DE1518650A1 - Process for the production of alkyl aromatic hydrocarbons - Google Patents

Description

Jt. Hx ^ «■

CONTINENTAL OIL · C (MPANY.PONCA CITY. OKLAHOMA _t Ü. S. A,

V «rfahrtm for the production of alkyl aromatic hydrocarbons«

The invention focuses on a process for the production of alkyl aromatic hydrocarbons, which are particularly suitable for the production of oil-soluble sultanates «

There are many possible uses for this in modern technology. Oil-soluble sulfonates «Large amounts of these substances are used, for example, as additives for lubricants. For this purpose the sulfonates are called selche • the one used in Fen * the so-called * overbased detergent

One of the oldest ways of obtaining oil-soluble sulphonates is the treatment of aromatic petroleum fractions with sulfuric acid. The sulphonates obtained are commercially known under the name mahogany sulfenates. These sulphonates are generally known! Since _e "ie sulfonates Meoenprodukte were inre production was dependent on the length% of the acid-treated Grundschaieröle _# the development of improved methods for the production of lubricating base oils has the fit of Mahagonisulfonaten substantially restricted.

More recently, a by-product which arises in the manufacture of dodecylbenzene has become a particularly satisfactory source of alkyl aromatic hydrocarbons which are suitable for the manufacture of oil-soluble sulfonates Friedel-Crafte-Katalyaaters prepared .Zueätzlick to "primary product Dedecylbenzol fall another alkylaromatiscke Koklenwaseerstoff fractions to" the obtained in ier distillation of the product of Alkylierungsreafction bottom fraction is provided as a post or Polydodecyikenzol "ekannt.Poetdodecylbenzol is a Sekr satisfactory starting material for the production öllöslicker sulfonates. jedock it has the disadvantage that _e * i _ee Zugänglickkeit directly Durck the production of the primary "product Bodecylkenzol determined.

909815/1171

BATH ORIGINAL

The subject of the invention is therefore an experience in the production of alkyl aromatic hydrocarbons, which are particularly suitable for the production of oil-soluble sulfonates. This experience is characterized by the fact that olefins with 3 to 18 carbon atoms in a molecule or their mixtures in one Mineral acid catalyzers "in the presence of the catalytically active serpent, which is obtained as a by-product in the alkylation of an aromatic hydrocarbon" it an olefin in the presence of a Friedel-Crafts - ^ - atalysater, dimerized, an aromatic hydrocarbon "it de" s · dimerizate obtained alkylated and in present-a Friedel-Crafte-Katalyeaters of de * Heaktiensgenisck the eberhalb i62,7 * C / * 2OM Hg _t distortion-looking · eberkalb 190.5 ^# C / 2O * m Hg, particularly the "eerhalb 2 # 4 ^ * C / 2O «nHg boiling fraction with a» Μ · η · - (branched.) Alkyl geal of »ekr as 5OS6," r »rassigned? 5%,» esenders 9Oj6, and preferably a «molecular weight of aekr as 32O,» especially 375 is ali separated in a known manner

The use of the Alkylierungsschlamiis as a catalyst for the dimerization of the Olefinaaterials featuring a preferred Ausführungsfom of ^v erfakrens of the invention "" dimer "means in connection" it de "" out of the invention that a substantial amount of the olefins used in the reaction are converted to Dieeren .In addition occurs during the Beak "tion cure formation of other polymer s. acid can, for example C-olefins to _C1. C. or olefins are olymeriiiert to Cg or C" _o ".

Compared to the known processes, the experience of the invention has the advantage that the alkylaromatics produced are the primary product of the reaction and not a Mebeny product such as postdodecylbenzene. Production of Sllöslicker sulfonates, which is probably due to the high Moeoalkylantoil

As ^EXAMPLES of useful olefins having 3 to 18 carbon atoms may be mentioned: propylene, butene, pentene, hexene, Honten.Okten.Nonen.Decen.IJndecen.Dodecen, Triiecenj ^ etradecenjPentadecenjHexadecenjHeptadecen and Okta.decen.Dies · Olofin-classifier can be straight or In addition, the starting material may contain HIX olefins with more than 18 carbon atoms. But this material is not dimerized. Olefins with 5 or 12 carbon atoms, both branched and unbranched, are particularly suitable.

BAD ORIGINAL ^ ₁ .

Egg preferred Qlefi * material for use in the process of "der Erfi" * u "g iet" i "mixture verherrechead branched 01efi" e with in general a 5 "i" 12 K ** lemst * ffat "mea, which i * der I * du * trie al · Cat-P * lyga »« li * iet umd l ~ Inryp »» Wft by Pelymerisatiea ν · η Prepyle * gew «aae» we «it we« manufactured, i * * em mas Pr * "yle" is lytic • marriage, Pelymerieati · "is derived .The ^V experienced by ei 's investment IIIR € ie k' t * *-described ia" Hytr "carl" · "PreceeHiag and Petroleum refiner" 4i (September 1962), page 190. The analysis of a typical test of this material resulted in a supplement:

Number of C atoms %

3 5 6th 3 7th 7th 8th 16 9 35 10 17th 11 11 12th 5

(A »a2yse» Terfahren was the Dampfvhaseachremategravhie) · Geigmete Cat-P * lyga «» li »e are those with f * lge * the Bie4» »he« me:

ye is suitable, C TteTTzugt, C

Siedehegi »* 30 hi» 26θ 57 here

5Ο9ί 37 called 260 138 called

E »dsiede» u * kt 52 to 399 218 his

Eim further hev "rzugtes Olefiamaterial is the D ** * ece frakti" m "us bucket catalytic P * lymerisati" * _# seinheit The "aterial is obtained · * is circulated in« «m eim Olefimgemisch eelaage by Eiaheit, his eime "Peak" T * a 12 is reached, i.e. bi · the olefin * with 12 C-atoms «* em the largest * iadiTiduelle * part of the mixture etellt ^ ime tyjische D »i« c ** »r» he shows rim *, de Features *:

Siedehegi »* 173 ^# C

1% 17 ^

556 178

10% 179

50% 188

905-210

co 95% 219

ο 97% 22 * t

<° £ * dsiede »u * kt 229

⁰ ^ Kückgewi ** u * g

<n specific weight 15.5 * C

- * Melekular weight 16O (cryeekepic in the Bemz!)

^ Amilimiumkt 51 * C (ASTM B-611)

"* Brechu» gsi * de ^ (25 * C)

BAD OFHGfNAU

generally because of the lower cost and the easier accessibility the use of Cat-Polygasolin preferred.

According to one embodiment of the method of the invention, dimerization is carried out of the olefins in the presence of a mineral acid catalyst pre * om * - Ben. In this process, the acid used must be taken from the reaction meae separated and the reaction mass washed with a basic solution, whereupon the desired olefin dimer is isolated.

Sulfuric acid is preferred as the mineral acid catalyst. One is suitable 80 to 8% sulfuric acid. 95% sulfuric acid is preferred, ^ he addition of the catalyst takes place in amounts of 0.02 to 0.7 wt .-! preferably 0.15 to 0.3 parts by weight per part by weight of olefins

Iff general, for the dimerization D ^B uck, temperature and residence time not kritisch.Aus economic ^ü ründen use atmospheric pressure is preferred aligning somewhat increased or decreased prints also applicable other.The appropriate ^ rea for the reaction temperature is from -10 to 75 C, preferably 20 to 55 C. A residence time of more than 5 minutes is satisfactory

According to the preferred embodiment of the process of the invention, the catalyst used for the dimerization of the phase of the alkylation reaction. This embodiment offers various advantages. For example, the catalyst is the same for both stages of the process and the procedure does not have to be as in the case of use a mineral acid catalyst are worked up before use in the alkylation reaction _e

£ s, the slurry is .ve-rwendet which egenwart in AJJ.ylierung of the aromatic hydrocarbon with the olefin dimers in ^w of a Friedel-Crafts' catalyst obtained "ale" Sart "slush for Dimerieierung, a corresponding ^ aterial by alkylation a suitable KW, eg Benzoljmit a suitable olefin, such as Cat-Polygasolin be produced when the process is started, a corresponding narrow _m of the slurry is used in the alkylation step of the _v erfahrenB in the dimerization step, suitable amounts are 0.25 * ± s ^, 0 wt ^X rush, preferably 0.75 1.25 weight -is "" parts per Gewo- ^ eil Olefin.Im allgeaeinen results from the use of lower amounts, a smaller degree of dimerization, while the use of larger ^ narrow uneconomical · .

9098 15/1171
BATH ORIGINAL

Temperature, pressure and ^V are as erweilzeit! Is the use of a mineral 'acid catalyst not kritisch.Für latter oeiden Size * applies the gesagte.Geignete there temperatures are between 15 "is 75 * C, preferably between 30 to 55 * C," The The reaction mixture is completely transferred to the alkylation stage «,

A typical oil fin dimer shows the following conditions: ASTM distillate * D-86.

Boiling start * 76 C 5% 87 10% 93 20% 116 30% 166 Where 199 50% 239 60% 273 70% 302 80% 333 90% 359 95% Decomposition Final boiling point

In general, all alkylated * substances of this group can be used as aromatic hydrocarbons. All xylene isoxers (ethynesenzene, naphthalene) and preferably benzene and teluel »Eoe» ee mixtures of suitable substances can be used _e All coaimeric degrees of purity are possible for the substances mentioned The refinery product streams which contain essential quantities of aromatic hydrocarbons are suitable -, - ζ.Β. as a mixed component in aviation »ekamite" ABC ", which consists mainly of toluene and contains smaller amounts of · ° β» ζβ1 and * d xylene isomers *.

Are suitable ■ "narrow in size from 0.2 ^x 10 weight ice rush, preferably 1 to 3 parts by weight ^X-rush part by weight of olefin per.

