BE646003A - - Google Patents

Description

       

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 tf: Process ttljrCx'Ont3ü ', 01'ltt'.
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  The present invention relates to a process for hydrog4nation and to the products resulting from such an oc6de.



  '' Belgian Patent No. 622,200 claims' a precedent which comprises the hydrogenation of a compound containing hard carbon, a catalyst containing nickel on a support, this catalyst being present at the operating conditions, mainly in nickel volume Elementary, this catalyst having been prepared by pure treatment of a catalytic material containing elemental nickel entering on a catalyst support with (a) elemental sulfur or (b) an organic sulfur compound, or (c) H23, or (d) C3Z 'or (e) m4lr;

  n, 7, e of two components or more chosen3 by ni (a), (b), (ci t {d}, This treatment being carried out

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 under conditions such that a small proportion of the nickel present in the catalutic material is thus combined with the sulfur *
It has now been found that the process claimed in
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 the breve'Ói-deeSU8 can be applied to the beisotive hydrogenation of * aqetylbene in the presence of dienenq. Operational conditions 8 have also been established for this operation.



  According to the present invention, a process is provided which comprises the hydrogenation of a carbon-containing compound, on a catalyst containing nickel on all support, nickel, which in all of the components is present in major proportion in good form of elemental nitkel. , this oa-talyer having been previously modified by treatment with (a) elementary sulfur, or (b) an organic compound of sulfur, or (c) H2S @
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 or (d) 082 'or (e) a mixture of two or more components chosen from (a), (b), (0) and Xd), this treatment being carried out results in conditions such that a small proportion nickel present in the catalyst is thus combined with the -outre,

   the process being characterized in that the feedstock is a hydrocarbon feedstock containing a major molar proportion of dienes and a small molar proportion of acetylenes, these proportions being considered in relation to one another. to the other, and in that the conditions are such that at least a substantial proportion of the acetylene is selectively hydrogenated and at most a small proportion of the dienes is hydrogenated.
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  The expressions "major molar proportion or imper" 'j aunt "and:" small molar proportion "as they apply to the composition of the feed-load denote respectively * to the monk, 0 moles" and "monk of 50 moles 41 Likewise, the expression * major proportion or import <t "., ry '' small proportion1" such that the applîqu4irg to the d * gr4 of the h <f! '.. nation .1gn1ti., u ,, s, ftt1t, ",, jt:" and .mo1%! / r:,: ',,;:;.

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 90 "t From '1" "" 1 \ 01, a quantity not greater than I of the dib. no is hydrogenated * Lu charter 4'a1u'1 \; a; .l.oA, Jar mppor * à ion eoattau dt 4i'n ...;, 4 '&o,;, 1'n'l, oontlflt de prdtdronoe in a mixture of more than 90,801 ..; of a diene or., in total, of 41'AI ', and of uni
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 amount not greater than 10 1101.% of a moitylene out in total.
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  4'.o4111n. ', Preferably dienes have the 0. $ * / or 04 # alenes, especially 1,3-butadiene, and when so are they. will be 03 or 04 acetylenes especially 1 * methyl ao4t, l.nl.



  Loo dienes and acetylenes may be practically the only hydrocarbons passing through the catalyst, the treatment thus avoiding the hydrogenation of the butadiene stream. However, the feedstock may also contain other hydrocarbons * # in particular of the h14rooarbu.

   res which are inert under the hydrogenation conditions, for example saturated hydrocarbons and also aromatics
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 and zone-oldfinte which are subject to very little effect due to the selectivity of the catalyst used. The diene (s) preferably constitute more than Q **% of the feed, in particular more than 50 mole%.



     In general, the rigor of hydrogenation
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 will be controlled by a suitable choice, in combination, of the reactor temperature and the space speed; a change in pressure will usually have a less marked effect.

   In general, the reaction temperature will be in the gamma of
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 90 to 15060j preferably in the range of 100 to 13000 *
The reaction will be mined in the presence of an aux containing free hydrogen, the feedstock may be
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 be in liquid phase, in gas phase or in mixed phase * In general, the space velocity "" U'I '-

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 hourly will be in the range of 100 to 10,000 .01ua .. per Yo-himat per hour $ the effective pre.11on due to the reaction will be due to the fill from 0 to 1000 pounds per square inch, and 1 <ratio 801 & 1- ri of 1 'hy41'os'n,. 3.

