Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/68—Catalytic processes with halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/70—Catalytic processes with acids
• • 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
  • C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/08—Halides
  • C07C2527/12—Fluorides
  • C07C2527/1206—Hydrogen fluoride
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/08—Halides
  • C07C2527/12—Fluorides
  • C07C2527/1213—Boron fluoride
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
  • C07C2527/126—Aluminium chloride

Definitions

• the present invention relates to a process for the preparation of alkylated aromatic hydrocarbons and, more particularly, to alkylbenzenes suitable for the production of detergents susceptible to biological degradation.
• olefins suited for the preparation of alkylated biodegradable detergents are obtained via the cracking (pyrolysis) of hydrocarbon mixtures, such as parafiinic waxes having special chemical and physical properties, or by cracking gas oil containing aromatic and naphthenic hydrocarbons at lower levels.
• this invention consists of a process for the preparation of alkylaromatic hydrocarbons suitable for the production of biodegradable detergents by using as starting materials (raw material) heavy fractions of petroleum of any composition with a boiling point range of from 300- 600 C.
• alkylaromatic hydrocarbons are obtained in very high yields and are suitable for the production of biodegradable detergents starting from petroleum fractions of compositions that, from an economic point of view, discourage their use according to the methods employed so far, that is, for example petroleum fractions that, because of a very low content of linear hydrocarbons, even lower than 15% by weight, and a very high content of aromatic compounds, even higher than 35% by weight, would not profitably be used for this purpose.
• alkylaromatic hydrocarbons obtained according to the process of this invention lead, through sulfonation with oleum or S0 and subsequent neutralization, to alkylated detergents which are totally biodegradable within a set period of time and which, additionally, display superior characteristics in regards detergency and product quality.
• this invention relates to a process for the preparation of alkylaromatic hydrocarbons suitable for preparing detergents which are biodegradable, and which process characterizes itself by the following steps:
• the preferred conditions for the steam cracking comprise a temperature ranging from 550 to 650 C., a pressure of between 1 and 5 atm., a weight ratio between the load of hydrocarbons and the fed steam varying between 8 and 12, and a feeding velocity defined as space velocity (that is the quantity (expressed in kg.) of load+vapour which in a unity of time (1 hr.) flows through a volume unit of the cracking coil (expressed in 1.)) comprised between 1.0 and 7.0.
• hydrocarbon mixture which contains linear and branched chain cyclic monoand polyolefins and aromatics with contents thereof varying according ot the cracking conditions and to the composition of the starting mixture.
• the mixture emanating from the cracking is subjected to fractional distillation to obtain a fraction with a distillation range of from 120 to 300 C., comprising, inter alia, olefinic hydrocarbons of from 8l5 carbon atoms, preferably a fraction with a distillation temperature range of from 160260 C., and comprising the olefinic hydrocarbons of C -C (c)
• This fraction is then subjected to an extraction treatment with urea by means of which the linear hydrocarbons (mainly the normal olefins) are separated from the rest of the mixture, subsequent to the formation of an adduct with the urea.
• the extraction with urea consists in extracting the hydrocarbon fraction, which fraction was separated from the mixture coming from the cracking, with a quantity of urea equal to 33.5- parts by weight of urea for one part by weight of product that may be transformed into an adduct, using a solvent for urea, preferably alcoholic such as, for example, methanol, and in a quantity equal to 0.51.2 parts by weight of alcohol per one part by weight urea.
• a solvent for urea preferably alcoholic such as, for example, methanol
• diluents there may be used those substances that are miscible with hydrocarbons, that do not form adducts with urea and that do not decompose the adduct formed by the linear hydrocarbons, for example, branched, chlorinated, aromatic hydrocarbons and the like.
• the extraction with urea is carried out in a mixer or other similar equipment that afiords intimate contact between the two phases that are formed: the solid phase, formed by the urea n-olefine adduct and the unreacted urea, and the liquid phases formed by all the rest, that is by the remaining non-linear hydrocarbons, saturated as well as unsaturated, cyclic and aromatic, together with solvent for the urea.
• the reaction to form the urea n-olefine adducts is carried out at temperatures generally between from about 0 and 35 C. Good results are obtained when operating at temperatures between about 0 and C. at contact times varying from about 20 to 60 minutes depending upon the degree of stirring.
• said isoparafiins being transformed into linear olefins and subsequently extracted with urea, same can be used with a view to the economy of the process by contributing to the increase of the final yield.
• the product of the urea n-olefin reaction is purified through suitable washings and filterings and is then de composed in the presence of a suitable solvent for the olefins by heating at a temperature of from 5080 C., with stirring, for a period of time generally around minutes.