A Friedel-Crafts allysator is used for the alkylation reaction. "If the alkylation sludge is used as the catalyst for dimerization" ₂ the addition of "refreshment *" is usually required for the alkylation reaction. Catalyst necessary. All Friedel Crafts analyzers are / are suitable for the process of the invention. Aluminum chloride is preferred, including aluminum chloride produced in situ, ie the product of the reaction of aluminum metal with hydrogen chloride _{or the like}

9098 15/1171 SAD ORIGINAL

In some cases it may be desirable to use a Preteneaater 2 «in addition to the Frieel Crafts catalyst. Suitable Compound E "are ChlerwsEersteff and water" Appropriate range of the amount of added * Protoaendenater are (for water) from 0.1 to 30 wt .- ^ preferably 3 to 10 ^u ew .-% of the aluminum used ea "iniuschlerids.Wird AluminiuH" etall plus hydrogen chloride used as Kp.talysa.ter, the range ν · η 4 to 25% by weight applies to the addition of water "

Aluminum chloride as a catalyst is used in ^M eng © a from 0.02 to 0.25 G _e w «-Tln. _t delayed 0.08 feie 1 _f i2 GeW ₀ -TIn. pr Weage * _e file "ßew _a -part Olefinausgaagsieaterial verv / endeteFür ia situ formed Al-uniaiuiiachlerifl apply the same" is Chlerwassere.t "ff in stöchiemetrlscliea. Excess used ».

A In the alkylation siad pressure, _v erweilzeit umd Seaiperatur micht critical "The latter is usually iai area Vea ice 5 75 C, preferably 25 to 55 C *

After completion of the Alkylieruag jRaaktienspredukt »it a basic solution is washed" Ih Nanchen FälDen is erwüaschtjZusätzklich »it an acidic solution With uad fezw.eder water v / _B ascheH Tuck" learn are feekenat the specialist.

The basic Gewfiscfesae ^ eakti®aapr®duct is then subjected to a certain determination, the required alkylaremati _* are distilled off, the intermediate products are removed and the desired alkylaremati * remain. See- throat water stiffness. The latter are those above i62 _f 7 * C / 20Eii) iHg, preferably above-204.4 * C / 20is * Hg -fractiomeM. The W fraction of the product usually occurs in the following way:

Fraktioa Teaiier natural area «* C pressure (

Benzene Boiling Teegina up to 65 200

(or 200 Boienteaiyeratar)

Intermediate product «.

Fraction A boiling regima up to * 6j · nZS " 20

Intermediate product »

B 125 to 163 20

In raanchea cases it may be desirable to return the material referred to as intermediate product action to the alkylation process. führea.-^ This is aßHanne aicht aetwendig _t kaBn jsdoch mns economic reasons be executed "

The alkylare substances obtained according to the invention _: possess throat hydrocarbons

90 98 15/1171 BADORfGtNAL

excellent properties "> They are an excellent Ausgangeieaterial for SuIfenierung.Sie have a" broom DERS hehen MeHealkylgehalt.Dies is contrary to the nature of the P "stdedecylbenzels _t made primarily from dialkyl & aterial be available .The Menealkylgruppe the erfindungsge""AESS produced * products is long (17 C-at »» e uad more) U »* branched following al '''s it Menealkylgehalt on selche ^v onnectivity reference genea *, a * which aromatic ^K it" one long branched alkyl group besitzea.Dh * * B ,, «ate ei» alkylated Teluel according to the invention is referred to as Meaealkylteluel ■, ebwehl nech an Alfcylgruppe »it is eiae * C-Ate * verhaaaea · The hehe M» n * alkyl content of the product manufactured according to the invention * seems to indicate the excellent * qualitya * to be barea Sulfeaate veraat "wertlich of waxed it» * _e Nachf "lgead are the characteristics of short zusamnengeetellti

Property suitable more suitable preferred

% M * a * alkyl content ^X »above 50« above 70 »is below 90

^ 8

»Ittl.M.lekulargew. "320» 350 375 -

Boiling range ^Λ 0 / Ζ0κΜ ^Κ ε " 163" 19Ο »Iserhalb

calculated on Μ · 1-% of all aromatics ο

The extension of the product is generally given by the boiling range. the material referred to as delayed serves according to SuIfeaieruag for manufacturing overbased detergents for lubricants, ebeaee like the above 190 * 0 boiling "aterial. Each are also the above 163 * G siedeaden alkylarematea for the preparation (after the sulfeaierea) vea residual inhibitors » and emulsifying agents geeif'-neto

On the basis of FIGS. 1 and 2, the two medications of the "experienced der." Invention will be explained in detail.