   'hlûooarml, In of the order of 0, t 100, and based on the non-biker products which must be hydrated, An advantage 1' & "101.111.1 'of the process of the award is that the hydration of the al1a.ntat1on feed can be carried out in the presence of an excess of hydrogen over the amount required * for the desired hydrogenation, so that a control of the amount of Hydrogenation = ically by limiting the amount of hydrogen al1a.nt 'is avoided. However, the amount of excess hydrogen has some influence on the degree of hydrogenation, an increase in the 801a1rl hydre ratio.
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 sene / hydrooarburl tending to increase hydrogenation.

   One can use 00 = 0 source of hydrogen, that is to say pure hydrogen, roof of the gai known as containing the h1dro.n., For example 00 gases released from an apparatus of r.tor = 1nB oatall1itu. .
The preparation of the catalyst and its activation can be carried out in any suitable manner, the trots
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 methods of which to boast being merely illustrative (a) The catalyst can be prepared on the basis by an impregnation technique by dissolving in water a nickel salt, for example nickel nitrate, and impregnating the material of support with this solution The support material may suitably be

   slurries in the form of granules or pellets of any desired dimensions, these
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 granules or pellets being drilled from the sup. crushed port. After impregnation, the Catalyst is dried and there is still a form in which it can be stored.
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 for long periods of tempx eano deterioration For u.1
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 Using the catalyst, 081u1-oi must be activated by heating to deoompor the% @ II in the a of the n1trat8, this 4-.and. United

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 ttaptarturt about 500 to 55000 and the D1ok.l se oomrtt ta the OX14 ..

   A final activation by reduction * he Aiokll 4t lll- t1 carried out in a current of 4 h, 4roctnl or a # in the context of hydro, has a temperature of 150 to 60,000 and at
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 tint effective pressure from 0 to 800 delivered per pouot oMyet your treatment time * depends on the teapere.ttu'and Typical conditions
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 queup when using a do "p1011t. ottalyst stand, are a duration of 16 hours at 50,000 It at 1 & petoulon atmo'Rh'- r1quIJ It 4fy * tuoirn degit with eepiolite however # if on chudoi
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 te at a temperature above 600 ° Ot (b) The catalyst can be prepared by browning. niait of ato nickel with! <support of ostalysiur puhriru, r, with then tranltormat1on of .41 years. in pastilles #! # before was
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 of o.t ".. 4tho4.

   of preparation is that a salt # such as forest ** -
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 te of nickell ut reduced directly to nickel (without passing through the oxide state) in a non-OX atmosphere; y4aD1I, by IX11Ipl. in an inert Sus or a stream 4 'h, 41'01'Z2 .., a temperature of 150 to 30060 * A treatment at 250 * 0 for 4 purses is usually suitable * This method presents the having.,. qt It is not necessary to chtmffwr large amounts of $ 1 & 11 "bones.

   up to temperatures of 50040 and above (0) The catalyst can be prepared by a technique which uses the oo * pl <x <xolubit in the water formed lONq, U '0.0 dis- all of the nickel tomato in the MCMnitqnWt complex and dissociated by heating to yield alokole tor.l1at8 Jtn using this oompl.% .. 01u b18 dome water, catalysts can be prepared by the 4'tmpr'nat1oA technique starting from normally insoluble oompoodo * 1 '<HM, such as 18 foralatt wet from ft1oktl. the eo * p6 << / di <! ) u <in the mmoul910 solution and the solution is used for the impregnation of granules or pellets of the ua11.r. 4..support.

   the catalyst were then dried and the aotiva110Z2 ... t carried out by Method 4'0i 'under (b) t After reduction, the aiekwl catalyst should only

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 do not come into contact with 11 $ 4r $ otherwise a sputiod oxidation of nioktl tn niokel oxide could and produce # The activated catalyst oont1lnt '41 pr4f4rlnol 1 k 50 ta weight, plus p rbioulièrtatat 9 to 250 by weight My-'
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 keep, in relation to the total weight of O.1al1 "', Oat.1f..ur. suitable for treatment with a * ma;

  Further containing and for use in the process of the invention are formed by nickel on a support of alumina, ki ... 1BUhr. chalk and militia gel *
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 A preferred catalyst salt formed by alokel on the sepiolite is a generally marketable clay which is found 4an8. nature and which can also 4 * ro
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 synthetically prepared * Hit has the ideal form i'g93 t x0p (H 1A d0 and lit @et known igaliarat all 1 not of "7eerrahsua".

