United States Patent (19 11, 3,931,273

Lanteri (45 Jan. 6, 1976

54 METHOD FOR SULPHONATIZING AND 3, 169,142 2/1965 Knaggs ct al....................... 260/458
SULPHATIZING ORGANIC COMPOUNDS 3,270,038 8/1966 Marshall............................. 260/458
WTH SULPHUR TRIOXIDE AND 3,531,518 7|1966 Ohren et al...................... 26015.3 R
APPARATUS THEREFOR
75 Inventor: Agostino Lanteri, Busto Arsizio, Primary Examiner-James O. Thomas, Jr.
Varese, Italy Assistant Examiner-Nicky Chan
73 Assignee: Costruzioni Meccaniche G. Mazzoni Attorney, Agent, or Firm-Young & Thompson
S.p.A., Busto Arsizio, Varese, Italy
22 Filed: Mar. 14, 1974
57 ABSTRACT
21 Appl. No.: 451,200
Related U.S. Application Data A continuous method for sulphonating and sulphating
(63. Continuation of Ser. No. 114,973, Feb. 12, 1971, liquid organic compounds with gaseous sulphur triox
abandoned. ide diluted with inert gas in a plurality of externally
30 Foreign Application Priority Data cooled, parallel reaction tubes with downward flow
communicating at the injection nozzles of the liquid
Feb. 23, 1970 Italy............................ 2099.1170 and gas reactants with a single chamber under uniforn
52 U.S. C. ......... 260/458; 260/459 R; 260/513 T; pressure, from which an additional inert gas flows into
260/505 R; 23/284 the several reaction tubes so as to equalize the pres
5l Int. CP............... C07C141/02; C07C 143/16; sures downstream of all of said injection nozzles in
order to provide for a uniform distribution of the reac
C07C 143/12: C07C 143/34 tants to said reaction tubes, as seen in FIGS. 1-5.
(58. Field of Search.... 260/458, 459, 513 R, 505 R, This method is applied to all the organic compounds
260/505 C, 457, 458 R, 458 C, 459 R, 513 T; susceptible to said reactions.
23/277 R, 284
7 Claims, 5 Drawing Figures
56 References Cited
UNITED STATES PATENTS
2,923,728 11/1957 Falk et al............................ 2601458

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ciple is described in Soap & Chemical Specialities, May
METHOD FOR SULPHONATIZING AND 1967, page 67. It includes a downward vertical flow
SULPHATIZING ORGANIC COMPOUNDS WITH reaction tube having an inner diameter of 5 mm.
SULPHUR TRIOXDE AND APPARATUS An increase in flow rate would involve an increase in
THEREFOR the tube diameter and length and, at the same time, an
increase in flow velocity. However, there are limits to
This is a continuation of application Ser. No. this purpose because the gas supply pressure may be
114,973, filed Feb.12, 1971, now abandoned. come undue and/or the product quality may be low
This invention relates to a continuous method for ered. Good reaction conditions are achieved by tubes
sulphonating and sulphating liquid organic compounds O of a comparatively small diameter or conduits in the
with sulphur trioxide gas. As used herein, the term form of rectangular or annular slot with a reduced
"liquid' means that the organic compounds to be pro thickness.
cessed are liquid at room temperature or at the temper Industrial reactors generally include a single reaction
ature at which they are reacted with sulphur trioxide. zone in the form of an annular conduit between two
More particularly, this invention relates to a method 15 concentric cylindrical surfaces, having a free cross-sec
and an apparatus for reacting organic compounds with tion suitable to the intended flow rate, or a plurality of
gas containing sulphur trioxide in a two-phase gas-liq parallel reaction zones in the form of circular tubes.
uid flow system consisting of parallel conduits. The These are downward flow vertical systems, wherein an
method is applicable to all of the organic compounds annular type of flow is naturally established in a wide
capable of reacting with diluted sulphur trioxide, either 20 range of gas velocities. However, it is important to
forming sulphonates or sulphates. maintain an essentially high velocity for the gas phase
Methods are known for carrying out gas/liquid reac in order to provide the liquid phase with velocity and
tions in two-phase cocurrent flow systems, wherein the turbulence, thereby ensuring an even reaction, an effi
required turbulence for causing the interphase contact 25
cient temperature control and a short residence time of
and heat transfer is essentially achieved at the charge of the product in the reaction Zone.
the gas stream energy. To this end, elongated reaction In these reactors the problem arises for evenly dis
zones are generally used in the form of conduits or tributing the liquid and gas reactants throughout the
tubes where the gas and liquid reactants are continu single reaction zone or in all of the parallel reaction
ously introduced from the same end. For example, U.S. zones. In this connection, known methods have several
Pat. No. 2,528,320 describes such reaction techniques 30 disadvantages.
for paraffin sulphochlorination with a gaseous mixture In the case of annular conduit reactors (see British
of gas sulphur trioxide and chlorine, characterized in Patent No. 1,029,029), a uniform free cross section is
that the superficial gas velocity is kept at a sufficiently required throughout the reaction zone. This gives rise
high rate to cause an annular turbulent flow. This type to highly strict accuracy problems in construction,
of flow is characterized in that the liquid is caused by 35 particularly where large reactors for important indus
the gas velocity to circumferentially flow on the inner trial productions are concerned. British Patent No.
