BE621878A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  "Improvements to catalyst regeneration *.
 EMI1.2
 



  The present invention lIt r.lti'1.e. 1, jréftéaértien dia ontalvs.s, t1l11.8 for conY'Jl0A with bats * 't <mp <t <' rature of hydrocarbons d, e narrow, ep6o, emea for Illomirï- let10n at low temperature of hydrooarburti parutt1A1Q "CL. and above boiling in the 'ebU111tioÁ range dt 1'.SI.AOI (that is to say up to 0t). The expression at baa.1: temp'rltu- re" means a temperature below 20480.



  Low conversion. hydfoMrbtU'ew temperature

 <Desc / Clms Page number 2>

 
 EMI2.1
 petroleum, especially the low temperature aerosol release of C 4 and higher pnrattlnic hydrocarbons boiling in the esaenoe boiling range can be achieved with certain catalysts containing an inorganic oxide, which is preferably alumina, a metal from the platinum and chlorine group, the chlorine being added to the catalyst, either in the form of a chloride
 EMI2.2
 alumina metal, for example aluminum chloride, or by reacting alumina with a compound of the general formula
 EMI2.3
 in which 1 and Y can be the same or different and
 EMI2.4
 are formed by H, Cl, Br, F or SOl.

   or in which X and Y together form 0 or S, under non-reducing conditions and at a temperature such that the chlorine is fixed by the alumina acne production of free aluminum chloride,
The preparation. of this second type of catalyst is claimed in British patent applications Nos.
 EMI2.5
 



  .8 / d and 38ol54 / 809 and their use for low temperature isomerization is claimed in UK Patent Applications Nos. 29.542 / fll and 29.543 / 81 * 0.8 two types of ontalysis gradually lose their activity and, being high cost materials, a considerable saving in pro
 EMI2.6
 If a catalyst regeneration method were available, this yield would be obtained,
It will be evident, however, that both types of
 EMI2.7
 catalyst differ 1l !:

  1pertunto with regard to their preparation * In the first type, said or active places are formed by the addition of both aluminum and chlorine, and in the second type by the addition of chlorine only. This affects the ability of the catalysts for regeneration, and

 <Desc / Clms Page number 3>

 
 EMI3.1
 The generation of catalysts of the first type presents considerable difficulties. It has now been found, however, that the
 EMI3.2
 tulysers of the second type can be regenerated.



  According to the present invention, therefore,. a
 EMI3.3
 p: roo4àé of regeneration of a catalyst which has been prepared by reacting an inorganic halGenab1 oxide: u. "eo a compound of the general formula:

   
 EMI3.4
 
 EMI3.5
 of which X and Y can be identical or 'u'tt': ren.'CiiJ and are formed by H, 01, Br,? or selt or daM which X 9% * psa wind together 0 or S, under .condition! no-. and at a temperature such that the chlorine is fixed by the oxida
 EMI3.6
 a production of free chloride, an oftalyst which results in a low temperature conversion process, ug, *** ing aom process:

  rJ.sat1on at low temperature, as finished 01-evanto comprises contacting the catalyst L at high temperature with a guz containing oxygen, and then
 EMI3.7
 When contacting the catalyst with a compound and ditiona law as defined above. Au catalysts are known and are used for high temperature Inomerluutton or reforming processes. It is also known that such catalysts can be regenerated, but catalysts.
 EMI3.8
 1- invention and] .t3ur tacbniquo of regeneration are different for the rllson:; 1 s: .l1vi.mtca.

   First, the oat.1; Ys.a'À :: - currents of e1'crmlng i. high temperature are not>. <snï ± 8. -, -UJ; A low temperature isomerization, the activity at low t;.;, 4 * .rature being, the result of the particular form in which the chlorine is present.

   In the second place, an oxidation seile one
 EMI3.9
 Rehlogening alone of high temperature reforming catalysts has normally resulted in improved improvement.

 <Desc / Clms Page number 4>

 
 EMI4.1
 derrabie of the activity of the catalyst, while it was found that
 EMI4.2
 the use of one or the being of these phases alone has no uvuntueeux effect on the catalysts used in the present
 EMI4.3
 Invention.
 EMI4.4
 The inorganic oxide, besides that it must be hUlOg6-
 EMI4.5
 .nable, should isolation exhibit the physical characteristics
 EMI4.6
 desired to make it suitable as a conversion catalyst
 EMI4.7
 of hydrocarbons.