   Else. information. oonoonmt sepiolite and its properties can be found in ughemintry and In4u8trr- from November 16, 1957 to pagre 1492 to 1499 *
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 The sepiolite exhibits a prior "on some other base, for example alumina, in which it reacts with the nickel Bel during the heating of the backing to sew the nickel soil. into oxides and that the final reduction Plut; itrr realities at a temperature lower than that which was born.
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 0480aire for nickel catalysts on a1ua1nl.



  In general, 16rlqa'on treats a catalyst
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 elemental nickel on a support $ with a compound containing
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 4u..ou.tr., .. a * high temperature # the degree of .l.ilt1.1.: R.t1oA is progressive as long as the oomposis contained * of the $ addition continue to pass over the catalyst and we obtain finally a very strong 4nt sulphide catalyst ta d <aMMtdwr <e * <found that some olu ... con. posed containing .otter, described # oi. * prèeo they are <fficM that for a greater degree linked * 4..u1.t \ l.1'a1i1oAI oient as well as) t-

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 near qU.tW1 a certain degree of 8u.1hra;: l. the use of q, uan;: 1; ', luppl..a;

  & 1I '"of oti oontemmt of the $ in addition to sound the alati oonditîono that precidly are sodlflt pst appreciably the degree of sulturattont. of lultur.1ion and $ of bone made, the degree of <nlfrtioa is determined by the choice of the compound containing * addition * The conditions of tulfurization which can be atodified <8
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 <have the temperature, pressure and flow rate * Habitutlliaent,
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 the sulfurizing agent will be used in the vapor phase.



  By the use of an organic compound of the $ besides which
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 have been able to achieve only a limited degree of sulphurization, it * and possible to obtain an ester which has been uniformly
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 sulphide on its surface * Although it is possible to use for sulphurization a calculated amount of an organic compound
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 sulfur which does not present this property, the resulting rice catalyst would, in this case, be sulphurized to an abnormally high degree.
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 lifted when the catalyst surface is easily accessible
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 to the organic sulfur compound although it is possible to give an average degree of cultivation equal to a shark value. the catalyst would be partly .ur-aotiv8 and partly xor * -Mtiv <.



  For the needs of the present deeoriptioni we have 01 ...
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 if the oOpO.'1 containing $ besides the way butWO10 8 OlaMt A Th10phn .., th1aoyoloalkan .. having at least 4 atomom of carbon in the nucleus and 8Ono- cultures of d: 1.alkyl ...



  Organic compound containing coulter # not included in class A (eg a! Marcaptans, thtaoyolobutanl, alkyl bitulfides, elemental sulfur, 1 '
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 hydrogen sulphide and the biwulfurw of oarbon) 1 Zen ûoaipooxtN of clause A only achieve a high degree of sulphurization, 00 = 0 previously described and ose oogpoado It is preferred for use in modifying the ma-

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 catalytic titra used * according to the present in.,. n; 1oA. In addition to Ilm-t1118a, the preferred class of oranal compound is 41.1 in the treatment of the catalyst according to iaveatton comprises thlophenes. Preferred thiophenes have 4 to 10 carbon atoms per molecule.

   Suitably # ut ## andnot oooo holding the addition taken mainly or wholly in the form of thiophenono A preferred option is a steamed *% sono * Cracked * produced by cracking in the presence of 4 'steam. at,
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 41. t111at8 fractions of petroleum, for example a primary flash distillation product or naphthas,

   and fractions preferably boiling in the range of 50 to 250 * 0. Temperatures
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 Preferred burnouts for the production of gasolines for use in the process of the invention troubleshoot 593 to 927 * 0 and suitable effective cracking pressures are in the range of 0 to 60 pounds per square inch. The gasoline% preferably has a total sulfur content of 0.005 to 0.2% by weight.



   Another clause of organic sulfur compounds that
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 the m8rcaptans can be used. However, in general, when elemental sulfur, H2S, CS2 or organic sulfur compounds other than the compounds of clause A are used, use of an excess of this% material over the amount containing the amount of sulfur required for the reaction with a small proportion of the nickel, will lead to excessive eulfuration of the catalyst} when this% is used
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 matter,

   they will be used in the etoeohiometric amounts necessary for the eulfuration of the required proportion of elemental nickel present in the catalyst.
Usually, the treatment of the catalyst to produce
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 evoking sulfurization will be real..a4 a temperature of 0 to 200 * C and any suitable pressure, which may be equal to, greater than or less than atmospheric pressure *

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 if it is treated with oat & 1, .. ur POU * be reallated in the presence of hydroc'n ..



