BE612036A - - Google Patents

Description

       

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  A process for the production of an alkylaryl compound suitable for the preparation of a bilogically mild detergent.
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  The present invention relates to a process for the production of detergents and other substances active on the surface which sul, t soft and evening! : thus ccris> i la ÙJèaI: Hion bl.olo, 'Íque:> 6!: dant the treatenent e purification of waters.

   From aBi] i; re read spcc-fqua, the present invention cc: 'identifies a process cr 1- = - oUjj.

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 of a ".i.Co.rJ.; 1ce straight chain ment of an aronia compound
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 ti-iue, starting from heavy naphtha fractions containing
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 straight chain paraffinas where the number of carbon atoms in the alkyl group of the alkylate r; i.a:; Liu-E. ' Desired, for i'urùs1 ".fin-t..l.er: .ent. '. n alkylate -Which, when it is coated or otherwise converted to a detergent product, is extracted with bacterial attack and degradation in
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 a subsequent process for the treatment of ires waste water which
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 follows the ast; lûi ae this detergent and evecustion .i 1'ZÉ: gOtlt
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 One of the most important issues that arise
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 d r.s x;

  3 population centers in -The whole world, is already the one to get rid of waste water containing:; :: '1: ;; of ...: i. your amounts of detergents, ... y ... have a ±, 4-coyj .'- ryl structure as the basis of the detergent molecule These aetergents produce stable foams in hard or hard water. .1 these in quantities so large that the foam clogs the
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 wastewater treatment facilities and is often
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 * rset2 in attffia concentration:, n1'm'f has these facilities to "destroy the bacteria necessary for a bi 'action:; l.:)gi" 1'.B sufficient for uI}' very suitable water. : S-1: 1 .. - '': ïv 11121 des nril'lÇjDnllX GC) 1) p: "b'LB5 of this type of detergent is the suifonste of éi.1.Coylç'l" 'j "the who,: vfii-3i: èi.: erit
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 of
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 what is produced with soaps / fatty acids is not specified;:

   s when s & j-njé with hard water count.-ni j: e3 calcium ions or mbgn4-sium in solution, and then 3 v3J compounds are antibacterial .. ticks, j. =. ;; -, :.: .. i ':: 1. ;; ':. # r., 3r-t is not ssuieaent tr =: s:, rte à r "ra-., ..., .., .....,. ''; .1.1 waste water treatment stage = s

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 in unchanged form and here it sëcā¯t The active tendency to ouE3aie,] lus s cial e: .szt when .- 'it is mixed by means of gasification devices and' agitators, but a stable foam is formed who is
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 transported throughout the milking installation; 'the waste water and! 3 & - does not precipitate even when further diluted with liquid water, whether it is ;;

     hard or soft. another guilty wall the deterts
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 of this type is represented by the alcoßlihemi: lw yolyoxyalkylés. These synthetic same feats also interfere with the anaerobic process of degradation of other materials, such as grease and thus increase
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 more the pollution problems of Baux.

   These diluted detergent soL.tL.:::.9 often enter water currents below the surface, which flow into the subsoil water mouths from which many localities derive their supply of water. water supplied to city water taps in private homes, factories, hospitals and alone. Occasionally dry detergent is present in sufficient quantities in tap water to produce foam in the drinking water when it comes out of the water.
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 tap.

   Although the effluent from the tr3.itewe facilities: úî. of wastewater can be clear, tons of synthetic detergents that have withstood treatment
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 of wastewater and which have survived h. action these bacteria, present in currents at the open air surface, are the cause of the formation of large masses of foam at the bottom of weirs and dams in water currents in countries where the population uses large quantities no synthetic detergents, during 1959 more than
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 6 :.

   Millions of kilograms at 'a''3nts active "! O surface

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   the unformed state, i.e. excluding inorganic salts added to commercial detergents) have been sold in the United States! Of this quantity of synthetic detergents which enter into the treatment of waste water throughout the United States, 24-'0 million kikogrms were of the sodium alkoylbenzene sulfonate detergent type (hard). ), not able to be degraded by bacteria.
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 all) <L4 {A suitable supply of water PU: -3, / co.m:

  Clean air, is essential for new growth and development in many parts of the country and for the safety of millions of people around the world. Alkyllarlyl based detergents such as 1- '' sodium alkylbenzene sulfonate have been shown to be more easily degraded by bacteria in wastewater if the alkyl part of the molecule is of a single, chain configuration. only when it comes to a more complex branched @string structure. For example,

   detergent compounds containing the hydrophobic alkylaryl group and having an alkyl side chain structure such as
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   are: more apt to be digested by bacteria than degents with the same chemical composition but having side chain alkyl group str tures such as
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Thus, detergents based on alkylaryl where the alkylated portion of the molecule has a structure corresponding to the straight chain structure of the alkyl group illustrated in the first of the two structures operated above,

   bilogically produce detergents
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 xxb with relative ease t>,> tèq mild which undergo / bacterial degradation in oi '- ly, waste water treatment plants while the products formed from alkylaryl hydrocarbons containing a branched branch alkyl rupe such as structure polymethylated shown in the second of the structures illustrated above, produce "hard" detergents which are much more resistant to bacterial degradation in the effluent leaving the wastewater treatment plants and appear as active detergents in the treatment tributary of waste water.



   One of the objects of the present invention is to produce alkyl aryl hydrocarbons in which the lateral alkali chain attached to the aromatic nucleus is a relatively straight chain capable of producing biologically mild detergents by the inclusion of a radical appropriate hydrophilic in the structure of the compound.



   Another object of the invention is to provide an alkylaryl hydrocarbon structure suitable for producing biologically mild detergents therefrom without adversely affecting the product return, the effectiveness of the final detergent product or its solubility in water.



   The present invention consists of a process for the preparation of an alkyl aryl compound particularly suitable for the preparation of a biologically mild detergent product starting from this compound, in which the aryl ring is mono-cyclic and the alkyl radical on the ring. aryl is a relatively chain group

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 straight cu.1; ':! having about 15 carbon atoms, a flesh refiner. the straight line having at least 95% nu-m-ale paraffin purity is S'1r "' t¯ EI of a naphtha pq r3l'l'iLl "'I with a boiling point between 12t; oC and c: 50oC. by zaz .'xiteent of selective se # ration at ,, rOUTJe
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 1.