tube walls, as in the central portion the gas flows 1,103,441 describes a reactor in the form of an annular
around the tube axis. U.S. Pat. No. 2,865,958 describes conduit provided with a cage stirring member rotating
a sulphonatizing method, according to which a mineral in the initial portion of the reaction zone in order to
40 ensure an even distribution and contact for the reac
oil containing olefine hydrocarbons and/or aromatic
hydrocarbons and gas containing sulphur trioxide are tants. However, this approach requires the use of a
introduced from an end into a tubular chamber. The mechanical stirrer which has to rotate at a high speed
organic liquid circumferentially enters the chamber closely adjacent the two surfaces.
and is dispersed in the gas jet centrally penetrating Particularly, in those reactors where liquid and gas
therein. 45 would flow in completely separate parallel conduits,
In most cases, such as in producing organic sulpho such as the tubular reactors this invention is related to,
nates and sulphates for detergents and similar uses, the an even distribution of the liquid and gas reactants is
reaction of the organic compounds with sulphur triox hampered by the changes which may occur in flow
ide is extremely rapid and exothermic. Moreover, sev resistance of the several elements. These changes may
eral products being obtained in this reaction, particu 50 depend on changes in the inner diameter within the
larly organic sulphuric esters, are unstable. Suitable ranges of commercial tolerances or the roughness of
means have to be used for ensuring an even contact of the inner surfaces. A certain change (in absolute length
the reactants, a rapid removal of the reaction heat and rate) in the inner diameter would cause a percentage
a short residence time of the product in the reaction change in pressure drop which is the higher as smaller
zone. Otherwise, charrings and other undesirable ef 55 is the tube diameter. Accordingly, while the reaction
fects would occur, which could adversely affect the conditions improve as the inner diameter of the tubes
quality of the final product. In these circumstances, an decreases, the conditions for evenly distributing the
annular turbulent flow is definetely useful, as enabling reactants become more unfavourable. These changes
an even interphase contact and an efficient tempera may be enhanced in the long run because of uneve
ture control by circulating cooling liquid outside the 60 nesses in corrosion and erosion. In addition to this, it
walls encircling the reaction Zone. occurs in two liquid/gas phase flows that an increase in
According to U.S. Pat. No. 2,923,728, an annular liquid flow rate or in liquid viscosity would cause an
turbulent flow for the liquid organic compound is es increase in the resistance to gas flow. Accordingly, it
tablished on the inner walls of a tube by propelling by may occur that in a reaction tube, where the liquid flow
an inert gas, as a mixture of sulphur trioxide and an 65 rate has an excess error (due to the metering element),
other inert diluent gas is introduced into the central there would be a shortage of gas flow rate, whereby in
Zone of the tube. This method is suitable for small scale the reactant ratio there will be an overall error which is
productions. A laboratory apparatus based on this prin the sum of the two errors. The same may occur in a

-
 3,931,273
3 4
tube where the liquid flow rate shows an error in short gible in relation to the pressure drops in the injection
age. Finally, there may be slightly different reaction nozzles for the gas reactant. In most cases of practical
conditions from one tube to another, which may result application for the present method, a sufficiently even
in changes in pressurc drop of the gas flow. distribution of the reactants is provided when the inlet
U.S. Pat. No. 3,169,142 describes a reactor formed pressure drops of the equalizing gas are some units
of tubes having an inner diameter of about 1 1 mm., in percent at the most of the pressure drop in the injection
which the distribution of the liquid reactant to the nozzles for the gas reactant. Under these conditions,
various tubes is effected by means of nozzles capable of the equalizing gas will be distributed to the reaction
building up a high pressure drop in order to minimize tubes, so that the overall gas flow rate of each tube is a
the effect of possible changes in the pressure down decreasing function of the resistance thereof against
stream the nozzles on the liquid flow rate. Similarly, the the gas flow. It is apparent from the foregoing that the
distribution of the gas reactant is effected by means of substantial pressure equalization downstream of the
nozzles capable of building up a high pressure drop distributing nozzles for the liquid and gas reactants is
relative to that in the reaction tubes. Thus, possible depending on a substantial equalization of pressure
changes in the tube resistance would scarcely affect the 15 drops in all of the reaction tubes. Generally, the
gas flow rate of each element, since the latter depends amount of equalizing gas would vary approximately in
on the overall pressure drop of the nozzle and tube. In the range of 8-19 percent of the total amount of inert
this system the drawback is in that most of the gas gas flowing in each tube. Generally, the inert equalizing
stream energy has to be dissipated in the distributing gas is air. The equalizing gas may be introduced into
nozzles and only a comparatively small portion is avail 20 the reaction tubes concentrically between the liquid
able for flow in the reaction tubes. Therefore, the gas reactant supplied to the inner surfaces of the tubes and
velocity or flow rate in the reaction tubes has to be the gas reactant injected into the central Zone of each
limited: substantially it is in the order of 15 m/sec., tube, or may be introduced together with the liquid
referred to the tube section. As a result of this, the gas reactant through convergent-shaped inlets of the reac
and liquid flow rate per tube is rather low. An increase 25 tion tubes and encircling the injection nozzles for the
in the liquid flow rate, without a corresponding in gas reactant.