Ia Fig.1 (mineral acid catalyst in the diaerization) Cat- ^ elygaselia is added via line 1 to the Diiaerieierreakter 3. Centered sulfuric acid is added via line 2. The stirrer k is used to stir Deer preduct is fed into the washing kettle via lines 5 and 6 ? brought to which the basic water solution is supplied via line 8, which is consumed via line 9 and withdrawn

10 ia a second washing vessel I2, in which basic washing solution via line

11 supplied wirt ^ The used washing solution is withdrawn via line 13 » ^ s deer Diaere reaches the fracti & nation via lines 13 and 1 ^ -

. 909815/1 171

BAD ORIGINAL 'ί & $ 0 · - *' Λ ": 'Λ' \

From there, the desired dimer is transferred via line 17 to the with stirring means equipped alkylation reactor 21 ge br eight. The by-products will * over Line 16 removed as Afe-Deetillat ",

I »the alkylation reactor 21 is fed via line 18 benzene» the aluminum «chloride catalyst is added via 19» * «r promoter (water) over 20. After completion of the alkylation process, the alkylation sludge is removed via line 23. The crude alkylate passes via lines 23 and 24 into a washing vessel 26. A sulfuric acid washing solution is added to this via line. The acidic sludge is drawn off via line 27. The acid-washed re-alkylate arrives then via lines 27 and 28 into a second washing vessel 30 _t, where it is washed with a basic washing solution added via line 29. The used washing solution is drawn off via line 31. The re-alkylate arrives via lines 31 and 32 in a fractionation tower 33 «The benzene is removed as a distillate via line 34. The intermediate fraction A _1, which has an assumed boiling range of up to 125 C, is removed via line

35 subtracted. Intermediate product B with an assumed boiling range of 125 . ■ ■ · ■ ^ oicyxate ··

up to 163 G is withdrawn via line 36 _e The desired bottom dimer fraction with a boiling point of above 163 ° C. is withdrawn via line 37 and transferred to a storage container.

In Fig.2 (alkylation sludge as XXXgXXiHBC dimerization catalyst) Cat polygasolin given via line 1 in the dimerization reaction vessel, which is equipped with stirrer 4. Recirculated aluminum chloride sludge from the alkylation reactor 9 is fed via lines 10 and 2 « After completion of the reaction, the reaction mixture from reactor 3 transferred via line 5 to the alkylation reactor 9 »via line 6 is Benzo is added. Fresh catalyst is added via line 7 to the alkylation reactor 9. Water is added as a reaction preventer via line 8 to The aluminum chloride sludge becomes the completion of the alkylation reaction withdrawn and transferred via lines 10 and 2 to the dimerization reactor The crude alkylate reaches a washing vessel 13 via lines 10 and 11, where it is treated with an alkaline wash solution introduced via line 12 The used washing solution is drained off via line 14. The Rohalky « lat is brought into a second washing vessel 16 via lines 14 and 15, where it is treated with washing water introduced via conduit. The used washing water is removed via conduit 18. The washed crude alkylate reaches fractionating tower 20 via lines 18 and 19, where benzene is produced evaporated via line 21. The intermediate product fractions ^ w ^ lel removed via lines 22 and 23, respectively. The desired di-alkylate bottom fraction is

yuaöj b / 11 7 1

BAD ORiGtNAl.

transferred via line Zh into a storage container

In both figures, only one fractionation tower is shown for the sake of simplicity. In practice, a number of fractionation towers are commonly used. D · ch independent ν · η type and number of the fraction used! always the »given» «the one equivalent boiling range · The treatment of the alkoxide with the appropriate washing liquids is familiar to the person skilled in the art and is not part of the invention,

The "achstehende" examples serve the detailed explanation of the process of Erfindu * g _o

example 1

This example explains the diaerization ve »Cat-PoIygasοli» under reference * ·· formation of a mineral acid catalyst

In a rait Buhrer, Bückflußkühler, thermometer and a 1 1 Tr * fftrichter equipped 12 1 Kellten were 6,000 g Cat Palygasolin gegeee ".Over de" T _r * pftrichter the stirred "K * l ¥ eni» just 1,200 were g 95-98? 6ige H ₂ SO. The reaction was exothermic. The addition of the acid was regulated so that a maximum temperature of 35 ° C was not exceeded. The temperature would also be added by partially immersing the flask in a EiswasserTiad geregelt.Nach completion of the addition of acid was Einhaltu »g of the temperature ve * 35 * C for another hour gerührteZu" settling of the sludge was the Reaktiensmasse in two 6 1 separatory funnel gegebe * _o After settling overnight * 1 4-98 g consumed "acid was drained and discard" .The product was washed twice with ei * em liter of 12.5% aqueous sodium hydroxide solution gewasche _»e After each washing" became the settling 1 or 2 1/2 hours ditched. 3 ^ 98 g of product were * subjected to distillation. A distillation according to ASTM D-86 showed that dimerization had taken place:

9098 1 5/117 1

■ »

BADORIGiNAU

Starting material
(Cat-P »lyKas» lin) Di * er product API density 60 Boiling range, C 47 5% 98 135 10 110 189 20th 127 233 30th 131 252 40 137 265 50- 143 274 60 149 283 70 157 294 80 174 312 90 205 334 95 - 334 Εκdsledpunkt 242 334 Recovery, % 94.0 96.0 Residue, % 2.0 1.5 Loss, % 4.0 2.5 Example 2

This example illustrates the dimerization using Tem dedecene of a mineral acid catalyst.

It was prepared as in Example 1. The Oat-Pelygaeelin was replaced by technical Dadeeea au® a recirculation pelymerieatioÄ. After three days of standing there was " 1,575 S consumed acid catalyst aTigetreKiit · The alkaline distilled product is shown in the list of 46. The Fralttisaea 2, 3 and 4 were * for later ^ examples a leeschriebeae Alkyli @ ruagsreaktieaea again mixed toBaeaen,

Parliamentary group no.