   It is preferably constituted by an oxide
 EMI4.8
 refractory selected from Groups II to V of the Periodic Table, for example, including silica, titanium oxide, beryllium oxide, boric anhydride, ziroone or III; sie. Mixtures of two or more oxides can be used if
 EMI4.9
 Preferred catalysts containing alumina or
 EMI4.10
 Up to 50 weight percent alumina films of one or more of the other oxides reported For the QOIDC, where 1U, the invention will be hereinafter described with reference to the Preferred inorganic oxide. ie alumina.

   Any suitable shape
 EMI4.11
 alumina can be used, preferably it is a
 EMI4.12
 forms known to be suitable as the basis for catalysts used in the OutulYtiquO reforming of hYdrOoarbu.
 EMI4.13
 oil res. In these bases, the alumina flet orumment of the
 EMI4.14
 gup! ttt <t-aluMine, from f 'Gtu-l: Ilum1ne or a mixture of these-01, with
 EMI4.15
 optionally a certain amount of amorphous alumina. A particularly preferred form derives from an alumina hydrate precursor in which trihydrtite predominates. A form oon-
 EMI4.16
 holding a major proportion of betll-.lum1ne trhdl'ot6e works particularly well.

   A good preparation method
 EMI4.17
 ration of alumina: pure hydrolysis of an aluminum ulooolate
 EMI4.18
 minimum, for example, aluminum aopropylute, dune one is equivalent to inert llydroonrburé. for example benzene. Others
 EMI4.19
 conditions being equal, the more the quantity of chlorine fixed by
 EMI4.20
 the alumina is high, the greater the activity of outa'lyfJ6Ur and oom-40 the maximum amount of chlorine that can be added is

 <Desc / Clms Page number 5>

 
 EMI5.1
 proportional it the superficial area, it is desired! that X9 ** lumino has a high supertisial area, for example 4a piM 9.4 250 m2 pure each, preferably greater than N00? per graaae * The alumina preferably contains a small amount - eg less than 25 weight percent, au.

   Metal QU. of a metallic compound having hydrogenation activity, and selected from groups Vlu and VIII of the Table. Mrio & lqn * 'The preferred metal is a metal of the platinum group which may be present in an amount of 0.01 to 5 percent by weight, of pr, 6, 6, * of 0.1 to 2 percent. in weight.

   Preferred metals. platinum group are platinum itself and palladium
 EMI5.2
 When the catalyst has shown signs of energizing and it is considered necessary to regenerate it, the flow of feed is stopped and the catalyst bed is purged to remove the reactant a. this can conveniently be done with an inert gas, eg nitrogen, a combustion gas from a regenerator
 EMI5.3
 of inert guz, or hydrogen.

   Bt drogen is especially preferred when it is normally used in the reaction zone during processing, the purge phase then being simple.
 EMI5.4
 plement achieved by stopping the circulation of the aborse d # mlimoiz .1
 EMI5.5
 tution, while continuing to pass the hydrogen. The temperature of the purge phase can suitably be good for the truitament, ie an internal temperature of '1804 * 0' The rate of circulation of the inert gas and the neestiostral time To give a suitable purge can be faollemeat d6extie, for example by analysis of the purge gas exiting the reaction zone, suitable gautzes being, for example, from 100 to 1000 volumes of gas per volume of catalyst per hour or more for
 EMI5.6
 10 minute & 12 hour periods.

   The pressure used is not critical and can be the same as that used during the treatment, however, like the subsequent treatment.

 <Desc / Clms Page number 6>

 
 EMI6.1
 with oxygen-containing gas will normally be carried out at atmospheric pressure, it will be necessary to focus the treatment! is carried out at high pressure, to reduce the pressure and it may be convenient to do this before or during the purging phase.



   The simultaneous presence of hydrogen and oxygen du-! rant regeneration would be clearly undesirable. 3i, by
 EMI6.2
 Therefore, the purging is carried out with hydrogen, .'3ydxagb- ne should be removed, for example by displacement with an inert gas, before the introduction of the gas containing oxygen *
The treatment with an oxygen-containing gas (hereinafter referred to for convenience as "combustion") should be carried out at a temperature and under conditions such as
 EMI6.3
 damage to the catalyst is avoided (for example conversion of the alumina of the catalyst to alpha -alumina, or crystallization of the platinum group metal when such a metal is pre-
 EMI6.4
 sent),

  a suitable overall range from 250 to 12oo.F. The preferred temperature range for combustion is 400 to 10006? 9 more particularly 400 to 900? The duration of combustion can be from two to forty-eight hours. If desired, combustion can be carried out with an increase
 EMI6.5
 , gradual temperature in the narame from 400 to 100C * y over a period of five to vinat hours.