crease in the gas flow rate, can be provided within For a more detailed description of the characteristics
determined limits by increasing the sulphur trioxide of the present method, reference is made to the accom
concentration in the gas, but this is normally prejudicial panying drawings, in which:
to the quality and particularly to the colour of the prod 30 FIG. 1 is a diagrammatic vertical sectional view
uct. Additionally, in most cases it is considerably ad showing a reactor for carrying out the method accord
vantageous to operate with a substantially higher gas ing to the invention (in this figure, A indicates SOst
velocity or rate, preferably in the range of 35-65 m/sec. inert diluent gas; B a liquid organic reactant, C an
in order to provide the liquid phase in the action tubes equalizing inert gas; D a vent; Ethe cooling water out
with turbulence and velocity. Under these conditions a 35 let; and F the cooling water inlet);
rapid and even reaction occurs in all of the liquid por FIG. 2 is a detailed view showing the device for intro
tions with a short stay time and minimum alteration of ducing the reactants and equalizing gas into the reac
the product. However, this requires some consumption tion tubes according to FIG. 1;
of the gas stream energy, particularly in the case of FIG. 3 is a horizontal sectional view showing the
sulphonation and sulphation products having a substan 40 device in FIG. 2 at the inlet apertures for the equalizing
tial viscosity at reaction temperature. To provide for gas,
this energy, it is necessary that a sufficient pressure FIG. 4 is a view showing another form for introducing
drop be available in said tubes. the reactants and equalizing gas into the reaction tubes
The method of the present invention enables to pro for use in the method according to the present inven
vide a substantially even distribution of the liquid and 45 tion; and
gas reactants to a plurality of parallel reaction tubes FIG. 5 is a diagram showing the inlet pressure drops
independently within sufficiently wide ranges of the for the equalizing air in a device as shown in FIG. 2.
changes in flow resistance which may occur in the As shown in FIG. 1, the reactor is formed of a prefer
several tubes, without any need for this to restrict the ably vertical cylindrical housing or shell 1 enclosing a
pressure drop in said tubes. To this end, the present plurality of reaction tubes 23 (for simplicity, three only
method provides a substantial pressure equalization in of such tubes being shown in the figure, but the reactor
all of the parallel reaction tubes immediately down can comprise up to more than one hundred tubes). At
stream of the distributing nozzles for the liquid and gas the lower end thereof the tubes are secured to the plate
reactants.
55
6 by means of sealing elements 12, while being welded
Accordingly, this invention relates to a method for at the upper end thereof to threaded connectors 13;
sulphonating and sulphating liquid organic compounds these are sealingly clamped (by suitable seals) in the
by diluted gas sulphur trioxide with inert gas in a plural lower portion of threaded holes in the flanged plate 7.
ity of externally cooled, parallel reaction tubes with The housing or shell 1, plates 6 and 7 and walls of tubes
downward flow, characterized in that the reaction 23 enclose the chamber 16, in which cooling water can
tubes at the injection nozzles for the liquid and gas 60 be circulated from end to end by baffles 4 and 4. For
reactants communicates with a single uniform pressure an efficient cooling, in chamber 16 there are also pro
chamber, additional inert gas freely flowing therefrom vided transverse baffles or other known devices (not
to the several reaction tubes, so as to substantially shown in the drawing). The inner diameter of tubes 23
equalize the pressures downstream of all of the injec can be within about 8-18 mm. However, an internal
tion nozzles for the liquid and gas reactants. This addi 65 diameter of 8-13 mm. is generally preferable to pro
tional inert gas is hereinafter referred to as equalizing vide a sufficient flow rate per tube and an acceptable
gas. As a principle, the equalizing gas freely flows to the quality of product. In order to obtain the desired reac
reaction tubes when the inlet pressure drops are negli tion degree, the tube length should increase as the
 3,931,273
S 6
inner diameter increases. Generally, the tube length is angle of about 22°. Connectors 42 have a tubular ex
0.8-5.0 meters and preferably 1.0-3.5 meters. A tension 43 enclosing the gas nozzle 26 and forming an
flanged plate 7' is fixedly mounted on flanged plate 7 annular passage 45, through which the liquid organic
and has lying exactly above holes at the threaded holes reactant downward moves to the apertures 47 between
in flanged plate 7, the connectors 14 passing there the end conical surface of connector 41 and the outer
through and being clamped at the upper portion of the rim of nozzle 26. The equalizing gas gets to this aper
threaded holes in plate 7 so as to seal (by suitable seals) ture passing through the annular conduit 46 between
on the flanged plate 7". The connectors 14 carry the the inner surfaces of connector 41 and the outer Sur
elements for introducing the reactants and gas into the faces of the tubular extension 43. Through said aper
reaction tubes. A chamber 17 is provided between the ture 47, the liquid organic reactant and equalizing gas
flanged plates 7 and 7' and communicates with the are concurrently introduced into the reaction tube 23
annular chamber 18 formed by the housing or shell 5 externally of the gas jet emerging from the nozzle 26.
