BE424910A - - Google Patents

Description

       

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  Process for the thermal treatment of carbonaceous materials and catalysts suitable for this use.

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   Processes are known for producing or improving liquid or fusible hydrocarbons such as gasoline, solvents, diesel oil, fuel oil, lubricating oil or paraffin, or gaseous hydrocarbons, by subjecting carbonaceous materials including the molecule contains more than one carbon atom at a time; thermal process involving, in the molecule of the raw material or a part of it, a disjunction of the bonds of carbon to carbon or of bonds besides the carbon and other elements, or the elimination of asphalts or resins or substances giving rise to them, and it has been proposed to operate in a large number of cases processes in contact with catalysts comprising a mixture of soft or several constituents.



   However, it has been found that in our processes particular advantages are obtained by operating with the contoct of catalysts comprising a mixture or a chemical compound (or soft) of a component (a) consisting of one or more metals of low nature-hydrogenating mount. atomic number between 25 and 30 in the form of preformed sulfur compounds, particularly preformed sulfides, or phosphor compounds, particularly phosphates (10 filled zinc phosphate always being a neutral phosphate), or both this and this one, and of a component (b) consisting of one or more metals having a strongly hydrogenating character and an atomic number of at least 42 groups 4 to 7 of the periodic system,

   or we have vanadium, chromium, nickel or cobalt or their compounds, the proportion by weight of component (a) in the catalyst being greater than that of component

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 (b).



   Ordinarily, the weight ratio of component (a) to component (b) according to the present invention is at least 51:49 and preferably between 55:45 -t 99.5: 0.5.



   The proportion of component (b) in the catalysts according to the present invention is in most cases not less than 5 parts by weight per 97 parts by weight of component (e.). The catalyst preferably contains 3 to 40 parts by weight of component (b) per 97 to 60 parts by weight of component (a). Very often 15 to 30 parts, for example 20 parts of component (b) per 100 parts of the mixture of (a) and (b) will be used. The specific proportions of components (a) and (b) are chosen in each case according to the materials to be treated, the results desired and the operating conditions under which they are to be employed.



  The optimum proportions and conditions can, if necessary, be determined by preliminary tests.



   The metals of a weakly hydrogenating nature whose atomic number is between 25 and 30 are manganese (25), iron (26), 10 copper (29) and lo zino (30). The preformed sulphuros of forest, manganese or zinc are selected components of component (a).

   In cases where it oxidizes several sulphides of the metals of component (a), the lower sulphides, for example ferrous sulphide, cuprous sulphide or manganous sulphide, will advantageously be employed. However, it is also possible to use higher sulphides or polysulphides of said metals, by oxomple of forric sulphide, ferro-ferric sulphide,

 <Desc / Clms Page number 4>

 
 EMI4.1
 copper, manganic sulphide, etc.

   As examples of other sulfur compounds d-: JSG.i ts metals of the constituent (n) making it possible to obtain good results, mention may be made of ferrous sulphate, copper sulphate, zinc sulphate,
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 manganese or sulphites, thiosulphates, mercaptides called metals, etc. In this connection, it is in particular possible to use the thionic salts of said metals.

   These thionic salts can be in thionic acid sols of the metals of component (b) or of other metals, most of the cases including
 EMI4.3
 posed sulphides so tr - :, nsfOrl1lOnt c.n sulphides under the reaction conditions. As phosphates we have c: nploicr :. Usually ortho-phosphates, but other phosphates, for example dos meta-phosphates or pyro-phosphates will be considered when used.

   Other phosphorus compounds which can be employed are phosphites or phosphides of such metals.
 EMI4.4
 Metals of a strongly hydrogenic nature: having an atomic number of at least 42 from groups 4 to 7 of the periodic system (component b) are molybdenum (42), tin (50), tungsten (74), rhenium (75) and uranium (92) and those or their compounds are the components of choice of
 EMI4.5
 do you ... nt (b ß:

   The metals of component (b) will be used pre-reronoo in the form of their COG8sés, in particular in the form of oxides, hydroxides, sulfides, sulfates, thio-acids or salts thereof, mercaptides or other sulfur compounds, but good results are also obtained with the halides, selenides, telltufixrüs, phosphates, carbonates or organic sols of said metals.