  The oxygen-containing gas may be oxygen or air, but the oxygen content of the gas is an effective factor in the ullity and the rate of combustion and the combustion.
 EMI6.6
 temperature reached, oxygen or air are preferably diluted with an inert gas, for example nitrogen.

   A suitable gas mixture would be made up of a mixture containing
 EMI6.7
 0.1 volume percent oxygen with the precise amount of oxygen and the rate of flow adjusted to give temperatures within the ranges specified above.
 EMI6.8
 The roclilination of the catalyst treated with oxygen

 <Desc / Clms Page number 7>

 
 EMI7.1
 can be carried out in a manner similar to 1: tiâlorption of the
 EMI7.2
 initial preparation of the catalyst, details having been given
 EMI7.3
 To this subject owe the British patent applications Nos. BO.SI1I 60 and 380 154/80 $ these detbils being taken back o1-8prs nottveau for
 EMI7.4
 the fuility.
 EMI7.5
 



  A particular characteristic of chlorination is the use of compounds of the general formula * indicated, these compounds giving a chlorination effect which produces other catalysts. pou> un conversion il busse tomp6rltur ". The examples 'Ht1'hAh && composas doniiunt of the active ol.ltulysenr3 and. c: a1., all, et.U" $ 1li.UÓ' "tifs illustrate the special nature of the oompoî .ea employees ,.
 EMI7.6
 



  Cuts giving outa- Compounds sounding ogit4m 1l: JtJurs uotitlJ ... ijwii 1l.J, ēurs. t '. '"Ji, ...--' retruohlo1'uro de ourbone (OC; 14).; 01110 ohlurbydr1qu. \,,., 3h, vxvortua (QHC1, chlorine (0 * -Z) Methylene chloride (OHaC12) Chloride meth: rle (ORJ01.) D1ohlorod1tlu '.) rcmeth.me (COl.; 1.,) Aostyle chloride (oel4cccll Trichlorobromomethand (C013Br) D1ohloroéhan. (CH2Cl-CH201: thioourbonyl tetrachloride-CH012 tetrachloride



  (CCOl) Tetraoh3.oroethyl & ne. (CCI., "Tetrah, oraethylna, CC. A
 EMI7.7
 In the case of compounds containing elements very much like chlorine, carbon and hydrogen, the treatment can add other elements to the catalyst, in addition to chlorine,
 EMI7.8
 For example, treatment with α3.ahiorod3, 'luorowtha, o so * .x results in the binding of both chlorine and fluorine to 1: lyssur. It has, moreover, been found that catalysts thus prepared are still noteworthy for low tea conversion and they may further have other properties resulting from the addition of the other elements. Preferred compounds doimact
 EMI7.9
 active catalysts are carbon tetrachloride, chic- '
 EMI7.10
 reform and ithylene chloride.



  The compounds covered by the general formula in)

 <Desc / Clms Page number 8>

 which X and Y together form oxygen or sulfur, of which
 EMI8.1
 phosgene and thiophosgene.



  The non-reducing conditions used for the chlorution can be inert or oxidative conditions, but later being used they result in catalysts which lose their activity more slowly during low-temperature injection. A suitable method of contacting the liquid. The alumina consists of panzing a gaseous quantity of the chlorine compound on Itmlumlneo either alone or pre-terencoo in a non-reducing carrier gas.

   Examples of suitable carrier gases are uzote, Ilutr or oxygen. Non-reducing conditions are essential,
 EMI8.2
 because reducing conditions tnnaent to convert the compound of
 EMI8.3
 chlorine to ohlorhyartic acid, which gave an inAQt1ti catalyst. The temperature for the ohlorution can be 149-593 * 0. The tendency to form free aluminum chloride increases with increasing temperature and care should therefore be taken when using the higher temperatures of the reported range.

