Europaisches Patentamt | | | | | 1 1| | | | | | | || | | || | | | | | | | | | |

(19) J European Patent Office

Office europeen des brevets (11) EP 0 817 674 B1

(12) E U R O P E A N PATENT S P E C I F I C A T I O N

(45) Date of publication

ation and mention
mention (51) Int. CI.6: B01 J 10/02, C07B 4 5 / 0 2
of the grant of the patent:
26.05.1999 Bulletin 1999/21 (86) International application number:
PCT/NO96/00065
(21) Application number: 96909396.2
(87) International publication number:
(22) Date of filing: 22.03.1996 WO 96/301 17 (03.1 0.1 996 Gazette 1996/44)

(54) MULTITUBE FALLING FILM REACTOR FOR THE CONTINUOUS MANUFACTURING OF

SULFONATED AND/OR SULFATED COMPOUNDS
FALLFILMREAKTOR MIT EINER VIELZAHL AN ROHREN ZUR HERSTELLUNG VON SULFONEN
ODER SULFATEN
REACTEUR MULTITUBE A FILM TOMBANT DE PRODUCTION CONTINUE DE COMPOSES
SULFONES OU SULFATES

(84) Designated Contracting States: (72) Inventor: Dahl, Birger

AT BE CH DE ES FR GB GR IE IT LI NL PT 1710Sapsborg (NO)

(30) Priority: 28.03.1995 NO 951178 (74) Representative:

Piesold, Alexander J.
(43) Date of publication of application: Frank B. Dehn & Co.,
14.01.1998 Bulletin 1998/03 European Patent Attorneys,
179 Queen Victoria Street
(73) Proprietor: Dahl, Birger London EC4V 4EL (GB)
1710Sapsborg (NO)
(56) References cited:
EP-A- 0 570 844 IUS-A-4183 897

