States Patent (19) 11 Patent Number: 4,778,662

Pinto (45) Date of Patent: Oct. 18, 1988

(54 SYNTHESIS PROCESS AND REACTOR 3,466,152 9/1969 Yamamoto et al. ................ 422/148
3,475,136 10/1969 Eschenbrenner et al. .
75 Inventor: Alwyn Pinto, Middlesbrough, 4,148,866 4/1979 Becker .
England 4,311,671 1/1982 Notman .
73 Assignee: Imperial Chemical Industries PLC, 4,321,234 3/1982 Ohsaki et al. .
4,359,448 11/1982 Schuurman et al. ........... 422/20 X
London, England
FOREIGN PATENT DOCUMENTS
(21 Appl. No.: 61,035
665748 7/1965 Belgium.
22 Filed: Jun. 12, 1987 993 3/1979 European Pat. Off..
626501 9/1927 France ................................ 422/48
Related U.S. Application Data 30.586 12/1963 Netherlands .
55446 6/1968 Poland ................................ 422/148
63 Continuation of Ser. No. 746,019, Jun. 19, 1985, aban 221229 9/1924 United Kingdom .
doned, which is a continuation of Ser. No. 442,978,
Nov. 19, 1982, abandoned. OTHER PUBLICATIONS
(30) Foreign Application Priority Data "Ammonia', Slacket al., Marcel Delcker, Inc, 1977, pp.
Nov. 19, 1981 GB United Kingdom................ 8.34920 321-322.
5ll Int. Cl'................................................ B01J 8/02
Slack et al., Chem. Eng. Progress 1953, 49(8), 393-40.
52 U.S.C. .................................... 422/148; 422/203; European Search Report EP 82.305701.
422/211 Primary Examiner-Michael S. Marcus
58) Field of Search ............... 422/158, 118, 200, 201, Attorney, Agent, or Firm-Cushman, Darby & Cushman
422/203, 208, 197, 148, 211 (57) ABSTRACT
56 References Cited A reactor suitable for synthesis of ammonia or methanol
U.S. PATENT DOCUMENTS comprises a catalyst bed 36 equipped with heat ex
1909,378 5/1933 Richardson ..... ... 422/148 X change tubes 32 supported by means 28-31 or 40, 42
1,927,286 9/1933 Jaeger et al. ... 422/208 providing catalyst fillable space between the tubes over
1932,247 10/1933 Kniskern ......... ... 422/48 X substantially their whole length. Preferably catalyst
1,962,301 6/1934 Etienne et al....................... 422/208 particles between the tubes and in an uncooled bed 36
2,052,326 8/1936 Uhde ............... ... 422/148 X downstream thereof constitute a single body of catalyst.
2,512,586 6/1950 Shengel ... ... 422/148 X The reactor is especially suitable for synthesis at low
2,538,738 1/1951 Stengel ................................ 422/148 pressures such that the heat transfer area provided by
2,744,813 5/1956 Paul ............. ... 422/208 X
2,852,350 9/1958 Kolbel et al. ....................... 422/2O1 the tubes is relatively low.
3,442,626.5/1969 Browne ............................... 422/148
3,458,289 7/1969 King et al. . 6 Claims, 2 Drawing Sheets

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U.S. Patent Oct. 18, 1988 Sheet 1 of 2 4,778,662
U.S. Patent Oct. 18, 1988 Sheet 2 of 2 4,778,662

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lyst-fillable space between them over substantially their
SYNTHESIS PROCESS AND REACTOR whole length.