  Usually the quant1114 of X * JMttUM oon1ltJW111 of the
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 loutrl which is reacted with the oa '& 111'ù, .ra such that # Uo will have 1 to 40 Mite 0 of * besides # relative to the elemental nickel content of the untreated oatslyo * U.



   The invention is illustrated without limitation by the following example.
Example
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 10 µl of an ok.1 catalyst is activated on .I, p1011- te containing zig by weight of n4, elemental okel # in lith, ..



  4roBn. (100 volum ../ volUtlt / heU1't) tu 25000 for 4 hours at the pressure at = opheriquop and it is partially fulfilled by treatment with a normal heptane solution containing 0, 'gr of thiophene per 100 mil of heptane at 3 ra.wxae / ro.uate / hour, and at 100 * 0 with 1fhydro & n. at 1000 vol.umes / tolue / hour for 4 hours at atmospheric pressure, The atomic ratio .or-
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 tre / niokel of the catalyst is J, 06.



  A feed mixture of 0 ol.tinyl hydrocarbon and hydrogen (10.15 v / v) is then passed to 1000-1200 vol / vol / lip e1s, 1 pressure, atmospheric over the catalyst. at various temperatures. Samples of feed and product, taken after 2-3 hours of operation, provide constant.
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 were analyzed by an ohronmtographiw in gas phase @ the results obtained being given in the following table

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<tb> Temperature <SEP> from.

   <SEP> catalyst, <SEP> C <SEP> 100 <SEP> 115 <SEP> 130 <SEP> 140 <SEP> 150 <SEP> 166
<tb> Food
<tb> Composition <SEP> of <SEP> hydrocarbons
<tb> C1 <SEP> Moles <SEP> + <SEP> - <SEP> 0.5 <SEP> 0.2 <SEP> 0.2 <SEP> 0.1 <SEP> 0.1 <SEP> 0 , 1
<tb>
 
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  2 le 2.2 2.0 ltg 1.6 1.5 193 1.1
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<tb> C3 <SEP> # <SEP> "<SEP>" <SEP> 9.15 <SEP> 10.13 <SEP> 10.37 <SEP> 9.8 <SEP> 9.8 <SEP> 9 , 57 <SEP> 9.1
<tb>
 
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 Butanes 6.8 7.1 7.1 7.3 7.2 792 794 Batene # 55.3 54.5 55.9 57.8 61.6 59 * 5 68.1 13atadiene- 193 26.1 25.3 2493 2391 1997 22.2 l4r2 Kethylacfty1.ne # 0.18 OulT 0.02 0.02 0.02 0.01 downstream Propa41ne # 0927 0.30 0.21 0.18 0.08 0.32 0.01
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 a Other than the proptdi! -3K

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 Coc resulted Show that u $ s,.



  , (e.) ': Le pélq, ylaÓéty3, ène', and hy @ ostinl! 40 taça, n ppaéc.a .. '' k; '010 to. tempeat'4req dep, yyant 00 0, the hydrogenation $ as much pirenquç .oompt ... 11500 and it doesn1t, n1j only slightly affected by
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 a further increase in temperature.
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 (b) Butadiena., 3 nteet not hydrogenated 4 un dlgr4
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 raises any to 100.0. but the hydrogenation probably increases as the temperature increases. 1nrr of 1004C, so that at 130 ^ cl the loss of goal e'éliN1'ti 11% and, â -166 G, this loss elél, ve at 46.