CO

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
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notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
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a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
Q. 99(1) European Patent Convention).
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 1 EP 0 817
EP0
817 674
Description
[0001 ] Multitube falling film reactors represent today a
well established technology, and is frequently the pre-
ferred reactorprinciple for sulphonation and sulphation
reactions, both giving advanced products; surfactants
for the cosmetic and detergent industry. The reactors
are assembled according to conventional principles for
a multitube shell and tube heat-exchanger with different
baffle-arrangements and cooling liquids, with water as
the dominating cooling liquid. Typical for all reactors are
separate chambers for diluted gas, organic compound,
cooling liquid and collection of finished products, cham-
bers mentioned from top of reactor to bottom outlet.
[0002] When producing surfactants for the said indus-
try, the gaseous and diluted reactant is sulfur trioxide,
typical organic compounds are liquids at 15 °C or
higher, the main variety of raw-material being alkylates
fatty alcohols, etoxilated fatty alcohols, alpha-olefins
and methyl-esters. Any chemical compound equipped
with a socalled flexible hydrogen atom might be sulpho-
nated or sulphated. (Sulphated for all compounds
where hydrogen is linked to an oxygen atom, sulpho-
nated for the linkage hydrogen-carbon.)
The overall chemical reactions taking place, are charac-
terized by the fact that diluted, gaseous S03 is a very
aggressive/reactive reactant, and that the reactions are
all extremely rapid and exothermic. Altogether, these
properties challenge the control of the molar ratio
between the reactants, and only with the very best con-
trol of both total and local molar ratio, the best products
are achieved. Any deviation in the molar ratio will una-
voidably result in increased quantity of undesired by-
products, and the main product will suffer from bad col-
our, lower active matter content, higher content of sul-
phates, higher content of nonsulphated/-sulphonated
organic compounds and consequently lower yield with a
higher raw-material consumption. In a MTR, where the
numbers of individual and parallel reactor-element
could be from two to more than hundred, the most
important parameter is the local molar ratio between the
reactants, and therefore the best possible and most
homogeneous distribution of organic compound to each
individual reactor-element. Even the smallest deviation
in local molar ratio, can not be fully compensated for
later in the process.
[0003] To avoid any misunderstanding, total molar
ratio is defined as the ratio between the total number of
moles S03 fed to the reactor divided by the total number
of moles organic compound fed to the same reactor. By
advanced dosing system for liquid sulfur/liquid sulfur
dioxide/liquid sulfur trioxide and finally organic com-
pounds, the total molar ratio can be kept almost con-
stant and without any significant impact on the final
product properties.
[0004] The local molar ratio, defined the same way but
between local flows of said reactants for each individual
nozzle-element, is predominantly depending on an even
74 B1
2
and homogeneous feed, kg/hour of organic reactant to
each individual nozzle-set from one common, organic
chamber, since a gas carrying a far lower viscosity has
a higher tendency of even distribution according to the
s principle of "the way of lowest resistance". The nozzle-
set construction will therefore appear as the decisive
and critical element for individual organic flow and local
molar ratio. In a MTR, all the nozzle-sets are fed from
one common, organic chamber. The nozzle-construc-
10 tion also allows a reactor to consist of only one reactor
element, where the total molar ratio becomes equal and
identical to the local molar ratio, accuracy only depend-
ing on the external dosing system.
[0005] Of great and vital importance is also an even
15 and homogeneous distribution of the organic film
formed circumferentially on the internal, surface of the
female part. This can be achieved, provided that the film
distribution/formation on the internal surface of the said
female part is determined by the same accuracy as the
20 dosing/metering of organic compounds of the nozzle-
set for all reactor elements. It means altogether that the
film-formation should be determined by the same accu-
racy as the dosing/metering of organic compounds, i.e.
a well defined annular slot in respect of length an width
25 for all known, operational conditions.
There are several, different concepts of constructions
available on the market and already patented, relevant
in this connection are following patents:
30 US 3,918,917 Nitto Chemical Industry Co., Ltd.
US 4,183,897 Construzioni Meccaniche G. Maz-
zoni S.p.A
FR 2,449,665 Ballestra Chimica S.p.A
EP 0,570,844 A1 Meccaniche Moderne S.r.l
35
[0006] These patents and constructional concepts
can be described and grouped by following:
precalibrated and selected/grouped orifices(materi-
40 als totally different from this patent), characterized
by a relatively long distance between the zone for
metering/dosing and the zone for film formation.
(Pre-selected/grouped orifices should not be mixed
up with the terminology nozzle-set and nozzle-set
45 construction described in this document.)
conical or cylindrical slots where even a lower accu-
racy(compared to this invention) of organic feed
only can be achieved through a mechanical adjust-
so ment of the slots length or opening by shims. If the
slot opening and slot length were well defined in
these constructions, and besides appeared with the
accuracy described in mentioned patents, no
adjustment by shims would be necessary. It is obvi-
55 ous that the location of the male part relatively to
the female part by shims, will be influenced by dif-
ferent pressure working on the main flanges/cylin-
drical plates(pressures different from the conditions
2
 3 EP 0 817 674 B1
during calibration), by the torque on single bolts for
tightening, by sealing material and finally by the dis-
tance between the cylindrical plates. The fact that
all individual nozzle-sets have to be calibrated
before start-up, also clearly demonstrates the 5
unsufficient definition of the opening and length of
the slots, resulting in a less homogeneous distribu-
tion of the film (different thickness around the wet-
ted periphery) on the internal surface of the female
part of the nozzle-set. ro
[0007] The main differences/disadvantages for
already known and operative constructions compared
to the nozzle-set construction described in this docu-
ment, can be summarized by following: is [0012] An accuracy level like this, has up till now not
higher tendency of air-pockets and thereby partly
blocking of organic feed during start-up. (Air-pock-
ets in the space between male and female part of
the nozzle-set.) 20 MTR reactors designed for heterogene reactions, even
partly more complex components, less easy to
machine.
need for time-consuming calibration both before
start-up and after an uncontrolled stop during oper-
ation, or after a routine washing/cleaning proce- 25 described by way of example only and with reference to
dure. The accuracy of this calibration will also be
influenced by the fact that normal plant conditions
are always different from calibration conditions,
generally lower accuracy for individual organic feed
compared to the total average of organic feed for all 30
nozzle-sets in operation.
generally will lower accuracy of metering mean
increased variation in film thickness,
tightening arrangement for the male and female
part of the nozzle-set will influence the accuracy of 35
individual nozzle-set supply and also said accuracy
for neighbouring nozzle-sets,
the neccessity of shims adjustment creates very
frequently tendency of increased leakages,
accuracy of metering will strongly depend on the 40
torque applied for tightening the bolts,
the individual supply from each nozzle-set will fur-
ther also be depending on pressure variations dur-
ing normal operation, pressures working on the
different cylindrical plates and giving different 45
impact depending on the location of the nozzle-set
on the said plates.