Thus the reactor differs from known reactors, in
This is a continuation of application Ser. No. 746,019, which the tubes are supported in a tube-plate. As a
filed June 19, 1985, now abandoned, which is a continu 5 result of the catalyst-filled space between the tubes,
ation of application Ser. No. 442,978, filed 11/19/82, catalyst particles can pass between them during charg
now abandoned. ing and discharging catalyst. Further, the catalyst parti
This invention relates to a synthesis process, espe cles between the tubes and those beneath it constitute a
cially a heterogeneous exothermic catalytic process continuous body of catalyst, so that an uncooled bed
such as for making ammonia or methanol, and a reactor O can follow the cooled bed without occupying so much
for carrying it out. reactor volume as would be required if separated beds
In such processes the reaction temperature must be were present.
controlled in order to obtain favourable chemical equi The reactor preferably includes such a bed having no
librium and to avoid damaging the catalyst. This has heat exchange surface or less than the tube-cooled bed.
been done by (a) disposing indirect heat exchange sur 15 The effect of such a bed is to increase the quantity of the
faces in contact with the catalyst or (b) by subdividing synthesis product by a small but useful amount, typi
the catalyst into a number of beds and cooling the reac cally 1-5% in ammonia synthesis at 30-120 bar abs.
tants between the beds by indirect heat exchange or by pressure or 0.1 to 0.5% in methanol synthesis at such
injection of cooler gas ("quench gas'). When indirect pressures. The resulting higher temperature of the gas
heat exchange has been used, the fluid on the cold side 20 at the outlet of such a bed increases the efficiency of
of the heat exchanger has usually been reactant gas at a heat recovery from it.
temperature below the catalyst inlet temperature, so The reactor preferably does not include in its shell a
that the heat exchange preheats that gas. It has been heat exchanger other than that provided by the tubes in
proposed to use other fluids such as boiling water but the catalyst bed. Thus the gas is brought to the tube
these have had limited use in ammonia synthesis, though 25 inlet temperature preferably outside the reactor shell:
more in methanol synthesis. this temperature is chosen so that the heat evolved in
Although in principle either method.could be used at the synthesis reaction is taken up in raising the gas to the
any synthesis pressure, for ammonia synthesis method catalyst inlet temperature. The absence of such a heat
(a) has been used mainly at pressures over about 250 bar exchanger increases the possible quantity of catalyst in
abs., which are now regarded as "high': see Slack et al., 30 a reactor shell of a given volume.
Chemical Engineering Progress 1953, 49, (8), 393-40. It The tube supporting means preferably comprises a set
is scarcely if at all been used in any ammonia plant of headers from which the tubes project upwardly
designed since about 1965 or having an output over through the bed. The tubes are preferably not rigidly
about 600 metric tons per day. Instead the multi-bed linked together otherwise than by the headers but are
reactor, especially with quench cooling between beds, 35 kept in position by one or more planar linked-ring
has been preferred and has afforded substantial advan frameworks permeable to catalyst particles, slidingly
tages in simplicity of construction and of charging and applied to the tubes and secured against vertical move
discharging the catalyst. For examples of quench reac ment. The resulting assembly is, apart from the upper
tors reference is made to U.S. Pat. Nos. 3,458,289 and ends of the tubes, immersed in a single body of catalyst
3,475,136. Their operating pressure is typically 150 or particles; any part of the body beneath the headers
220 bar abs. and will be referred to as "medium pres constitutes the uncooled bed:
sure'. The means feeding the gas from the upper end of the
Since 1976 attempts have been made to develop an tubes is conveniently a closed chamber above the sur
ammonia synthesis process at a still lower pressure, for face of the catalyst.
example as described in U.S. Pat. No. 4,148,866 (specifi 45 In an alternative arrangement the tubes are Field
cally 33 at), and European published applications No. tubes, each closed at its bottom and fed by way of an
993 (specifically 47 bar abs.) and 26057 (105 bar abs.). internal tube leading downwards from an upper set of
Whereas EP No. 993 does not disclose any particular headers or a chamber.