   UliOJ ", -VJ-t fJ1 ccsistant e! R: '- 3vrption at molecular sieve, formation a'aadttct
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 of Ur: 36 and fv1'1atiúli of addâct tniourea, the separated right cnain8 paraffinic hydrocarbon is converted into a derivative acting at the ..3:, ÚJre (the ùl. :: fines, belonging to the group of hydrocarbons may .c # olCtliaQUQS and alkyl halides. and a 3r-) Í.-atÜ ,,, q compound selected from the group consisting of benzene, toluene, xylene, ethylb..zene, methylethylbenzene and phenol is alkyl-i with the derivative acting in the manner aes, 1 fines to form the monoalkylate of said aromatic compound.



  The alkylaryl hydrocaroon product according to the present invention mentioned here as being an "alkylate" constitutes a starting point for the repair. 11ne (1.3..0th variety of detergents, some of which S'J!: t é31 "'r, e .." .; useful as generally active agents
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 surface uar.s these applications as tanning agents, agents
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 ! 'aâ ¯ tcis4n. "311t, bar soaps, and a wide variety -1'. :: tr08 useful applications in most applications of which an aqueous solution of the detergent or active agent
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 at the surface enters the water treatment system
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 waste for treatment at a remote facility
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 wastewater treatment.

   Thus, the alkylate product according to the present invention can be sulfonated and neutralized by means of a suitable alkaline base such as hydroxide.
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 sodium to form the so-called a, aium alkyl sulfonate detergents, which are widely used for household, commercial and industrial consumption.

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  Another major class of detergents based on the alkylaryl part of the molecule are the derivatives
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 Oxyalkylated compounds in which the phenol base can be prepared starting from an alkylated hydrocarbon. Yet another class of detergents derived from alkylaryl hydrocarbons are the polyoxyalkylated aniline and the alkoyianiline derivatives of the alkylate which are soluble products in water and are formed by nitration of the alkylate by catalytically reducing the alkylate nitro. -substituted resulting to form the amine and then polyoxyalkylating the amine to form the resulting detergent.

   Still other products having an alcuylaryl base are very well known in
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 Technically, although the alkylated sulfonates provide the most important source of current pollution and are therefore the most common end-use product obtained from the alkylated product of the present invention. The term "aryl" as used herein refers
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 with a rpntzG; re :: JC1Lccycllque ring which can be a hydrocarbon or which can contain various radicals .lciéazres as substituents, such as parele l ': lyd'oxy1e and the amino group.



  In the present process for the production
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 relatively straight C: 1 substituted alkyl aromatic hydrocarbons usable as heat forming materials to be treated in the production of bioobically soft surface active agents and more particularly water soluble detergents, the source of the agent. alkylation giving the straight chain alkyl group on
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 the: = aromatic nucleus, is an important factor in the synthesis of the relatively straight chain alkylated product of the present process.

   In order to produce an alkyl hydrocarbon

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 aromatic in which the alkyl group is a long chain group containing 9 to 15 carbon atoms and having a relatively straight chain structure, the alkylating agent condensed with the receptor consisting of the aromatic hydrocarbon must also have a structure relatively straight chain since, in the most favorable situation, the alkyl chain penetrar.t in the aromatic nucleus will have a secondary structure even if one uses a 1-normal olefin as alkylating agent in the condensation with the receptor constituted by aromatic hydrocarbon.

   This secondary structure of the resulting alkylate follows the well-established principles of Organic Chemistry which establish that the alkylated chain which penetrates, binds to the aroma nucleus on the carbon atom of the mono-olefinic chain having the most small number of atoms of rogen, and even when 1-olefins are used as a -e..t alkylation, the point of attachment of the alkyl chain which penetrates will be located on the carbon atom olefinic ci-.aine number 2 as follows:

     
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The degree of branching in the alkyl chain of the resulting alkylate will depend on the degree of branching of the olefin chain used as the alkylating agent in the above reaction and therefore the normal 1-olefins will produce the degree. lowest branching

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 of the alkyl chain attached to the aromatic nucleus of the resulting alkylate.

   It has now been found that one of the preferred sources of normal olefins which upon alkylation will give alkylates in which the alkyl part of the molecule has the maximum degree of linearity are normal s / paraffins which upon dehydrogenation. under controlled conditions to maintain the linearity of the olefinic product, produce an olefin in which the double bond remains between the number 1 and number 2 of the carbon atoms in the chain, and which are present as straight chain paraffins in a moiety boiling point equal to that of kerosene containing about 9 to 15 carbon atoms in the molecule (paraffin.

   These paraffins, when dehydrogenated in the presence of catalysts which possess a minimum of isomerating activity, give normal or straight chain 1-olefins capable of giving alkylates by alkylation where the alkyl group has the maximum degree of linearity.



   Any suitable source of normal paraffins can, of course, be used to feed the separation phase of the present process, including an appropriate boiling point fraction of a straight-run petroleum distillate, or products. of the Fischer Tropach reaction which include paraffinic hydrocarbons between the limits C9-C15, formed by hydrogenation of carbon monoxide in the presence of ur. catalyst of the metal metals of the iron group, the hydrogenated products of the polymerization of ethylene which include:? refined;

     having 9 to about 15 carbon atoms, hydrogen acids which, on complete reduction, produce araffinic hydrocarbons

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 having a straight chain configuration as well as other sources of such paraffinic compounds, all contemplated herein, as the source of the filler material in the present process.

     While any of the above normal paraffins can be used as the main feedstock in the present process, the cheapest and generally preferred source of normal paraffins is kerosene boiling between about 170 ° C and about. 240 0 containing the desired C9-C15 paraffins, which by conversion to a derivative acting like olefins; followed by condensation with an aromatic compound yields a hydrocarbon radical having sufficient hydrophobic activity to provide the required hydrophobic portion in the structure of the detergent molecule.

   However in all sources of paraffins to. straight chain mentioned above a significant proportion of branched chain isomers are present in admixture with paraffins / normal, which if converted to their analogs acting like olefins, do not give alkylates desired having a straight chain alkyl group.