[0008] The nozzle-set represents the most vital com-
ponent/part of any multitube falling film reactor, and this so
invention relates mainly to the design, construction and
assembling of all the individual components comprising
a nozzle-set.
[0009] The invention therefore provides a multi-tube
falling film reactor as recited in claim 1. ss
[001 0] The preferred nozzle-set described in this doc-
ument has a well defined annular slot having a fixed
length and a fixed width under all known operational
3
4
conditions. The necessity of complicated and less relia-
ble arrangement for calibration like shims etc is elimi-
nated, and the preferred nozzle-set will also give a
substantial increase in the homogeneity of the film thick-
ness. There is no need for calibration before start-up, or
time-consuming re-calibration after a stop in the plant.
[001 1] A model of a preferred embodiment of the reac-
tor according to the invention with more than 30 parallel
nozzle-sets in full size has been tested, and by introduc-
ing the average flow xav, g/min, for all nozzle-sets, all
individual flows are covered by the range:
been reported, and the reactor with the new nozzle-set
will be named the NCN reactor, which means: No Cali-
bration Needed.
[0013] The NCN nozzle-set may be installed in all
for reactions where for instance reactive particles are
present and suspended in an inert liquid, (inert to the
gaseous reactant).
[0014] Some preferred embodiments will now be
the accompanying drawings in which:
Fig 1 is a longitudinal section of a complete and
assembled multitube falling film reactor Type NCN,
with three individual nozzle-sets fixed to reactor-
tubes partly in section.
Fig 2 is a detailed assembly drawing for one com-
plete nozzle-set comprising a female part, a male
part, respective tightening arrangement, tightening
bolts and sealing system all arranged on two indi-
vidual and separated cylindrical plates.
Fig 3 is a cross section of Fig 2 A-A enlarged, and
shows in detail the six channels for liquid, organic
feed to the expansion chamber.
Definitions/terminology
[0015]
Nozzle-set: A complete unit comprising a female
part, a male part, respective tightening arrange-
ment, tightening bolts and sealing system.
Reactortube: A conventional tube, total length 5-7
m, and fixed to the female part of the nozzle-set.
The reactortube represents in this way the zone for
the chemical reaction taking place, and transfers
heat of reaction to the surrounding and circulating
cooling liquid.
Reactor-element: A complete unit having as inte-
gral parts one nozzle-set, one reactortube and
finally sealing arrangements.
Multitube falling film reactor. Fig 1: A complete
reactor unit including from two to more than hun-
 5 EP 0 817 674 B1
dred reactor-elements together with separate
chambers for distribution of gaseous reactant, liq-
uid organic reactant, cooling liquid, collecting
chamber for finished product and connections for all
material flows. 5 [0018] Liquid, organic reactant being fed from a cen-
Reactorhead: Includes the nozzle-sets and the
organic chamber defined and limited by a cylindri-
cal plate fixed to a cylindrical spacer fixed to a
counter-flange bolted and sealed to the lowest
cylindrical plate. 10
Calibration of nozzle-set: Manual and time-con-
suming work for all individual nozzle-sets, at least
the reactorhead must be fully assembled to accom-
plish this procedure. A quantity of organic reactant
normally corresponding to the nominal capacity of is
the reactor, is fed to the common organic chamber,
and all the individual flows leaving nozzle-sets or
reactortubes, are carefully determined by weighing.
Based on the measuring results from this proce-
dure, an arithmetic average for the individual flows 20
is calculated, for instance Xav. Any deviation outside
a predetermined and acceptable range, will have to
be adjusted for by replacement of the shims having
thicknesses different from the ones originally
installed. Normally this procedure will have to be 25
repeated uptil several times to reach a range
described by:
For reactortechnology of yesterday, average + 2.5%
is quite usual and rather seldomly average + 1.0%
is reached. Unfortunately, the same reactortechnol-
ogy can neither confirm nor guarantee this
range/limit of deviation during normal, operational
conditions.
Detailed description of the invention.
[001 6] With reference to the attached figures, Fig 1,
Fig 2 and Fig 3, together with the definitions and termi-
nology listed in para 3, a complete, multitube falling film
reactor will include more than two reactor-elements in
parallel, chamber 4 for distribution of the gaseous reac-
tant, chamber 11 for distribution of organic reactant,
chamber 25 for cooling liquid and chamber 53 for col-
lecting of finished product, chamber 53 being defined by
plate/flange 29/31 and the conical bottom cap 32, all
mentioned parts from reactor top to reactor bottom/out-
let. All the chambers are separated from neighbouring
chamber with plates/flanges 8, 9 16, 18, 27, 29 and 31 ,
sealing systems, outer cylindrical mantle and conical
caps 3/32 at top and bottom respectively. At the outlet of
each reactor-element, stuffing-boxes 28/30 installed in
plate 29 efficiently prevent leakage between cooling-
chamber 25 and collecting chamber 53. These stuffing
boxes allows thermal, longitudinal expansion of reactor-
tubes during normal plant conditions/operation.
6
[0017] The upper chamber 4 being fed through 1 and
limited by a conical top cap 3 and the upper plate 9
together with the flange 8, evenly distributes the gase-
ous reactants to all individual reactor-elements.
tral pipe-line and distributed to the organic chamber 11
through several feeding-tubes 12. This chamber 11 is
also equipped with a on/off ball-valve for de-areation
during start-up and operation. The chamber 11 is
vented to the surrounding atmosphere. The operating
pressure in chamber 11 is given by the pressure drop
through the annular slot 21 and the gas pressure in the
reactortube 24.
[001 9] Liquid, organic reactant is fed from the com-
mon chamber 11 to each separate nozzle-set at 13
along the total periphery of female part 19 and further to
the expansion-chamber 20 through the longitudinal
feeding channels Fig 2/Fig 3 40. The organic reactant is
perfectly metered and distributed through the annular
slot 21 forming a continuous and uniform falling film 50
on the internal surface of the female part 19. At the out-
let of the slot 21 , the liquid organic reactant from cham-
ber 11 meets the gaseous reactant from chamber 4,
immediately starting the exothermic and heterogeneous
chemical reaction. The heat of the reaction is trans-
ferred to the outer surface of the reactor-tube, and con-
tinuously removed by the circulating cooling liquid in
chamber 25. The cooling liquid fed to the same cham-
ber through 26, leaving at 22. The finished product from
all reactor-elements is collected at the bottom of the
reactor in chamber 53, leave at 34 and further down-
stream treated in a special separator/cyclone for the
separation of gas/liquid.
[0020] The complete nozzle-set will according to this
35 document include a male part 10, a female part 19,
tightening arrangements 5/6 and 14/15 respectively,
and sealings 7/1 7 respectively.
[0021 ] Female part 19 equipped with integral tighten-
ing flange 41, is fixed to the plate 18 by the tightening
40 ring 15 and two - four bolts 14. The cylindrical plate 18
separates the organic chamber 11 from the cooling
chamber 25. The integral flange on female part 19 has
a height equal to the depth of the tightening-ring 15 at
43, thus forming a completely even surface and
45 together with sealing 17 comprise a sealing system
between the female part 19 and the plate 18. Built-in
distance/clearance 42 between the said female flange
41 and the said tightening ring 15, efficiently prevents
radial forces to occur and acting on the female part 19
so through 41 .
[0022] The position of the female part 19 is according
to above only determined by the cylindrical opening in
plate 18. Longitudinally, the position is determined by
the applied torque on the bolts 14, sealing thick-
55 ness/compressibility and additionally by different pres-
sure- and temperature-conditions during operation. A
cylindrical section/spacer between flange 16 and upper
plate 9 forms together with the lower plate 18 the said
4
 7 EP 0 817 674 B1 8