B «denproduct» Loss, trap Used batch

Boiling range until at 5 «« Hg weight the parliamentary group until K until 52 C. and c. (( s3 ex atm.) 1 717.4 until 85 ' CVl 557.0 (emtspr « 92 508.7 52 102 246.9 85 higher 289.0 92 90.0 102 VJl 409.0

909815/1 171
BATH

Example 3

Example 1 was repeated with the changes that instead of 20% 10.40 and of sulfuric acid as a catalyst ". The boiling ranges of the The products obtained are shown in the table:

85% H ₀ SO ₁₁

API density Mf 8 79 60 ASTM distillation 148 123 according to D-86, ⁹ C 182 131 Start of boiling - 2.6k iMt 5% 162 282 15 ^ 10 203 295 163 20th 232 31 k 175 30th 250 318 196 ifO 261 328 218 50 271 338 • Vn 60 281 3 ^ 2 262 70 291 - 282 80 306 J> h2 284 90 328 H 95 «.-" ' Final boiling point . 332 example

This example explains the alkylation of v * * Be "z * l" it eat pelygaselim dimer with the use of aluminum chloride from catalyst.

1,162 g of benzel were placed in an iron with stirrer, reflux cooler and a 5 l Kelbea equipped with a 500 cca staircase funnel, which could be heated and cooled. It was stirred. Then 25 g of AlCl and 1 g of water (that was in each case half of the amount to be added ») The dropping funnel was filled with _{500 g of the diaeren from Example 1 e} The addition of the diners took a period of 30 minutes

Diaftrn v / ere 12.5g AlCl- and O 5g _t water zugegeTien.Eine same addition erf · Ig co y ■ . _u

Ot e after the second aa third of the day has flowed in. After the end of the supply

CD , m -

After an hour, I was gently stirred. Then the whole thing turned into one

~ * A- 1 separating funnel filled. After standing for one hour a 1 ^ 1.8 g were smoked

AluüiniuechleridschlaMi separated. The product was with 65 cc »95-98% iger "^ Sulfuric acid washed. After. Standing for one hour, the acidic sleep was »» un- ^ removed and washed d-cs preduct "it 250 cc" 25% NaOH solution. After 2 hours if the washing solution was removed, 1 465 g of preduct for the 'distillation were The results are shown in the table:

'90 9815/117 1

Fraction No. Boiling range etc" . 'C / 2O' * ed SewichtT κ Batch 1 (Benz!) bie 18 (200 »» Hg) 882.1 2 51 1O4.2 3 51 " 96 198.4 k 96 ". 111 102.2 B * demproduct 111 and about that 155.9 Loss Trap 11.5

NrΛ and ^ ^ edenpr domestic product were again Zuba »» e "ge" iecht u »d» it 2O # Oleu "sulfated, Pr * kg alkylate wurdea 1.069 kg HSO get ₃ H" .The Sui feßeäure Teeeaß ®1e KemTsinationegewicht RRNN hh6 and ergaT »egg» ¥ erT »aeic calcium sulfenate of very good quality.

The same experiment was repeated axt D * dece »p * lymereai. It was» 71.3g B®de * pr®dukt »it © iaea SiedepuÄkt v ·» eberhalls 111 * C / 20 »» get Hg ».

Example 5

This game explains the diiaerization by Cat-Pelygaseli »under V _er we * - iuag v © a Alusixiiuaclilvrielschlamin ale Kat © ly @ at®r _e

The Eealctiem was generally carried out with a heater, reflux cooler, T-her "* aeter and a" 1 1 hopper equipped "3 1 Kelbea _e 566.6g Cat-Pelygas * li" was "xh € ea The piston was thrown, Dana was / over a period of time "v" a 30 meow * the same® Memg® AlCl -'-Alkylierungsscfelasuii passed "During the first 10 minutes of the addition, the Bealcti © sisMaese ν · η 2k warmed to 3k 0 u »ter use eiaes HQiaaastels.f / ähremi the remaining addition was" esa content at 35 C. at this temperature, also n "ch one hour after completion of the addition v @ h AlkylxerschlasH stirred" the 'I'e "pera door was Daaa the k "l ¥ eHinh" lt i "a separating funnel-sr" U1 "he night had the ^ ©" isch in two phases -getrenat "(in the usual execution of the procedure the whole * .EeaJcti®nspr © duct used for the alkylation "Dia Treaauag fulfilled here EUr ₈ UBi the properties of the Diaeren teestiaaen au) _s It was" 602, ^ g ■ Schlamsi and 298.9 g the product received ".In -der." The following table compares the boiling characteristics of the initial value with that of the product:

909 8 1.5 / 1 1.7 i
SAD OBfQ) NAi

API density

ASTM-B * etillati * n
»Oh D-86,» C

Begin *

5 % 1G 20 30 ko 50 60 70 80 90

95 Em ie

- 13 - • 1518650 Cat polygaeolin Cimeres 58.0 to, 7 51 76 116 87 125 93 132 116 136 165 139 199 238 1 ^ 9 273 157 302 172 323 194 359 218 cracked 226 Example 6

This example explains the dimerization of a "wide dodecene fracti ·» " using aluminum hoses as a catalyst.