   Therefore, in order to form the alkylate product having the maximum degree of finality and the most advantageous properties with regard to its biological degradability, the paraffin feed introduced into the olefin production phase of the present process must be subjected to a process. separated in order to separate and isolate the constituents of the paraffinic mixture having the desired straight chain structure, as will be described below.

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  The separation and the rCLt.!: J8rd tion of normal ,, a remade with fractions at hydrc.ca ::. Jures which contain them is based on a separation method which selectively differentiates between normal paraffins and isoparaffins, and between normal paraffins and cyclic paraffins, and thus calls for a separation process of the mole sieve type in which the upstream separation is selective for normal constituents
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 present in the mixture of paraffinic isomers.

   Several methods of molecular scale type separation exist having sufficient selectivity to give product streams of normal paraffin purity of at least one of. Preferred release agents having this degree of selectivity is a molecular sieve sorbent characterized by its chemical composition as being a dehydrated metal alumino-silicate having a zeolite structure in them.
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 alumino-silica crystals and containing these pores with a cross-sectional diameter of about 5 Antnromic units. The ctisiensiùs are sufficient to allow the entry of aliphatic paraffinic compounds 0'01 diniques but use is not sufficient to allow

  entry of compounds ->. branched chain or These cyclic compounds. The metallic constituent of these compositions
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 z ':; 01itiQ'Jes is chosen from alkaline earth metals, reference calcium and magnesium, which not only are the most effective but are also the least c ^; them pariai the various derivatives of alkaline earth metals.

   These molecular sieve sorbents which are prepared
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 by selective crystallization this metallic 2 'alumino-silicate ùar.s aes s .. lut aqueous ions ae s .digue silicate or other source to, rie above silica, source

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 of alumina or aluminum hydroxide, and an alkali metal hydroxide, and containing certain proportions
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 specifiau9b of these oxides as well as water, are prepared by combining water, sodium silicate ("water @lass" 0 or a silica salt free of sodium or an alcohol ester or silicic acid such as ehtyle orthoeilicate,

   alumina or an alkali metal aluminate and sodium hydroxide in sufficient proportions
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 For the following reports of reagents indicated on their oxides: 12 J / Si: 1, tu - 3.0 Sic. / A1: u, 5 - I, 3 ii2 ", Í2ra2u: 35 - 2o0 and heating the aqueous mixture to a temperature between
40 C between about 400 and about 120 C for a period of
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 until about 4 hours or until the oe? ri s rate is complete, according to the temperature of the reaction.

   The crystals which precipitate are the sodium form of alminosilosts .¯ ^ - '¯1¯r.ue have the following empirical cooking: 1,00,2 1, Al sl, 85v., 5 S. / YH where is sodium, if sodium derivatives are involved in the preparation,: Jet any of the alkaline earth metals can also be used, and Y has a value up to about 6. Calcium derivatives or
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 other alkaline earth metals (having pore diameters of about 5 An. strom units, required by / The present process) of the above alkali metal salts are prepared by exchange
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 The alkaline α-talal iris leaves the above zeules with a water-soluble alkaline earth metal salt, such as an aqueous solution of calcium chloride.

   Crystals

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 hydrates resulting from alumino alkaline earth silicate
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 are then dried and calcined at z tL.:¯ra nrRe ranging; euis about 150 up to about 5:ù C, to hydrate the water of crystallization and thus develop pores having
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 the required diameter of about ites .4riestrome and .eus this form the product is activated COIXJ1 the molecular goose for the present separation process.



   Another class of release agents, which are selective for normal compounds including olefins, if present in the mixture of hydrocarbons, is urea which.
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 s., -, are ces C'.12 "t ::. tuan.t; e by the forl: J.3tiúIl of an adjuct or clrthrate fies urea with the compound -t c'elaiiie (4, right Crystals of urea or an aqueous urea solution are mixed with the hydrocarbon fraction at a temperature of between about 10 ° C. and about 35 ° C., the crystalline substance forming as soon as the urea is mixed with the Traction hydrocarbonée, the normal constituents of which
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 'rivent be separated, the crystals being fil1;

  liquid reflux remaining and then being decomposed separately by raising the temperature of the separated crystals or displacing the normal urea-bound hydrocarbon as a clathrate with a preferably sorbed compound, such as
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 alcohol, including methanol, ethanol, 1> 1'01-8nol norraal, etc., an aldehyde such as propionaldehyde, acetaldehyde, etc. or other aliphatic compound containing a polar radical.
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  The straight-chain hydrocarbons which are found in the first line of hydrocarbon isomers can also be separated from the cyclic and isoparaffinzaues constituents "", present in the mixture, by bringing this mixture into contact.
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 -JU -, constituents tux bj, with thiourea yes form selectrveuent adducts avsc uanq / if.UT 1lfY "" .. t with form select.LVef.1ellt adducts with

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 with raraified chain and cyclic constituents, leaving the normal hydrocarbons present in the Relance in the form of a stream of raffines which can be withdrawn from the
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 clathrate furrr: between thiourea and .the cyclic constituents are isr¯rarafy '.. niques.

   Separation methods using separation agents. above are well known in the art and may be referred to for specific details of the techniques of the present
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 roc'2d ,.



  The straight chain aliphatic hydrocarbons 8.arés of .dëlan. Hydrocarbon a'isomers with a M'oulli point similar to that of kerosene by the separation process described above is according to the present; the combination process, subjected to a debydrogenation reaction in these c. , x, dehydrogenation reaction assists and Qu rresenct '' '' an apl-'r catalyst,., ;;

  rie dehydro filiation, which will Y'J) ta 'result in the production of a mono 1-olefin having the same number ri lator.16B of carbon as the initial l.ar3f'finic charge having the same chain structure straight line U8 the load, that is to say without isonerization in a structure with branched chain.
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 The n-paraffins are thus converted into mono-olefins which undergo condensation with an aromatic compound containing a hydrogen atom.
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 nuclear replaceable to form the present alkylated product.

