Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
  • C07C5/333—Catalytic processes
  • C07C5/3335—Catalytic processes with metals
  • C07C5/3337—Catalytic processes with metals of the platinum group
• • 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
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids

Definitions

• ABSTRACT Improved processes for obtaining biodegradable detergents of good color using less sulfonating agents and minimizing or abolishing the requirement for decoloring; in which a mixture including ortho-dialkyl benzenes having linear alkyl radicals and linear olefin hydrocarbons (prepared by cyclization dehydration of normal paraffin stock having 14 to 24 carbon atoms) is sulfonated and neutralized twice with the organic phase from the first sulfonation forming the charge for the second.
• the efflux from at least the second neutralization is saponified and the aqueous phase of such saponification efflux yields the desired detergent.
• the first sulfonation is effected in the presence of a deficit of the sulfonating agent with respect to the sulfonatable hydrocarbons and the second with an excess.
• the present invention relates to a method of obtaining compositions of sulfonates by sulfonation of mixtures of olefin and aromatic hydrocarbons. It also re lates to the alkaline sulfonates obtained by means of this process, as well as to the use of the said sulfonates as detergents.
• alkaline sulfonates these sulfonates are generally obtained by sulfonation of hydrocarbons and then neutralization of the sulfonic acids.
• the most generally used of these hydrocarbons are the alkyl benzenes.
• the structure of the alkyl radical determines the biodegradability of the resultant detergent, i.e., the ability of the detergent to be biologically degraded by microorganisms living in water.
• the presence of a single tertiary carbon in the alkyl radical is a cause of hardness of the detergent.
• the present trend is towards the obtaining of softer and softer .detergents. For this reason, alkyl benzenes whose alkyl radical is perfectly linear are being used more and more.
• orthodialkyl benzene sulfonates having a total number of carbon atoms between 14 and 24 and entirely linear alkyl radicals constitute good detergents. Moreover, they are rapidly degraded by bacteria. During subsequent work, they have shown that the products resulting from the sulfonation of a mixture of aromatic hydrocarbons (whose principal components are orthodialkyl benzenes having linear alkyl radicals) and of linear olefin hydrocarbons constitute, after neutralization, very good biodegradable detergents.
• An object of the present invention is to carry out a process of sulfonation of a mixture of olefin and aromatic hydrocarbons which avoids the above-described drawbacks.
• the applicant has evolved a process of sulfonation in stages, which does not require the prior separation of the components of the mixture and which can be applied to a mixture of hydrocarbons both with or without paraffins.
• a second sulfonation carried out on the organic phase coming from the first treatment by an alkaline base, the said second sulfonation being carried out in the presence of an excess of sulfonating agent relative to the sulfonatable hydrocarbons present;
• the respective treatments by an alkaline base of the efflux from both the first and second sulfonations consist of a neutralization at ordinary temperature, followed by a saponific'ation under autogenous pressure at a temperature of between C and 300C.
• the first treatment by an alkaline base of the efflux from the first sulfonation consists of a neutralization at ordinary temperature
• the second treatment consists of a neutralization at ordinary temperature, followed by a saponification under autogenous pressure at a temperature of between 100C and 300C.
• the charge which comprises a mixture of sulfonatable hydrocarbons may also contain nonsulfonatable hydrocarbons such as paraffins and naphthenes. This is generally the case when the charge is prepared by dehydrogenation of normal paraffins.
• gaseous sulfuric anhydride sulfur'trioxide
• the amount of sulfur trioxide used should be such that there is a deficiency thereof with respect to the sulfonatable hydrocarbons: a ratio of the number of sulfur trioxide molecules to the number of sulfonatable hydrocarbon molecules of between 0.60 and 0.99, and preferably close to 0.8 for example is suitable.
• a ratio of the number of sulfur trioxide molecules to the number of olefin molecules of between 1.0 and" 1.5, and preferably between 1.0 and 1.2 for example is suitable; thus the major part of the olefins is sulfonated, while only a small part of the aromatic hydrocarbons is.
• the applicant has observed that the alkyl aromatic hydrocarbons are less reactive than the olefin hydrocarbons having the same number of carbon atoms.
• the efflux from the first sulfonation is subjected to neutralization (hereinafter called the first neutralization) at room temperature by an alkaline base; for instance caustic soda, when it is desired to prepare sodium sulfonates.
• an alkaline base for instance caustic soda
• the first neutralization is followed by a saponification (hereinafter called the first saponification) by an excess of base (for instance, caustic soda) under autogenous pressure at a temperature of between 100C and 300C.