   In either case, component (a) and component (b) will be used in the form of preformed sulphides. We

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 to prepare these in various ways and see their use according to. present invention. For example, metals or their oxides, hydroxides or other suitable compounds can be subjected to a sulphurizing treatment under conditions which allow a complete transformation by means of sulphurizing agents such as hydrogen sulphide, sulfur, carbon disulphide, 'aptans, etc.

   Uri another process is the. precipitation of polysulphides from an aqueous solution, these polysulphides being - 'then if one is subjected to a thermic treatment one sees a transformation into lower sulfuros. Very suitable sulphides are also those which are prepared by pyrogenic decomposition of the corresponding thionic soils. It may be advantageous to subject sulphides to treatment with sulphurizing agents in order to remove the last traces of oxygen therefrom.



   It is advantageous that the various constituents of the catalyst exist in a state of intimate mixture with one another.



   Mixing of catalyst constituents can take place in various ways, eg mechanically.



  For example, components (a) and (b) can be prepared separately and then mixed.



   It is often preferable that the intimate mixture or compound of constituents (a) ot (b) is obtained directly in the chemical preparation of the catalysts, for example by simultaneous chemical transformation ;, of a mixture or compound of constituents (a) and ( b) or rudiments thereof. Different components of component (a) or component (b) (or two), or other catalysts comprising mixtures of strongly and weakly hydrogenating components can also be prepared by said simul-

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 tanned.

   It is thus that alloys containing the base metals of constituents (a) and (b) in suitable proportions and which are in a finely divided state, for example powder, filings or turns, are sulphurized under vigorous conditions. , with a view to producing mixed sulphides. In this way, powders, filings or turnings of molybdenum or tungsten steels can be transformed into interesting mixed sulphide catalysts to be employed according to the present invention.



     On the other hand, we can decompose a scl formed by an acido thioniquo of a metal of the constituent (b) and a base metal of the constituent (a) to obtain mixtures of sulfuros,
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 but in this case and in general, in order to produce the catalysts employed in accordance with the present invention, further amounts of a component or rudiment of component (a) should be added before, during or after. decomposition of thionic salt.
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  In the. preparation of said catalysts by simultaneous chemical formation of the rudiments of their constituents there is 3gr.lcmol1t mv # '1tz, fra to be employed as material primarily a mixture of solutions of corresponding riietlliqucs soils and to obtain , ù312.nges caatlytiqucs according to the present invention or mer-jngcs of their rudiments by precipitation, -. tion simultwnéo. pf'.r example, we can mix in suitable proportions ;;> bl-5s solutions of sulphates, halogens, nitrates or FèC8tr: t ..: s do "for, do l1lf" \ ngr> .nèsc, de zinc or copper are t, -. ni 'that rudi: i.: all of the component hydrogenating friblcmcnt (,) rv-1-ecd, .s solutions of the rudiments of the component fortem:

  nt hydrognnt (b), for example with solutions of nickel or cobalt salts or thionic salts

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 or halides of the metals of (b), or with
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 solutions to:, the 'u'-ionic salts or alkali metals of the balances derived from the salts of component (b), such as, for example, chromic acid or molybdic acid, and you can precipitate the desired rii6l - neuc.

   Likewise, it is possible to dissolve in a suitable solvent mixtures of basic ingredients (r.) And (b) in the proportions prohibited according to the present invention and precipitate, then by means of a suitable precipitant, , for example, ammonium carbonate, ammonium sulfate, hydrogen sulfide, oxliquo acid or soils of oxaliquo acid.



  If necessary lo precipitate mixto r. Thus obtained sore: onsuitc trr.ns-
 EMI7.2
 formed an art <; lyscar SLÜVI'.nt 1. presented invontion pC.r a treatment conv:? ^^ blc, by oxompic pnr sulphuration. D "Other metals or metal compounds can be added in suitable proportions before, laying down or after ootto trrns- formation:

     
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 A good catalyst is obtained by oxidation by mixing a solution of ferrous sulphate with a proportion
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 A suitable amount of ammonium thio-molybdate dissolved in an amount of a solution of tpmr-aonium sulfide sufficient to precipitate the boron, in which case a precipitate of a mixture of iron sulfide and iron thio-molybdate will be obtained.