   As the temperatures used will normally be above the volatilization temperature of the
 EMI8.4
 aluminum chloride, the formation of free aluminum chloride is readily detected by its occurrence in gaseous reaction products. When trouting a compound of alumina and a
 EMI8.5
 mettil from the platinum group, precautions should also be taken to prevent the formation of volatile complexes of plutin, the tendency for such complexes to increase again with an increase in temperature.

   When we
 EMI8.6
 deals with compounds of une and a platinum group metal, the temperature is preferably 149 to 371 C10. the compounds <'1.'. platinum on alumina being more particularly treated at w32- 31680. and the oomposca of palladium on alumina and 260-34300 La is
 EMI8.7
 coloring / exothermic reaction and the temperatures read a, pa3-.

 <Desc / Clms Page number 9>

 
 EMI9.1
 These are the initial temperatures used, whereby the '"is preferably set as indicated 1-iSpt., * #" **** j n1è1'e that the maximum temperature does not exceed COOY # # ** 9B * 4.

   preference not greater than ô3O ** 3V The rate of addition of the compound of oblort this defeat ferenoe as low as practicable to ensure a uniform oblorettou and to avoid a rapid increase in te # p'ra-
 EMI9.2
 ture following the exothermic reaction The rate of addition
 EMI9.3
 preferably does not exceed 113 percent by weight of pure chlorine ooopo # 4 1JOI40 catalyst per minute If * u * 10% carrier is used, the circulation rate is preferably 200 vol per volume of catalyst per hour, an OCJ2V * "adjustable gamma ranging from 200 to 1,000 volumes per volume per hoes ZA pressure used is suitably atmospheric pressure <The amount of chlorine fixed by catalyst 441 * will depend on many considerations than those which apply during the preparation of the catalyst,

   the amount of chlorine which can be added without the formation of free aluminum chloride being proportional to the surface area of the oatalygout being about 15 a, 3 x 1 C * jutâmes per square meter of 1 t. At the initial level of the catalyst. A maximum chlorination is purity, but lower amounts of chlorine will give more active ingredients, a suitable range of, per oon "q, l1at, do 2 x 10 at 3.5 x 10th * 4 grams per meter Oari * i.

   It is likely that the tr: d. The combustion rate has removed a reasonable amount of the initial chlorine, and in practice amounts of up to 50 percent by weight of the pure chlorinating compound by weight of the catalyst used can be fed to the ## '- analyzer during the process. chlorations A control of the reaction by:
 EMI9.4
 an indication of when it is total can be obtained,
 EMI9.5
 for example, using thermocouples to measure the temperature increase caused by the temperature reaction.

 <Desc / Clms Page number 10>

 
 EMI10.1
 and / or by aD81ysis of the gsz leaving the reaction zone * The reohlorinated catalyst is. of preruncel oalo1nê before rut111sut1on in a manner similar to that of order in
 EMI10.2
 British patent application 140-32.505 / 61.



  The various phases of the regeneration process. as well as the preferred conditions, can be summarized as shown below in the table on
 EMI10.3
 , Table 1
 EMI10.4
 
<tb> Phase <SEP> Gas <SEP> Preferred <SEP> range <SEP> Remarks
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> phase <SEP> uaz <SEP> of <SEP> temperatures
<tb>
 
 EMI10.5
 #y ¯¯¯¯ # Precaloi Hydrogbne 150 - 50 pure to remove repetitive pressure nuances until the pressure! .tao8phériqM Calclnn- Ouz inert.} \ '100' e :: rp'Í'uture regulated by the controlled ù'oxygEN ¯¯¯.ju.



  Reohlora. ..lr and col 4M .... of chlorination tlon, adjusted for injection 'ad COl. 36 not 8500% OC1 totúl injected Up to: 50 percent by weight in the tool.



  '' #. "m- soc Te # prutura éleJisq OalolUB-, ir * uw gous lion circulation air and then lowered Up to L50-5500? 0
 EMI10.6
 This intention is particularly suitable
 EMI10.7
 for use in combination with a process for the low temperature isomerization of low temperature hydrocarbon hydrocarbons 0 "and higher yawning in the gasoline Ób \ 1111 flame, the catalyst being regenerated com.-Uti described oi-ovunt and then reused in the process c1'1sou.1ria.it1on at low temperature.



