DE1917299A1 - Sulfonation process - Google Patents

Description

The invention relates to the sulfonation of sulfonatable organic reactants and in particular the sulfonation of benzenesulfonates containing a linear alkyl group using sulfur trioxide.

Organic sulfonic acids and organic sulfonates long increasing importance due to their application the production of liquid detergents or detergents and especially in the production of relatively salt-free Cleaning agents or detergents that have good solubility properties to have. Usually the sulfonated detergents are made using a sulfonation process produced in which the reaction mixture contains a residue of sulfuric acid and water as a by-product, so that exhausted acid is produced. If the sulfonated so formed Product neutralized with sodium hydroxide, for example the exhausted acid forms sodium sulfate. While the use of sodium sulfate for some purposes is desired, it is to be used for other purposes.

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1917289

separated undesirably, especially in processes for the production of salt-free cleaning agents or detergents with good Solubility properties. In the latter case the sodium sulphate must be removed. .

Lately the disadvantages of the previous sulfonation reactions are to a large extent due to the use of sulfur trioxide in the sulfonation of sulfonatable ones organic reactants have been overcome. For example, U.S. Patents 3,259,645 and 3,350,428 continuous suIfonierungsverfahren shown in which a sulfonatable organic reactant «like an alkylaryl hydrocarbon, a fatty alcohol, a methoxylated one Alkylphenols an O (-olefin or the like., Using is sulfonated by sulfur trioxide.

Although the aforementioned processes in which the sulfonation of sulfonable organic reactants a mixture of sulfur trioxide and air is used, have eliminated a considerable number of the problems associated with the known methods, nevertheless exist nooh to some extent a problem of excessive sludge viscosity during neutralization. Accordingly Various attempts have been made to solve the problem of mud viscosity, the ancient neutralization of the sulfonated organic reactant is linked to switch off and thereby the use of higher solids contents to enable.

It has been proposed to reduce the viscosity of the sludge by adding sodium sulfate and similar salts. It is evident, however, that when a salt-free product or one having only a low salt content If product is desired, the use of such salts to lower the viscosity of the sludge is economical is disadvantageous.

It has also been proposed that only an inert solvent or a similar material in the SuI-

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to use carbonate sludge during the neutralization process. However, this has not proven to be advantageous, since the addition of such a solvent increases the viscosity is not degraded enough to compensate for the adverse results ^ those of the addition of such Solvent in terms of purity, etc. occur.

Accordingly, there is a great desire in the industry to provide a process which will reduce the cost the viscosity of the sulfonate sludge during neutralization permitted and thus enables a higher pesticide content, than was previously achievable by conventional methods. I.

According to the invention it has now been found that this desirable result can be achieved by cosulfonation of the sulfonatable organic reactant and a lower alkyl substituted aromatic compound and preferably by adding further amounts of the aromatic compound substituted with a lower alkyl can be obtained after digestion of the cosulfonated product.

Accordingly, it is a primary purpose of the invention to provide a new suIfonierungsverfahren which the Eliminates shortcomings and disadvantages of the known methods. I.

Another purpose of the invention is to provide a new suIfonierungsverfahren which is based on Orund the reduced viscosity of the sulfonation sludge enables high levels of pesticides to be used.

Another purpose of the invention is to provide a new SuIfonierungsverfahren in which a sulfonierbarer organic reactants substituted with one, with a lower alkyl aromatic hydrocarbon is kosulfoniert and preferably after the digestion of the Kosulfonate zuslitzlicher, substituted aromatic with a "niede ren alkyl hydrocarbon added and digested again.

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Another purpose of the invention is to provide a method * for sulfonating one of one with a lower alkyl substituted aromatic hydrocarbon and an alkylbenzene mixture in such Way that a low sodium sulfonate content and results in a minimum of undesirable side reactions.

Further purposes and advantages of the invention will appear from the description below.

The advantages and features of the method according to the invention indicated above are achieved by cosulfonation a sulfonatable organic reactant and a lower alkyl substituted aromatic hydrocarbon obtain. Suitable aromatic hydrocarbons substituted with a lower alkyl are, for example: o-xylene, m-xylene, p-xylene, toluene, ethylbenzene, cumene, Butylbenzene etc.