organic chamber 11. To avoid eccentrisity between always located at the lower position of the two lips 48
plate 9 and 18, plate 18 is equipped with at least two and 49.
conical guiding pins entering corresponding holes in [0027] The distance 46 between lip 48 and 49 being
flange 16 with a high degree of precision. normally 2.0 - 3.0 mm, will permanently and automati-
[0023] The female part 19 is internally machined form- 5 cally compensate for all sorts of external forces tending
ing one half 44 of the expansion chamber 20. This to move in longitudinal direction the male part 10 rela-
machined part 44 of the expansion chamber 20 is iden- tively to the female part 19 or opposite.
tical to the other machined half 45 located at the outer [0028] The pressure drop in the annular slot 21 deter-
surface of the male part 10. Together the two halves mines the flow from each nozzle-set, and with the annu-
comprise the said expansion chamber 20. The female to lar slot being constant even when male parts moves
part 19 is fixed to the reactortube 24, length 5 - 7 m, at relatively to the female part or opposite(limits stated in
23. above relation), the same pressure drop will remain
[0024] The male part 10 is equipped with a similar, constant and finally thereby the flow.
integral flange 38 with the height corresponding to the [0029] In other words, for any complete nozzle-set
depth of the tightening ring 6 at 35. Together, flange 38 15 equipped with a constant slot opening 21. the flow will
and ring 6 form a completely even surface and together remain constant as long as the distance 46 is within the
with sealing at 7 comprises a sealing system between limits of said relation and thus giving a constant slot
the male part 10 and the plate 9. Built-in distance/clear- length 47 indepent of variations in operational condi-
ance 37 between the said male flange 38 and the said tions. The nozzle-set will permanently need no mechan-
tightening ring 6, efficiently prevents radial forces to 20 ical arrangements for adjusting the relative position of
occur and acting on the male part 10 through 38. male and female part to influence or adjust the individ-
The said tightening ring 6 is equipped with oversized ual flows, and there will be no need neither for calibra-
holes for bolts. In combination with the said clearance tion nor re-calibration.
37, the clearance between the holes in the plate 9 and [0030] The invention therefore comprises a multitube
male part 10, the said oversized holes 36 efficiently pre- 25 falling film reactor with a nozzle-set as described in
vent any radial forces to occur and act on the said flange details above, showing an uptil now unknown accuracy
38 nor the total male part 10 of the nozzle-set. The and without the necessity of complicated and less relia-
important centering of the male part 10 into the female ble mechanical arrangements for final adjustments of all
part 19, is according to above only determined by the individual flows. Additionally, any need for calibration
guiding zone 52. 30 before start-up, or re-calibration in connection with
[0025] Longitudinal channels 40 machined on the uncontrolled stops and routine maintenance, is elimi-
outer surface of the male part 10, lead the organic feed nated compared to other, similar constructions.
from the chamber 11 to the expansion chamber 20. The invention has been described according to one
The size and number of these channels are carefully embodiment of the invention, and alternatives may be
selected to give maximum guiding surface in combina- 35 made by one skilled in the art. The invention embraces
tion with low, linear velocity of the liquid making this noz- all such alternatives which are clearly in family to and
zle-set self-deareating during start-up and operation. within the protective scope of the following claims.
Self-deareating as terminology is consequently applied
for any gaseous component being present before start- Claims
up and/or dispersed gasparticles in the bulk flow of 40
organic that might occur during normal operation. The 1. A multi-tube falling film reactor for the continuous
male part 10 of the said nozzle-set is externally sulphonation and sulphation of a liquid organic sub-
machined to form one half 45 of the expansion chamber stance by reaction with gaseous S03, wherein the
20. Characteristic for this invention and construction is reactor comprises at least two reactor elements,
that both the length 47 and the opening of the annular 45 each element consisting of a nozzle set comprising
slot 21 is defined once for all and under all known oper- an inner male portion (10) and an outer female por-
ational conditions, provided that the lower lips 48 and 49 tion (19), which portions (10, 19) are in their respec-
of the halves 44 and 45 respectively under the said con- tive upper part provided with an integral flange
ditions always will be separated a distance 46 and with device (38, 41) for mounting to a fiat chamber plate
the lip 49 at the lower position. The feed of organic liquid so (9) and a second chamber plate (18), respectively,
to or from the nozzle-set, will according to this invention the female portion (1 9) is in its lower part connected
only depend on the channel length 47 which is well to a reactor tube (24) which in its lower part is
defined for all nozzle-sets and constant opening of the mounted to a third chamber plate (29), whereby in
annular slot 21 formed between the male and female use each reactor element is fed with an organic
part.The said distance 46 between the said lips 48 and 55 substance from a common feeding chamber (11)
49, will be determined according to following relation: through longitudinal channels (40) defined on the
[0026] The length of half-chambers 44 and/or 45 in outside of the male portion (1 0) and via an expan-
expansionchamber 20 >distance 46>0 The lip 49 sion chamber (20) and further down in the reactor