  When the process costs in low temperature isomerization, the feedstock of the process is preferably a material containing a major proportion of pontanes,

 <Desc / Clms Page number 11>

 
 EMI11.1
 hexanes or a mixture of these paraffins. F: 1t,.:; O of a11 .. solution containing a major proportion of hexanes or freely preferred parts. If it is desired to isomerize only normal paraffins, the feed can first be drawn to separate the normal paraffins from other hydrocarbons and these normal paraffins are contacted with the catalyst.
 EMI11.2
 sor of isomerization. Such a separation-can be rlii? 1. suitably, using so-called molecular sieves.
 EMI11.3
 



  The product of the isomerification reaction is little, ** that can even be treated to recover the normal paraffins - <- "- <# verties which can be reoai.ées the reaction zone of> .. a ±:, y reation Such a separation can also be carried out in a suitable way, thanks to uux tuutia dita ll101él) u.1ai: rE'8.



  The feed is 1vcn taê: euesLh J '"" l te of sulfur, water and aromatic hydrocarbons.
 EMI11.4
 



  The isomerization can be carried out in the following cceu (,. tions, in liquid phase or in vapor phase.



  Temperature 50-400 F, from pre: f'è: rol1
150-350 F.



  Atmospheric pressure - 2000 117 per square inch, of reference 225 - loco delivered. * ,.



  Space velocity: 0.05-10 volumes per volume per hour, preferably
0.2-5. f Hydrogen / hydrocarbon molar ratio: 0.01-20 / 1. preferably 1.5-15 / 1.



  If desired, we can add to the d @ zone
 EMI11.5
 tion a halhydric acid, spéoialeaent ohi.orh, c3sa acid, or a compound giving rise thereto, under the conditions. - "', reaction, either directly or pure addition to the feed or the hydrogen-containing gas used. The halhydride is present in an amount up to a weight percent of the feed load.



  The invention is illustrated by the following examples

 <Desc / Clms Page number 12>

   Example..!
 EMI12.1
 (1.) Preparation of the catalyst, grazed lub ml. of an oocmerolol compound of platinum and doaw ittraineo comprising v, 57 weight percent platinum and 0.81 weight percent chlorine on alumina, spread charged to a glass reactor and processed as next :
 EMI12.2
 (a) the catHlysau-r compound was seized in a
 EMI12.3
 circulation of nitrogen at 500 1 for two hours. The speed apa-j
 EMI12.4
 t3, alo hourly of the ga was 500 volume * Per volume per hour over the entire treatment, a downstream circulation operation *, j te being used.



   (b) the catalyst component was treated with 24
 EMI12.5
 weight percent (p4r: 14U weight ratio of loaded catalyst) of curtoae tetrachloride k 5QQ020 The C014 was added taste. dropwise into the stream of nitrogen carrier gas above the catalyst bed, the vaporized COl4 being carried over the catalyst.
 EMI12.6
 sor by the a: ote carrier gas. The rate of CCl4 addition was not assumed to exceed 0.8 grams per minute.



   (o) The treated catalyst was flushed with nitrogen at 500 F for an additional hour and then deharged into an airtight sco vessel. This catalyst was
 EMI12.7
 designated by oatalyst A.



  (ii) Use and deacoti-yntion of catalyst A
Four 30 ml samples. catalyst A previously were checked for their activity for
 EMI12.8
 an isomerization of henna at temperature under the following conditions:
Temperature: 270 F
 EMI12.9
 Pressure "50 pounds per square inch Molar Ratio
 EMI12.10
 Hailia 3.5 / 1 Hourly space velocity of liquid: volumes per volume per hour.

 <Desc / Clms Page number 13>

 



    @ The feedstock was a C6 fraction de-
 EMI13.1
 sulphurous, desaroated. obtained from a light meat plant and containing 0.1 percent by weight of 0014 as additives Average processing time; was 50 hours, while the
 EMI13.2
 The initial 18 percent conversion of 2,2diehylbae in the unstabilized liquid product fell to an average of 12.5 percent by weight after 50 hours. Catalyst particles
 EMI13.3
 exhausted were purged for one hour at 37067 with o. <l'bt. drogen and were cooled to ambient temperature under nitrogen.