   In an alternative method of synthesis of the alkylate recovered from the paraffinic charge, the normal paraffin is converted into an active compound.
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 3. the way of ..1efinJs, which is then condensed with an aromatic reagent to formally present alkylated product.

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  Thus, the n-paraffin is first subjected - the halogenation
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 for example, reacting chlorine with liquid n-paraffins until mono-halug.i.ation is complete, then the resulting alkyl chloride is used. with the desired aromatic hydrocarbon present in anhydrous aluminum halide, such as aluminum chloride, under reaction conditions in which the halide
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 of hydrogen is liberated and the monoalkylate formed by condensation, the aromatic hydrocarbon with the alkyl halide is formed.



  In this condensation the n-alkyl salt formed by
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 halo ± enativn of n-paraffins, when they are brought into contact with the aromatic hydrocarbon ei. presence of aluminum oxide, acts in the capacity of the corresponding olefine in the presence of an alkylation catalyst., the halogen radical of the metal combining with the atom
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 ':' 'reaplarable h7droeme on the nucleus of the hydrocarbon ar ,, 7--3t, ciue for the halide of' n: tdro ':; 8ne and the free bond on the alkylated residue comes together with the bond binds onto the aryl ring to form the alkylate.

   Expression
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 "" gcti f aEi!: 'a: t 2 the manner .ïes ul.iines "is referred to -' 1 fine e = .1e -L1me forced by the dehydrogenation of paraffin or the alkyl halide formed by halogenating
 EMI15.6
 n-araffin. the conversion of straight chain paraffin rec .., r.-e, by the method of separa!;

  The above ion of the mixture of 1) al.ißm tic and, or cyclic hydrocarbons in their mono-olefin analogues 4 ues by dehydroénativn, is made with .., erasures taken between about 4ljuoc and about 61 ... 00C in presence of a particular type of catalyst which is particularly suitable. this conversion without isomerization in normal paraffins to their branched-chain iSOparc.fYinques analogs, thus maintaining the straight-chain character of the product, to correspond with that of

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 the charge of araffinic hydrocarbons.

   Suitable catalytic agents which minimize isomerization of the aliphatic feed and / or olefinic product are the neutral oxides of the Group VI elements of the substance.
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 Periodic System, e and preferably the oxides of chromium, molybdenum, tungsten and uranium deposited from an inert support, more particularly on a support free of acid ions and more preferably still of alumina, the
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 mixture containing from 0.5 gas up to about 20% by weight of Group VI metal oxide, and more preferably between about 2% and about 10% of such an oxide.

   Particularly preferred catalyst compositions are alumina-chromium mixtures containing from 5 to about
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 12., of chromium oxide and alumina-molybdenum containing from 2 to about 20% molybdenum oxide. The above mixed catalysts of this type may contain from about 1 to 10% by weight of an alkali metal oxide, such as potassium or lithium oxide.
 EMI16.5
 The reaction da de s hydrogenation is preferably carried out at relatively short periods of contact between the catalyst and the paraffins constituting the.

   charge and at a pressure in the vicinity of atmospheric pressure. Thus, the duration of contact of the charge with the catalyst can be a relatively short period of time, at a flow rate corresponding to an hourly liquid space velocity included in the other about 0.1 and about 2.0 volumes of liquid per volume of catalyst per hour .;

   
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 Oar.s the preferred method of operation, the desn3ruroém reaction. tion made in the absence of hydrogen, but hydrogen
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 o; rra be added to the feed to reduce the carbon c iati-on on the catalyst.: endnt reaction. general, diversion ciiarge the reaction. General, C.,: 3Ve3'SiCr dP the charge of oh raffina n-r.i3ie #. the analog;

  Aono-olefinic goose which

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 corresponds does not go to completion by a single pass of the feed through the catalyst bed and in order to increase the concentration of mono-olefin in the dehydrogenation product it is generally preferred to separate the mono-olefins from with unconverted normal paraffins and put them back into the dehydrogenation zone
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 The separation of the mono-olefinic product from the non-c warned paraffins can generally be accomplished by passing the dehydrogenation reaction in the liquid phase through a bed of a suitable adsorbent which selectively retains the olefinic component on the surface of the liquid. adsorbent without adsorbing normal paraffin.

   Suitable adsorbents of this type include silica gel particles, activated charcoal (such as coconut husk charcoal), activated alumina such as calcined bauxite) and the like. Solvar: t extraction can also be used to perform
 EMI17.2
 la a s'0aratioll of mono-ol fines with paraffins!:.! t! l '-; S, 9aro 1 ta -P4 1 Il Cà -n + fi the reaction of de ± h: rdrcgé: r.3tia : n.7 using solvents such as methyl alcohol, phenol, ethylene:; lycol, diethylene glycol, aqueous solutions ria :, hos - hate copper and silver, or other solvents well known in the art.

   It is necessary to emphasize the fact that 1L'q all the dehydrogenation catalysts known in xi, 'ahlli ('. 2, .1e the déstydro; cix; atiol1 r.'a,: irrra as for ¯ -ire the: .1 ') .. J-oL.fiue desired da: .s which the Ú'A: "'. L9 bond is in position 1 when the paraffin comes into contact with the catalyst under the conditions of
 EMI17.3
 - :::, :: sh;: "1rogér.at" iun.

   Thus, the ae dehy catalysts (: r0c; é! .Ati0r.:. ;; 2: have an acidic cox. Following dai.s 1: such as 8 '] -... rs of catalyst containing ae c ions -chloride C "llibll.es

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 or other halogen ions in a fixed form in the catalyst composition, not only effect
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 d - 'shydj: desired venation but also cause isomerization of normal fine caraf in various branched chain structures, which by subsequent alkylation
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 and converting the resulting alkaylate to the deterrent substances (give it an alkyl chain of branched-chain structure possessing the resistivity above) to bacterial degradation.

   L'is, -,:. Él'Ísaticl. Long-chain paraffinic hydrocarbons result in the production of various isomers at all degrees of ratification and all kinds of positional isomers which -car dehydrogenation and subsequent alkylation of the
 EMI18.3
 nucleus' 3ro;: ntiue would give alecylates having #: alkyl / branched chain groups. Therefore, the catalyst compositions mentioned above and the more preferred mixtures of alumina plus chromium oxide, and alumina plus molybdenum oxide, are special.
 EMI18.4
 which are desirable in order to carry out the dedication phase of the present process.