which is welded outside the flanged plate 7'. The annu Good results are obtained when the outer diameter of
lar chamber 18 communicates with chamber 17 by 15 nozzles 26 is substantially the same as the inner diame
means of radial holes 21 in the protruded portion on ter of the reaction tubes 23 and the end of nozzle 26 is
the flange of plate 7. By means of this connection, some recessed by 2.0–3.5 mm from the converging end of
inert gas can be supplied to chamber 17 and distributed connector 41, whereby the thickness of aperture 47 is
therefrom as equalizing gas, as described below. A the range of about 0.4-0.7 mm. The arrangement in
chamber 19 is located over the flanged plate 7' and FIG. 4 is particularly suitable for reaction tubes having
defined at the top by the separating flanges plate 8 and 20 an inner diameter of 6-10 mm. In these cases, also the
laterally by the cylindrical housing or shell 2, the liquid arrangement in FIG. 2 can be used, however requiring
organic reactant being supplied from this chamber 19 the use of gas reactant injection nozzles having a small
to the reaction tubes by means of the distributing noz diameter to provide a suitable thickness for the annular
zles 25 mounted on the connectors 14. The top portion 25 apertures 29. However, the arrangement in FIG. 4 can
of the reactor between the separating flanged plate 8 be used also with reaction tubes of a larger diameter
and the flange cover or lid 9 and laterally defined by and affording, for example, substantially the same re
the cylindrical shell or housing 3 comprises the cham sults as those obtained by the arrangement in FIG. 2 in
ber 20, from which the gas reactant is supplied to the the case of reaction tubes having an inner diameter of
reaction tubes by means of the distributing nozzles 26 3 mm.
centrally secured to the connectors 14 and passing 30 The equalizing gas in chamber 17 flows from periph
through the separating flanged plate 8; the latter is ery to center while being distributed to the reaction
provided with holes at the threaded holes in the flanged tubes 23 through holes 22 and annular conduits 27
plate 7", fitted with sealing elements 15. The flange 11 (FIG. 2) or annular conduits 46 (FIG. 4). The pressure
is for connecting the reactor to the outlet conduit. differential building up between the periphery and
The elements for introducing the reactants and 35 center of chamber 17 because of the gas flow will vary
equalizing gas into the reactor in FIG. 1 are shown in depending on the diameter of the chamber or the num
greater detail in FIGS. 2 and 3. As metered by means of ber of reaction tubes and the equalizing gas flow rate,
nozzle 25, the liquid organic reactant moves down the however being always quite negligible and in the order
conduit 24 to the space 30 between the connectors 13 of 1 mm. water column, or less.
and 14 in the threaded hole in plate 7; by means of the 40 The inlet pressure drop of the equalizing gas in reac
annular aperture 28 between the inner cylindrical sur tion tubes 23 is mostly localized at apertures 29 (FIG.
face of connector 13 and the outer cylindrical exten 2) or 47 (FIG. 4), where the gas flows together with the
sion surface of connector 14 and the conical connector liquid organic reactant. The thickness for apertures 29
31, the liquid is distributed therefrom on the periphery 45 or 47 will depend on the liquid organic reactant fligW
externally defining the annular aperture 29 opening rate related to the inner perimeter unit for tubes 23 and
into the reaction tube 23. The gas reactant is metered minimal and maximal equalizing gas flow rates. At the
by means of nozzle 26 and concentrically injected into minimal flow rate, the inlet velocity of the equalizing
the innermost portion of reaction tube 23. Preferably, gas should be sufficient to prevent the gas jet emerging
the outlet mouth of nozzles 26 is flared by a cone angle 50 from nozzles 26 from diffusing into the apertures 29 or
of about 7. The equalizing gas enters the radial holes 47. Such a diffusion may cause a premature reaction of
22 of connector 14, travels along the annular conduit the organic compound with sulphur trioxide and colour
27 between the inner cylindrical surface of the final development. On the other hand, the inlet pressure
section of connector 14 and the outer surface of nozzle drops, within the flow rate range required for equaliz
26 and penetrates the reaction tube 23 concentrically ing the changes in resistance of tubes 23, should be at
between the liquid reactant and the gas reactant jet. 55 a maximum some units percent of the pressure drop
The annular apertures 28 are of a rather narrow thick provided by the gas reactant nozzles 26. In the above
ness to cause the liquid to be distributed on the whole shown apertures, the inlet pressure drops are generally
periphery, but such however to exhibit only a minimal within 20-120 mm water column for equalizing gas
flow resistance. Generally, this port is between 0.5 and 60 flow rates in the range of 8-19 percent of the total inert
1.2 mm. Preferably, the thickness for the annular aper gas flow rate per tube. In order to set up the above ratio
tures 29 is in the range of 1.0-1.8 mm and the length of pressure drops the nozzles 26 are dimensioned in
thereof is in the range of 5-30 mm. connection with the gas reactant flow rate, so as to set
FIG. 4 shows a further convenient arrangement for up a pressure drop generally in the range of 0.10-0.35
introducing the reactants and equalizing gas into the kg/cm.
