BE621879A - - Google Patents

Description

       

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  "Alky14tton refinements of hy8axbt, 'e atomat1que ...
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 The painted invention relates to the alkylaeloa
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 of Aromatic hydrocarbons with olefins * or compotes acting as olefins.
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  The alkylation of aromatic hydrocarbons with - ol ± 1 "es is a well known reaction which may be carried out ** using, as a catalyst, a halide of 1Idll-cr.ft .. for example aluminum chloride or trifluoride. boron ,, or an acid, for example fluoeenque acid.

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 The invention relates to the use of a novel catalyst class in the alkylation reactions of hydroca n1 * '* eO "matiquos.



  According to the present invention, a pcc 'd! ') All the alkylation of aromatic hydrocarbons comprises the reaction of an aromatic hydrocarbon with an ole ±. ; <"# $ * compound acting under oleH.ne conditions, \ 11 :: 1" ition, with a catalyst prepared by contacting dt ry; ..Uic tW <2c
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 a compound of the general formula:
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 in which X and Y may be the same or different and
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 are chosen from H, Cl, Br, F or SCI, or from l11tlcul1 <'I fit Y
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 together form 0 or S, under non-reducing conditions and
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 at a temperature such that the chlorine is fixed by t t, 11. '::: llt1e
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 without production of free aluminum chloride.
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  Preferred aromatic hydrocarbons besides monocyclic aromatics, for example benzene or benzene, <If the small payment method be applied. aromatic isas polynucltltircl1. for example naphthaletio and Alkyl naphthalene beds, and also to compounds comprising two or i! several aryl groups, for example dîpheiiyl, olefin $
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 may contain one or more double bonds and may
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 be acyclic or cyclic oliftnels.

   They are preferably acyclic olefins having 2 to 18 carbon horns, for example ethylene. propylane, butants, isobutylene, peneonca or a propyl tetramer (olefins can also be employed, and oletines can be used. also be mixed with other material ** i, L-rtea, for example nitrogen or * natural hydrocarbons, this is l.1l'i that streams of refinery gas containing one or more: hydro ...:

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 iniquitous key carbides can be used, for example the pro
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 normally gaseous product from an apparatus 4, thermal or catalytic cracking.

   Examples of suitable compounds which act as olefins are alkyl halides, especially chlorides and bromides, having more than 2 carbon atoms.
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 per molecule, which are capable of being dihydrohalogenized to form olefinic hydrocarbons, for example chlorides of aliphatic aoycliquos hydrocarbons having 2 to 6 atoms of to bone,
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 The conditions)! The alkylation rate will depend on the reagents employed, but the temperature will be nominal in the range of 0 to 300 ° C., preferably bzz to 200 ° C. and the pu! "- aion will go from atmospheric pressure up to. 1000 liVl '..! p" ,,'; 1! i squared.

   The aromatic hydrocarbon is preferably in proportion to the olein or relative to the working compound:; ", .... 11 $ *. * # Fin., Suitable ratios being 2/1 to 20/1. Des 1'4 ')!'. JCII: tt <.



  Higher levels tend to reduce the formation of polyyltylea products and are therefore especially advantageous when producing predominantly inono-alkylated products. The liquid spatial rate of the aromatic hydrocarbon may be in the order of 0.1 to 20 volumea / volumo / hour, preferably 0 5 Volumes / volume / hour.



   The process is preferably carried out under anhydrous conditions and with water-free reactants to minimize loss of halogen from the catalyst.
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  The catalyst used and its process of pr = a 'Con are described in British patent applications t: "30821/60 and 36154/60.



   One of the peculiar characteristics of the preparation of the catalyst is the use of specific compounds of the general formula indicated, which compounds give a
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 specific form of chlorination that produces Active catalysts

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 for low temperature conversion.