  (0) The hydrogenation of: '1'opadien, is general.J.t.mr-1' blable to the hydrogenation of butad..enet but the. First: sa; ' : QJf more easily hydrogenated. The hydrogenation is inexistent. , p, 4100aG but 130 C, 33riz were rSexdus loooct but 130OC9 33% were '. \ erdue and, 15 09 a 55% lost:;. a .. lost, XIII For .'hg Ilu'Qépa1iii .ên eé3setwe d a.1; h; r; l.,. EJé1V ": ..1 \ t of butt \ .f1ih'J, 1 tt: jJQU, xsatfi. Wt'f. ', tg of' 0 &;; 'have, advantageously concern the oond; 1.ton or, you F 1 ,.' 1if 'é9a of at least 100 * Q, La 7, a, you superior d1 1 °. te u- ^ ru dey md du degree to which h1dJ: Ot: 6rit \ .tipn;: 4: a 4n; 13 can, lérdn>; tS 911 f9; i: 'e.v'P'r'tnn² pe} \ + 8' 'de, 'l ,.' 1: x 1; p, "1P. ' . (1 \ 1.p1. P, ôuf; ',; J.,;) "A1') '1' Î În 'p3'C,', f 'C .3, ty .4'v s'' F 'fr,,!', A T! ' , 'g rc't Ali 9, bJ1' ,: sup tU \.

   Q..tyq 'QO.9Â.IIs, euir 4a u, l, 7 xx.aks. 'r "eO! iI,' l 'on4 + tp.'pa' ²d1] r1f ',.;,' f.e". i: p "aP..oykt # ür6tfl.Ft '3'; ', ç; I r.; r.> r,' X, 7Y7gī: 'i 4'.,. ': aR, q". 7 '.



  '.' 'ayt E ..; "Q,' bÌilt." t ¯ F-. ? 'F', 'Lr' 'yyllall ff, .jl: fna1; ",: .. 01J, To'., Fl.:P,Qf41" 1. \ f ',' t 'L 4 J2S (OR ( d) du Cflt or {r qn i 1ft \ 4fi1C} 1. 1 "Ii; l (. 9O.t $ ie PI1 ''" (bH '' - 'ir! i'Q', '' s3 '. ¯ lîti4 aous des ÇOAdÜtonS, tt (tQ 'q 1p.e' 1ï.; tp \ Q)? or.ft '1 niokel clanie çatlyoeur aci, at 1, s nickel pray do 1 .. - f9 {\ p: lt; lée i +1)

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 Dhow, this process being characterized in that the. feed load
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 mentation is a hydrocarbon feedstock contained ', a significant molar proportion of dienes and a small proportion.
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 tien molar acetylenes, these proportions being COAf; Id ';

  r4., * t ,.), relative to each other, and in that the conditions * are such that at least a significant proportion of the acetylenes are selectively hydrogenated and that an amount not greater than one small proportion of dienes is hydrogenated.



   2. A process according to claim 1, wherein the diene (s) constitute greater than 50 mole% of the feedstock.



   3. A process according to claims 1 or 2, wherein the sharps are C3 and / or C4 dienes.



   4. A process according to claims 1, 2 or 3 wherein the feedstock, considering its content of dienes and acetylenes, consists of a further mixture.
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 10 moes ib from one in acetylenes.



  5. A following process:. 'Unequoonqao of revr4Qea tiona 1 to 4f in which the hydrogenation temperature ps of a 150 <C,' ## {'Un plr9 euivantf-la rsvand.aat.o. ,. '' h yx.



  MlP temperature of hyd., Roéna.or "is 100 J '*' * '*' Pi * temperature of hydrogenation, is 100 t3a * <î * '. #.



  # \ r '# * "' 1 .'.-. o 7. A process according to one that
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 hold 1 to 6, in which there yi? ae epatiale d9Yton "'1 toof1e from 1Q0 to, 10OOO volûpies pa vole he.ôg1! 3> * | * ||
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 , \ "effective, and the order It '0 to 1000 Sèvres by QU.) Q.ft? | i gb 3.8 eLppprt mo} .air.e <3.'hydrogen 3,' byp fa 1-Kj 'JI1Qt1i 'y' '' - '' '' '' '' .-. ' rdya âe 0.5; at 1PO, based on the produced p 'ftpii'teM'îïf 4 *' Vv rV1, 5 190, n B baat sr the !! prol1 \ .titfJ n. \ {,; 'rl. .



  . , g; Y "trim. ' , '.' 1.:,"1 8. A following process), 'any d rOV') i41l'fp ... tio e 1 to 7t in which the oompase aoufr * HtjLi9 <pr le. f 1 # "'";, .. P'q1: the pre-treatment of the oatalyaeur is a compound of olcsse 4 detî **'! ï denies 01-f; leSB \ .ts.

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  3? * ïïi l |; i | llM '&# â * î *; * p' ..M