• a suitable solvent for the olefins such as benzene because, such being the case, there can be directly obtained the mixture of n-olefins dissolved in the aromatic hydrocarbons, which, in the presence of the Friedel-Crafts catalyst, directly yield the alkylaromatic hydrocarbons.
• n-olefins dissolved in solvent and, on the other hand, urea which can be reused for forming the adduct with other linear olefins.
• the mixture of linear olefins also comprising the aromatic hydrocarbon used as a solvent for the olefins in the decomposition of the adduct is fed into the alkylation apparatus, into which there is also introduced an alkylation catalyst of the Friedel-Crafts type, such as, for example, AlCl .I-ICl, BF .HF or HF.
• an alkylation catalyst of the Friedel-Crafts type such as, for example, AlCl .I-ICl, BF .HF or HF.
• the quantity of aromatic hydrocarbon must be equal (if it is the case by a subsequent addition) to the quantity required by the alkylation reaction, i.e., the molar ratio of aromatic hydrocarbon to olefin may vary from between about 4:1 to 8:1.
• the sulfonic acid thus produced is then neutralized With sodium or potassium hydrate, ammonium hydrate, amines, amino-alcohols, etc., so as to effect a paste or a liquid to which can be directly added additives and other constituents necessary for the formulation of commercial detergents.
• the detergent formulations both in powder form or as a liquid, which are prepared by taking as a base the alkylaryl-sulfonates obtained according to the process of this invention may contain additives that are normally incorporated in conventional commercial products, for example, they may contain other compounds of superficial activity, tripolyphosphates, optical bleaching agents, hydrotropies, foam-promoters, foam-inhibitors, foam-stabilizers, perfumees, corrosion-inhibitors and so on.
• a typical formulation may consist of the following components:
• the active substance is formed from a mixture of alkaline alkylbenzenesulfonates differing from each other in the lengths of the linear chains attached to the benzene rings.
• biodegradability test was carried out with the same method on the active substance (mixture of monoalkylarylsulfonates) without all the components present in the formulation. Again the biodegradability turned out to be greater than 90%.
• the active substance was subjected to the so-called River Water Test vis-a-vis the usual commercial products and again the detergents obtained displayed excellent biodegradability.
• the River Water Test is a control method proposed by the British Institute, Committee on Methods for the Analysis of Trade Efiiuents (see The Analyst, volume 82, page 826, 1957).
• This method consists in preparing a solution of detergent of very low concentration (around parts by weight per million) in river water in which the absence of anionic detergent has been previously ascertained, and in determining the residual concentration of non-degraded detergent at certain set intervals of time.
• the examples are characterized by four processes that ditfer from each other by whether or not they include the phase of separation of the hydrocarbons with a linear chain: by the type of separation chosen, as an example, i.e., separation by solvent or by urea; at which point of procedure this latter type of separation is carried out, i.e., whether the separation by urea is carried out before or after the steam-cracking phase.
• the operations follow the order indicated in the following scheme:
• Example 1 A definite quantity of heavy gasoil obtained by vacuum distillation of the residue of a topping of Libian crude oil and which had the following characteristics:
• reaction mixture stratified into two liquid phases which were diflicult to separate, the lighter one being formed of excess benzene and of monoand polyalkylbenzenes, this latter phase, after decantation, washing with an equal volume of water, neutralization with 5% NaOH and subsequent fractioning separated a fraction having a distillation range of from 2703 60 C., and containing the monoalkylbenzenes.
• 100 parts of the fraction containing the monoalkylbenzenes were introduced into a reactor provided with a very efiicient stirrer (for example, a turbine) and fitted with a suitable cooling system.
• a very efiicient stirrer for example, a turbine
• the lower phase was then removed and the upper phase conveyed to a reactor fitted with a slow blade stirrer.
• a solution of 20% NaOH at such a rate that the temperature did not exceed 50 C. and in such a quantity as would be sufiicient to bring the pH of the slurry to about 7 and 9, and preferably between about 7.8 and 9.2.
• the C -C (-250 C.) had the following composition:
• the C -C fraction was then subjected to alkylation with benzene in the same way as described in Example 1, and by using a quantity of benzene with a molar ratio benzene/C C fraction equal to 6.1, a quantity of anhydrous AlCl in amounts of 3.6 parts by weight of AlCl per 100 parts of C -C fraction, and the other values (temperature, time, etc.) remaining unchanged.
• Example 3 A definite quantity of heavy gas oil obtained from the vacuum distillation of the topping residue from Lybian crude oil and having the following characteristics:
• composition of the wax was as follows:
• the C -C fraction (with a distillation range of from 170-250 C.) displayed the following composition:
• n-olefins obtained from 100 parts by weight of starting gas oil amounted to 1.62 parts byweight (100x0.222 0.107 0.686:1.62).
• the C -C fraction (170250 C.) was subjected to alkylation with benzene in the same manner as described in Example 1, and by using a quantity of benzene equal to a molar ratio of benzene/C -C fraction equal to 6.1, a quantity of anhydrous AlCl equal to 3.3 parts by weight of A1Cl for 100 parts of C C fraction used in the alkylation, and by maintaining the temperature at 33 C. for 60 minutes.