  One can, if there is, place sulfurcr oomplémontaircmont os precipitate.



     In an analogous manner, one can add to a solution of chloride forriquo a solution of tungstato
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 d '(, i'.1 [.10n1 µm in an excess of ammonia which should be sufficient for the precipitation of iron, We thus obtain a mixture of boron hydroxide and iron tungstate which we will transform

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 EMI8.1
 we have a mixture of sulphides p;, r trr i tC.:l..:nt gu into a.) sulphide solution of r '' '. 1Uoniur.1 or rU medium of hydrogen sulphide back high tot1per '"' turs.
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  Catalysts according to lr-. present invention can
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 will also be obtained by not adding ".nt sulfur ;, d'r.r.noniur..l to solutions r: rfcrv .. ^. nt of a soil loan of iron, zinc , do manemnese or copper ot cutr-3 ready for nickel or cohnlt soils in suitable proportions.



  Another way to prepare catalysts 1: 1ixtQs follows 10. The present invention is to include in the prescribed proportions a 61nngc of sulfides L.1 and Ql- leagues which are strongly hydrogenated. 'n.ts ct nppart # nrnt CU group comprising the constituent (b), r.1élrng.: .. that we r.ur. obtained is sulphurized in conun los metals or conpositions ri6, t, lliquos cor- rospondr, nts, with a sulphide; 1é t ".llique ¯pp.rtcn ^ .nt ru group comprising () l1r.nt lo constituent (".) . A cr.tr.lyseur thus prepared
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 often has a stronger ;: activity than a product obtained
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 on,: lëlrng (f ".nt sii: = pli: -1 :: t les; il, :: s catalyst constituents in 3a.-os proportions.



  A further feature of the invention is to provide highly active catalysts according to the present invention to provide a sulfide born in t .ll iq u:;; = pp == rtznr, nf t <'. u group couprc- rlnnt lo constituent f1 "iblc ::,. mt hidroe, 6nri-it (,, .. ,,) <" U nuen of a solution of a proportion cOl1v ..; nr.blo of the strong constituent '..icnt hydrogénrnt (b) or a rudiment thereof.



  Such ctlysurs can be obtained from the sulfides of iron, zinc, 'ar'.ngr.nèse or copper, or back:' 1'31f'j'l ± .; :, s containing them, nu :: loyn of solutions d :, proportions cOlNcn1 "bl: s of constituent (b) or of sos rudiments, pc.r c.:.., aplo of thionic salts or hrÙogÓi1Ures

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 of metals of group 6 of the periodic system, or salts
 EMI9.1
 Dl:

  Aliquos or alkali metals in acids or thio- a.oidos derived from these substances, or by means of solutions of compounds of nickel or cobalt, for example their halides, nitrates, acetates and sulphates. This impregnation '
 EMI9.2
 can be carried out on inriorgornt the sulphides of the constituent (a) in ln solution of constituent (b) or do rudinonts do 00 last or one 'Pspcrgc, -int We then dry the have (1.lys'Jur ot s 'it is necessary to sulphide it or trnitf'.nt by means of a gaseous or volatile cor? .pos6 of sulfur or by means of vapor of sulfur at hi', ut0 ter.ipérc'.turo ot under high preference.

   It may also be desirable to provide the constituent (a) of the oor. The neoossary planont to constitute (b) it being noted in pr6soliec with an oolloldnlo solution of the constituent (b) from which the latter will be absorbed. -
On the other hand, it is possible to put the component (a) in the presence of a true solution of the component (b) from which the latter then precipitates on this one or in which one fora pass 10 component. (b) in the state of colloidal solution in which it will be adsorbed by component (a).