   The following examples of compounds giving active catalysts and inactive catalysts illustrate the specific nature of the compounds employed.
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 odgzr pomoses d2nnat active catalysts catalysts lr.actlifo Carbon tetrachloride (0014) Chiorhydxic acid (HCx) Chloroform (CKC1-) Chlorine (Cl 2) Methylene chloride (CH2012) Methyl chloride (CH3Cl) 0! Lcoro! aorodethane 0012'2) Acdtyl chloride (C1CQC.) Tr1chlorobromomêthano <CCl38r) nlchloroethane (GHC1 CtC) Thtocarbonyl tetrachloride Tetraahlorodthane (CC1, SC1) <CHC12-CHC12) Tetrachloroethane (GHC1 CtC) Tetrachloride of thtocarbonyl Tetraahlorodthane (CC1, SC1) <CHC12-CHC12) Tétrachlnel (in the CCl2] compounds of the other elements of CCl2 CtC than chlorine, carbon and hydrogen, the treatment can add
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 these other * element * to the catalyst in addition to chlorine.

   For example, treatment with dichlorodifluoromethant results in the attachment of both chlorine and fluorine to the catalyst.



  It has also been found that the catalysts thus prepared are
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 still active for low temperature conversion, and that they may have, in addition * other properties resulting from the addition of the other elements. It has also been found that small quantities of halogens (especially chlorine) which may be present in the alumina prior to the chlorination treatment of the present invention do not affect the activity of the catalysts for low temperature conversion, although such halogens cannot contribute in any way to the reduction. the activity of the catalyst.

     Thus, the alumina used may already contain up to 1 percent by weight of chlorine and / or fluorine, as when, for example, the material which is chlorinated by the process of the present invention is a. catalyst normally used for reforming; of hydrocarbons from the gam-

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 me of gasoline boiling. Preferred compounds providing active catalysts are carbon tetrachloride, chloroform and methylene chloride.



     The compounds covered by the general formula in which X and y together form 0 or Si are phosgene or tiophosgene.



     Any suitable form of aluminum containing active acid sites or locations can be employed. This is a characteristic of activated aluminas which contain halogenatable sites, often having a base hydrogen atom *, and which can be surface hydroxyl groups *. Chlorinating compounds react with these surface sites removing an oxygen atom from them, and producing oxides of carbon, and / or phosgene and: sometimes water, although the catalysts still contain a measurable amount of hydrogen.

   The amount of chlorine added to the tatalyzer is preferably in the range of 1 to 15 percent by weight, the precise amount depending on the initial surface area of the alumina, as measured by absorption of alumina. low temperature nitrogen. It has been found that the maximum amount of chlorine that can be added without the formation of free aluminum chloride is proportional to the surface area and is about 3-3.5 x 10-4 grams / square meter.

   Maximum chlorination is preferred, but lower amounts of chlorine still give active catalysts, a suitable range, therefore, from 2 x 10-4 to 3.5 x 10-4 g / m2.



   If desired, the alumina can: contain one or more other refractory oxides chosen from the oxides of the elements of groups II to VI of the Periodic Table, for example beryllium oxide, zirconia, boric anhydride, silica, titanium oxide, or vanadic anhydride, preferably in an amount of less than 50 percent by weight. The catalyst may also contain, if desired.) a small amount

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 proportion, preferably less than 25 weight percent, of a
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 metal or a metal compound having hy {ho (, nl1nt.

   and selected from the VIA or VIII groups of the Oil Table, for example a metal of the platinum group, which may be present in an amount of 0.01 to 5 percent by weight. * 3 <? R> this dfijn such metal or such a metal compound necet cc | -end-i: îî: cL; - estiel1epour the development of the process of the present invention.
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  The non.-reducing conditions Ut.t11tH ('' 1 for chlorination can be inert or oxidizing conditions, eer
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 last being preferred. A suitable procedure for bringing
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 The tact of alumina is to pass a stream of the chlorine compound over the alumina. either alone or, do prôtérenca, in a non-reducing carrier gas. Examples of liortcurs
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 suitable are nitrogen, air or oxygen,
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 The conditions no. Reducing conditions are - "intifiiGS, because reducing conditions tend to convert the exposes of chlorine to chlorohydrofluic acid, resulting in an inactive I.ti. The temperature for chlorination may be d "149 ù 593 * C.

   The tendency to form free chloride cI f / JlulniU '! 1
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 increases with temperature and, therefore, precautions
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 should be taken when using the higher temperature readings of the specified rubber COUt! 1't (! the t prntur (; t1 used
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 will normally be higher than the volatilization temperature
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 tion of aluminum chloride, the formation of chloride <"altjnii.