5
 9 EP 0 817 674 B1
tube (24) through an annular channel (21) formed
between the outer circular surface of the male por-
tion (10) and inner circular surface of the female
portion (19) of the nozzle, the organic substance
then reacting with the S03 gas which flows down in
the reactor tube (24) through the inner bore of the
nozzle from a common gas distribution chamber
(4), the reactor tube (24) and the lower part of the
nozzle being further arranged inside a common
cooling chamber (25) whereby in use the resulting
product from all reactor elements is collected in a
collecting chamber (53) at the bottom of the reactor,
wherein the longitudinal channels (40) are
extended along the complete contacting/guiding
surface (52) between the outer surface of the male
portion (1 0) and the inner surface of the female por-
tion (19) of the nozzle, respectively, characterized
in that the expansion chamber (20) is formed as a
circumferential groove/milling (45) in the outer cir-
cumferential surface of the male portion (10) and in
that the height (47) of the annular channel (21)
between the outer surface of the male portion (10)
and the inner surface of the female portion (19),
and thereby the volume of the annular channel (21)
itself, is constant with respect to axial displacement
of the male portion (10) inside the female portion
(19) and thereby every reactor element will main-
tain a constant flow rate under varying process con-
ditions.
30
2. Reactor according to claim 1,
characterized in that the expansion chambers (20)
in the various reactor elements are formed by coop-
eration between said groove (45) in the outer cir-
cumferential surface of the male portion (10) and a 35
circumferential groove/milling (44) in the inner cir-
cumferential surface of the female portion (19) of
similar volume as the groove (45) in the outer cir-
cumferential surface of the male portion (10), the
lower circumferential edge (49) of the groove (45) of 40
the male portion (10) during operation having a dis-
placement (46) in relation to and located below the
lower circumferential edge (48) of the female por-
tion (19), the displacement (46) is larger than zero
and less than the height of each groove (44, 45). 45
3. Reactor according to claim 1 or 2,
characterized in that the number of longitudinal
channels (40) is six.
4. Reactor according to claim 1, 2 or 3,
characterized by one of the two reactants being
present as gaseous reactant and the other partici-
pating reactant present as a liquid at ambient tem-
perature or temperatures corresponding to the
reaction conditions, the said reactor assembled as
a conventional multitube shell and tube heat
exchanger with separated chambers for gaseous
10
reactant (4), liquid organic reactant (1 1), cooling liq-
uid (25) and collection of finished products (53).
5. Reactor according to claim 1, 2, 3 or 4,
5 characterized by further comprising a plurality of
nozzle-sets, from two to more than hundred, and
where the said liquid organic reactant is fed to the
common organic chamber (11) through a plurality
of separated feeding tubes (12), the organic cham-
w ber (11) being defined by said first and second
cylindrical chamber plates (9) and (18), counterf-
lange (16) and finally cylindrical spacer fixed and
welded to said first chamber plate (9) and counterf-
lange (16), a diluted gaseous reactant is further fed
75 to the common gas distribution chamber (4) limited
by a flange (8), first cylindrical chamber plate (9)
and conical top cap (3), and that finished product is
collected in collecting chamber (53) defined by a
conical bottom cap (32), third cylindrical chamber
20 plate (29) and counterflange (31), the third cylindri-
cal chamber plate (29) equipped with stuffing boxes
(28/30) for reactor tube (24) and arranged at the
reactor bottom/outlet.
25 6. Reactor according to anyone of the previous
claims,
characterized in that each nozzle-set comprises a
male portion (10) fixed to the said first chamber
plate (9) by bolts (5) and a tightening ring (6) and
sealing (7), and where the height of the respective
integral flange device (38) exactly equals the
machined depth of the tightening ring (6) and forms
an even surface against sealing (7), and by the
clearance (39) between the male portion (10) and
the well defined hole in the said plate (9), clearance
(36) between bolts (5) and said ring (6) and sealing
(7), and by clearance (37) between said integral
flange (38) and said ring (6) all to give a tight seal-
ing between said gas distribution chamber (4) and
said liquid organic reactant chamber (11) without
any radial forces acting on the male portion (10)
and/or without any forces transferred between the
first and second cylindrical chamber plates (9) and
(18), further the female portion of the nozzle-set in
said reactor is fixed to the second cylindrical cham-
ber plate (18) according to the same principles as
for the male portion (10) to said first chamber plate
(9), but without having the same clearance between
female portion (19) and the corresponding hole in
50 the second cylindrical chamber plate (18).
7. Reactor according to anyone of the previous
claims,
characterized by said male portion (1 0) of the noz-
55 zle-set is concentric relatively to female portion (1 9)
and achieved in that a guiding surface (51) on the
male portion (10) exactly fits into the corresponding
guiding surface of the female portion (19) and that
6
 11 EP 0 817 674 B1
said concentric location is only determined by the
guiding surfaces and the length of the same sur-
faces, and by feeding channels (40) externally
machined on the male portion (10) having number
between two and twelve lead the organic feed from 5
liquid organic reactant chamber (1 1) to the expan-
sion chamber (20), and by the selection of six (6)
feeding channels a maximum of guiding surface is
achieved in combination with said de-areating prop-
erties, and by the ratio between effective guiding w
length and the external diameter of male portion
(10) is designed to be within the range 1.1 - 3.0 and
preferably is 1.5 to secure maximum concentric
guiding, further the said reactor having a said
female portion (19) equipped internally with a 75
machined half (44) of the expansion chamber (20),
the other half (45) being machined externally on the
male portion (10) and by the well defined length
(47) of the annular slot (21) achieved by a distance
(46) between the lower lip (48) on the female por- 20
tion (19) and the lower lip (49) on the said male part
(10), further the said lip (49) in the said reactor
always at the lowest location for the two lips (48)
and (49) and the said distance (46) permanently
larger than zero and permanently smaller than 2s
each of the length of the two halves (44 and 45) of
the expansion chamber (20).
8. Reactor according to anyone of the previous
claims, 30
characterized in that the height of the expansion
chamber groove (45) in the male portion (10) of the
nozzle is different from the height of the expansion
chamber groove (44) in the female portion (19) of
the nozzle, and further described by the following 35
relation:
0 < Distance (46) between the lower lip (48) on the