reaction tubes. Plates 7 and 7" are provided with 65 The highest difference in pressure downstream of the
threaded holes which are identical and properly overly gas reactant distribution nozzles is given by the differ
ing for receiving the connectors 41 and 42. An end ence in inlet pressure drops for the equalizing gas cor
portion of connectors 41 are convergent by a cone responding to the maximal and minimal flow rates. This
 3,931,273
7 8
difference is related to the maximal difference in resis kg/cm and at a convenient temperature in order not to
tances of the parallel reaction tubes. The maximal per result in condensation and obstruction of the distribu
centage difference in gas reactant distribution to the tion nozzles or solidification of the organic compound
reaction tubes is as from the following relation: within the supply chamber. In the case of high melting
point organic compounds, also the equalizing gas
should be at a convenient temperature to avoid solidifi
cation at the inlet of the reaction tubes.
APA(A max-A, min) - X 00 The reaction temperature will vary according to vis
cosity and melting point of the liquid phase and fully
10 generally is in the range of about 30°-1 10°C. To this
wherein AP is the pressure drop at the gas reactant
nozzles, while A max and A min are the inlet pressure end, it should be noted that the temperature will vary
drops for the equalizing gas corresponding to the maxi along the reaction tubes: it increases instantaneously at
mal flow rate and minimal flow rate, respectively. Simi the initial contact zone of the reactants because of the
larly, the maximum difference in liquid reactant distri extremely fast reaction, whereupon the heat subtracted
5 by external cooling will gradually prevail on the heat
bution can be estimated. Since the pressure drops generated by the reaction and the temperature will
caused by gas flows in holes 22 and conduits 27 (FIG. drop.
2) or conduits 26 (FIG. 4) are about 30 percent or less The reaction tubes may be of such a length to effect
of the total inlet pressure drop for the equalizing gas,
the pressure differential downstream of the liquid dis 20 a substantial cooling of the reaction mixture, or of a
tribution nozzles is minimal. Accordingly, nozzles can length just sufficient to provide a substantially com
be used having a pressure drop which is comparatively plete absorption of sulphur trioxide; in the latter case
low when related to the required liquid flow rate. This the reaction product is further cooled at the reactor
is desirable in order to avoid a too high velocity for the outlet, before or after the separation of the exhaust gas
Streann.
liquid, which may cause erosion on the inner surfaces 25 The method of the present invention is applicable to
of the precision gauged holes.
The pressure drop in the reaction tubes 23 may be sulphonating and sulphating all of the organic com
also substantially higher than that in nozzles 26. There sulphur trioxide. ofThe
pounds capable reacting at a liquid state with gas
compounds may be unitary, or
fore, the restrictions in the prior art can be overcome as mixtures of homologous terms or isomers, or both.
to the liquid flow rate and gas speed in the reaction 30 Examples of these compounds are olefines having a
tubes.
linear or branched chain containing
The superficial gas velocity in the reaction tubes atoms with an inner or end double bond 8 to 20 carbon
resulting from the overall inert gas flow rate, e.g. SO (alpha ole
diluting gas and equalizing gas, is generally in the range fines); the aromatic hydrocarbons and aromatic hydro
carbons substituted by a linear or branched alkyl chain
of 20-80 m/sec., preferably 35-65 m/sec. At lower 35 containing up to 25 carbon atoms, such as alkylben
velocity than the minimal level indicated, the inter zenes and particularly dodecylbenzene and tridecyl
phase contact may be unsatisfactory, or the liquid benzene; the fatty alcohols having a linear or branched
phase may be overheld in the reaction zone. Within the chain containing 8 to 20 carbon atoms, such as lauryl
above shown velocity range, an interphase mixing oc alcohol and cetyl-stearyl alcohol; the condensation
curs which increases as the gas velocity increases; the 40 products of ethylene oxide with fatty alcohols and fatty
interphase surface is complex and liquid portions acids having 8 to 20 carbon atoms and with alkylphe
would leave the continuous phase for entering the gas nois having an alkyl chain comprising 8 to 16 carbon
phase and then re-entering the continuous liquid phase. atoms; the fatty acids containing 8 to 20 carbon atoms
For velocities exceeding the maximal level indicated, and their esters. Also mixtures of compounds having a
liquid portions would tend to be gradually and more 45 different chemical structure can be used as starting
firmly suspended in the gas phase as minute droplets materials, such as alkylbenzenes and fatty alcohols and
which may unduly react with sulphur trioxide or be also mixtures of compounds reacting with sulphur tri
drawn by the outlet exhausted gas. oxide with other compounds not reacting there with,
The concentration of sulphur trioxide in the gas, as such as fractions of mineral oils containing aromatic
the latter becomes diluted with the inert gas for equal 50 products.
izing the pressures and contacts the liquid organic reac Furthermore, the method of the present invention
tant, is generally in the range of 2-12 percent by vol can be used also for other gas/liquid reactions occur
ume, preferably 3-6 percent by volume. The molar ring through heat development or absorption, provided
ratio of sulphur trioxide and organic compound will that still an inert gas may be used as equalizing gas.
vary according to the nature of the latter and is in the 55
EXAMPLE
range of 0.9-1.2, more generally 0.95-1.15.