In addition to the cosulfonation, it is preferred the sulfonatable organic reactant and the lower alkyl substituted aromatic hydrocarbon after digestion of the sulfonation product an additional amount of the lower alkyl substituted hydrocarbon is added to the system and digested further.

Any organic reactant may be used in the invention, such as sulfur trioxide or a capable of reacting like material to yield a sulfonated product. The method according to the invention is particularly applicable to the sulfonation of organic compounds containing an aromatic nucleus and of organic compounds containing an olefin bond, these organic compounds being sulfonated supply surface-active materials.

Such sulfonatable ones to be used in the invention organic compounds include, without limitation, olefins containing about 8 to 20 carbon atoms, such as octene,

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Decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, tetradecadiene and octadecadiene; olefinically unsaturated acids such as oleic acid and linoleic acid; and branched-chain or '■,' straight-chain substituted derivatives of monocyclic and polycyclic aromatic hydrocarbons in which the alkyl group contains from about 8 to 20 carbon atoms, such as octylbenzene, nonylbenzene, decylbenzene, dodecylbenzene, tridecylbenzene, detradecylbenzylbenzene, tetradecylbenzylbenzyl, tetradecylbenzylbenzene, detradecylbenzylbenzene, detradecylbenzylbenzene, detradecylbenzylbenzene, detradecylbenzylbenzene, detradecylbenzylbenzol , Tetradecyltoluol, Dodecylxylol, Dodecyläthylbenzol, Dodecylisopropylbenzol, octylbiphenyl, decylbiphenyl, Tetradecylbiphenyl, "Octadecylbiphenyl, Dodecylmethylbiphenyl, Isopropyltetradecylbiphenyl, methylnaphthalene, Äthylnaphthalin, isopropyl naphthalene, hexylnaphthalene, Octylnaphthalin, decylnaphthalene, Tetradecylnaphthalin, Octadecylnaphthalin, Dodecylmethylnaphthalin, fithyltetradecylnaphthalin like.

In the invention, sulfonatable organic compounds can be used as organic reactants which themselves or whose predecessors have been subjected to a previous sulfonation treatment, so that double or polysulfonated products are obtained.

The alkylbenzenes which are preferably used in the practice of the invention are known in the art i known, and they can be represented by the structural formula

are represented, in which R is an alkyl radical with a straight or branched chain, which is at least 8 carbon atoms and preferably contains 8 to 20 carbon atoms. Such alkylbenzenes and their preparation are shown in a large number of patents, for example

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wise in US patents 1 992 16O, 2 161 173, 2 210 902, 2 218 472, 2 223 364, 2 220 099 and 2 597 834.

Particularly preferred organic reactants that which can be sulfonated by the process according to the invention are the benzenes containing a linear alkyl group, where the linear alkyl group is 8 to 20 and preferably Contains 12 to 16 carbon atoms.

According to the invention it has been found that the cosulfonation can be carried out under essentially the same conditions as are usually carried out in the sulfonation of sulfonatable organic reactants are used. While it was previously believed that such materials as xylene, toluene, etc., difficult to sulfonate, since a considerable amount of sulfonation occurs during SO ^ sulfonation If there is a tendency to form sulfones, such side reactions are eliminated or considerably reduced, if, according to the invention, such materials are kosulfoniert with a further sulfonatable organic reactant will. It is therefore unexpected that the Kosulfonierung the organic reactant and with a lower alkyl substituted aromatic hydrocarbon goes smoothly under the usual reaction conditions without undesired side reactions as a result of the Sulfonation of the aromatic hydrocarbon substituted with a lower alkyl occur.

In the method according to the invention, in general a 4 to 20 # molar excess of sulfur trioxide, based on the total amount of sulfonatable Reactants, used, this excess depending on the raw material to be sulfonated. Furthermore has a temperature in the range of about 32 ° to about 49 ° C in the suIfonierungsverfahren according to the invention as suitable proven. Of course, something higher or lower temperatures and slightly higher or lower amounts of sulfur trioxide are used, if this is necessary for

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special purposes is desired. In this respect it should be pointed out again that it has been found according to the invention • That the cosulfonation of the sulfonatable organic reaction partner and the lower alkyl substituted aromatic hydrocarbon goes smoothly, if sulphonation parameters are applied, as s! e in general in the manufacture of sulfonate detergents be applied.