synthesis reactor, U.S. Pat. No. 4,148,866 and EP No. The reactor can be of the "hot-wall' or cartridge
26057 clearly teach use of a multi-bed quench reactor, 50 type: in the latter event the space between the cartridge
similar to what has been used at higher pressures. A and the shell can constitute the source of the supply of
tube-cooled synthesis has recently been described in reactant gas to the tubes. Preferably this is effected by
UK No. 2046618. means of vertical headers each extending upwardly
We have now found that for such low pressure pro from the bottom of the cartridge and each feeding a
cesses the quench reactor is subject to the serious defect 55 plurality of cooling tubes. An alternative structure
that its volume must be very large, and that it is possible would use the Field tube arrangement, supplying gas
to design a much smaller reactor capable of no less through headers at the top of the cartridge.
ammonia output. Our reactor is based on a new way of According to a second aspect the invention provides
providing indirect heat exchange surfaces within the a process of ammonia synthesis at a pressure under 120
catalyst bed, following an analysis of the requirements 60 bar abs which is carried out in a bed of promoted iron
of these low pressure processes. catalyst in heat exchange with a coolant flowing in a
According to the invention a reactor comprises a direction generally parallel to the direction of reactant
vertically oriented bed for particulate catalyst, a plural flow in the catalyst bed.
ity of vertically oriented heat exchange tubes within the The pressure is preferably over 30 bar abs. The heat
bed and means to supply reactant gas to the bottom of 65 exchange surface area provided is preferably under 20,
such tubes and to feed it from the upper end of such especially in the range 3 to 15 m2 perm of catalyst. This
tubes downwardly through the bed, characterised in is substantially less than was considered necessary in
that the tubes are supported by means providing cata high pressure ammonia synthesis.
 4,778,662 4.
3
This aspect of the invention rests on the realisation ing manholes 18 at its upper boundary and discharge
that the heat evolved per unit volume per unit time is port 20 at its lower boundary, port 20 passing through
relatively small because of the relatively large catalyst an aperture in shell 10. It is formed also with an aperture
volumes practicable at low pressures. As a result, the for gas inlet pipe 22, gas outlet sieve pipe 24 impervious
heat exchange can be provided by a small number of to particulate catalyst, and gas outlet 26 leading through
relatively large tubes; and thus the justification for an aperture in shell 10. Gas inlet pipe 22 leads down
abandoning the tube-cooled catalyst bed in the medium wards to primary header 28, from which project sec
pressure processes no longer applies. Our process is also ondary headers 30, from which in turn project tertiary
favoured by the lower catalyst outlet temperatures used headers 31 and thence cooling tubes 32 leading through
in the new low pressure processes, specifically in the 10 promoted iron catalyst bed 36 into chamber 34. Header
range of 350-410° C., instead of 400-480 C. for the 28 as shown is one of a set of pipes arranged as the
old high-pressure or medium pressure processes. These spokes of a wheel having its centre on the axis of pipe
are catalyst bed outlet temperatures; it is evident that 22. These radiating spokes are supported by a set of
the temperature in regions of the catalyst remote from transverse beams 29, of which one is shown, welded to
heat exchange surfaces must be higher, but in the low 15 the walls of cartridge 16. Beam 29 are disposed so as not
pressure processes is unlikely to damage the catalyst to block the spaces between the pipes of header 28, and
even at considerable distances from such surfaces. Thus thus there is a single continuous body 36 of catalyst.
the reactor preferably used is clearly more than a low Tubes 32 at or near their upper ends and also, if desired,
pressure analogue of the old high pressure reactor. at one or more intermediate levels, are kept at their
Such an ammonia synthesis process is very conve 20 required mutual separation by linked-ring framework
niently carried out in a reactor according to the inven 33, which like beams 29 and headers 28, 30 and 31,
tion but is not limited thereto; other possible reactor affords free passage of catalyst during charging or dis
arrangements include horizontal gas flow or radial flow charging the bed.