  Following dehydration of normal paraffins' C, ri..v,, AW4 of mixed viuuuili, 1 ± 3 ne> an-irn-r *, - <,, - no * - i --- Eûü.s the form of a relatively pure 1-olefinic concentrate, Ia is used as an alkylating agent for
 EMI18.5
 a (:! (J '() c'3rbide arú: rL8tiqu'3 aonr.-cyclic alco-rldble or; .. h.ol ch-isi dam the group consisting of toluene, benzene, xyl-ce, ethylb-2 !: Úne, methylethylbenzene, diétr.yl "oe.J.Lzène and ## r.cl,;" denying an I: lOno-alcoyJ8te which e the final product #irs and!}, -R 'ser.-ç proceeded .

   The alkyl reagent is to .rif-3rer.ee e: '' 'ct ": e in the presence of a suitable catalyst ¯¯..1¯: ..rr .l.t1 reaci-ion 1e ion, in: <êr.éxal * re ..-; i.re --le characterized as a, compound

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 with acid action yes catalyzes the reaction reaction of
 EMI19.1
 transfer taking place in the process.

   Acidic anomalous compounds having alkylating activity include certain mineral acids, such as sulfuric acid containing not more than about 15% by weight of water and preferably less than about 8% by weight of water, including sulfuric acid catalysts already shipped, which are
 EMI19.2
 recovered from the alkylation of isoparaffins with mono-olefins, hydrofluoric acid with a concentration of at least 90% and containing less than 1 lof by weight of water,
 EMI19.3
 anhydrous liquefied anhydrous hyarcfrene fluoride, anhydrous aluminum chloride or aluminum bromide,
 EMI19.4
 Boron 1-rifluoride (of .reference used in admixture with concentrated hydrofluoric acid) and other active catalysts
 EMI19.5
 acid,

   more particularly of the Friedel-Crafts class of saltings: vtalliues. The particularly preferred catalyst for 1 ... resolves. alkyl reaction is hydrogen fluoride containing at least 85% and more, preferably at least 98 ,.



  This hydrogen fluoride. Sulfuric acid with a concentration of at least r '- :, up to lu0%, also constitutes a referential catalyst. In the process of condensing the compound arCratinM with Mmo-o-o] ôfiw i # n, #,, ...



  .īs, Î1Û; L1Ù-p-C1) rf'inc >> 7 --4.ure u'nyaroene b - Ijr exerts, in liquid phase and the aromatic compound feels charged crars a =., tnclave under pressure and stirring, followed by addition to the stirred mixture of the carbide ave? ror¯o-olef.r: icue, the resulting melare then being maintained for more than 1 a, continuous iteration, at a temperature between about -2 (jOC and about 30.0.

   In order to maximize the r ### cticn d.alcoyate starting from the mono-ol - fine loaded in the process, it is generally preferred that the ratio if ¯¯ * -. # - # Si.iqas g ï-eqctif olefinic charge in the alkylation reaction be greater

 <Desc / Clms Page number 20>

 that 1: 1 and preferably between the limits of about 2: 1 and about 15: 1 moles of aromatic per mole of ol & fine. The effluent mixture is separated to recover the organic portion of the reaction effluent from the catalyst employed, and the organic mixture is then fractionated to recover the excess aromatic hydrocarbon from the alkylaromatic product residue which remains in the distillation zone as a residue at higher boiling point.

   In most of these cases, when the molar ratio of aromatic to monoolefin charged into the process exceeds 1: 1 and preferably between about 5: 1 and about 10: 1, the mono-ol & fine is more or less completely consumed for the reaction (condensation and a mono-alkylate is obtained rather au'un aromatic poly-alkyl-substituted alkylate as the main product of the process.



     As mentioned above, the n-paraffin recovered from the mixed paraffin feed is also able to provide the source of the alkyl group in the final detergent product by converting the n-paraffin to an α-n-alkyl halide. weaving in the manner of olts, and condensing the resulting halide with the aromatic reagent used in the present process. Condensation of the aromatic reagent with the alkyl halide is in many cases the preferred way to obtain the alkylate.

   Thus, the n-paraffin is first converted to its mono-halide derivative by adding the halogen (preferably chlorine or bromine) of the n-paraffin at a temperature which results in the substitution of a single atom. of halogen for one of the hydrogen atoms in the paraffin chain, For example, chlorine is bubbled through the n @@ araffin maintained between

 <Desc / Clms Page number 21>

 about 10 C and about 50 C until mono-halogenation is complete, which depends on the average length of the
 EMI21.1
 paraffins contained in the mixture -the n-paraffins.

   In most cases, the halogenation results in the formation of an n-alkyl halide (i.e., a substitution product of a halogen in which chlorine occupies the number carbon atom. 1). Then the alkyl halide
 EMI21.2
 The result is: condensed with the aromatic reagent by mixing the alkyl halide with the aromatic reagent and adding to the mixture, an anhydrous aluminum halide constitutes
 EMI21.3
 with aluminum chloride or aluminum bromide, in an amount of between 2% and approximately 20 (preferably ink 5.- 3t approximately 1c :;) by weight of the alkyl halide while now the ra,; urE) er r3 about -10 C and about 50C.

   In this condensation reaction, an excess of the aromatic reagent (.: E uzs G. 1 up to about 15 1 moles of aromatic per mule of alkyl halide) is used to facilitate the - # ration -: s: zo: u -alkylate, rather than the polyalkylate, and the aromatic excess is recovered from the r'-acll-i-ri mixture ar distillation.
 EMI21.4
 



  The alkydate obtained by one of the condensation reactions mentioned above constitutes the raw material or starting charge for the preparation of the detergent.
 EMI21.5
 final or: .rf3lt active on the surface. Thus, a very effective detergent is prepared from the alkylate by sulfonation, which produces the mono-sulfonic acid derivative, followed by neutralization with a salt-forming base such as sodium hydroxide, to form a detergent consisting of a sulfonate.
 EMI21.6
 Water soluble alkyl aryl. The alcoholate can also be nitrided to form a ring substituted mono-nitro derivative, which is catalytically reduced to the analogue.