The experiment in Example 5 was repeated with the change that a gasoli »was used, the maintenance of which was separated at 177 C boiling constituents The table shows the boiling characteristics of the Preductee in comparison to the exit theater.

Starting material

Dimereβ product

API density _ 37.4 ASTM distillates after D-86, * C beginning
5% i? l 78
86 10 185 88 20th 187 117 30th 188 187 4o 189 . 205 50 I90 236 60 192 295 70 196 329 80 202 350 90 216 95 251 cracked end 262

Recovery, %

97.0

15/117 1 BAD OBiQiNAL

Example 7

This example shows the influence of the tea temperature in the warming of Cat pelygasolin.

The experiment from Example 5 was repeated with the change that the dimeri at 25, 30, V? and 55 * C.

25 * G 30 c - - 45 C , 55-2. API density 42.4 42.0 98 % 1 _f O 40.5 ASTM distillation 134 after D-86, * C 173 Start of boiling 51 229 - - 5 % 28 265 93 - 10 97 293 97 92 20th 131 322 132 131 30th 166 354 178 171 214 379 232 226 50 252 Example 8 270 268 60 283 311 3OC 70 312 330 330 80 348 351 351 90 377

This example explains the alkylation ν · η Benz ·! As with these Cat-Bolygaselin using aluminum metal and hydrochloric acid as freshly added K4alysi3.tre _e

A diester prepared as in Example 5 was used. The reaction was carried out in a 5 liter Eelbea, which was equipped with a stirrer, reflux condenser, thermometer and a 1,000 cm stepping funnel and could be heated and cooled Glasrehr »it frit used * to introduce the Chl * rwassersteffs in the Reaktionsge" isch.Überschüssiges HGL gas was from the vapors herausgewaschea.1 500g B® "z" l, 5O9,% g spent AlCl_-Schlamai _l as in example 5, 5.05 g of Aliigi * iui * etall and 2.5 g of water were placed in the grater. The mixture was stirred. 77.4 g of dimeree were added from the attached staircase funnel, while hydrogen chloride (1.00 After the first and second thirds of the dimer had been fed in, 2.6 g of aluminum and 2.5 g of water were added. The temperature was kept at * fO®C. After the addition of the dimer (30 ^Ivi in. ) would throw at the same temperature while increasing the HCl current to 2, O1 & ecm pr * minute, stirred for another hour.

BATH-

• - ■ 15 -

geviech was transferred into a filter funnel. After sitting for one hour was *? 8ig AlCl_-Schlaiici e »t. The r« dukt was 250 cc »25% NaOH washed *. The used washing solution was wiped off after 30 minutes * the distillati · * were 1? O2g of Predukt Gew # ** e ». It showed cowardice South characteristic:

Fraction No. boiling range. * C / 20amHg weight

Batch

3
4th

B »ienfrakti · *
^v erluet, trap, etc.

Example 9

This example explains the alkylation v · * T * lu * l with the same Cat-P «lygas · - Ii * UHter Verwe» duiig (
Scheiiprodukt facti · *.

1,698.0 up to 18 (at 20OmUaHg) 1 214, cit big 51 115, ^ 51 to 96 184.5 96 to 111 49.0 • over 111 117.7 67.4

Use of an A1G1 catalyst and recirculation of an intermediate

Eb was done like i * Example 5 got * it diaeres used _{0 The} acti "n was i * ei * e" ¹ } 1 Kelben carried out, which "it stirrer, Bückflußkü33.1er, TherBi © iaet © ru" d ei * eai 1 000 ccja stair funnel was equipped and heated and cooled k »* iite.F« lge * de reacta * te »were used:

1 500 g T * lu!

417.3g consumed AlGl ^ -Diiierieatieasechla «* 500 g intermediate product from the same experiment

(Boiling range 51 to 96 * G / 20 * KHg) 542.3g dimers *
50.0g AlGl
2.0g water as Heakti® »sfr« ai »t» r

T * lu * l, AlCl, ~ Schlaaiii and was Zwischenpredukt * i "de" Kelb @ B * _e gegebe Bsima "was stirred for u * d half the A1C1- (25.0 g) u * d de» water (1, 0g) eye give * and the dimers from de "Tr" pftrichter zugetr "pft.Nach feed deg first uai * aweiten third was _Ä jeweil _e 12.5g AlCl ^ _{6 5 0,} 5 g of water was added _e the addition of the Diäteren took 30 Minuten.Bei 40 ^# C was further stirred. After one hour of settling in a 4 l separating funnel, 60.5 g of AlCl 4 flakes were separated off. The product was washed with 250 cc of 25% strength NaOH. After one hour of settling * was * 2,379 g · product for the distillate! · »received»,

9098 15/1171
BADORiGlNAt

Frakti "n Mr. Siedebarcick, ° C / 20" MHg weight,

Carge - 2,368.1

1 - Me 29 (20OmMHg) 1,357.1

2 »51 83.9

3 5.1 "96 696.3

4 96 "111 59.2 B" demfrakti "n" feerhall · 111 159.2

, Trap, etc. - 12, k

The fractions are further characterized by the following aaalya values:

Frakti * 2 3 4 B »dc *

Br «M number 0.30 0.16 0.32 0, ^ 1

Melecular weight 170 233 311 Λ18

^ is obtained from the aliphatic to the aromatic * Pretens 7,7 8,2 11,3 13 _f 9

Estimated proportion of
free aliphatics. '
Kermsagnetiache Beeananzanal «

J> k 21 18 8.