through a vertical annular-section bed. FIG. 1b shows the deposition of tubes 32 within
The H2:N2 ratio can be approximately stoichiometric, 25 linked-ring framework 33. Each tube 32 can be
that is, in the range 2.5 to 3 but is preferably in the range equipped with an internal core or turbulator or both, for
1.0 to 2.5, especially 1.5 to 2.3, as disclosed in our co all or part of its length, to increase gas velocity or turbu
pending European application No. 49967. lence and thus to improve heat transfer. Alternatively
The invention provides also a methanol synthesis or in addition, tubes 32 can be finned.
process over a copper-containing particulate catalyst in 30 In a hot-wall vessel the same internal constructional
a reactor according to the invention. features would be present but cartridge 16 would be
The methanol synthesis is preferably at a pressure in replaced by a pressure-resisting shell. External shell 10
the range 30-120 bar abs. and a temperature in the range is then, of course, not required and the reactants feed to
160-300 C. The catalyst usually contains also zinc the vessel is, after external preheating, direct to 22.
oxide and one or more further oxides, such as of chro 35 The reactor shown in FIG. 2 resembles that of FIG.
mium (and UK Pat. No. 101.0871) or of a metal from 1 in its outer shell 10, manholes 12 and 18, cartridge 16,
Groups II-IV of the Periodic Table (our UK Pat. No. ring-girder 17, port 20, sieve plate 24, reacted gas outlet
1159035) or possibly for example manganese or van 26, tubes 32, chamber 34, catalyst 36 and ring frame
dium. For such a process the cooled catalyst bed has a work 33. It differs, however, in the arrangements for
heat transfer area in the range 5-20 m2 per m3 of cata 40 supporting tubes 32 and introducing gas to them. The
lyst. reactor gas inlet 15 is now at the top of shell 10. Car
The reactor is suitable also for the catalytic synthesis tridge 16 is formed on its underside with apertures 37:
of dimethyl ether, of alcohols higher than methanol or note that this region of FIG. 2 shows items 17, 20, 24, 26
of hydrocarbons, from carbon monoxide/hydrogen and 37 which are not in the same plane of section. From
synthesis gases and for the zeolite-catalysed conversion 45 each aperture 37 there extends upwards a vertical
of methanol and/or dimethyl ether to aromatic hydro header 38, from which branch tubes 32. The lowermost
carbons, operated in isolation or in conjunction with part of catalyst bed 36 is not now fully adiabatic, since
catalytic synthesis thereof. heat removal through vertical headers 38 can take
Preferred forms of the invention are shown in the place: if desired, these can be insulated, however.
accompanying drawings, in which: 50 The reactor of FIG. 2 could be modified to a hot-wall
FIG. 1a is a sectional elevation of a reactor in which type by replacing cartridge 16 by the pressure-resisting
the process of ammonia synthesis or methanol synthesis shell and supplying internal vertical headers from an
can take place, and which itself is a further aspect of the external lagged header.
invention; In the flowsheet shown in FIG. 3, dry compressed
FIG. 1b is a section on line b-b in FIG. 1; 55 fresh ammonia synthesis gas 40 from a generation sec
FIG. 2 is an alternative reactor according to the in tion (typically comprising steam natural gas reforming,
vention; and shift, CO2-removal and residual carbon monoxide re
FIG.3 is a flowsheet of a preferred process according moval by methanation or selective oxidation) is mixed
to the invention. at 42 with recycle gas to be described and heated to
In FIG. 1a reactor outer shell 10, constructed to 60 eactor shell inlet temperature in secondary heat ex
withstand the pressure at which the synthesis is to oper changer 44. It is then fed to reactor shell 10 at 14, heated
ate, is formed with an upper manhole 12 for charging further in the space between shell 10 and cartridge 16