  The free 1'111.1 \ 1 is easily disconnected by its coin-1 (6 gaseous reaction products. When treating a co-ipesi '* <î alumina and a metal of the platinum groupa, p1: tC.:"th)n ', J (' ... should also be pl '11100 to prevent the faith of volatile platinum complexes, the tendency to such complexes increasing again with increasing frequency. .not due to temperature When dealing with compounds of alpine and a metal of the platinum group, the temperature is preferably

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 1490 to 371 C., platinum compounds on alumina being more
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 particularly treated at 232-316OC-9 and the compounds of pallae dium on alumina at 260-3430C.

   The chlorination reaction is too-thQrm1qu and the temperatures specified are the initial temperatures employed.



   The rate of addition of the chlorine component is as low as practicable to ensure uniform chlorination and to avoid a rapid rise in temperature.
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 due to the exothermic reaction, the rate of addition is not preferably 1.3% by weight of the camp of chloroxide per weight of catalyst per minute. If tm sat pastor is used, the circulation rate is preferably at least 200 vdt! Si & s! / Volume of catalyst per hour, a range co) ivon4b: ', * removing from 200 to 1000 volumes / volume / hour, The pressure used is sett and conveniently atmospheric pressure.
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  The active catalyst is susceptible to lysis in the presence of water and: it should. therefore be tested under anhydrous conditions. Likewise, the materials used. readings in the preparation of the catalyst should be equal to 8t. free of water.



  The invention is illustrated by the examples yes. vanta, Example 1 An alumina having an area
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 surface area of 350 m2 / sram starting from isopropylate dl * lu. minimum, as follows.
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  1200 grams of sodium isopropylate were dissolved in 6 liters of benzeneAna1ar. 4 liters of deionized water were added with vigorous stirring. After half an hour, the benzene layer was decanted and 4 additional liters were added.
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 of deionized water and stirring continued overnight. The alumina hydrogel slurry was centrifuged and
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 washed with 12 liters of deionized water to remove any isopro-

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 residual panel.

   We obtained 3,200 grams of a yarn cake. be containing approximately 300 grams of alumina. After drying and calcination, the following were placed: 150 mi. alumina in a vertical reactor maintained at 390 ° C. and purge with dry nitrogen circulating at 100 µl per minute for 1 hour. We then added
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 30 ml. of dry carbon tetrachloride drip to the catalyst heated over a period of 30 minutes, while the asote pur-80 was maintained. Finally, the talt compound was swept with dry islet for an additional hour.



   The chlorine content of the resulting catalyst was 12 weight percent,
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 The Catalyst was used to react propylene and bensane 4 at a temperature of 30 pounds per inch of pressure and a space velocity of benzene of 1 vol \ 1novol \ 1no / houru. the benzene / propylene molar ratio was 4.7: 1.



   Analysis of the product, after 11 to 12 hours of treatment, gave the following composition Benzene 73.2% by weight
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 Cumene 16.9. Il D1 "'i..opropy1bendne 7.7% fi Tri-loopropylbeiizene 1.7%" Tetra-isopropylbenzene out3% "The fraction of D1-isopropylbenene (7.7% by weight of the product) was a mixture of the three isomers, namely: 1.2 isomer 0.3% by weight (4%)
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 1.3 isomer $ 1% "(40 /.) 1.4 isomer 4.3%" (567.) (100%) Example 2.

   150 ml were prepared. an alumina
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 having a surface area of 300 m2 / 8mmrune starting with aluminum propoxide in a manner similar to that described

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 in Example 1.
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 tealumina was placed in a V81: ttcd reactor. maintained at 300 ° C and purged with dry nitrogen circulating at 100 ml per minute for half an hour.

   Then 30 al.
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 of dry carbon tetrachloride was drip-fed over a half-hour period, and then the catalyst was finally purged with dry nitrogen for an additional 1 hour. your chlorine content of the resulting catalyst was
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 do lp, 3 weight percent the carbon content being: negligible (less than 0.01% by weight).