Sulfe »ieru» g the zueamüengeMiscktexi Frakti ** eia k and 5 »it 20%» Oleu »resulted in pre kg alkylate 0.9 ^ kg HSO ^ H,

9 0 9815/1171

fNSPEGTED

15186bü

:. . Example 10

This example explains the alkylation ν · η benzel with dimerea gas «lin in a technical * test facility»

* Similar procedures * as in the "" examples * 1 and 4 were used Distillation of the re-alkylate yielded the following fractions:

fraction

3 4

5 6

7 8

10 11 12 13

15th

tTransition temperature *, C wt. -% of the batch

61.3
5.08 1.84 1.90 1.82 1.88 1.82

1.93 1.92 0.57 1.87 1.95 1.92 1.09 13.15

until 46 / ' lOOmaiHg It 124 / 2OaUHHg Il 138 Il Il 144 Il ti 151 15amHg It 150 10at «ed ι » 146 5MBlHg Il 152 Il Il 157 31UIH5 Il 16i It Il 170 Il η 178 ti It 183 Il ' H 186 Il above 186 ti

Some of these factions have been analyzed further!

Isomer distribution

Fraction No. «of the mixture % ψο ' % ~

Μ · η · Par & di Metadi

15th

11,12,13,14, 11,12,13,14,15

Molecular weight (• SM «» etric)

76.7 20.6 2.7 417 97.6 2.4 - 314 84.3 13.7 2.0 380

For other F _ra ti "nen and Frakti" NSGE "ic was the boiling characteristic

bestinuat j

9 0 9 8 15/1171

2 -1"- 11 and 12 11 1518650 Fr shares 3 to 10 11 to 1? ASTM distillate! · »
after D-86, * C 1** 335 Start of boiling 170 260 3 * 3 327 5 % 178 268 3 * 5 35 * 10 * 186 270 3 * 6 360 20th 19 ° 27 * 3 * 7 366 30th 196 278 3 * 7 371 * 0 - 203 282 3 * 8 375 50 208 286 3 * 8 381 60 215 291 3 * 9 387 70 222 297 350 397 80 230 305 351 * 05 90 23 * 316 . 352 - 95 2 * 3 325 352 - Final boiling point 98.5 327 ■ 96.0 - Recovery 3 *, 1 97.0 30.3 83 API density 31.6 30.1 example

This ^example shows the high menealkyl content of the Dineralkylat-Bedenfraktien s.

. ^ά was β as in Example 5 gearbeiteteAus per 500g ^ at-Pelygaselin and Alkylierungsschlaa "were 588g Hehes Diaieres IMSS 3S8g repression» »erhalten.Die alkylation as-in Example 9 ₀ executed only was held BenzelTeluel

. -Used. ^ aa. reheDiwere und'der% * ti © neschlaffi "were in the Reaktiensgefäß gegeben.Die further reactants ware» 1 500g Beazel _f 50g AlCl-, 2g water uad 183g bucket between. 125 uad 2i8 ^@ C / 20mMHg ®iedeni @ a Fraktiea.'After the washing, the rhe alkylate was subjected to a fractionated distillation _{0 the} over 2i8®C / 20miaHg boiling point fraction away i89g. The menaalkyl content was 9%. ^J) as ^w »lekulargewicht was * 06 _s

Example 12.

The experiment in Example 11 was repeated in the first process step

O ■ ■ 1 - ir

53 * g of rehes-BiMeres and * 39g of DiMerieatiensschlaam were obtained. In the "Alky" · ^ lation step, the batch of intermediate fractions was increased to 38 * g. cni96g of efeertell 2i8®c / 2O »m% siedemden ^ edenfraktiea were obtained .Menealkyl- - * h * lt 9 ^U %, melecular weight 388 ",

- * ■ ■. Example 13

This example shows that the method of the invention ₉ excluded kentinuierlich

SAD ORIGINAL

"9-

leads and the entire Beakti «asgeÄXSch ans dem Dimerisierreakter ia de» Alkylating reactors are given k * aa.

Ia dea deaerating reactors, kept at 38 to ¹ K) ^- C, were given 11 g of Cat P lygas lia and alkylation sludge before meows. The residence time was 30 minutes.