In the cosulfonation process according to the invention, the aromatic hydrocarbon substituted with a lower alkyl can be supplied in any amount, depending but it is preferable to side reactions to a minimum to reduce, up to about 10 wt.% to use of a lower alkyl-substituted aromatic hydrocarbon, preferably cumene, toluene or xylene. Even if this amount of xylene or similar material is fed to the reactor in the cosulfonation reaction, the desired side effects, such as, for example, sulfone formation, are not encountered at all or at most to a very small extent.

In the preferred embodiment of the invention the acid sludge after the digestion of additional aromatic carbons substituted with a lower alkyl j

Hydrogen added and then digested further. "

In this embodiment of the invention that is from the Product obtained initially during the sulfonation reaction a period of 10 minutes or more before a second portion of the lower alkyl substituted aromatic hydrocarbon, preferably cumene, toluene or xylene, is added. Depending on the amount of the second Part of the lower alkyl substituted aromatic hydrocarbon that is added after digestion the duration of the second digestion can be up to about 50 minutes. After the first phase of settlement may be the aromatic substituted with a lower alkyl

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Hydrocarbon can be added in a maximum amount of about 4 Qevi.% .

In the drawing, the method according to the invention is illustrated schematically. In this embodiment of the invention, it is believed that the lower alkyl substituted aromatic hydrocarbon is xylene is used and that as a sulfonatable organic reactant a benzene containing a linear alkyl group is used. Of course, any and all of the above reactants can be used in the method according to the invention.

The xylene passes through a line 12 and the alkylbenzene via a line 14 into the sulfonation reactor 10, while sulfur trioxide via a line 16 at the bottom of the reactor 10 is introduced. Any conventional sulfonation reactor can be used for carrying out the process according to the invention can be used, however a preferred type is that disclosed in U.S. Patents 3,259 and J5 350 428 is indicated. A good distribution of Reactant in the reactor is very important. The sulfonated .Product leaves the reactor 10 via a line l8 and enters a container 20, from which a part of the sulfonated product is returned to the reactor 10 via a line 22.

The sulfonated product overflows from container 20 a line 24 into a first cyclone 26, from which excess gases are removed via a line 28. The acid exits the first cyclone 26 via a conduit 50 into a first digester J52, in which a digestion is carried out for a period of about 10 to 30 minutes. At this point the product can either go straight to a neutralizer for neutralization and for final processing in the production of the cleaning or Detergent sulfonate can be added, or it can be added to him according to an embodiment of the invention, as shown in FIG

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Drawing is illustrated, additional xylene can be added via line ^ 4 when it leaves the digester 32 via line J> 6. Optionally, the digested sludge containing the additional xylene can be fed to a second digester JQ , in which a further digestion takes place for an additional period of about 10 to JO minutes and from which the digestion product is either fed via a line 42 into a second cyclone 40 in order to strip off any unreacted xylene that is still present, or is fed directly to the neutralizer. Exhaust gas is discharged through line 44 while the product is fed to the neutralizer through line 46 with a small amount of water, approximately 2 %, added through line 48 to break up any anhydrides present in the system. At this point, the usual neutralization and further work-up of the product can be carried out in order to produce a cleaning or detergent sulfonate.

Since it is possible that after the second digestion small amounts of unreacted xylene or the like Material can be left behind, which depends on the amount fed, and since even small amounts an undesirable one Have smell of them for use in a liquid If cleaning or laundry detergents are unsuitable, the excess xylene or similar material should be removed from the system removed. This can be done in a simple manner by air stripping can be achieved. This stripping can be caused by the sulfonic acid in the from the first SuIfonierungsreaktor recirculated coming exhaust gas flow and then separated in the second cyclone. Accordingly, the exhaust gas exiting the system contains traces of Xylene.

According to the preferred embodiment of the invention add 3.0 to 5.0 wt. # xylene to the system for cosulfonation and 1.25 to 4.0 wt. # xylene after the first digestion

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ration added, a total of about 6.0 to 9 * 0 wt. $ Gives optimal results. Accordingly, it is through this introduction of xylene into the system is possible, the viscosity of the sulphonate sludge considerable down to a point with no problem of excessive sole viscosity or gelation during neutralization occurs, as well as significantly reducing the amount of sulfuric acid or sodium sulfate in the neutral product.