female portion (19) and the lower lip (49) on the
said male part (10)
< height of any of the two expansion cham- 40
ber grooves (44,45) 2.
Patentanspruche
1. Mehrrohren-Rieselfilmreaktor zur kontinuierlichen 45
Sulfonierung und Sulfatierung einer flussigen orga-
nischen Substanz durch Reaktion mit gasformigem
S03, mit mindestens zwei Reaktorelementen, von
denen jedes ein Diisenaggregat mit einem vor-
springenden Innenteil (10) und einem riicksprin- so
genden AuBenteil (19), deren oberer Teil mit einem
angegossenen Flansch (38 bzw. 41), mit dem sie
an einer ersten Kammerplatte (9) bzw. an einer
zweiten Kammerplatte (18) angebracht werden,
versehen sind, umfaBt, wobei der untere Teil des ss
riickspringenden AuBenteils (19) mit einer Reaktor-
rohre (24), deren unterer Teil an einer dritten Kam-
merplatte (29) angebracht ist, verbunden ist und im
7
12
Betrieb jedem Reaktorelement aus einer gemein-
samen Zufuhrkammer (11) uber in Langsrichtung
verlaufende Kanale (40), die an der AuBenseite des
vorspringenden Innenteils (10) gebildet sind, und
uber eine Expansionskammer (20) und weiter
unten in der Reaktorrohre (24) uber einen ringfor-
migen Kanal (21), der zwischen der zylindrischen
AuBenseite des vorspringenden Innenteils (10) und
der zylindrischen Innenseite des riickspringenden
AuBenteils (19) der Dtise gebildet ist, eine organi-
sche Substanz zugefiihrt wird, die dann mit dem
S03-Gas, das aus einer gemeinsamen Gasvertei-
lungskammer (4) uber die innere Bohrung der Dtise
nach unten in das Reaktorrohr (24) stromt, reagiert,
wobei die Reaktorrohre (24) und der untere Teil der
Dtise weiterhin in einer gemeinsamen Ktihlkammer
(25) angeordnet sind und im Betrieb das Produkt
aller Reaktorelemente in einer Sammelkammer
(53) am Boden des Reaktors gesammelt wird,
wobei sich die in Langsrichtung verlaufenden
Kanale (40) zwischen der AuBenseite des vorsprin-
genden Innenteils (10) und der Innenseite des riick-
springenden AuBenteils (19) der Dtise uber die
gesamte Lange der Kontakt-/
Ftihrungsflache (52) hinweg erstrecken,
dadurch gekennzeichnet,
daB die Expansionskammer (20) als umlau-
fende Nut (45), die in die Mantelflache des vorsprin-
genden Innenteils (10) gefrast ist, gebildet ist und
daB die Hohe (47) des zwischen der AuBenseite
des vorspringenden Innenteils (10) und der Innen-
seite des riickspringenden AuBenteils (19) gebilde-
ten ringformigen Kanals (21) und somit das
Volumen des ringformigen Kanals (21) selbst kon-
stant ist, wenn das vorspringende Innenteil (10) im
riickspringenden AuBenteil (19) axial verschoben
wird, so daB in den Reaktorelementen der Durch-
satz bei unterschiedlichen Verfahrensbedingungen
konstant bleibt.
Reaktor nach Anspruch 1, dadurch gekenn-
zeichnet, daB die Expansionskammern (20) der
Reaktorelemente gebildet sind durch Zusammen-
wirken der in der Mantelflache des vorspringenden
Innenteils (10) gebildeten Nut (45) mit einer umlau-
fenden Nut (44), die in die Innenflache des riick-
springenden AuBenteils (19) gefrast ist und ein
ahnlich groBes Volumen wie die in der Mantelflache
des vorspringenden Innenteils (10) gebildete Nut
(45) aufweist, wobei der untere umlaufende Rand
(49) der Nut (45) des vorspringenden Innenteils
(10) im Betrieb in bezug auf den unteren umlaufen-
den Rand (48) des riickspringenden AuBenteils
(19) eine Verschiebung (46) erfahrt, bei der er
unterhalb des unteren umlaufenden Rands (48)
des riickspringenden AuBenteils (19) bleibt und die
Verschiebung (46) groBer als Null und kleiner als
die Hohe der Nuten (44, 45) ist
 13 EP 0 817 674 B1
3. Reaktor nach Anspruch 1 oder 2, dadurch gekenn-
zeichnet, daB die Anzahl der in Langsrichtung ver-
laufenden Kanale (40) sechs betragt.
4. Reaktor nach Anspruch 1, 2 oder 3, dadurch
gekennzeichnet, daB einer der beiden Reaktions-
partner als Gas und der andere Reaktionspartner
als Flussigkeit, deren Temperatur der Umgebung
oder der Reaktionsbedingungen entspricht, vor-
liegt, wobei dieser Reaktor den Aufbau eines her-
kommlichen mehrere Rohren aufweisenden
Rohrenwarmetauschers mit getrennten Kammern
fur den gasformigen Reaktionspartner (4), den flus-
sigen organischen Reaktionspartner (1 1), die Kuhl-
flussigkeit (25) und fertige Produkte (53) aufweist.
5. Reaktor nach Anspruch 1, 2, 3 oder 4, dadurch
gekennzeichnet, daB er weiterhin mehrere, zwi-
schen zwei und mehr als hundert, Diisenaggregate
umfaBt, wobei der flussige organische Reaktions- 20
partner der gemeinsamen organischen Kammer
(11) uber mehrere separate Zufiihrrohre (12) zuge-
fLihrt wird, die organische Kammer (11) durch die
erste zylindrische Kammerplatte (9), die zweite
zylindrische Kammerplatte (18), einen Gegen- 25
flansch (16) und ein zylindrisches Abstandsstiick,
das an der ersten Kammerplatte (9) und dem
Gegenflansch (16) befestigt und angeschweiBt ist,
gebildet ist, ein verdiinnter gasformiger Reaktions-
partner der gemeinsamen Gasverteilungskammer 30
(4), die durch einen Flansch (8), die erste zylindri-
sche Kammerplatte (9) und eine konische Deck-
kappe (3) begrenzt ist, zugefiihrt wird, das fertige
Produkt in der Sammelkammer (53), die durch eine
konische Bodenkappe (32), die dritte zylindrische 35
Kammerplatte (29) und einen Gegenflansch (31)
gebildet ist, gesammelt wird und die dritte zylindri-
sche Kammerplatte (29) mit StopfbLichsen (28/30)
fur die Reaktorrohren (24) ausgestattet und am
AuslaB bzw. Reaktorboden angeordnet ist
6. Reaktor nach einem der vorhergehenden Ansprii-
che, dadurch gekennzeichnet, daB jedes Diisenag-
gregat ein vorspringendes Innenteil (10), das
mittels Schrauben (5) und eines Festspannrings (6)
an der ersten zylindrischen Kammerplatte (9) befe-
stigt ist, und eine Dichtung (7) umfaBt, wobei der
angegossene Flansch (38) eine Hohe aufweist, die
exakt gleich der abgespanten Tiefe des Festspann-
rings (6) ist, so daB an der Dichtung (7) eine glatte
Flache entsteht, durch den Zwischenraum (39) zwi-
schen dem vorspringenden Innenteil (10) und dem
in der Platte (9) prazise gebildeten Loch, durch den
Zwischenraum (36) zwischen den Schrauben (5)
und dem Ring (6) und der Dichtung (7) und durch
den Zwischenraum (37) zwischen dem angegosse-
nen Flansch (38) und dem Ring (6) eine hermeti-
sche Abdichtung zwischen der Gasverteilungs-
14
kammer (4) und der Kammer (1 1) fur den flussigen
organischen Reaktionspartner gebildet wird, bei
der auf das vorspringende Innenteil (10) keine
Radialkrafte einwirken und/oder keine Krafte zwi-
s schen der ersten zylindrischen Kammerplatte (9)
und der zweiten zylindrischen Kammerplatte (18)
iibertragen werden, und das riickspringende
AuBenteil des Diisenaggregats bei diesem Reaktor
nach den fur die Befestigung des vorspringenden
10 Innenteils (10) an der ersten Kammerplatte (9) gel-
tenden Prinzipien, jedoch ohne einen Zwischen-
raum zwischen dem riickspringenden AuBenteil
(19) und dem entsprechenden Loch in der zweiten
zylindrischen Kammerplatte (18), an der zweiten
is zylindrischen Kammerplatte (18) befestigt ist.
7. Reaktor nach einem der vorhergehenden Ansprii-
che, dadurch gekennzeichnet, daB das vorsprin-
gende Innenteil (10) des Diisenaggregats zum
riickspringenden AuBenteil (19) konzentrisch ange-
ordnet ist, was durch exakte Einpassung einer Fiih-