• the saponification can be effected either on the organic phase alone, after separation by settling, or on the mixture of phases obtained after the neutralization.
• the purpose of this saponification is to transform the sultones into sulfonates.
• the saponification efflux is separated into an aqueous phase and into an organic phase which is subjected to a second sulfonation.
• the efflux from the second sulfonation is subjected to a neutralization (hereinafter called the second neutralization) at ordinary temperature by an alkaline base (for instance, caustic soda) and then to asaponification under pressure (hereinafter referred to as the second saponification) under conditions similar to those of the first neutralization and of the first saponification.
• the second s'aponification can be effected either on the organic phase alone, after separation by settling, or on the'mixture ofvphases coming from the second neutralization.
• the efflux from the second saponification is separated into an organic phase, which for all practical purposes no longer contains sulfonatable hydrocarbons, and into an aqueous phase.
• the efflux from the first neutralization is separated into an aqueous phase and into an organic phase.
• the organic phase is subjected to a second sulfonation, effected under conditions similar to the first, in the presence of a moderate excess of sulfur trioxide with respect to the residual sulfonatable hydrocarbons; a ratio of the number of sulfur trioxide molecules to the number'of sulfonatable hydrocarbon molecules of between 1.0 and 1.4, for example, is suitable.
• the absence of saponification prior to the second sulfonation results inthe presence of sultones in the organic phase treated in the second sulfonation.
• Each of the aqueous phases obtained after neutralization and/or saponification in either of the specific embodiments of the invention contains sulfonates.
• Detergents can therefore be prepared from each of these phases or their mixtures.
• the detergents prepared from the aqueous phases coming from the first sulfonation are richer in olefin sulfonates than those prepared from the aqueous phases coming from the second sulfonation. This property makes it possible to obtain detergents of given compositions which are enriched to a greater or lesser extent in olefin sulfonates (hydroxy alkyl sulfonates and alkenyl sulfonates) or orthodialkyl benzene sulfonates.
• the aqueous phases taken individually or in mixture (and in particular those which come from the neutralizations), can be treated with a slightly alkaline solution at a temperature of between C and 300C to improve the final color of the detergents prepared from them.
• a slightly alkaline solution at a temperature of between C and 300C to improve the final color of the detergents prepared from them.
• Such a treatment can be carried out in thepresence of a hydrocarbon which need not necessarily be the one from which the sulfonation charge'was prepared.
• One particularly advantageous application of the process of the invention resides in the sulfonation in two steps of a charge obtained by passing a fraction of normal paraffins having a number of carbon atoms of between 14 and 24 over a cyclizing, non-isomerizing, dehydrogenation catalyst consisting, for instance, of chromium oxide and potassium oxide which have been deposited on alumina or of platinum, lithium and arsenic deposited on alumina.
• the charge subjected to the first sulfonation on the one hand then consists of nonsulfonatable products which serve as diluents and which are primarily unconverted normal paraffins and a small quantity of naphthenes, and on the other band also consists of sulfonatable products which are olefin hydrocarbons, primarily linear mono-olefins, and aromatic hydrocarbons, primarily ortho-dialkyl benzenes (the alkyl radicals of which are linear).
• FIG. 1 relatesto the first specific embodiment of the process of the invention
• FIG. 2 relates to the second specific embodiment.
• a charge of hydrocarbons with carbon atoms numbering between 16 and 21 comprises on the one hand aromatic and olefin hydrocarbons (formed primarily of ortho-dialkyl benzenes, the alkyl radicals of which are linear,-and of straightchain mono-olefins) and on the other hand paraffins and small quantities of naphthenes, and is introduced via the line 1 into the first sulfonation reactor 2.
• aromatic and olefin hydrocarbons formed primarily of ortho-dialkyl benzenes, the alkyl radicals of which are linear,-and of straightchain mono-olefins
• paraffins and small quantities of naphthenes is introduced via the line 1 into the first sulfonation reactor 2.
• One percent by weight gaseous sulfur trioxide in nitrogen is introduced into the reactor via the line 3, the gas escaping from this reactor via the line 4.
• the efflux from the first sulfonation enters a first neutralization reactor 5.
• 4 N caustic soda in excess is introduced into the reactor 5 via the line 6.
• the first distillation efflux is saponified under autogenous pressure, at a temperature of 160C, in the first saponification reactor 7.
• a separating device 8 makes it possible to isolate an organic phase which is introduced via the line 9 into the reactor 10 in which it is subjected to a second sulfonation.
• Sulfur trioxide diluted in nitrogen is introduced into the reactor 10 via the line 11 with the gas escaping from said reactor via the line 12.