 <Desc / Clms Page number 22>

 mono-amine-substituted.

   This amine is then condensed with ethylene oxide or propylene oxide to form the corresponding polyoxyalkylene detergent product, preferably containing from about 10 to 15 units of oxyalkylene. In the case of the phenolic alkylates, these are converted. directly into detergent products by oxyalkylation with ethylene oxide or propylene oxide (preferably however ethylene oxide), until the product contains 6 to 15 approximately units of oxyethylene per molecule.



   The present invention will be illustrated by the examples which follow.



  Example I.



   In the following comparative preparations, a "straicht-run" petroleum fraction obtained from a crude oil from Pennsylvania and having a boiling point between 170 and 220 C and having the following composition according to the general classes of hydrocarbons was used. :
 EMI22.1
 
<tb> C10-C15 <SEP> Paraffin <SEP> aliphatic <SEP>: <SEP> 73%
<tb>
<tb> C9-C15 <SEP> Naphthenes <SEP>: <SEP> 24%
<tb> C8-C15 <SEP> Aromatics <SEP>:

   <SEP> 3%
<tb>
 
This fraction is resolved into the following two classes of components: 1) straight or normal chain paraffins and 2) mixture of isoparaffinic and cyclic hydrocarbons, the normal paraffins recovered are then dehydrogenated to their mono-olefin analogues and these are then used to alkylate benzene, the recovered benzene alkylate is sulfonated, followed by neutralization of the sulfonic acid resulting in the alkylaryl sulfonate salt.

   This product is then compared (quant, detergency and biological softness) with the corresponding sulfonate salt of the alkylate formed in

 <Desc / Clms Page number 23>

 
 EMI23.1
 alkylating benzene with: e t: ¯Glan; e of branched-chain olefin contained in a tetrameric fraction of propylene with a boiling point of between 170 C and 225 C approximately.
 EMI23.2
 the normal paraffins in the Ils7craii-ht-runl * fraction are separated therefrom by contacting the i-tela .-. Ee with pelletized molecular sieves in alumino-silicate Air Products Co., 5A molecular sieves ").

     To carry out this separation, the straight-run fraction of kerosene is poured at room temperature (25 C) into a vertical column of the tarais and of sufficient capacity to force a sieve column 1.542 meters long to contain.
 EMI23.3
 la.rfc 1 7.6 liters of the particles of ta read 5A, each particle pyy.t -i * a ;. , BaIS10r1 approximately 5.2mm x 3.2mm. A r = ir effluent washed from the bottom of the column of the nis consists of the hydrocarbon freed from n-paraffin. the normal cL..¯t.; aaats do not paraffin in the fraction of W rosene (about 37, "of the total volume of kerosene) remain in the clorrae soraes, on the joints particles of ta.¯.s .

   Ia, reduced refined res. areal occupying the surface of the particles e T2: r.ic: su snicvé the lu civrue by washing the: -amis with @ sopentane which can then be separated by ristillation
 EMI23.4
 # 6f rd ': its.



  After completely draining the wash column. centane, n-paraffins s.rbées, removed from the chnivje kerosene,.-descrambled by filling the column with liquid n-.entane at 5 C, allowing n-pentane to displace the n-paraffins derived of 1, -é rosé I sorbed on the molecular sieves by the ri'acticn effect of ..asse and * pr-, s 1>. minutes the surrounding liquid, The sieve particles are. draina dar.s a collect at distillation flask.

   The l. column is again filled with n-pentane and after allowing to stand for another 10 minutes, the liquid in
 EMI23.5
 the yield -8t drained into a second distillation flask.! * |

 <Desc / Clms Page number 24>

 distillation of the n-peptane out of the flowing stream left
 EMI24.1
 in each case, a residue of kerosene n-paraffins (9ô of normal components of a chain length C11-C15) in each vial, 96% of the total residue being in the first vial.



   The n-paraffins recovered from the kerosene fraction in the above test are stranded subjected to dehydrogenation by passing them through a
 EMI24.2
 small pilot plant with üé reactor ;; yûrvgénaû.on existing in a vertical steel pipe with a slowness of 0.9144 meters filled with an alumina catalyst plus chromium oxide containing 12% by weight of oxide
 EMI24.3
 ie chrome, and surrounded by an electric heater element c. rlé t :: ercos tatiqa; e: aent which Eaintfnait the bed of catalyst 520 C and at atmospheric pressure during the passage of the paraffinic feed through the bed of
 EMI24.4
 vs;

  3t'31 =! FeuJ "at an hourly liquid space velocity of 1.2 feed volumes because of the catalyst volume per hour. The effluent from the t ...... reactor ost 2 '; :: 1', 1 : 0i, 1i '"liquefied in a condenser rrrii by water, the non-condensed gas removed from the upper part of the condenser. A rendering of r: Jvllo-o1 '; f.tnes representing 73 by weight based on 5U * read the normal load affln'3 is recovered from the total product.

   The product
 EMI24.5
  l.il = ic which is formed from various isomers of position 2 .., -, b19 bond is separated from unconverted haraffins by passing the liquid product of dehT r, a "atisn - tr3: 3r8 astonishing activated particles of silica orel, the civic component being retained 1, a1 'the silica gel 81i the paraffin passing through the column under for:, 18.:] 9 raffinate.

   L3S ulefinae are recovered from "031 silica -, 1 absorbate mor.rm -; ---,. Cor; d ;; ,, -, ¯809, r: Jl.t cie al :: sorbat mOrJ (J-nl.7; ... 0; ¯ ..- mùj. 0 '"' e'1" e \ n9 00: 1 3-: 5 .. a <isurb8ble pref.ratiel. -..-. .. 1 '-. Uezene,

 <Desc / Clms Page number 25>

 
Zes n-olefins recovered by the method described above are then mixed with 10 molar proportions of benzene low on the average molecular weight of the olefins considered as having a value of 168 (dodcene) and the mixture of hydrocarbons is cooled to 0 C to In so doing, a sufficient amount of hydrofluoric acid of 98.5% concentration is added (with stirring) to give an acid: olefin weight ratio of 1.5.