rungsflache (51) des vorspringenden Innenteils
(10) in die entsprechende Fiihrungsflache des
riickspringenden AuBenteils (19) erreicht wird, daB
diese konzentrische Anordnung nur durch die Fiih-
rungsflachen und die Lange dieser Flachen
bestimmt wird, daB zwischen zwei und zwolf
Zufiihrkanalen (40), die auf der AuBenseite des
vorspringenden Innenteils (10) spanabhebend
gebildet werden, die organische Substanz von der
Kammer (11) fur den flussigen organischen Reakti-
onspartner zur Expansionskammer (20) leiten,
wobei durch Wahl von sechs Zufiihrkanalen ein
Maximum an Fiihrungsflache in Kombination mit
Entliiftungseigenschaften erreicht wird, daB das
Verhaltnis zwischen der effektiven Fiihrungslange
und dem AuBendurchmesser des vorspringenden
Innenteils (10) im Bereich von 1,1 bis 3,0 liegt und
vorzugsweise 1,5 betragt, urn maximale konzentri-
40 sche Fiihrung zu gewahrleisten, daB das riicksprin-
gende AuBenteil (19) des Reaktors weiterhin mit
einer abgespanten Halfte (44) der Expansionskam-
mer (20) ausgestattet ist und deren andere Halfte
(45) auf der AuBenseite des vorspringenden Innen-
45 teils (10) spanabhebend gebildet ist, daB die pra-
zise Festlegung der Lange (47) des ringformigen
Schlitzes (21) durch einen Abstand (46) zwischen
dem unteren Absatz (48) des riickspringenden
AuBenteils (19) und dem unteren Absatz (49) des
so vorspringenden Innenteils (10) erreicht wird, daB
sich bei diesem Reaktor der Absatz (49) immer
unterhalb des Absatzes (48) befindet und daB der
Abstand (46) immer groBer als Null und immer klei-
ner als die jeweilige Lange der beiden Halften (44
ss und 45) der Expansionskammer (20) ist.
8. Reaktor nach einem der vorhergehenden Ansprii-
che, dadurch gekennzeichnet, daB sich die Hohe
8
 15 EP 0 817 674 B1
der Expansionskammernut (45) des vorspringen-
den Innenteils (10) der Dtise von der Hohe der
Expansionskammernut (44) des riickspringenden
AuBenteils (19) der Dtise unterscheidet und durch
die folgende Beziehung beschrieben wird: 5 (10) a I'interieur de la partie femelle (19) et chaque
0 < Abstand (46) zwischen unterem Absatz (48)
des riickspringenden AuBenteils (19) und unterem
Absatz (49) des vorspringenden Innenteils (10) <
Hohe der Expansionskammernut (44) oder der
Expansionskammernut (45). ro 2.
Revendications
1. Reacteur multitube a film ruisselant pour la sulfona-
tion et la sulfatation continues d'une substance 15
organique liquide par reaction avec du S03 gazeux,
dans lequel le reacteur comprend au moins deux
elements de reacteur, chaque element consistant
en un ensemble d'injecteur comprenant une partie
male interne (1 0) et une partie femelle externe (19), 20
lesquelles parties (10, 19) sont munies dans leur
partie superieure respective d'un dispositif de bride
en une seule piece (38, 41) pour le montage sur
respectivement une premiere plaque de chambre
(9) et une seconde plaque de chambre (1 8), la par- 25
tie femelle (19) est raccordee dans sa partie infe-
rieure a un tube de reacteur (24) qui est monte 3.
dans sa partie inferieure sur une troisieme plaque
de chambre (29), chaque element de reacteur est
par la alimente lors de I'utilisation en une substance 30
organique provenant d'une chambre commune 4.
d'alimentation (11) par I'intermediaire de canaux
longitudinaux (40) definis sur I'exterieur de la partie
male (10) et via une chambre de detente (20) et
plus vers le bas dans le tube de reacteur (24) par 35
I'intermediaire d'un canal annulaire (21) forme entre
la surface circulaire externe de la partie male (10)
et la surface circulaire interne de la partie femelle
(19) de I'injecteur, la substance organique reagis-
sant ensuite avec le gaz de S03 qui s'ecoule vers le 40
bas dans le tube de reacteur (24) a travers le per-
gage interne de I'injecteur a partir d'une chambre
commune de distribution de gaz (4), le tube de
reacteur (24) et la partie inferieure de I'injecteur 5.
etant en outre disposes a I'interieur d'une chambre 45
commune de refroidissement (25), le produit resul-
tant de tous les elements de reacteur est par la
recueilli lors de I'utilisation dans une chambre de
recueil (53) au fond du reacteur, dans lequel les
canaux longitudinaux (40) s'etendent le long de la so
surface totale de contact/guidage (52) respective-
ment entre la surface externe de la partie male (10)
et la surface interne de la partie femelle (19) de
I'injecteur, caracteriseeen ce que la chambre de
detente (20) est formee comme une rainure/frai- ss
sage circonferentielle (45) dans la surface circonfe-
rentielle externe de la partie male (10) et en ce que
la hauteur (47) du canal annulaire (21) entre la sur-
9
16
face externe de la partie male (10) et la surface
interne de la partie femelle (19), et par la le volume
du canal annulaire (21) lui-meme, est constante par
rapport a un emplacement axial de la partie male
element de reacteur conservera par la un debit
constant dans les differentes conditions du pro-
cede.
Reacteur selon la revendication 1, caracterise en
ce que les chambres de detente (20) dans les diffe-
rents elements de reacteur sont formees par coo-
peration entre ladite rainure (45) dans la surface
circonferentielle externe de la partie male (10) et
une rainure/fraisage circonferentielle (44) dans la
surface circonferentielle interne de la partie femelle
(19) de volume identique a la rainure (45) dans la
surface circonferentielle externe de la partie male
(10) , le bord circonferentiel inferieur (49) de la rai-
nure (45) de la partie male (1 0) presentant pendant
le fonctionnement un deplacement (46) lie au et
dispose en dessous du bord circonferentiel infe-
rieur (48) de la partie femelle (19), le deplacement
(46) est superieur a zero et inferieur a la hauteur de
chaque rainure (44, 45).
Reacteur selon la revendication 1 ou 2, caracterise
en ce que le nombre des canaux longitudinaux (40)
est egal a 6.
Reacteur selon la revendication 1, 2 ou 3, caracte-
rise en ce qu'un des deux corps reagissants est
present comme corps reagissant gazeux et I'autre
comme corps reagissant participant est present
comme in liquide a temperature ambiante ou aux
temperatures correspondants aux conditions de la
reaction, ledit reacteur est assemble comme un
echangeur de chaleur tubulaire multitube classique
avec des chambres separees pour un corps reagis-
sant gazeux (4), un corps reagissant liquide organi-
que (1 1), un liquide refrigerant (25) et le recueil des
produits finis (53).
Reacteur selon la revendication 1, 2, 3 ou 4, carac-
terise en ce qu'il comprend en outre de nombreux
ensembles d'injecteurs, de deux a plus de cent, et
dans lequel ledit corps reagissant organique liquide
est introduit dans la chambre organique commune
(11) par I'intermediaire de nombreux tubes d'ali-
mentation separes (12), la chambre organique (1 1)
etant definie par lesdites premiere et seconde pla-
ques de chambre cylindriques (9) et (18), une con-
tre-bride (16) et finalement un element
d'ecartement cylindrique fixe et soude auxdites
premiere plaque de chambre (9) et contre-bride
(16), un corps reagissant gazeux dilue est en outre
introduit dans la chambre commune de distribution
de gaz (4) limitee par une bride (8), la premiere pla-
 17 EP 0 817 674 B1 18