As already mentioned, the introduction of the xylene or similar material into the cosulfonation reaction causes no adverse effects emerged because of side reactions are reduced to a minimum or completely switched off .; Furthermore, by introducing xylene or the like Material after the first digestion caused no measurable side reactions that affect the yield or the Impair the purity of the desired sulfonate.

According to a further embodiment of the invention becomes the neutralizer after the suIfonierungsvorgang Xylene sulfonate, toluene sulfonate, cumene sulfonate or the like. direct added. Such an addition also reduces the viscosity of the neutralized product by it helps render the detergent sulfonate product substantially soluble. This embodiment can either alone or in conjunction with the cosulfonation of the sulfonatable organic compound and that with a lower Alkyl substituted aromatic hydrocarbons can be used to lower the sludge viscosity and enable the use of a higher level of pesticides.

Furthermore, according to a further embodiment, the Invention has been found that the digestion of sulfonated or kosulfonated products, in which the primary sulfonatable material composed of a linear alkyl group containing benzene, can be carried out effectively without stirring and with a minimum of backmixing »So he

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possible, as well as in the case in which a cosulphonizable, aromatic hydrocarbon substituted with a lower alkyl • is used, the use of one linear alkyl group-containing benzene with or without such a cosulfonatable material provides a sufficient reduction the viscosity of the neutralized product, "so that to carry out the digestion of such a sulfonated material without agitation and without substantial back-mixing is possible.

Of course, if the benzene is a linear alkyl group containing, the execution previously described ä of the invention, ie, using a kosulfonierbaren, substituted with a lower alkyl aromatic hydrocarbon, such as xylene, sulfonated according to the viscosity of the neutralized product is even further reduced so that this is an extremely effective embodiment.

The invention is described below in terms of some specific ones Examples explained in more detail.

example 1

Various sulfonation reactions were carried out, the sulfonatable organic reactant being a benzene I containing _{a linear C 12 alkyl group}

and xylene were used.

Different runs were made in which the amount of xylene supplied to the Ko sul'f onierungsreakt ion, the additional amount of xylene introduced into the system after digestion and the duration of the after xylene addition after one Ten minute first digestion was changed following additional digestion. The molar ratio of the sulfur tripoxide to the sulfonatable material was 1.10: 1 in most cases, but smaller ratios were also used used.

After the final digestion, a small amount of water

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ser, about 2 % _t based on the originally introduced alkylbenzene, was added to break up the anhydrides which could have remained in the system. The sludge was then neutralized with caustic soda. An analysis of the product with regard to the content of free oil (ether extract, percentage of active ingredient), the color and the ratio of sodium sulfate to active ingredient gave the results listed in the table below:

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Tabel

sample
No. Alkyl
benzene -
supply
ζ .Reak
gate in
% Xylene
supply
ζ. Reak
gate in % Xylene
supply
z. Di-
died
in % Duration d.
first
Digerie
tion in
Min. Duration d.
additional
Digerie
tion after
supply
of xylene
in min. Mole ratio
from SOr ₅
to sul ^
fonierba-
rera mate
rial analysis ether
extract
^ more active
Duration
part colour
after
Velcro. Relation to
Sulß-t to act.
component 0 96.77 3.23 0 10 - 1.10 1.63 34 3.4 / 96.6 1 95, ^ 5 3.17 1.38 10 10 1.10 1.47 32. 2.3 / 97.7 2 95.45 3.17 1.38 10 20th 1.10 1.50 35 2.0 / 98.0 3 95.45 3.17 1.38 10 30th 1.10 1.53 35. 2.1 / 97.9 © 9 94.0 3.12 ■ 2.88 10 10 1.10 1.57 33 1.5 / 98.5 GS?
Ci ^ 94.0 3.12 2.88 10 '20 1.10 1.57 30th 1.6 / 98.4 <§ »
£? ■ · 6th 94.0 3.12 2.88 10 30th 1.10 1.56 32 1.4 / 98.6 m
***** ¹ 7 92.9 3.09 4.01 10 10 1.10 1.79 30th 1.1 / 98.9 ! Q 92.9 '3.09 4.01 10 20th 1.10 1.77 40 1.0 / 99.0 j 9 92.9 3.09 4.01 10 30th 1.10 1.74 40 0.8 / 99.2 .ff? » I ίο 96.77 3.23 0 10 - 1.10 1.57 41 3.4 / 96.6 11th 96.77 3 * 23 0 10 - 1.10 1.83 35 3.4 / 96.6 α » 3.23 2.7 10 10 1.08 2.0 44 2.0 / 98.0 j % Ά - - 10 10 i, o6 4.0 38 1.5 / 98.5 _ ^ . .a. -'— "- ^ - CD

ΓΟ CC CO

The values obtained for Sample Nos. "J, 8 and 9 show that, with respect to a minimum salt content, optimum results were obtained by adding approximately k % by weight of xylene to the digester.