   They were unloaded in a container
 EMI13.4
 Seo, airtight, and they were mixed thoroughly to ad sur to uniformity. This catalyst was referred to as a catalyst.
 EMI13.5
 (ili) Prepnrat.i.Q.n .., .. & *, catalyst ilO
A 30 µl charge of catalyst B was introduced into a glass rotator and added with 14 weight percent 0014 (based on the weight of catalyst), exactly.
 EMI13.6
 aoer.1U described for the preparation of catalyst A. this 08'i11r "U was designated as catalyst (iv) ertiodū.outalysu, r.jt) A charge of 30 µl.

   du'oatalyaeuy B was ohauttât pure stages Until 9Z081 in air The temperature was a-
 EMI13.7
 nt \ born up to 1 '. \ 500.:11' in two hours, engnec-tée of 1 "'ehaq <i <place' 1
 EMI13.8
 re until a temperature of 930 * Y and then maintained 1 This last temperature for two hours, (v) yët.JLondULMjtu], ¯a6U A loaded with 30 ni * of the oütll, .t # r 3 was ohaut- fée by steps up to 930 * Y in air, exaotically OO # m8 d6- orit for catalyst D. The tool was then loaded into a glass yéMOtouf and treated with 14 potir-cent in polde of 001, exactly 001111118 described for the catalyst A. This 00-talysour was referred to as catalyst 1.

 <Desc / Clms Page number 14>

 
 EMI14.1
 



  (vl) Activity Tests Small portions of the catalysts n, this D and were analyzed for chlorine content and carbon content. The remaining portions were M'ite checked for their activity for a soil: low temperature drisl1t1on under the same oono.1. tio.:-,,:J and using the same feedstock as described in 'Play here.
 EMI14.2
 before. The results of the activity tests are summarized in ta-
 EMI14.3
 bleau a below and they are compared with the results obtained with fresh catalyst II.



  Board. 2
 EMI14.4
 ¯¯Msaltats of M'Uv1t6 Cataly- Chlorine, Cll1.'bo ... Conversion to 2,2 "'dl [: ét"; lbu .... ne "-I> O' 'under? For - nu, one hundred by weight 5 ct'iit an {pour '"### -> - # -. ..¯¯p. ## "#!" l1G.8 1 nt: initial {in- 21 hou! '') ;: 1 50 hours l: tll. 1 vj ['01 \ 6 hoaro8ï t.

   J'PWi ï W i .¯ "-" "'1. --- tH" .II 1 1 ï 1 1 r J t; A i 11, S 0.0> '; 18 15.5 13.5 9 (G 1.1 ': 1, 9 Ur 3.t.' ir 0.753 8 -, 1! Or it E, 10.5 1 0.02 .tu% 16 ,, - ¯ .... 1 ". '"
 EMI14.5
 
<tb>
<tb>
 
 EMI14.6
 The results are on what concerns the contents of Chlorine and cjrbfMM which catches it: .ÙY1fmr d $ '. Ot1v (It had a content of ohloro r; .dt11to and a content of 3o c-trbone oon alderable, cip.'dtivuscnt mt cntulyaear trdla A. -: 1 <1 (1 l'l'tohlora- tion for dOl1l "r the datiilyaour C, iUCl :: 6ntn1 t lu '". <ut) f (, -Ijltlre Nuis ne rlt1t1.1sIJ1t quo 'uj-.u1-;

   a degree XJlfâitô !! pul..nt the t- nour of ourbùnet An ohU'ln'i \ V6 Cana of the air for the oatalysou1 "li had for result Ilorilbvemont of the carbon also targeted the leon1bement of the chlorine Eutalycuar U which had been heated in 1 '

 <Desc / Clms Page number 15>

 
 EMI15.1
 air to remove carbon and then re-chlorine alone had chlorine and carbon contents similar to those of fresh Catalyst A.



  The activity test on catalyst B showed that
 EMI15.2
 The deouotivation was permanent and that additional keyaectivatiou occurred with continued use for the airsutlon. your tests on catalyst 0 which was 6 &# - chlO. \ f6 killed unheated in 3. '1rf st on catulyutue D which had been ohnut: t'6 in 10 air mats not rechlordo contro that none of the treatments n 'swallowing effect uP: Pfêc1abl. on the a <s <tiv1tÓ of o.tllys13u.