que de chambre cylindrique (9) et un couvercle et en ce que le rapport entre la longueur efficace de
superieur conique (3), et en ce que du produit fini guidage et le diametre externe de la partie male
est recueilli dans une chambre de recueil (53) defi- (10) est mis au point pour se trouver dans I'inter-
nie par un couvercle de fond conique (32), la troi- valle de 1,1-3,0 et est de preference de 1,5 pour
sieme plaque de chambre cylindrique (29) et une 5 assurer un guidage concentrique maximal, ledit
contre-bride (31), la troisieme plaque de chambre reacteur presentant en outre unedite partie femelle
cylindrique (29) etant equipee de presse-etoupes (19) equipee de maniere interne d'une moitie usi-
(28/30) pour le tube de reacteur (24) et etant dispo- nee (44) de la chambre de detente (20), I'autre moi-
see au fond/sortie du reacteur. tie (45) etant usinee de maniere externe sur la
10 partie male (10) et en ce que la longueur bien defi-
6. Reacteur selon I'une quelconque des revendica- nie (47) de la fente annulaire (21) est realisee par
tions precedentes caracterise en ce que chaque une distance (46) entre le rebord inferieur (48) sur
ensemble d'injecteur comprend une partie male la partie femelle (19) et le rebord inferieur (49) sur
(10) fixee a ladite premiere plaque de chambre (9) ladite partie male (10), ledit rebord (49) dans ledit
par des ecrous (5) et un anneau de serrage (6) et 15 reacteur etant toujours a la position la plus basse
une etancheite (7), et dans lequel la hauteur de dis- des deux rebords (48) et (49) et ladite distance (46)
positif respectif de bride en une seule piece (38) est etant en permanence superieure a zero et en per-
exactement egale a la profondeur usinee de manence inferieure a chacune des longueurs des
I'anneau de serrage (6) et forme une surface plane deux moities (44 et 45) de la chambre de detente
contre I'etancheite (7), et par I'evidement (39) entre 20 (20) .
la partie male (10) et le trou bien defini dans ladite
plaque (9), un evidemment (36) entre les ecrous (5) 8. Reacteur selon I'une quelconque des revendica-
et lesdits anneau (6) et etancheite (7), et par un evi- tions precedentes caracterise en ce que la hauteur
dement (37) entre ladite bride en une seule piece de la rainure de chambre de detente (45) dans la
(38) et ledit anneau (6) pour fournir tous ensemble 25 partie male (10) de I'injecteur est differente de la
une etancheite hermetique entre ladite chambre de hauteur de la rainure de chambre de detente (44)
distribution de gaz (4) et ladite chambre de corps dans la partie femelle (19) de I'injecteur et est en
reagissant organique liquide (1 1) sans force radiale outre decrite par la relation suivante :
agissant sur la partie male (10) et/ou sans force 0 < distance (46) entre le rebord inferieur (48) sur la
transferee entre les premiere et seconde plaques 30 partie femelle (19) et le rebord inferieur (49) sur
de chambre cylindriques (9) et (18), la partie ladite partie male (10) < hauteur de I'une quelcon-
femelle, de I'ensemble d'injecteur dans ledit reac- que des deux rainures de chambre de detente (44,
teur est en outre fixee a la seconde plaque de 45).
chambre cylindrique (18) selon les memes preci-
pes que pour la partie male (10) a ladite premiere 35
plaque de chambre (9) mais sans presenter le
meme evidement entre la partie femelle (19) et le
trou correspondant dans la seconde plaque de
chambre cylindrique (18).
40
7. Reacteur selon I'une quelconque des revendica-
tions precedentes, caracterise en ce ladite partie
male (10) de I'ensemble d'injecteur est concentri-
que relativement a la partie femelle (19) et est rea-
lisee en ce qu'une surface de guidage (51) sur la 45
partie male (10) s'insere exactement dans la sur-
face de guidage correspondante de la partie
femelle (19) et en ce que ladite disposition concen-
trique est uniquement determinee par les surfaces
de guidage et la longueur des memes surfaces, et so
en ce que les canaux d'alimentation (40) usines de
maniere externe sur la partie male (10), au nombre
de deux a douze, conduisent I'alimentation organi-
que de la chambre de corps regissant organique
liquide (1 1) vers la chambre de detente (20) et en 55
ce qu'une surface maximale de guidage est reali-
see par le chois de six (6) canaux d'alimentation en
combinaison avec lesdites proprietes desaeration,

10
■*U 01 / Oft Dl
EP 0 817 674 B1
EP 0 817 674 B1

13