US3492343A - Sulphonates - Google Patents

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Publication number
US3492343A
US3492343A US632402A US3492343DA US3492343A US 3492343 A US3492343 A US 3492343A US 632402 A US632402 A US 632402A US 3492343D A US3492343D A US 3492343DA US 3492343 A US3492343 A US 3492343A
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Prior art keywords
olefin
olefins
acid
treatment
colour
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US632402A
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Philip James Garner
Howard Neilson Moulden
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Lever Brothers Co
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Lever Brothers Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/17—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with acids or sulfur oxides
    • C07C7/171—Sulfuric acid or oleum

Definitions

  • the invention concerns a process for the purification of olefins from which olefin sulphonates having an improved colour can be obtained.
  • the process involves treatment of an olefin, especially a commercial alphaolefin, with sulphuric acid under specific conditions, followed by treatment with an earth.
  • This invention relates to sulphonates of olefins, especially of commercial alpha-olefins of carbon chain length 10-22, to a process for preparing them, and to their use in detergent compositions.
  • Useful actives for detergent compositions can be prepared by allowing SO to react with olefins of chain lengths ranging from C -C with subsequent hydrolysis/neutralisation to the salt.
  • olefins of chain lengths ranging from C -C with subsequent hydrolysis/neutralisation to the salt.
  • the sulphonate derived from commercially available alpha-olefins is too highly coloured to be acceptable for use in finished detergent products.
  • alpha-olefins especially those which are derived from the cracking of petroleum hydrocarbons, known as cracked wax olefins, tend to be straw coloured and to contain not only coloured impurities but also compounds which may be colourless in themselves but which give rise to highly coloured compounds on reaction with S
  • These intensely coloured compounds which appear to be present in the sulphonate product in very small concentrations are thought to be polysulptonated polyenes, possibly derived by oxidation and subsequent sulphonation of the hydrocarbon chain of some of the more reactive impurities. They are believed to account for much of the sulphonate colour.
  • the coloured compounds obtained in the sulphonation of commercial alpha-olefins are not necessarily linear and may well be derived from the non-straight chain impurities. They might also be formed from olefin dimers or from fragmented olefins, but the major colour body precursors are believed to be polyenes and particularly the cyclic dienes.
  • the present invention is concerned with a means for producing acceptably coloured sulphonates from commercial olefins.
  • it is concerned with a means of removing the undesirable colour-forming compounds from the olefins before sulphonation, so that the final sulphonate product has an acceptable colour.
  • the invention is applicable to cracked wax olefins as such and is particularly useful therewith since the combined cost of these olefins and the purification process of this invention is much less than the cost of the other commercially available olefins made from ethylene by a Ziegler polymerisation process.
  • the latter type of commercial olefins generally give better coloured sulphonates but if the process steps of this invention are employed some of these Ziegler olefins can be purified thereby.
  • the cracked wax olefins contain typically -95% straight chain alpha-olefin, the remainder being a mixture of many hydrocarbon types, including branched, cyclic, internal olefins and smaller quantities of dienes.
  • the Ziegler olefins similarly contain 85-90% straight chain alpha-olefins but the remainder is mainly a mixture of 2-a kyl-l-olefins. Whilst the Ziegler olefins are usually water-white, nevertheless on sulphonation, colour can develop, and the product is then unsuitable for detergent compositions.
  • the present invention which provides a process for the treatment of olefins prior to sulphonation to make possible the production of an alkali metal sulphonate of a good colour which is suitable for inclusion in a detergent composition, is appreciably simpler than the foregoing proposed process. It completely eliminates the many washing steps and the distillation step and it does not isomerise the olefin. Indeed, in many cases, the present process renders unnecessary a bleaching step for the sulphonates so prepared, and this, as will be apparent to those skilled in the art, is a considerable advantage.
  • the present invention provides a process for the purification of olefins which comprises subjecting the olefin to treatment with sulphuric acid under conditions which do not give rise to olefin sulphation or isomerisation to yield an acid layer and an olefin layer, phase separation of the layers and treatment of the olefin layer with an absorbent.
  • the treatment with sulphuric acid should be such as to avoid, substantially isomerisation, particularly when alphaolefins are to be purified since retention of the olefinic double bond in the alpha-position ensures that the sulphonate group adds itself to the end of a long chain, a positioning which is desirable in detergent actives. It should also avoid polymerisation and formation of the esters of sulphuric acid.
  • the acid treatment removes the more powerful colour precursors, which are believed to be, in the case of the cracked wax olefins, the more basic alkyl-cyclopentadienes, and the open chain conjugated dienes.
  • dialkylsulphate formation in the criticality of the conditions for effective acid treatments of olefins has not hitherto been appreciated.