   When the treatment was QOt! 1'bine <IJI oonuue in the o: 1t..l'ceu3: '] 1, the Qutul..vee \ 11l nevertheless had to?:.? M? I6
 EMI15.3
 its initial activity *
 EMI15.4
 1.:Xom2le (i) PgëurlonJuQiiJlMur 65 gM) !. t.iea composed of platinum, alumina of a 4t.1locne, containing 0.5? weight percent of plut1nt m OeUl one poured chlorine on I $ nlwUnee ètiiiont ohujgéa in a green r4notour loti 1 tu.bu.lJh'e of glass, and we let P48 sor down in the catalyst in a stream of nitrogen - 40 liters pure houpe. L-1 temT.lér1ture of Iatolyoour was elf - v6Q Until ,. 550 * y and kept at this value.



   Pr! 's had. :: we injected the tetraobloeure of 0, r'bone in the stream of nitrogen at the rate of 13 grams per hot "ro, lu steam 6t, It was carried over the catalyst bed. Took sweet hours , when ..6, Grammos of carbon tetrachloride spread l) hSÜU over 1: c, "t, lyel1r, the injection was stopped; ; after a purge carried out r> nclunt an additional hour u4 :, do azotq ù 5dOQF, the was cooled, until the tcri perutura Hl.; blunte and discharge rupidoont in a dry container, etunono h l'1i: r 4ezio 1I1.:\c;:nnt ltton of the catalyst weight of 6, ç 'pour-'oout was observed and 1Q outalyaeur appeared Eraser Follows the lll \: tly.t9:

 <Desc / Clms Page number 16>

 
 EMI16.1
 Chlorine ï! 3, i> percent by weight Carbon c7,4: percent by weight redrvcbno:

   0105 percent by weight :, re, aa, aa ,, e J47 Mutra ourréa per hertz = 0 Voluiaa des ppeen s 0.9 milliliter pu gyam-
 EMI16.2
 
<tb> trio
<tb>
 
 EMI16.3
 (11) n, et1l,: 6nf; .t1MJnJ d11 r "QHtlpI1Z, Z5 graoswes du Oh1!) L:, rsor, were loaded in a" uot.u and testas for what OCJ1Qen the uotiv1té are the non-editions 041vontes 'H70 "? E5o pounds per inch Otlrl' molor ratio of hydrogen / hydrocarbons of 8.5: 1
 EMI16.4
 hourly space velocity of. liquid of 1 volume per volume per hour,
 EMI16.5
 xer chiirees ol1wmtot1on u.1I1: L1aea and the r "sul .. tutu obtained are given to tQb! 1.uuu; i $ u1" mnt, After 66 hours of treatment, the putulyaeur 'tut xébriéx6 for the following procedure 'have.



  The reactor was purged for one hour with hydrogen and then reduced to the near atmospheric pressure tb1t. Ap.1, 'èa baloyuea du> ¯yrtscua uveo of nitrogen, an air circulation of bzz liters per hour was established. The temperature was high Bo1gneu3o: nant to avoid a Qombust1un due "leak", according to 10 processes o1upr u: a) S7Q - 400 y {3/4 hours ago b) 400 - 45QClF: 1 hour 0) 450 - 500 * 3? l hour d) 500 - 9Q0 * F: 4 1/4 hours e) 9CO "F;

   1 hour Particular p.r6Qt \ .t1o; .s were taken in the tepr.tturo zone from 400 to COQ (l1! '0/11' the start of the "oom.bus- tion" etIÍ (H3ll.b16 CHI 1'rv1l \ 1fn1t ÜIIIW ootto ll1l.lmù do 1.tJI, .p, 'rllturr.H',

 <Desc / Clms Page number 17>

 The catalyst was cooled to 55 ° C. with circulating air, and then it was treated with 8.4 grams of tetrachlorare carbon (32.3 percent by weight of the catalyst) over one hour.

   A maximum catalyst temperature of 575 F was recorded 7 minutes after the start of the treatment with carbon tetrachloride *
At the end of the addition of the carbon tetrachloride, the temperature of the catalyst was raised to 900 ° F in the same manner as for phases (d) and Ce). under an air circulation of 15 liters per hour and then it was brought back to 270 F. After buloyuge with nitrogen, the conditions of the activity being restored at all.

 <Desc / Clms Page number 18>

 
 EMI18.1
 



  TABLE & U3
 EMI18.2
 Treatment Hfcv-s-38 Chars 1 + 6 39 Charge 2 + 49 66 72 108 0.1 hours hours 0.1 hours * hours Charge 3 + hours hours CC1.-. eD C014 in Otl of 0014 ¯¯¯¯¯¯¯¯¯¯¯¯ weight i ¯¯¯¯¯ -weight ¯¯¯¯¯ ¯¯¯¯ in weight it.