catalyst, a bottom gas inlet aperture 14 and two other and fed via gas inlet pipe 22 into tubes 32 in the upper
bottom apertures to be described below. Within shell portion of catalyst bed 36. In that upper portion synthe
10, supported by perforated ring-girder 17, is cartridge 65 sis take place and evolved heat is continuously removed
16 which, since in operation gas at the same pressure by heat exchange with the gas inside tubes 32. In the
will be outside and inside it, is made of relatively light lower portion of bed 36 further reaction takes place and
gauge metal. Cartidge 16 is formed with catalyst charg the temperature is allowed to rise. The hot reacted gas
 4,778,662
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is withdrawn by outlet 26 and cooled with external run off at 52. Unreacted gas passes out overhead and is
high-grade heat recovery (as boiler feed water, steam or fed to circulator 56, which increases its pressure by
steam superheat or more than one of these) in primary 10-20%, providing the synthesis recycle stream fed to
heat exchanger 46. It then passes to secondary heat point 42. A purge stream is taken at 58 and is usually
exchanger 44 already mentioned, then to low grade heat passed out to other uses, for example as a fuel or as
recovery and final cooling (including moderate refrig hydrogenating gas. However, it can be fed to separation
eration) represented generally by 48. The temperature is section 60. Here it is washed with water to remove
now below the dewpoint of ammonia and the gas is methanol, dried and resolved cryogenically or by ab
passed catchpot 50 from which liquid product ammonia soption or selective diffusion into a hydrogen-rich
is run off at 52. Unreacted gas passes out overhead; at 10 stream and a waste stream 66, which may have fuel
this stage it contains less hydrogen per nitrogen mole value. The hydrogen-rich stream can be returned to the
cule than the gas fed to reactor 10, because ammonia methanol synthesis at 54 if the synthesis gas composition
formation uses three H2 molecules per nitrogen mole requires it or can be passed out to other uses, especially
cule, but at 54 it receives a feed of hydrogen-rich gas to ammonia synthesis. Methanol recovered in item 60 is
be described below. The mixed gas is fed to circulator 5 passed to the main product offtake and thence to distil
56, which increases its pressure by 10-20%, and is then lative purification (not shown).
divided at 58 into a synthesis recycle stream (which is In a typical ammonia synthesis (output 1000 metric
fed to point 42) and a hydrogen recovery stream. This tons per day) the temperatures, pressures, gas composi
stream is fed to separation section 60. Here it is washed tions and flow rates are shown in the Table 1. The heat
with water to remove ammonia, dried and resolved 20 transfer area is 12 m2 perm of catalyst using tubes of 37
cryogenically or by absorption or selective diffusion mm outside diameter.
TABLE 1.
Temp. Press. Gas composition 26 v/v Flow rate
Position C. bar H2 CH4 Ar N2 NH3 kg mol hl
abs.
22 inlet 255 87.0 60.47 6.73 1.56 2.49 3.75 27737
32 outlet 396 87.0 60.47 6.73 156 27.49 3.75 27737
36 at 29 360 86.0 54,438 7.183 66S 25.973 10.74 25984
24 40. 85.5 51.797 7.382 1.71. 25.3 13.8 25289

into the hydrogen-rich stream fed to point 54 and a In a typical methanol synthesis process (output 2525
waste stream 66, which may have fuel value. The aque metric tons of methanol 100% per day) the tempera
ous ammonia is distilled under pressure and the result tures, pressures, gas compositions and flow rates are as
ing anhydrous ammonia is fed out at 64 to the main shown in Table 2.
TABLE 2
Pr.
Temp. bar Gas composition 2a v/v. Flow rate
--- v- Position "C. abs CO CO2 H2 CH4 N2 CH3OH H2O kg mol ht
22 inlet 100
32 outlet 240 ) 79 4.82 3.23 82.7 8.50 0.32 0.33 0.009 85547
36 at 29 265.9 79 2.35 2.20 79.97 9.21 0.35 4.52 140 7897
24 269.8 77 2.24 2.8 79.89 9.23 0.35 4.67 1.42 78754

product offtake 52. 45

For methanol synthesis the flowsheet shown in FIG.