  • Use of the test enables any olefin to be successfully treated by the process of the invention to yield satisfactory sulphonates.
  • the sulphuric acid strength is conveniently 7098% by weight H 80 preferably 80-90Z. 86Z is usually the preferred acid strength for reasons which will be given later. It is advantageous that sulphuric acids of this strength are not corrosive to mild steel, a convenient structural material.
  • the amount used should lie within the ratios olefinzacid volumes of 100:0.1 to 4:1. It may be convenient to recycle the acid sludge, in which event, the olefinzacid ratio may be as high as 1: 1.
  • the temperature at which the acid treatment is carried out can be from -100 C. preferably 50 C. provided of course that the temperature is greater than the freezing points of the acid and the olefin.
  • the time of contact is of the order of 0.560 minutes, preferably 220 minutes. The olefin and acid conveniently are stirred together.
  • the range of acid strength suitable for the treatment can be wide, the combination of acid strength and contact time, quantity of acid and temperature is critical in order to confine the reaction to the compounds which cause high sulphonate colour in the crude olefin, and o avoid xcessive occurrence of r action of the a phaolefins themselves.
  • the stronger acids are used, short contact times, lower temperature and smaller quantities of acid are needed to avoid occurrence of sulphation and isomerisation.
  • the weaker acids need longer contact times and higher temperatures, together with a larger ratio of acidzolefin, to enable suflicient reaction with the undesirable impurities to occur.
  • a selected quantity of the olefin to be purified is treated with sulphuric acid of strength lying within the range 93% H 50 (w./w.) at concentrations of 0.5 to 10 vol. percent for a time of up to 50 minutes.
  • the mixture is allowed to phase separate and the resulting olefin layer is subjected to a standardised earth treatment, viz, l 6% type 237 fullers earth is mixed with the olefin layer for 8 minutes with settlement for the necessary period for clarity.
  • the infra red spectrum of the resulting olefin is then recorded, the absorbance being measured at 6.25 and 8.4 to provide a measure of sulphation, and at 10.1 and 10.4a to provide a measure of olefin isomerisation.
  • the acid treating conditions should be such that the ratio of absorbance at 8.4; to that at 6.25 is preferably zero but in any case no greater than 0.25, and to avoid olefin isomerisation, the acid treating conditions should not allow the ratio of absorbances at 10.4 to 10.1/L to be greater than that in the starting olefin.
  • the ratio of absorbance at 8.4 to that at 6.25;. lies between 0.15 and 0.25, colour improvement is effected, but the final detergent sulphonate product may contain an unduly large amount of nondetergent organic matter. In this case, it may be necessary to remove this by, for example, solvent extraction in order to produce a product satisfactory for detergent use.
  • a cracked wax C1548 olefin (ex Chevron Chemical Co.) was acid treated using different values for acid strength, quantity and contact time and the resulting olefin layer subjected to the standardised earth treatment of the test.
  • the product resulting from the acid treatment is a mix ture of two phases viz. a lower dark coloured acid layer, and an upper red olefin layer.
  • the acid treatment is carried out as recommended so that little or no sulphation as evidenced by the 8.4 micron absorbance ratio occurs, the mixture readily separates in the subsequent settling stage. If however, undue sulphation has been allowed to take place, the acid layer does not settle so readily and sulphation continues to occur in the settling stage. This causes difiiculties in the acid removal step and eventual olefin spoilage.
  • the two phases are separated as cleanly as possible, for example by centrifuging and the olefin layer is immediately treated with an adsorbent preferably in absence of atmospheric moisture.
  • This olefin layer is neutral and requires no treatment prior to subjection to the adsorbent.
  • the sludge layer can be recycled for acid treatment of fresh olefin.
  • the two treatments i.e. acid followed by adsorbent can be carried out directly, i.e. sequentially Without an intermediate step such as a washing step.
  • Suitable adsorbents are fullers earths, Celites (registered trademark) activated charcoal, clays or a claylike material, aluminas, silicas, and aluminosilicates.
  • the amount of adsorbent used is 115%, preferably 05-10% by weight of the olefin.
  • the preferred adsorbent is an acidactivated fuller earth, for example that available as Type 237 from the Fullers Earth Union Co. Ltd., Redhill, Surrey, with which the amount is preferably 1.36% by Weight. This quantity is disproportionally less than is required with other fullers earths, which are in turn, preferred to the remaining above-specified adsorbents.
  • Silica gel, especially the chromatographic grade is also an etficient adsorbent, but has a far shorter life than has a fullers earth as measured by the quantity of olefin it will treat.
  • the amount of material requiring removal from the olefin layer is of course a factor in determining the amount of earth to be mixed with the olefin layer.
  • Contact time is of the order of 5-10 minutes.
  • the temperature at which the olefin layer and adsorbent are mixed is usually room temperature. Mixing is achieved by any of the usual methods, e.g. mere stirring together for example, for about 5 minutes, or percolation of olefin layer through the bed of adsorbent. The mixing need only be mild in nature.
  • the adsorbent removes the coloured compounds which stay dissolved in the olefin layer and which were formed by the previous treatment of the olefin with sulphuric acid; i.e. it removes the materials which harm the product sulphonate and which cannot be removed by purely physical methods by settling, centrifuging and which react with water to give coloured olefin soluble compounds.