   The above-mentioned processes for preparing a common
 EMI9.3
 dosages of catalysts which can also be used to prepare other catalysts containing dosages oonstituents
 EMI9.4
 weakly hydrogenating it is mixed with a lower proportion of strongly hydrogenating constituents.



   Mixed catalysts according to the present invention can also be obtained by common or crystallization.
 EMI9.5
 00; *. R! Lo GX08plcs do chemical compounds of the constituent

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 (a) with component (b) likely to be used
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 dircctoacnt Cü :: lï.10 c? tr, li; so <#rs following ^ .¯a the present invonticn we can mention the soils resulting from metals (a) and thio-acids of metals (b), for example iron thio-tungstate, zinc thio-molybdate, which can be considered to be compounds of the sulfides of the respective metals.

   However, and as already stated, these thionic salts usually contain too little component (a) for the purposes of the present invention, and therefore adequate amounts of component (a) must be thoroughly incorporated.



   Typical examples of good catalytic converter mixtures for use in this invention include:

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 Parties Oonsti killing (EL) Parties 0ons ti'taafit (b)
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<tb> 99 <SEP> Ferrous <SEP> <SEP> 1 <SEP> bisulfide <SEP> of <SEP> tungsten
<tb>
 
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 90 "If 'r 10" If "il 80 If" "20" If "n 75 f9 19 25 n tt t, 55 Il' '" 45 n rr tir 85 Il "15 nn molylidèno 75" If tt a5 "If" 55 If "fi 45,

  1 tut fi
 EMI11.4
 
<tb> 85 <SEP> "<SEP> 15 <SEP> mixture <SEP> do <SEP> sulphide <SEP> nicke-
<tb>
<tb>
<tb> both <SEP> and <SEP> do <SEP> bisulfide <SEP> of
<tb>
<tb>
<tb> tungsten
<tb>
 
 EMI11.5
 85 manganese 15 molybdenum bisuifuroe
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<tb> 85 <SEP> "<SEP>" <SEP> 15 <SEP> "<SEP>" <SEP> tungsten
<tb>
 
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 75 fui tt 25 rr n il 70 "" 00 "molybdenum 70 Sulfur do zinc;

  0 'r "tungsten 70 if" If .30 tut molybdenum 60 fui Il 40 n tungsten 60 ty Il 40' t "molybdenum
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<tb> 80 <SEP> Ferrous <SEP> sulphide <SEP> 20 <SEP> cobaltoux <SEP> sulphide
<tb>
<tb> 80 <SEP> "<SEP>" <SEP> 20 <SEP> "<SEP> nickelous
<tb>
<tb> 75 <SEP> "<SEP> 25 <SEP>" <SEP> of <SEP> rhenium
<tb>
 
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 95 Il If 5 If "Il If
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<tb> 55 <SEP> to <SEP> 75 <SEP> "<SEP> 45 <SEP> to <SEP> 25 <SEP>" <SEP> "<SEP> vanadium <SEP>
<tb>
<tb> 60 <SEP> phosphatos <SEP> de. <SEP> copper <SEP> 40 <SEP> bisulfide <SEP> of <SEP> molybdenum
<tb>
<tb>
<tb> and <SEP> do <SEP> zino <SEP> on <SEP> pro
<tb>
<tb> port, <SEP> equimol.
<tb>
<tb>
<tb>
<tb>



  60 <SEP> -d - <SEP> 40 <SEP> "<SEP> tungsten
<tb>
<tb>
<tb>
<tb> 70 <SEP> phosphate <SEP> of <SEP> iron <SEP> 30 <SEP> molybdate <SEP> of ammonium
<tb>
<tb>
<tb> 60 <SEP> n <SEP> "<SEP>" <SEP> 40 <SEP> "<SEP>"
<tb>
<tb>
<tb>
<tb>
<tb> 90 <SEP> sulfuro <SEP> ferrous <SEP> 10 <SEP> acid <SEP> molybdic
<tb>
 
 EMI11.11
 70 "30 tungstic shot
 EMI11.12
 
<tb> 80 <SEP> "<SEP>" <SEP> 20 <SEP> pho <SEP> spho-molybda <SEP> to <SEP>
<tb>
ammonium <tb>
<tb>
 

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 A sulphurized alloy of 22.7 parts of tungsten + 0.5 part of molybdenum + 1.1 part of nickel + 1.4 part of vanadium + black powder; A sulphide alloy of 6 to 7 parts of chromo + 0.5 part of molybdenum + the remainder of iron.