3 can be used as a whole but is more commonly modi In this process the heat transfer area using tubes of
fied by omission of shell 10 and of item 10 and the con outside diameter 37 mm is 13 m2 per m of catalyst.
nections to and from it, that is, by using a hot-wall The catalyst volume in both processes is 10-15% less
reactor. Dry compressed fresh methanol synthesis gas 50 than would be required using a conventional quench
40 from a generation section (typically comprising reactor. The reactor volume is lower, since as much as
steam gas reforming, water removal) is mixed at 42 with 75-90% of the cartridge volume can contain catalyst.
recycle gas to be described and heated to reactor inlet Since the catalyst can be very easily discharged and
temperature in secondary heat exchanger 44. It is then replaced, the reactor volume for ammonia synthesis can
fed via gas inlet pipe 22 into tubes 32 in the upper por 55 be made still smaller by designing for a shorter catalyst
tion of catalyst bed 36. In that upper portion synthesis life than has been customary, for example 2-5 instead of
takes place and evolved heat is continuously removed 4-10 years.
by heat exchange with the gas inside tubes 32. In the I claim:
lower portion of bed 36 further reaction takes place and 1. A reactor suitable for the catalytic synthesis of
the temperature is allowed to rise. The hot reacted gas 60 ammonia or methanol comprising:
is withdrawn by outlet 26 and cooled with external heat (i) an outer shell constructed to withstand a pressure
recovery (as hot pressurised water or medium pressure in the range 30 to 120 bar absolute;
steam) in primary heat exchanger 46. It them passes to (ii) inlet means to supply reactant gas to said shell;
secondary heat exchanger 44 already mentioned, then (iii) outlet means to permit removal of reacted gas
to low grade heat recovery and final cooling repre 65 from said shell;
sented generally by 48. The temperature is now below (iv) means defining a single, vertically oriented, cata
the dewpoint of methanol and the gas is passed to catch lyst bed region within said shell, containing a fixed
pot 50 from which liquid product aqueous methanol is bed of particulate catalyst and including means
 4,778,662
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defining a space above an upper surface of said particles, slidably applied to the tubes and secured
catalyst bed; against vertical movement.
(v) a plurality of spaced-apart header pipes immersed 3. A reactor according to claim 1 intended for use in
in said bed of particulate catalyst; ammonia synthesis at a pressure in the range 30-120 bar
(vi) means to feed reactant gas from said inlet means 5 abs., in which the heat exchange surface in the tube
to said header pipes; containing portion of the catalyst bed is in the range
(vii) a plurality of vertically oriented heat exchange 3-15 m2 per m3 of catalyst in said tube containing por
tubes having open upper ends and extending up tion of the catalyst bed.
wardly from said header pipes, said tubes being 4. A reactor according to claim 1 intended for use in
immersed in said bed of particulate catalyst for O methanol synthesis at a pressure in the range 30-120 bar
substantially their whole length but opening at the abs, in which the heat exchange surface in the tube
upper ends into the space above the upper surface containing portion of the catalyst bed is in the range
of the catalyst bed, so that the catalyst continu 5-20 m2 per m3 of catalyst in the tube containing portion
ously fills the spaces between the tubes and be of the catalyst bed.
tween the header pipes thereby defining a tube 15 5. A reactor according to claim 1 wherein the catalyst
containing portion of the catalyst bed, and the bed region comprises a cartridge within, and spaced
catalyst also extending below said header pipes from the walls of, the shell and the means for supply of
thereby defining a catalyst bed portion having no reactant gas from the inlet means to the header pipes
heat exchange tubes extending therethrough; and includes the space between the cartridge and the shell
(viii) means to feed reacted gas from the lower end of 20 wall.
the catalyst bed region to said outlet means. 6. A reactor according to claim 1 wherein there is no
2. A reactor according to claim 1 in which the heat heat exchange surface within the shell other than that
exchange tubes are kept in position by one or more provided by the tubes ink thek catalyst bed region.
planar linked-ring frameworks permeable to catalyst s

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