  CoEpoaantt% by weight Propane # trace trace 1 trace - trace trace Inobutane 0.5 ot5 2 0, $ 0.5 0 * 5
 EMI18.3
 
<tb> n-butane <SEP> tra-ce <SEP> trace <SEP> trace <SEP> trace <SEP> trace <SEP> trace <SEP> trace <SEP> trace
<tb>
 
 EMI18.4
 Isoentane trace 285 285 trace trace trace 1 1 n-Pentane * t5 115 * t5 1.5 X lut5 0.5 0.5 2t2-Dimétlbutane 3t5 24 23s5 ot5 10.5 1 2.5 28.5 29 2,3-Dillethylbutane 33.5 4Ot5 40 c: 25 c: 36 5Ot5 | 39 40 39 3-Met!> Ylpeataa * 23 1.5.5 16 16 15 1295 22.5 l5t5 15t5 n-Hexane 30 11 11 31 15 29 I !;

   30 10 1095 C. liaphthenea 5.5 * t5 ** 5 i3s5 12.5 15 4.5 4 4 Benzene none 0.5 trace 0.5 none 07 etc. - He, 5 6 10 -
 EMI18.5
 
<tb> Sulfur, <SEP> parts <SEP> by <SEP> ¯
<tb>
 
 EMI18.6
 million 0.6 - 250 0.7 -

 <Desc / Clms Page number 19>

 
The results given in Table 3 show that at the beginning, when the feed contained little out of benzene, C7 and higher hydrocarbons, and sulfur, satisfactory operation was obtained. When the power charge
 EMI19.1
 When the catalyst was used to include these components, the activity of the catalyst was reduced. By regeneration of the tool and return to the initial feed, however, the activity of the catalyst was fully restored: a RldT7 C. Tx ONS 1.

   A process for the regeneration of a qat catalyst was prepared pure reaction of an inorganic oxide 1: ullo8éno'blt! L with a compound of the general formula
 EMI19.2
      in which X and Y can be the same and different and
 EMI19.3
 are formed by 17, 01, Br, F or Sol, or in which X and y together form 0 or S, (all under non-reducing conditions and at a temperature such that the chlorine is fixed by the oxide a production of chloride free, catalyst which is deactivated by a nozzle temperature conversion process comprising contacting the catalyst at an elevated temperature with a
 EMI19.4
 gas; containing oxygen, and then the toohlorination of the catalyst


    

Claims (1)

lyser by bringing this-01 into contact with a compound of the general formula given above, under the conditions specified 2. A process according to claim 1, wherein the halogenatable inorganic oxide is alumina or a mixture. EMI19.5 Cà of alumina avee.jucqu'a 5r Dour-oant by weight of one or more oxides chosen from groups II to V of Table PJrlod1u $. 3. A method according to claim 1 or re. VÎ3ndioé, 1tion 2, in which the catalyst contains a small pro ... portion of a metal or metal compound having activity <Desc / Clms Page number 20> EMI20.1 h1drQgênte, and chosen among the groups Vla and VlH of the Table. Periodic. 4. A method according to claim 3, in which EMI20.2 which ct41Yocur contains 0.01 to 5 by weight of a platinum group medium. 5. A process, according to any one of the sales EMI20.3 dications 1 to 4, in which lo trq1teH \ nt over a MHz containing oxygen is carried out at a temperature of Z50 to 1200. 6. A method according to claim 5, wherein the temperature is 400 to 1COO F. 7; One proceeded according to any one of the returns. EMI20.4 ùioutiona at 6, whereby the 8ttz oon'tem'nt oxygen oon .. holds 0.1 to 5 percent by volume of oxygen. EMI20.5 Bo A process according to any one of claims 1-4 7, wherein the rohlorut1Qn is carried out with a non-reducing gug for the chlorine compound. 9 * A method could be any one of the following. 8, whereby the rechlorination temperature is 300 µl. 11C08F. 10. A process according to claim 9, wherein the catalyst contains a platinum group metal and the temperature is 300 to 700 F. 11. A process for regenerating a catalyst, as described above, in particular in the examples.