   Those catalysts which are formed entirely or substantially from a mixture of components (a) and (b) in the proportions indicated (concentrated catalyst) will often be employed. However, it is sometimes advantageous to use cos catalysts deposited on porous supports with a fictitious surface or mixed with them (diluted catalysts), such as activated carbon, bleaching earth such as that which is known under the name of "Terrana". , fuller's earth, Florida earth or diatomaceous earth. These supports will advantageously be activated by appropriate prior treatments.

   The coals which have undergone a preliminary treatment are the supports of choice in the process according to the present invention, in particular those which will have been activated by treatment by means of water vapor, for example the small coko do lignite treated by means of steam. sulfuric acid and water vapor. Siliceous supports such as bleaching earths will advantageously be activated by treatment with fluorinated hydrogen or fluorine.



   It is sometimes advantageous to treat the supports, before or after having deposited the cetalytic substance thereon, by means of other acids, for example hydrochloric acid, nitric acid, phosphoric acid, boric acid, etc. . or by means of gas retort the hydrogen, lcs volntils sulfur compounds free of oxygen, los halogens, los oxides of carbon, hydrogen phosphorus, otc., advantageeusc-

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 at high temperatures and, if necessary, under pressure.



   The catalyst can be deposited on the support by precipitation or adsorption from a collodal solution prepared or not prepared in situ, or by impregnation by means of a solution with subsequent desiccation, or by other methods. Los components due constituents (a) ot (b) or their rudiments can be deposited on the support simultaneously or successively. A chemical transformation such as sulfurization can then be carried out, if necessary.



   As examples of dilute catalysts according to the present invention there may be mentioned: 80 parts of activated carbon + 12 parts of forroux sulfide + 8 parts of tungsten disulfide; 80 parts of bleaching earth + 16 parts of ferrous sulphide + 4 parts of chromic acid.



   In addition to the specified proportions of components (a) and (b) the catalyst may also contain other components. As they may be employed, they are mixed with other catalysts, for example metals or metal compounds.



   If the catalyst contains, in addition to the specified components (a) and (b), supports or other components (or both), it is desirable that the sum of the weight of components (a) and (b) not be less than the total weight of the catalyst * For example, if supporting substances are used, the catalyst will usually contain proportions of between 20 and 90% by weight in particular between 40 and 85%, for example 50 to 80%.

   In catalysts employed according to the present invention which contain

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 EMI14.1
 not only the constituents (r \) and (b) but also other compounds, nts or carrier substances, If. proportion of the constituent (b) no devrc. not, preferably, Atrc less than 0.5 d by weight of the whole cc.tr.lyscur.



  In combination or cn mslango r.vcc said mixture of constituents z) ot (b) and, according to these, convonblos proportions chosen according to the results to be obtained, it is possible to use metalloids cornui, lc sulfur or halogens such as iodine :, bromine or chlorine, or their compounds except hydrogen, nimonir.c'ue or carbon.



  Following are the requirements of the process in which it is used; of.tr.lyseur can be either placed in the donor in the reaction space or else finjEunt dispersed among the materials to be treated, either nvrnt, or p.'ndr'.nt, or c.near 1, ur chc.uffngo Pre ^ .lr: blc scit still during the course of 1 "rér.olion. The proportions of dispersed ctn1ysur cciployés vary according to the needs and can rise for example up to 0 or weight to be included. po, r oX \ 3r, lpl ::. between 1 and 10% by weight.