• the efflux of the second sulfonation is introduced into the second neutralization reactor 14.
• 4 N caustic soda in excess is introduced into said reactor via the line 15.
• the second neutralization efflux is saponified under pressure at a temperature of between 150C and 260C in a second saponification reactor 16.
• a separator 17 makes it possible to isolate and discharge through the line 18 an organic phase which contains the paraffins and the small quantities of naphthenes which were present in the initial charge, as well as small amounts of residual unsaturated derivatives.
• the aqueous phase collected in the separator 17 as well as the aqueous phase collected in the separator 8 are conducted via the lines 19 and 20 respectively into an enclosure 21 where they are simultaneously subjected to de-oiling.
• the solvent is introduced into the enclosure 21 via the line 22.
• a separator 23 makes it possible to isolate an organic phase, which is introduced via a line 24 into a column 25, where it is subjected to distillation so as to separate the oil at 26 and
• the initial and final parts are identical to those of the first embodiment.
• the similar parts of FIGS. 1 and 2 have therefore been designated with the same reference numbers in the drawings.
• the efflux from the first neutralization is introduced into a separator 31 from which there is extracted an organic phase which is introduced at 32 into a second sulfonation reactor 33.
• Sulfur trioxide diluted in nitrogen enters said reactor through the line 34.
• the gases escape from the reactor via the line 35.
• the mixture enters a second neutralization reactor 36 into which 4 N caustic soda in excess is introduced via the'line 37.
• the efflux from the second neutralization reactor as well as the aqueous phase collected at 38 in the separator 31 are subjected in the reactor 39 to an alkaline saponification under pressure at a temperature of between 150C and 260C.
• the efflux of the saponification is introduced into a separator 40 from which an organic phase is removed at-41 and an aqueous phase at 42.
• the organic phase 41 is formedof the paraffins and the traces of naphthenes which were present in the initial charge as well as of small quantities of residual unsaturated derivatives.
• the aqueous phase is subjected to de-oiling in the enclosure 21. The rest of the treatment is the same as that which was described with reference to FIG. 1.
• EXAMPLE I This example does not fall within the scope of the invention. It is given to describe one method of obtaining a sulfonatable charge and by way of comparison in order to describe a single-stage sulfonation process.
• a mixture of normal hexadecane and hydrogen is passed into a reactor at a temperature of 420C (the hour space velocity of the liquid normal hexadecane being equal to 1 and the hydrogen/normal hexadecane molar ratio being equal to 5).
• the reactor contains a cyclizing, non-iso'merizing, dehydrogenation catalyst.
• This catalyst consists of platinum, lithium, and arsenic deposited on alumina. The amounts of platinum, lithium and arsenic are equal to 0.75 percent, 0.50; and 0.36 percent respectively of the total'weight of the catalyst.
• the sulfonation charge thus prepared contains 10.4 mol% olefin hydrocarbons (about 82 percent of which are straight-chain mono-olefins) and 4.4 percent aromatic hydrocarbons (of which about percent are ortho-dialkyl benzenes having linear alkyl radicals).
• the rest of the charge consists of unreacted hexadecane and of traces of naphthenes.
• PROCESS OF SULFONATION IN A SINGLE STAGE The charge prepared in this manner is subjected to sulfonation at 22C by gaseous sulfur trioxide diluted to a concentration of 1 percent in nitrogen for a period of 75 minutes.
• the theoretical molar ratio of sulfur trioxide consumed by the sulfonatable hydrocarbons is about 1.5.
• the efflux of the sulfonation is neutralized by 4 N caustic soda.
• the organic phase obtained is treated at 250C in an excess of caustic soda in an autoclave for 1 hour. After settling of the mixture, there is obtained a new aqueous phase which, after having been brought back to a neutral pH, is added to the first.
• the experimental molar ratio of sulfur trioxide combined with the sulfonatable hydrocarbons is equal to 1.52.
• the residual unsaturated products represent less than 1 mol% of the hydrocarbon phase.
• the aqueous solution of detergent was subjected to decoloration by sodium hypochlorite at a temperature of 100C for 1 hour.
• the amount of hypochlorite consumed is 50 mols per 100 mols of sulfonate.
• the color measured after decoloration under the same conditions as above is equal to 3.5.
• phase After separation of the organic phase, said phase is subjected to a second sulfonation, also carried out at a temperature of 22C., but for a-period of 30 minutes and with an excess of sulfur trioxide with respect to the sulfonatable hydrocarbons present, said excess being 30% by weight.
• the efilux is then subjected to a neutralization (second neutralization).