   The
 EMI25.1
 -.elance is maintained within the temperature limits of 0 '1, C, erdani; a period of one hour, after which the :::; 18l; -a is allowed to settle and the lower acidic layer is 3 *; ir4e of the upper hydrocarbon layer. The . .dehydrocarbon is then washed with diluted caustic for ē? : .e: '19 hydrogen fluoride dissolved and then distilled ## / .; r;:. 1 J', rH excess benzene and a small amount l ':::,' 1; "', , 'J <J: ": boiling point aliphatic mothers 1; 1..LI close to -" lr ;. "! .-') 1, fine. The residue, consisting of 6% of 2: al .yl-banzena, represents a yield by weight of .3c -: ': 18te based on the olefin charged.



  L-- reduces alkylate when subjected to analysis i .. 'r¯.-¯. > - .y-; consists of secondary alkyls of the living "# r 'y' ;;....
 EMI25.2
 
 EMI25.3
 # -a 1: -it 1 3ot ias normal alkyl radicals coutgiia-t between jt 1:, '; - .. na? of carbon on the lû: nu ie 1, chain and î¯: '*' - -j. to: ¯ a nar between jet 14, a proportion r.-: ... r. : .fi5 of the product having the structure where B is .'iTh'le ..:, n- r: .iecyl.

 <Desc / Clms Page number 26>

 



   A second sample of alkylate is prepared by alkylating benzene with a tetrameric fraction of propylene boiling between 170 and 225 C, by the same method as specified above for the preparation.
 EMI26.1
 n-olefinic alkylate, The propylene tetramer consists of a mixture of homologous e + isomers, all of which are of the radiated chain structure of the following type
 EMI26.2
 Each of the alcoylatee prepared as fun above
 EMI26.3
 is:

   tallow had es. :! {: 1.anging the alkylate with an equal volume 'the liquefied n-butane and then with' the 30% oleum added
 EMI26.4
 au,;: ela! c of dilute alkylate in the form of a weak stream flowing over the cooled surface of a rotating cylinder, the surface of the cylinder being cooled by circulation of salt water cooled to -10 C over the inner surface of the
 EMI26.5
 '::! .. i.1'lGr; ::

   3.mecuro that this one turns, scraped and the mixture is re-spread on the surface of the cylinder by a stainless steel blade, the n-butaue evaporating in a
 EMI26.6
 hood 3.nakes that the heat of reaction raises the temperature and subjects the butane to. i'ûulllUn, in r.31nt8: ar'jt the temperature at 0 C or near G C.
 EMI26.7
 



  The sulfonation reaction mixture is diluted el. : daL.e8; t with the .lacs and the acids are then neutralized with, O: 1 <2r- <(the sodium hydroxide to an H equal to 7. The aea, 1 '' .- '"<.. you can find solids of cretra-light color, cùf .: Jltt3,;. eLt 2:) JtJ!) le! " :: anK water. the evaporated solids are extracted with: E) 't &? t0 at 70p to recover zrc..aui1; s daßr3: lt; ï

 <Desc / Clms Page number 27>

 
 EMI27.1
 sodium sulfate and are then mixed with sodium sulfate = sodium forming agent to give detergent compositions containing a 60-40 weight ratio of sodium alkylaryl sulfonate to sodium sulfate.



    Each product sixths when subjected to the
 EMI27.2
 d8tergence by the ¯v - standard test mode Laundar V - .. F: 'ter removed a synthetic soil composition from a fabric
 EMI27.3
 cotton (muslin swatch). The i-rociui "1 ..



  # .repaired from propylene tetrameric alkylate is ca [1i.d8r 'as been! .t about 112 as effective as sodium iuroleate, and the product prepared from n-oliüiic alkylate is about 114% as effective as standard sodium oleate at equal cuncer.trations using
 EMI27.4
 'a3 water r 71 C, C "I:'. 1": 16 solvent in the "SOluliicn da dt6rbelLt and: ...- 3S!. 'rart t the eß1'wcacitdu detergent by the determination 8 the reflection .ce white light samples of textiles washed in the detergent solution and in
 EMI27.5
 grabbing the reflectar.c: e that is obtained with that `` i a 8c.aúUllor:

   washed in sodium oleate solution. a, eci: ar.till ons of each of the detergent preparations CÍ-r; eSSl! S sort sf.f.iaréI: len.1i submitted. conditions ct: r2itsr.8r; t simulating those of waste water treatment S v 8fi '"rip. i; f; 7'rr.; n" ,,'} 'O lus i; gllY "} oP1J: oi ;; f '", i; The removal of each dried rutilations out of a synthetic mixture of wash water of known composition.

   A 0.3% solution / aqueous of each of the above detergents (3.78.5 liters each) is prepared and to each of the solutions is added
 EMI27.6
 0.227 kf. '. of urea (for: providing nutrient nitrogen) 0.091 kg. of,:. ".- .., '1 t of potassium (to supply the nutrient -Su.).,:; 1 k. R- <e potassium phosphate (to provide the nutrient - (, 4) and' traces a zinc, iron, magnesium, # aais, copper, calciuu and cobalt, to give the nutrition s' ¯

 <Desc / Clms Page number 28>

 required by the bacteria which are added to each of the solutions in the form of 0.4536 kgs. of activated residual sludge coming from an ire water treatment plant.

   The simulated waste water composition placed in a large circular tank is then subjected to agitation as air is introduced to the bottom of the tank in the form of fine bubbles through glass nozzles. About 50 cm3 of the samples i the residual water suspension are removed from each of the reservoirs at three hour intervals after an initial 24 hour digestion, filtered, and equal amounts of the filtrate (50 cm)

   are drawn from the shake flasks to determine the level of foam produced after aeration of each of the filtrate samples under similar test conditions. 50 cm3 of the samples of each of the initial, undigested, detergent solutions, shaken for 10 minutes in the test apparatus, produced essentially equal volumes of foam, 15 cm high.