• Example 4 A certain quantity of heavy gas oil obtained from the vacuum distillation of the topping residue of a Lybian crude and having the following characteristics:
• a quantity of wax was obtained equal to 16% by weight with respect to the quantity of gas oil.
• the wax obtained displayed the following composition:
• the C -C fraction -("-250) had the following composition:
• the monoalkylate, sulfonated and formulated under the same conditions as those described in Example 1 displayed a biodegradability as determined according to the German test, of less than 50%
• the same test was carried out on the non-formulated product consisting solely of sodium alkylbenzenesulfonate 1 1 and in this case also the biodegradability was lower than 50%.
• the pure product i.e., the non-formulated alkylbenzenesulfonate
• the results of the River Water Test are directly recorded in Table II.
• the crystals of the adduct were then mushed into about an equal quantity by weight of methylisobutylketoue, filtered again, and then dried in order to completely eliminate the solvent.
• the adduct was then decomposed with water at a temperature of from about 6080 C.
• the oily phase consisting for the most part of the parafiins which had formed the adduct with the urea, was then separated from the urea solution (which may be recycled) weighed 18 kg. and had the following composition:
• the wax thus obtained was subjected to steam cracking under the following conditions:
• Temperature C 610 Pressure atg 1 Weight ratio of feed charge/stem 110 Space velocity kg. (feed charge+steam)/h.
• the pure product i.e. the non-formulated alkylbenzenesulfonate was also subjected to the River Water Test. The results of this method were not altogether satisfactory. The results of the River Water Test are directly recorded in Table II.
• Example 6 A certain quantity of heavy gas oil, having the same characteristics as the gas oil used in Example 1, was subjected to steam-cracking under the following conditions:
• the solid mass (adduct of the urea with n-olefins) comprising isoand cycloolefins and aromatics, was separated from the oily mass, and from the methanol through filtering (centrifugation).
• the methanol containing 10 kg. of dissolved urea, was separated by decantation and could be utilized in other charges without further treatment. From the oil the methanol dissolved by distillation was recovered.
• the adduct (143 kg.) was then suspended in 100 kg. of anhydrous benzene and then filtered or centrifuged.
• the recovered benzene could be used just as it was for the washing of the subsequent charges, or could be immediately purified by distillation.
• the solid filtrated mass was then suspended in 72 kg. of anhydrous benzene and brought to 65 C. for 30 minutes, under constant stirring and the adduct decomposed with quantitive separation of the urea.
• the urea (110 kg.) was then decanted and could be used without further manipulations in successive operations.
• the extraction yield based on the normal olefins contained in the C -C fraction was equal 110
• the molar ratio benzene/C C purified fraction was equal to 6.0.
• the alkylated liquid was then decanted, washed and neutralized, and was then fractioned in the same way as that described in the preceding examples.
• a fraction was obtained having a distillation range of from 270360 C. and containing the monoalkylbenzenes.
• the yield of monoalkylbenzenes based on starting charge of heavy gas oil was equal to 1.93 parts by weight for 100 parts (10 0X0.073 0.258 1.03:1.93).
• the product thus prepared was then subjected to the biodegradability test according to the aforesaid German test and exhibited an actual biodegradability of 97%.
• Example 7 In a preferred form of execution, a fraction of gas oil of high boiling point, having a distillation range of from 350-550 C. and having the same characteristics of the gas oil used in Example No. 1, was subjected to steam cracking under the following conditions:
• the extraction yield based on the olefins contained in the C -C fraction was 93.0%
• control procedure according to this method is common to all examples with respect to the quantity of the substances used and with respect to control times, wherefore it will be described hereinafter and will be valid for all examples.
• the pasty masses obtained through neutralization of the alkylbenzenesulfonic acids obtained by sulfonation of the fraction of C -C monoalkylbenzenes
• This process was carried out separately for each example.
• the purified sodium alkylbenzenesulfonates corresponding to the seven examples were introduced separately to glass vessels containing river water in such quantity as to have an initial concentration equal to about 10 p.p.m.; the concentration was checked with methylene blue.
• the glass vessels were locked and the solutions stored at room temperature.
• a comparative solution was prepared following the same procedure, i.e. a solution of commercial sodium alkylbenzenesulfonate obtained from tetrapropylene (10 p.p.m.)
• the eight solutions are analyzed periodically according to the methylene blue method.
• the concentration of the product corresponding to each example was compared with the concentration of the alkylbenzenesulfonate derived from tetrapropylene.

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Citations (3)

• 1965
  • 1965-10-13 NL NL6513234A patent/NL6513234A/xx unknown
  • 1965-10-15 GB GB43755/65A patent/GB1110940A/en not_active Expired
  • 1965-10-16 DE DE19651493111 patent/DE1493111A1/de active Pending
  • 1965-10-18 US US497513A patent/US3444261A/en not_active Expired - Lifetime
  • 1965-10-18 FR FR35268A patent/FR1450245A/fr not_active Expired
  • 1965-10-19 BE BE671088D patent/BE671088A/xx unknown
  • 1965-10-20 ES ES0319033A patent/ES319033A1/es not_active Expired
  • 1965-10-20 SE SE13562/65A patent/SE324357B/xx unknown

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