  The cataiyâcur was used for the tdaitkr latta of benzine with a gas stream containing: 93 pomfûtne by volume of ethylene and 3 yet by volume of hydvg) gbno at a * 1'r .., lon of 200 pounds per square inch oc z one speed spatial ben zèna da 1.5 voludte / wlume / hour. the bonzènel molar ratio of thythne was 4/1. An analysis of the products carried out * harsh * at different times of treatment and at different t; aperaeur <reaction dosed the following results
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 Iloures sous trattemont 3-4 9 - 10 Tompdrtture de drafting ta. 12J tic Banana% weight S6.4 76.3 EthytbeMMM io n bzz Ci, 1 Oi.d6hylbeMz & Me fi 0 1.4 '3.6 Ethyl or1 ° rii 0 0 trace 6M6 <t
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<tb> sueridure
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 Sxefflftla 3.

   The chlorine content of the catalyst was 10.3% by weight and the chlorine content of the catalyst was prepared by the process due to Itexmpla.
This catalyst was used to react benzene with an olefin-containing gas from the oil.

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 high pressure tor of a steam cracking apparatus. The gas contained 19.3 mole percent ethylene and 7.2 mole percent propylene.



   The alkylation temperature was 150 ° C, the pressure was 150 pounds per square inch, and the benzene / olefin mole ratio was 6.4: 1. Analysis of the product after different treatment periods and at different benzene space speeds gave the following results:
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 Hours under treatment 6 "7 8 -9 11. 12 space velocity of the bant, v / v / 'hx. R 1.5 T 2.0"' 3. ............... 1 .



  Benzene% / wt 81.3 85.9 90.8 tbylb.èn8 ",., 4 7.2 1.8 t8opropyt8 benaùno" 3 r 4 5.7 6, Alkyl * banzèno. 8up & riour8 "1.7 1., 3 i, 3 A particular characteristic of the results is that, although
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 that the roundness of ethylbenzene decreases with an aeerolaaemenfc of the space speed $ per mandement: of 18oprptbàn. auumanque you Idgéramonto what indlquo! \ 'use of spattalot speeds higher than this: possible with propylene.



  REVIEWS 1. A process for the alkylation of aromatic hydrocarbons, comprising the reaction of an arltic hydrocarbon with an olefin or an olein-acting compound under the conditions. alkylation with a catalyst prepared by contacting alumina with a compound of the general formula
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 where X 6 Y can be the same. where different t have been chosen from H, Cl. Br # r. or SC1, or in which X and Y together form 0 or S, under non-reducing conditions and at a temperature such as silk chlorine fixed by alumina without production of free aluminum chloride.

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  2. One does as much as: claim 1, wherein the aromatic hydrocarbon is; a mono-cyclic aroma.



  3. A process according to claims 1 or 2, which deino, '1', is olein, an acid having 24 m carbon atoms, 4. A process according to claims! t, 2 or 9, in which the temperature of the reaction of alkylt: i.oK * $ t from 0 to 300 * CSf preferably from 15 If 2QO * C.



  3, A following method; It = * ulaac da rov * n. at 4, 4 * nn which 14 reaction pressure dfer ..



  Igtton v4 dg IA atmospheric supply at 1000 Hv </ pW3 <at square, do A method according to any one of rtven. dicutiom 1 to 3e in which the aromatic hydrocarbon is; 8M excess over the olefin or am compound Acting sewn * the. fine in the ratio of 2/1 to 20/1.



  7. A process harms any one of them. dtaattons 1 4 6, in which 14 liquid spatial vtteano do Il aromatic hydrocarbon is: da 0,!. & 20 ua, unaa, / ver, umarxa, dq pre-existing 49 0.5 5 v / v / hour, 8, A method according to any 1 rov. dtcA4toni l 7, in which, the catalyst contains çhlqro ae a quantlifed of 2 x to "4 4 3 | 3!, 0" & Vmnoglmùer4 caxrj de 10Arq tntutaie de Alumina, 9, A process M't! any one tempered dia.8, wherein the chlorination temperature is 9 "to 59300.



  10. A process for the alkylafcion of hydrocarbons & tfo [nat: j. (; M9s. Tjtc !, yua describes ciwdeasus notainment 4aï? 8 examples
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 data,