The gas reactant containing sulphur trioxide can be This example relates to the gas reactant distribution
obtained by evaporating commercial stabilized liquid in a reactor as shown in FIG. 1, formed of commercial
sulphur trioxide or sulphur trioxide obtained by oleum drawn pipes having a rated inner diameter of 11 mm.
distillation in a stream of inert gas, such as nitrogen, 60 and a length of 1850 mm. The reactor is designed for a
carbon dioxide or more usually dry air, or by elemental liquid reactant flow rate of 7.2 kg/h per tube (referred
sulphur burning in a stream of dry air and conversion of to dodecylbenzene) and a total air flow rate of 17
sulphur dioxide to sulphur trioxide. In any case, a flow Nm/h. The annular inlet apertures for the liquid reac
of gas or dry air can be by-passed ahead of the gas tant and equalizing air having a thickness of 1.5 mm
sulphur trioxide production system and used as equaliz 65 and a length of 20 mm. Under the above set forth con
1ng gas. ditions and under a pressure of 0.5 kg/cm (in the
The gas reactant containing sulphur trioxide is sup equalizing air chamber), the inlet pressure drops for
plied to the reactor under a pressure of about 0.3-1.3 the equalizing superficial air are graphically shown in
 3,931,273
10
FIG. 5. The air velocity in the reaction tubes, referred EXAMPLE 3
to the tube cross-section, is about 50 m/sec. The aver
age equalizing air flow rate is 2 Nm/h per tube. The This example relates to sulphation of a commercial
main air stream of 15 Nm/h per tube is used for sul fraction of linear synthetic fatty alcohols having an
phur trioxide dilution. The equalization for changes in 5 even number of carbon atoms, mainly C2 and C. It is
total air flow rate is contemplated, as due to changes in quite similar to commercial lauryl alcohol and has an
tube resistance, within a maximum of 6 percent, that is average molecular weight of 198. The characteristics of
the reactor and air flow rates are the same as in Exam
within 1 Nm/h per tube. Thus, the equalizing air flows ple 1. A molar ratio of sulphur trioxide and organic
to the several tubes in amounts from 1.5 to 2.5 Nm/h
per tube. The inlet pressure drops for the equalizing air compound of 1.00 is used. The organic reactant is
10
are of 40 and 70 mm water column, respectively. By supplied to the reactor in a rate of 6 kg/h per tube and
using gas reactant distribution nozzles capable of pro sulphur trioxide is evaporated in the main air stream in
viding a pressure drop of 0.20 kg/cm, the maximal a rate of 2.42 kg/h per tube. The concentration of
difference in distribution is: sulphur trioxide in the gas reactant is 4.3 percent by
15 volume; as an average, it drops to 3.8 percent by vol
ume when the gas reactant encounters the equalizing
2000 air and contacts the organic reactant. The organic reac
2000-70-40 - 1) x 100 = 0.75% tant has a solidification temperature of about 22°C and
is supplied to the reactor at 29°C. The temperature of
20 the gas reactant is 40°C. Cooling water at 29°C is circu
EXAMPLE 2 lated within the reactor. In the gas reactant supply
chamber the pressure is 0.53 kg/cm, and in the equal
This example shows the sulphonation of commercial izing air chamber the pressure is 0.30 kg/cm. The
dodecyl benzene having a branched side chain and reaction mixture exits from the reactor at 37°C. After
average molecular weight of 245. The characteristics of 25 separation of the exhausted gas, the resultant (fatty
the reactor and the air flow rates are as shown in Exam alcohol sulfate) is rapidly cooled to 32°C and then
ple 1. A molar ratio of sulphur trioxide and organic neutralized with a 6 percent sodium hydroxide solution
reactant of 1.07 is used. The organic reactant is sup in a continuous mixer provided with cooling. During
plied to the reactor in a rate of 7.2 kg/h per tube and 30 neutralization, the temperature is maintained at 36°C.
sulphur trioxide is evaporated in the main air stream in The neutralized product contains 3.0 percent petro
a rate of 2.52 kg/h per tube. The concentration of leum ether extract and 1.2 percent sodium sulphate on
sulphur trioxide in the gas reactant is 4.5 percent by the basis 100 percent active material. The 5 percent
volume; as an average, it drops to 4 percent by volume aqueous solution of active material has a colour corre
when the gas reactant encounters the equalizing air and sponding to 20 units on Klett scale.