  Catalysts placed in a permanent position can be
 EMI14.2
 ployor in the form of pieces of irregular or useful shape
 EMI14.3
 ment in the form of shaped snlidos * Clust r. as well as these '
 EMI14.4
 catalysts can be used in the form of small cubes,
 EMI14.5
 cylinders, pills, 2, tanofill, stars, prisms, grids, balls, Incrymic solids, etc. These farms can be obtained by oxomple n ^ .r moulr'.go under pressure. These catalysts may be placed irregularly, or evenly arranged in the reaction vessel, where they are supported by any supporting truiis or devices. Backs on IF v. Coarse ins or fine ins can be supported

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 EMI15.1
 by do In, netr.llique canvas, grids, ote.



  Los mixed catalysts according to the present invention can F ^ .. or.:it be employed in the form of true or collold-.1 solutions, Ds dr-ns los said thoruiguos treatments and if there are liou dos Dti0ros raw orbonéGs solidos can be impregnated.



  One, the most striking features of these octetnlysours when used in the procedures following the grim invasion is high. dogrs to which they resist to a port of activity when dos carbonaceous c <'ntin; rit or fprmc.nt dos asphaltic cu resinous substances Are treated th.JrD1iquomont cru moyon hydrogen or souaises in a cracker *
Another advantage of the catalysts according to the present invention is that, insofar as they are employed in heat treatments for the production of gasolines, the latter possess high octane numbers. In fact, in numerous treatments, these catalysts possess a specific activity which results in the formation of aromatic hydro-trees or in the maintenance of the aromatic character of the raw materials.



   Apart from that, the mixed catalysts of the present invention are usually less expensive than catalysts formed solely of component (b). Moreover, the component (a) which is found in a predominant proportion in the catalyst according to the present invention is in many countries easier to obtain than the component (b), and the fact that while achieving this economy one can obtain results as good or better than when operating
 EMI15.2
 re by means of an otclyseur formed only from the constituent

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 (b) is both surprising and welcome.



   In at least one of the above-mentioned ratios and usually in others also the catalysts according to the present invention are better than catalysts composed of one component (a) or (b) or of mixtures of these components in proportions. other than those specified here.



   Examples of treatments coming within the scope of the present invention will now be described in more detail.



   The heat treatments specified herein are ordinarily offered at temperatures within the range of 180 to 700 C., for example 250 to 650 C., more particularly 300 to 600 C., and the Most of these treatments are carried out at temperatures between
400 ot 500 0.



   For each particular heat treatment, the appropriate prossions will be used. better for that. Thus, depending on requirements, atmospheric pressure or high pressures, for example do 20, can be used,
50, 300, 500, 800, 1000 etm. or more. In exceptional cases where it is advantageous to operate under reduced pressure, proceed. so.



   The heat treatments according to the present invention in which particularly remarkable advantages are obtained are those which are carried out with the addition of hydrogen or of gas containing a. sufficient proportion of free hydrogen ,.



   Cos heat treatments in the presence of hydrogen or gas or containing gas are usually carried out at temperatures.

 <Desc / Clms Page number 17>

 
 EMI17.1
 raturas included cntr .: w50 and 650 C. ct cn generally between 580 ct 550 0. The pressures employed are usually l ::. n., z sUy0ri, 'urvs at 20 atm. and generally, preferably, greater than 50 1 "t ,,. For oc-rt'ines revotions, oopondi nt, one p. '; ut use atmospheric pressure or legal prossions. 5, c:; ùi; iit suprr .normr.l :: 8, pcr example of pressures of 10 r, t #; 1. However, in general, pressures of about 100, 200, 300, 500, 700 (tl11. and some or.s ntiuc z0 r: tm.



  The. proportion of hydrogen maintained at the ospp.oo do r: ^ cticn ot the parts subjected to high temperatures and rr'.ttr.ohr'.nt if there is vr.rio in an lc .rbc measure s> iiv-; it 1i. '. nr.turo of raw materials processed or following 1 res, ùt, t continued. It is possible to use an generr. 1 ct pnr ton of the treated carbonaceous third 500, 600, 1000, 2000 m3 or more of hydrogen measured under the normal conditions of temperature temperature of pressure. Ln minimum proportion per tonne of 'mr'.tière ca: rbo; zêc tight of about 100 m3 of hydrogen and in good quantity of gold.S we can'. implement dos quantities up to about 300E, 4000 , 6000 or 8000 m or more, the optimum general conditions to be employed in each particular case are well known to technicians.