• the organic phase coming from said neutralization after settling, is sub- .jected to a saponification (second saponification) in caustic soda at 250C. After settling, a new organic phase and a new aqueous phase are obtained.
• the mixture of all the aqueous phases constitutes, in this example, the detergent.
• Example I11 relates'to other tests which were carried out under conditions similar to those of Example 11. The results of these tests are also indicated in Table 1. Test 111; is identical to Test I I, Test I11 differs from Test i l only in the molar ratio of sulfur trioxide consumed to the remaining sulfonatable hydrocarbons, the
• a mixture of paraffin hydrocarbons having a number of carbon atoms of between 16 and 21 is subjected to a cyclizing non-isomerizing, dehydrogenation under conditions identical to those described in Example 1.
• the sulfonation charge After separation of the hydrogen and of the cracking products, the sulfonation charge has the following composition, expressed in mols:
• the first and second sulfonations are carried out at 25C. with sulfur trioxide diluted to 1% in nitrogen. The reaction times are'70 and 60 minutes respectively.
• the molar ratio of sulfur trioxide used to olefin hydrocarbons present is equal to 1.2 in the first sulfonation.
• the molar ratio of sulfur trioxide used to sulfonatable hydrocarbons is equal to 1.3 and corresponds therefor to an excess of 30 percent sulfur trioxide.
• the results obtained in these tests have been entered in Table 11 below.
• the AST M color of the aqueous solution containing the total amount of thefso dium sulfonates, measured cent. under the conditions described in Example 1, is 3.5.
• composition of the aqueous phase in -NaRSO 55 89.9 89.4 55 78.5 85.0 Na,SO 3 14.5 44.0 31.8 14.5 36.6 29.0
• composition of the Aqueous Phase (mol7r of sulfonatable Hydrocarbons used in NaRSO 68.6 99.4 98.5 Na SO 3 11.0 26.9 19.1
• An initial charge obtained by the method described in Example 1 is subjected to a first sulfonation at 22C. with gaseous sulfur trioxide diluted to 1 percent in nitrogen.
• the molar ratio of sulfur trioxide used to olefin hydrocarbons is close to 1.2.
• the efflux of the sulfonation is subjected to a first, neutralization at room tem-. perature by means of 4 N caustic soda and is tlienpa 40 rated into an aqueous phase and an organic phase.
• Theorganic phase is subjected to a second sulfonation by means of sulfur trioxide diluted to 1 percent in nitrogen.
• the experimental molar ratio of sulfur trioxide combined with sulfonatable hydrocarbons is equal to 1.26.
• the ASTM color of the aqueoussolution, measured under the conditions described in Example 1, is equal 60 to 1.5.
• the process of the invention makes it possible to sulfonate a mixture of olefin and aromatic hydrocarbons under the best possible conditions. Its application to hydrocarbons having a number of carbon atomsof be- 65 tween 14 and 24 results in biodegradable detergents under particularly advantageous conditions. As a inatter of fact. it makes it possible simultaneously to effect with respect to the sulfonatable hydrocarbons is reduced and at the same time it decreases the production of sodium sulfate. Moreover, the sulfonates obtained are of light color and do not require further decoloring.
• step (a) is about 0.8 and the ratio in step (e) is be tween 1.10 and 1.40.
• step (d) e. a saponification treatment by an alkaline base of either the organic phase or the mixture of organic and aqueous phases from step (d).
• step (a) is close to 0.8 and the ratio in step (d) is about 1.0.

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• 1970
  • 1970-11-24 FR FR7042195A patent/FR2115557A5/fr not_active Expired
• 1971
  • 1971-11-11 DE DE19712156087 patent/DE2156087A1/de active Pending
  • 1971-11-12 CH CH1644171A patent/CH540889A/fr not_active IP Right Cessation
  • 1971-11-19 BE BE775549A patent/BE775549A/fr unknown
  • 1971-11-20 IT IT31422/71A patent/IT941232B/it active
  • 1971-11-22 ZA ZA717835A patent/ZA717835B/xx unknown
  • 1971-11-22 GB GB5422471A patent/GB1328743A/en not_active Expired
  • 1971-11-23 SE SE7114997A patent/SE381652B/xx unknown
  • 1971-11-23 AT AT1008671A patent/AT313308B/de not_active IP Right Cessation
  • 1971-11-23 CA CA128,373A patent/CA955263A/en not_active Expired
  • 1971-11-23 US US00201501A patent/US3803058A/en not_active Expired - Lifetime
  • 1971-11-24 LU LU64332D patent/LU64332A1/xx unknown
  • 1971-11-24 NL NL7116154A patent/NL7116154A/xx unknown

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