contacts the organic reactant. The temperature of the 35 For a reactor of the prior art, formed of tubes having
organic reactant is 20°C, whereas the temperature of approximately the same dimensions as those used in
the gas reactant is 45°C. Cooling water is circulated this example, the flow rate shown is about 2.3 kg/h of
within the reactor at a temperature of 34°C. The pres lauryl alcohol per tube, while sulphur trioxide concen
sure in the gas reactant supply chamber is 0.75 kg/cm, 40 tration in the gas reactant is 4.5 percent by volume.
whereas the pressure in the equalizing air chamber is EXAMPLE 4
0.55 kg/cm. The reaction mixture exits from the reac This example relates to sulphation of a commercial
tor at 60°C. After separation of the exhausted gas, fraction
dodecylbenzene sulphonic acid is rapidly cooled at number ofof carbon linear synthetic alcohols having an even
atoms, chiefly Cs, Cs and Cao and
42°C, then kept in digestion for 20 minutes to complete 45 an average molecular
the reaction and finally hydrated with 1 percent water tics of the reactor andweight of 263. The characteris
air flow rates are the same as
to decompose the residual anhydrides. Dodecylben
Zene sulphonic acid contains 1.6 percent unsul shown and
in Example 1; a molar ratio of sulphur trioxide
organic reactant of 0.98 is used. The organic reac
phonated material (determined by extracting with pe tant is supplied
troleum ether the product meutralized with sodium 50 tube and sulphurtotrioxide the reactor in a rate of 7.2 kg/h per
is evaporated in the main air
hydroxide) and 1.6 percent sulphuric acid. The prod stream in a rate of 2.14 kg/h per tube. Sulphur trioxide
uct neutralized with sodium hydroxide in 5 percent concentration in the gas reactant is 3.9 percent by
aqueous solution of active material has a colour corre volume and as an average it drops to 3.4 percent by
sponding to 40 on Klett scale (40 mm. cell, No. 42 volume when the gas reactant encounters the equaliz
filter). 55 ing air and contacts the organic reactant. The solidifi
For a reactor according to the prior art, formed of cation temperature of the organic reactant is 44.7°C,
tubes having approximately the same dimensions as the latter being supplied to the reactor at 52°C. The gas
those used in this example, a flow rate is shown of reactant temperature is 46°C and the equalizing air is
about 5 kg/h dodecyl benzole per tube, but with a con pre-heated at 50°C. Cooling water at 44°C is circulated
centration of sulphur trioxide in the gas reactant of 60 within the reactor. In the gas reactant supply chamber
about 8 percent by volume. According to experience, a the pressure is 0.6 kg/cm and in the equalizing air
reduction in sulphur trioxide concentration in the gas chamber the pressure is 0.36 kg/cm. The reaction
reactant to 4-5 percent by volume would enable to mixture exits from the reactor at 51°C. After separation
substantially improve the product colour; however, this of the exhausted gas, the resultant (fatty alcohol sul
involves a substantial reduction in dodecyl benzole 65 fate) is rapidly cooled to 45°C, then neutralized contin
flow rate in order to maintain the pressure drop within uously with 5 percent sodium hydroxide solution, main
the reaction tubes in an acceptable value for an even taining the temperature at 45°C. The neutralized prod
distribution of the reactants. uct clearly dissolves in hot water. It contains 9.5 per
 3,931,273
2
cent petroleum ether extract and 4.3 percent sodium 1. An improved process for continuously sulfonating
sulphate on the basis 100 percent active material. The and sulfating a liquid organic compound selected from
5 percent aqueous solution of active material has a the group consisting of olefins, aromatic hydrocarbons,
colour corresponding to 45 units on Klett scale. alkyl aromatic hydrocarbons, fatty alcohols, fatty acids,
EXAMPLE 5
fatty acid esters, ethoxylated fatty alcohols, and ethox
ylated alkyl phenols, wherein the liquid reactant con
The sulphation in Example 4 is repeated in a reactor sisting of said sulfonatable and sulfatable organic com
formed of tubes having the dimensions as shown in pound and a gaseous reactant consisting of a mixture of
Example 1, except using the distribution system for the sulfur trioxide and inert gas are fed, each from a single
reactants and equalizing air as shown in FIG. 4, O space, through distribution means, to a plurality of
wherein the ends of the gas reactant nozzle is recessed externally cooled parallel reaction tubes with down
by 3 mm from the converging inlet of the reaction tube. ward annular two-phase flow to effect sulfonation and
Air and reactant flow rates and the other operating sulfation of said compound, which process comprises:
conditions are the same as in Example 4. The neutral introducing said liquid reactant circumferentially into
ized product has substantially the same analytical com 15 said tubes, introducing said gaseous reactant centrally
position and the same characteristics of solubility and into said tubes immediately beyond the introducing
colour as the product of Example 4. openings for said liquid reactant, introducing to said
tubes further inert gas from a further separated single
EXAMPLE 6 space through said introducing openings and in contact
20 with said liquid reactant, the flow rate of said further
This example shows the influence of gas velocity in inert gas being in the range of 8-19 percent of the
the reaction tubes on the colour of the product, relating overall inert gas flow rate in each tube, the pressure
to the sulphation of the fraction of fatty alcohols in drops of said further inert gas at the entrance of said
Example 4. The characteristics of the reactor are those tubes being in the range of 0.5-8 percent of the pres
shown in Example 1. The total air flow is 10.3 Nm/h 25 sure drop in the distribution means of said gaseous
per tube, 8.3 Nm/h per tube of which entering as dilut reactant, so that said further inert gas actually distrib
ing air for sulphur trioxide and as an average 2 Nm/h utes to said tubes producing an overall gas flow rate in
per tube as equalizing superficial air. The air velocity each tube which is a decreasing function of the resis
related to the tube cross-section is about 30/m/sec. The tance therein to the gas flow, thereby substantially to
organic reactant flow rate is reduced relative to that in 30 equalize the pressure downstream of all the distribution
Example 4, in order to prevent a too high gas reactant means for the liquid and gaseous reactants in order to
concentration from affecting the colour of the product. provide for uniform distribution of the reactants to said
The organic reactant is supplied to the reactor in a rate reaction tubes without limiting the pressure drop
of 3.6 kg/h per tube and sulphur trioxide is evaporated therein, which is utilized as an energy factor for in
in the main air stream in a rate of 1.07 kg/h per tube. 35 creasing liquid reactant flow rate, promoting heat re
Sulphur trioxide concentration in the gas reactant is 3.5 moval and interphase mass transfer and reducing liquid
percent by volume and, as an average, it drops to 2.8 phase residence time.