The Reaktienegeeisch from the Dimerisierreakter is transferred ia dea Alkylierreakter and feei 38 ⁰ C gehaltea.Zueätzlick wurrdea feigende stiffness in dea reactor eiagege1 "s:

Beazel 33g / billion

AlumiaiüBieetall 0,26g / Mia,

Water 0.05g / ml * or similar

ECl 8.3 g / billion (8 The »riea) ⁺

⁺ "8 theeries" means that the 8-fold ^{BtochieaetriBche} ivi tightly interwoven, which would be necessary to convert the seeded Al metal into AlCl-

After washing and fractional estillates of the alkylate ergalu there is a yield of soil fractions. ν · η SJXXJi ^ JK 36j5 ^ _t refer to the used Cat-Pelygaselin, accordingly one. Austeß vea 4.02 g / oil in _e The M «a« alkyl content was 95% and the molecular weight was 375.

DiMer-alkylate- edeafrakirienea was made from di erea Cat-P lygae * liia et al hergestelJ.t _e SchHieröle with eiaea additional pork butcher Sulfeaate erbrachtea good Meterea "· 'Prüfwerte.Die ⁿ ehrzahl of the tested mixtures showed a Jf80-Stusden passage ~ i * Caterpillar S-1 Test

According to the process of the USA patent (USA application No. ₀ 15 031), alkylarates obtained from Cat-P "lygas" were processed into sulfenic acids and these further processed into overbased magnesium sulphates. The latter showed a base. number v «about 300 (determined in glacial acetic acid) _{or similar}

9 0 9 8 15/1171
BATH ORIGINAL

Claims (1)

JL / ■ '^ XDf, i ^ 5 1 8 6 "b Ü 1, Proceed "to Herat" lluag alkylareaatiecher throat "waesersteffe, which i * sfcee «* dere suitable for the production of oil-soluble sulfeaates» et si »d. thereby Ölefia * with 3 * is 18 throat looseness »in Melekül eder iere »mixture® ia 9age * wart aimes mi * eralacid-Katalyaaters eder i» $ ege »wart • it cata. Kehleiiwaeeeretef fm "it ei * e * Olefi" i "present ei" ee Friedel-Grafte-cata- lysts "" fills, iimerized, "an areaati- • cher throat * wa" eer "teff" it "gets it * e »Dimerieat i» ^ ege »wart ei» e · Friedel-Crafte-Kataiysatera alkylates u »4 from the reaction» egemiech the rather «hai» ■} 62 _ί 7 * 0 / 20ηΜΆ§, ν · τζ \ χ £ 9ΐΒ9 eberhal "19O.5 * C / 2O" mHf, "eee" dere die elierhalb 20 ^, 4 ⁹ C / 20ia "Hg siedeade Fralctle""itei" em Me "ealkylgehalt real more ale 50 #, v" sometimes "Ehr" Is 75, "e.ee" dere more than " 9 ^W % tuid denied a melecular weight Tsa" more than 320, "ese" ders more than 375 i * "eka ** ter Weiee a ¥ gotre-n »T 2 «, V®rf» h2 * @ a mack speech I ₁ by g @ k @ »» £ calibrates that the i »eralsSure ~ ^K atalyaat * r ia Mexge» Te »0.02» i · 0.7 wt .-Parts » _t delay> by 0.15 to> 0.3 parts by weight», by 3ew »» part of olefins which are used as catalytically active sleep. V ■ Sludge in the amount of 0.25% by weight used for part by weight of olefin 3 · Move »» oh Amspruck 1, thereby geke ** shows that Friedel-Crafta Catalyst in »Me» ge »re» 0.02 »ie 0.25 parts by weight», delayed 0.08 ei « 0.12 part by weight of "* yre part by weight of Olefi" used and against "e" if an "Eeaktie" epremeter, the "u" ewei "e Waeeer, i" Me * gea ve "0.1 »I · 30 Oew.-Si.Terzuge · wise 3 »is 10 wt. ~ ^, 1iezegea on the most set catalyeater, set will. 4 "Move" "ach A *" "ruch 1, thereby geke" "draws" that the arematic Throat "w * seersteff i" Me "ge" ve "0.2 ice 10 parts by weight" "Y" risugsweiee 1.5 "is 3 parts by weight per part by weight of olefin is used. · 5. Proceed "Oh A" claim 3, by the fact that the Friedel-Crafte catalyst Alumi "iu" chlerid eder in situ aue Chlerwassersteff u "d Alumi" ium " metal-made aluminum is used. 6. Traversing «sk» ach A * s _? ruch 2 / characterized in that sulfuric acid is interwoven as the mineralic acid catalyst 9098 15/1 17 1
OFHÖINAl 7o proceed »» according to claim 1, characterized, «Let as aromatic Kehlenwassersteff · Ββκζ · 1 »the T» lu «l« the Gβmi containing such stiffnesses corner can be used « 8. Process «, according to claim 1, characterized in that the olefin is a · D * decen-Frakti »n« the an at-P «lygas * lin with a» boiling range ν · η Beginning of boiling 30 ¥ is 26O * C, 50% 37 T »is 26O * C _(end boiling point 52 ¥ is 399 C, v »rzugsw» ia · «it a» boiling range ν · η Start of boiling 57 * ia 182C, 50% 138 to 196 * G, End boiling point 218 to 2? 4-C is used" 6AD ORIGINAL