  • the adsorbent removes traces of the highly coloured acid layer which may not have been removed in the preceding phase separation.
  • the adsorbent treatment can be applied in one or more stages. The number of stages and the quantity of earth needed to obtain the required olefin quality depends on the quality of the starting olefins.
  • the preferred amounts are 3 l.3% earth or 1X 6%.
  • a one stage treatment has the obvious advantage of less handling and filtration. Where olefin is, because of inefficient mechanical separation, remaining on the earth, it can be recovered therefrom by simple boiling of the earth in water for a short time. Phase separation subsequently yields 75% olefin recovery. The residual earth maintains sutficient activity to be re-usable although possibly in greater quantity, for further olefin pre-treatment.
  • the adsorbents may be removed from the olefinic layer by filtration or sedimentation. Suitable methods are with filter presses, meta filters or solid bowl centrifuges.
  • sulphonates derived from olefins treated in this way are suitable for inclusion directly into detergent products. Others may require a bleaching treatment but in contrast to the sulphonates of the untreated olefins it is possible to bleach them to an acceptable colour level, i.e. the olefins pretreated according to the invention are much more amenable to bleaching treatment.
  • the process according to the invention may of course be applied on a continuous basis.
  • the accompanying figure emphasises the need for short times of mixing the acid and olefins when acids of strength greater than 86% are used.
  • the control of mixing time presents no problem and the operation can be carried out batchwise.
  • batch operations are not feasible since the time taken to add the reagents to the mixing vessel can very often be greater than the maximum allowable mixing time. In large vessels it is virtually impossible to avoid mixing during the addition of the reagents. Continuous operation is thus to be preferred to enable control of mixing time.
  • the invention is also concerned with the additional step of preparing the sulphonate from the purified olefins. It is preferred to sulphonate using dilute S0 gas, e.g. SO air using a film reactor, particularly a falling film reactor, having cooling water at about 20 C.
  • the sulphonation conditions are selected from an olefin to SO ratio, (expressed in moles) of from 1:0.7 to 1:2, preferably 1:1 to 1:15; a reaction temperature of 4080 C., a residence time of olefin in contact with the SO /air stream of 0.5- 30 seconds, preferably 520 seconds.
  • the SO /inert gas stream is preferably SO air in concentration SO :air of all S0 to 1:99, preferably 15:85 to 2:98.
  • concentration SO :air of all S0 to 1:99, preferably 15:85 to 2:98.
  • conditions are usually 2045 C., 5-10% vol. percent in air, 1.0:1 to 1.5 :1 sO zolefin (in moles) and a reaction time of 1050 minutes.
  • sulphonation of the purified olefins may be achieved, for example, reaction of atomised olefin with a diluted S0 stream.
  • the requirements are far more stringent, and Lovibond colours of 0.7-0.9 red and 2.53.0 yellow are considered satisfactory.
  • the improvement in colour of the sulphonate resulting from the process is sufiicient for direct inclusion of the product into detergent compositions.
  • althrough the colour of the sulphonate has been improved substantially, bleaching is required to bring the colour levels to the desired standard.
  • Example 1 The results were as follows, and show the greatly improved colour properties of the sulphonates of Example 2 over those of Example 1.
  • the olefin from the settler was passed to a second earth treating tank.
  • the earth was removed from the olefinearth slurry using a metafilter and the olefin which was contain little or no di-alkyl sulphate and no more internal olefin than was in the olefin before treatment, as judged by infra-red analysis.
  • the foregoing results clearly demonstrate the improvement in sulphonate colour obtained by the pretreatment of the olefins according to the invention.
  • EXAMPLE 18 The improved bleachability of sulphonates of pretreated olefins will now be illustrated by way of Example 18. This shows that the sulphonates from pretreated olefins can be bleached to a lighter colour than can the sulphonates of the untreated olefin, and that less bleaching agent is required for this operation.
  • a process for the manufacture of alpha-olefin sulphon'ates the improvement yielding an alpha-olefin sulphonate with acceptable color for use in a detergent composition which comprises treating an alpha-olefin with from about 2% to about 7% by volume of sulfuric acid having an acid strength of about 85% to about 87% by weight of sulfuric acid for about 2 to about minutes so as to avoid sulphation and isomerization of said olefins, and to provide an olefin layer and an acid layer, phase separating said olefin layer, treating said olefin layer with an acid-activated fullers earth, separating the purified olefin layer therefrom, and subjecting the resulting olefin to sulphonation and neutralization/ hydrolysis.
  • a process according to claim 1 wherein said acid contacting conditions are 85 87% acid strength (by weight H 80 2-7 vol. percent H 50 and 2-10 minutes.
  • a process according to claim 1 wherein said adsorbent is selected from an earth, a clay, activated charcoal and a silicate.
  • a process according to claim 1 which includes an additional step of treating said purified olefin layer with at least one treatment with said earth.
  • Patent 3.492 .343 Date -AW Invent 1-( Philip James Garner and Howard Neilson Moulden It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
  • Claim 3 line 1 change "Claim 1" to -Claim 7.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US632402A 1966-04-26 1967-04-20 Sulphonates Expired - Lifetime US3492343A (en)