In all cases, there was no problem of excessive sludge viscosity during neutralization or gelation of the sulfonate sludge. This makes hence the viscosity-reducing effect of cosulfonation according to the invention and the addition of xylene after a first digestion, recognizable.

example 2

The runs with sample nos. 1, 4, 6 and 9 of the Example 1 were repeated with the exception * that instead of of the xylene an equal amount of toluene was used. In all cases the results obtained were identical to those obtained for the corresponding samples of Example 1.

Example 3

The runs were repeated with Sample Nos. 2, 7 and 8 of Example 1, with the exception that an equal amount of O ^ -Cumene was used instead of the xylene ₍ Again, essentially the same results were obtained as for the corresponding Samples of Example 1 were obtained.

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Claims (1)

Claims 1. A process for sulfonating a sulfonatable organic reactant to produce a synthetic one Sulphonate detergent or detergent, thereby characterized in that a cosulfonation in the presence of up to 10 wt. $ 6 of a cosulfonatable, with a lower alkyl substituted aromatic hydrocarbon. 2. The method according to claim 1, characterized in that that an * olefin with 8 to 20 carbon atoms or an alkylben- ™ zene whose alkyl group contains 8 to 20 carbon atoms is used as the sulfonatable organic reactant and that xylene, toluene or cumene is used for the aromatic hydrocarbon substituted with a lower alkyl. 5. The method according to claim 2, characterized in that that the sulfonatable organic reactant is a benzene containing a linear alkyl group and for the with a lower alkyl substituted aromatic hydrocarbon xylene is used. 4. The method according to any one of claims 1 to 3, characterized in that the product of the cosulfonation of the sulfonatable organic reactant and the aromatic hydrocarbon substituted with a lower alkyl, after it has been subjected to digestion for 10 to 50 minutes, up to 4 ., 0 wt.% of additional substituted aromatic with a lower alkyl hydrocarbon is added. 5. The method according to claim 4, characterized in that the digestion without stirring and without substantial back-mixing carried out at a temperature of 52 ° to 49 ° C will. 6. The method according to claim 4 or 5, characterized in that that after the addition of the additional, with a 909845 / 17U lower alkyl substituted aromatic hydrocarbon a further digestion was carried out for 10 to JO minutes will. 7. Method of sulfonating a linear alkyl group containing benzenes, characterized in that after the sulfonation a digestion without stirring and without Substantial back mixing is being done. 8. The method according to claim 7, characterized in that that the digestion for 10 to 50 minutes with a Temperature from J52 ° to 49 ° C is carried out. 9. A method for sulfonating a sulfonatable organic reactant for the production of a synthetic sulfonate cleaning agent or detergent, characterized in that the sulfonatable organic reactant in the presence of up to 10 wt. $ Of a cosulfonatable, substituted with a lower alkyl aromatic hydrocarbon a temperature of 32 to 49 ° C is sulfonated with sulfur trioxide, which is applied in a molar excess of 4 to 20 %, based on the organic reactant, the sulfonation product at a temperature of 32 ° to kcpqfa'ähvenü. Digesting for 10 to 30 minutes and neutralizing the digested product. 10. The method according to claim 9, characterized in that after the digestion of the sulfonation product up to 4.0 wt. % Additional aromatic hydrocarbon substituted with a lower alkyl are added. 11. The method according to claim 9 and 10, characterized in that the digested sulfonation product after Addition of the additional, lower alkyl substituted aromatic hydrocarbon for 10 to 30 years Minutes. 12. The method according to claims 9 to 11, characterized in that as sulfonierbarer organic reactant is an olefin having 8 to 20 carbon atoms or an alkylbenzene _s the alkyl group of 8 to 20 carbon atoms 909845/174 contains, is used and that for those with a lower Alkyl substituted aromatic hydrocarbon xylene, toluene or cumene is used. 90984S / 1744 Blank page