percent by volume when the gas reactant encounters 2. A process according to claim i, wherein the tem
the equalizing air and contacts the organic reactant. perature in said reaction tubes is in the range of about
The temperature of the organic reactant, gas reactant 40 30°-1 10°C.
and equalizing air are those as in Example 4. Cooling 3. A process according to claim 1, wherein the pres
water at 46°C is circulated within the reactor in order sure drop in said distribution means for the gaseous
to maintain the reaction mixture outlet at 51°C. After reactant is in the range of 0.10-0.35 kg/cm and the
separation of the exhausted gas, the resultant (fatty pressure drops of said further inert gas for equalizing
alcohol sulfate) is cooled and neutralized as shown in 45 the pressures, at the entrance of said reaction tubes, is
Example 4. The colour of the product neutralized in 5 in the range of 20-120 mm. column of water.
percent active material aqueous solution corresponds 4. A process according to claim 1, wherein the molar
to 75 units on Klett scale. As in test 4, the air flow rate ratio of SO to the organic compound is in the range of
for diluting sulphur trioxide is then increased to 15 O.9-1.2.
Nm/h, the other conditions being left unaltered. The 50 5. A process according to claim 1, wherein the con
colour of the novel product neutralized in 5 percent centration of sulfur trioxide in the gaseous reactant is in
active material aqueous solution corresponds to 37 the range of 2-12 volume percent.
units on the Klett scale. It is still more significant that 6. A method according to claim 1, wherein the fur
the increase in air flow rate causes for some instants the ther inert gas for equalizing the pressures flows to the
outlet of very dark sulphation product from the reac 55 reaction tubes concentrically between the liquid reac
tor. The liquid reactant which, at a low gas velocity, tant supplied to the inner surfaces of the tubes and the
tends to stay for too a long time within the reaction gas reactant injected in the central zone of each tube.
tubes and darken is "blown out,' while the new flow 7. A method according to claim 1, wherein said reac
regime corresponding to the increased gas flow rate is tion tubes have an inner diameter in the range of 8-18
set up. 60 mm and a length in theck range
: . .
of 0.8–5.0
k.
meters.
What is claimed is:

65
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 3,931,273
DATED : January 6, 1976
INVENTOR(S) : Agostino LANTERI
It is certified that error appears in the above-identified patent and that said Letters Patent
are hereby Corrected as shown below:
Heading (54) title, change to --SULPHONATING AND
SULPHATING--
Column l, title, change to --SULPHONATING AND SULPHATING--.
Column l, line 32, change "trioxide" to --dioxide--.
Column 2, line 51, after "or" insert --in--;
O line 59, change "the long run" to --long
service--; and
line 6l, change "two liquid/gas phase flows"
to -- a two-phase gas-liquid flow.--.
Column 3 line 52, after "all" cancel "of".
Column 8, line 53, change "through" to --with--.
to Column 9 lines 59 and 65, change "benzole" to
--benzene--
Column l0 lines 25, 26, 64 and 65, and column ill,
lines 44 and 45 cancel the parentheses.
Column l2, line l, change "sulfonating" to
--sulphonating--
o line 2, change "sulfating" to -sulphating--
line 7, change "sulfonatable" to
--sulphonatable-- and change "sulfatable" to --Sulphatable--
line 9, change "sulfur" to -sulphur--;
| line 12 change "sulfonation" to
--sulphonation--
o line 13, change "sulfation" to -sulphation--;
line 5l, change "sulfur" to -sulphur--.
eigned and evealed this
e Thirtieth Day of November 1976
(SEAL Attest.

RUTH C. MASON . C. MARSHALL DANN

O Attesting Officer Commissioner of Patents and Trademarks