   For each of the solutions subsequently sampled, the results of the determinations of the foam level which are an empirical measurement of the value of detergent remaining in solution, are given in Table I below, for each of the samples:

   

 <Desc / Clms Page number 29>

   TABLE 1.Quantity of foam produced with 50cm3 samples of wastewater solution at various intervals of the wastewater treatment halo
Height of the foam in cm.

   
 EMI29.1
 
<tb> sample <SEP> Duration <SEP> of the <SEP> Alkoylate <SEP> tetramer <SEP> Alkoylato
<tb>
<tb> n <SEP> treatment <SEP> of <SEP> propylene <SEP> of olefin <SEP> to
<tb>
<tb> ¯¯¯¯¯¯¯ <SEP> in <SEP> hours <SEP> ¯¯¯¯¯¯¯¯¯¯¯¯¯ <SEP> string <SEP> right
<tb>
<tb>
<tb>
<tb> 1 <SEP> 0 <SEP> 15 <SEP> 15
<tb>
<tb>
<tb>
<tb> 2 <SEP> 24 <SEP> +3 <SEP> 14 <SEP> 13
<tb>
<tb>
<tb>
<tb> 3 <SEP> 24 <SEP> + <SEP> 6 <SEP> 14 <SEP> 12
<tb>
<tb>
<tb>
<tb> 4 <SEP> 24 <SEP> + <SEP> 9 <SEP> 13.5 <SEP> 10
<tb>
<tb>
<tb>
<tb> 5 <SEP> 24 <SEP> +12 <SEP> 13 <SEP> 8
<tb>
<tb>
<tb>
<tb> 6 <SEP> 24 <SEP> + <SEP> 15 <SEP> 13 <SEP> 7
<tb>
<tb>
<tb>
<tb> 7 <SEP> 24 <SEP> + <SEP> 18 <SEP> 12.5 <SEP> 6
<tb>
<tb>
<tb>
<tb> 8 <SEP> 24 <SEP> + <SEP> 24 <SEP> 11.5 <SEP> 5
<tb>
<tb>
<tb>
<tb> 48 <SEP> + <SEP> 6 <SEP> 11, ..

   <SEP> 4
<tb>
<tb>
<tb>
<tb> 10 <SEP> 48 <SEP> + <SEP> 12 <SEP> 10.5 <SEP> .2
<tb>
<tb>
<tb>
<tb> 11 <SEP> 48 <SEP> +24 <SEP> 10, <SEP> 1
<tb>
 
The repaired detergent sample of the alkyl coylate (branched chain tetramer remains active (e.g. produced foam) even after 108 hours.



  Example II.



   A test similar to the above test, but performed using a detergent prepared by oxyethylating alkylates, one sample of which contains a C12 alkyl group derived from propylene tetramer and the other sample is a C12 alkyl group derived.

 <Desc / Clms Page number 30>

 
 EMI30.1
 of a normal olefin produced by dehydrogenation
 EMI30.2
 of a normal paraffin separated from a. narhte e (. -: s ... ::: 11 :: 'u "-run,
 EMI30.3
 has given results having essentially the lead
 EMI30.4
 character than the results illustrated in Table 1 above, in that the detergent product prepared from h chain alkylcite;

   king is also biologically degradable to you
 EMI30.5
 more pronounced than the alkylate product
 EMI30.6
 ., 1e: fi1Jl as u branched chain.



  I "Y 'DIG.'l'It3ir $.



  1. Process for the preparation of a cuspos .. alkyl ar4re l-.ar!; Ieul t :: reI: 1ent suitable for the preparation of a mild biological detergent product starting from this compound, however the aryl nucleus is mono-cyclic and the alkyl radical on the aryl ring is a relativ'3 chain group: 'leJ.t aroite
 EMI30.7
 containing from about to about 15 carbon atoms
 EMI30.8
 characterized in that a straight-cilinal paraffin with a normal paraffin purity of at least i5} is separated from a rl,: ji, h'i; t ;! .r ',;: refl'i. :: iqt.:c point, j' 1ull.ii, .iLJn between 125 0 and 25o C by a treatment of selective separation of the r '' .pe consisting of arr sorption au tarais molecular,.:. 0rca tion of urea aid and thiourea aduct formation, n ;;

  "rVc (r (I'.1st j..ara- finue l chain rights separated is converted to a derivative acting at the r, 1811 olefins, belonging to the group of nionōole hydrocarbons the inique s -.- t halides nlcoyles had a. :: w: i: arosaiic acid chosen from the 'ru :: po c..szst at in sheepskin, toluene, xylene, ethylbenzene, ru tflylbe2lzèr¯e and phenol, is alkyl with the said derivative acting ù. la, - 'L: i.2re des') l.; end>: s to form the mono * alkylate '1' -: it c "mixed arcr-iatiqre.

 <Desc / Clms Page number 31>

 



  2. Method according to claim 1, characterized
 EMI31.1
 in c that the straight chain paraffin r} ered with paraffinic naphtha is converted to an iniquitous mono-key hydrocarbon by dehydrogenation of the paraffin
 EMI31.2
 î-Orcale in the presence of a non-acidic dehydrogenation catalyst.



     3. Method according to claim 2, characterized in that the dehydrogenation catalyst is a mixture of alumina plus chromium oxye, containing an alkali metal oxide.
 EMI31.3
 



  4. Process according to claim 1, characterized in that the separated normal paraffin is converted into an alkyl halide acting in the same way as olefins, by halogenation of said paraffin having a selected from the group consisting of chlorine and ironie, and then the resulting alkyl halide is condensed with the
 EMI31.4
 ': i t c (r.:; aromatic er. r5senoe of a catalyst consisting of cll -: aluminum chloride or aluminum bromide.



  5. Receded according to any one of claims 1 - 4, charac1; Élisé '1. that the paraffinic straight-chain hydrocarbon 'l': a! 8;, eL 18ra: normal fine grain of at least 95 is separated from a "straight-run" hydrocarbon distillate at
 EMI31.5
 -: d: boiling t between 170 C and 2ü.



  6.xrocedë for the production of an alkyl aryl compound c ".: Ve1.81: t for the ration of a product dete-ent b3olot: irte" ent ri .1;: X :, substantialient c L :: e described.