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GB18187/66A GB1159728A (en) 1966-04-26 1966-04-26 Purification of Olefins and preparation of Sulphonates therefrom

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AT (1) AT283296B (2)
BE (1) BE697619A (2)
CH (1) CH495930A (2)
ES (1) ES339781A1 (2)
GB (1) GB1159728A (2)
GR (1) GR32682B (2)
LU (1) LU53525A1 (2)
NL (1) NL144916B (2)
SE (1) SE364954B (2)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3699157A (en) * 1970-04-06 1972-10-17 Chevron Res Color reduction of olefin sulfonates
US3758608A (en) * 1971-08-26 1973-09-11 Texaco Inc Process for acid treating of olefins
US4940831A (en) * 1989-02-15 1990-07-10 Phillips Petroleum Company Purification of cis-olefins

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2563369A (en) * 1949-01-04 1951-08-07 Shell Dev Refining fuel oil
DE1217367B (de) * 1964-04-08 1966-05-26 Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Brüning, Frankfurt/M Verfahren zur Herstellung von Alkensulfonaten
US3306945A (en) * 1964-03-11 1967-02-28 Union Carbide Corp Purification of unsaturated hydrocarbons by adsorption using a molecular sieve adsorbent
US3322844A (en) * 1964-05-20 1967-05-30 Gulf Research Development Co Process for purifying a normal alpha olefin
US3328460A (en) * 1964-02-04 1967-06-27 Allied Chem Process for sulfonation of organic compounds
US3331882A (en) * 1964-10-29 1967-07-18 Exxon Research Engineering Co Separating alpha monoolefins using a steamed faujasite molecular sieve

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2563369A (en) * 1949-01-04 1951-08-07 Shell Dev Refining fuel oil
US3328460A (en) * 1964-02-04 1967-06-27 Allied Chem Process for sulfonation of organic compounds
US3306945A (en) * 1964-03-11 1967-02-28 Union Carbide Corp Purification of unsaturated hydrocarbons by adsorption using a molecular sieve adsorbent
DE1217367B (de) * 1964-04-08 1966-05-26 Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Brüning, Frankfurt/M Verfahren zur Herstellung von Alkensulfonaten
US3322844A (en) * 1964-05-20 1967-05-30 Gulf Research Development Co Process for purifying a normal alpha olefin
US3331882A (en) * 1964-10-29 1967-07-18 Exxon Research Engineering Co Separating alpha monoolefins using a steamed faujasite molecular sieve

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3699157A (en) * 1970-04-06 1972-10-17 Chevron Res Color reduction of olefin sulfonates
US3758608A (en) * 1971-08-26 1973-09-11 Texaco Inc Process for acid treating of olefins
US4940831A (en) * 1989-02-15 1990-07-10 Phillips Petroleum Company Purification of cis-olefins

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CH495930A (de) 1970-09-15
DE1643106B2 (de) 1975-08-21
SE364954B (2) 1974-03-11
LU53525A1 (2) 1968-03-18
BE697619A (2) 1967-10-26
AT283296B (de) 1970-07-27
ES339781A1 (es) 1968-08-16
DE1643106A1 (de) 1971-06-09
GR32682B (el) 1967-08-02
NL6705918A (2) 1967-10-27
GB1159728A (en) 1969-07-30
NL144916B (nl) 1975-02-17

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