  It can be -vcnt-.goux to operate by introducing Si'.21S interruption of 1 ('. Biftièrc cr.r'oonéo new in the container):' lt of reaction and or: we withdraw without intorruption back products. If necessary, one can use several reaction vessels in which it is possible, if necessary, to apply different conditions of temperature or of prossion (or of one… and the other) and in which can be successfully used dos differci-ts catalysts. Sufficient reaction products \

 <Desc / Clms Page number 18>

 
 EMI18.1
 The threeforms can be removed in n.% - r, 1 from any of the reaction vessels.

   Q, ur.nt m? X subjects which will have L1SJ.ffi s..Ell1:; nt r'jr'gi, we can restore them c.u cycl :; or treat them dr.ns a new one, r ± c1) 1: have de. reaction; For example, substances whose boiling point is higher than that of gasoline can be restored to the cycle by the destructive hydrogenation of the medium oil.



  The g ('. Z hyrdrojgéri = rits to use' cli "'. Ns 1'". Reaction pcuve-nt trc constituted, 91 ".1 'cie hydrogen alone or pnr tnelanscs in C0.0. T., ; nn.nt,}> ('. 1' example a mixture of hydroGene. and 'G.ZOtQ, or g-vz at, l'. ^. u or hydrogen l '; le1r :: ::. gé? .VIC of the anhydride c ^ .rbo: zic; Lto, of hydro'3no sulphide, of l ,. er¯u vapor or of ::. 1eth:), - c or r.utrc.s hydrocr.rburc: s in oonvenrblos or cor: li, iodos. The gases will be., v, -it ... gcu- sursiont 0r.1plored in the fCrl.1é cycle and their composition may be adjusted as needed.



  Los tr.Liz d ': ". 1 Ll .., ¯lt tion eaployed will be J.1:". BitucllG- (slow between 0.2 and 1.5 kéj, p' - '. R liter of space of rec, ction et orr hour, 5: ¯ ^ is one can; .ussi "; l: lplo7 :: r other t.7, ux dtli?: L; it.tioil following the cs.



  Vr, l: '- gcs cO.1siâ.Órr'blos are obtained according to the present invention of;': 18 l'lljdro,; ':; nr-tio: 1 destructive d # ratières c; .rbol1 ': ;;:; S cc: .u ..: ..: irà- it is species of anthrax, y coripris s 1r. coal and lignite, 6. '\. ltrvs'' .tieres c, .rbo :: 10 ':; S solids CO! îl.1G 1.-'. peat, oil & shale and timber,: 11 ': i8 plus pt..rtict.tliër :::: t dr.ns hrdroG-5I1r: destructive tion of' jl [\ tiàr,:. 8 c: " .1'bcJIlvcs liquids or fuses 00 :: 1 :: 1;:; oils: 'ii- n01': ', l.::s, tars. And distillatic products: J, from tr ^ z: sforw .. tio; i:, t dl ..; xtr-ction d ;. such Litter cr.rbOn0GS solid, liquid or fusible.

   One can resort to a tjllc

 <Desc / Clms Page number 19>

 
 EMI19.1
 destructive hydrogenation to produce hydrocarbons from
 EMI19.2
 all kinds such as ,. fuels and in particular r.ntid0tonrte fuels, solvents nfphtes, r.ioy.n! lcs oils, 1 petroleum lr.::ip:-.t, diesel oils, o0! bustiblcs oils and lubricating oils , and where appropriate by-products OO'1'.1Ç phenols.



  A; another operation to which the projsa = 1t :; Applicable invention is the oraquago, by ixoiiple the orr'.quc.go of oils, :: oy = nn ;; s, dis gr.s oils or dos oils louros. The s ".t <; lysùrs can be fincnent to be spcrsàs in the.!: M.tièrc praraèrc, CO: .1 ':. LC they can be placed in the enclosure of oroÇ {ur8c. Atro gases can be introduced. , for example coizùi heating fluids or OOl: 1llO agents' protectors.



  This is how we can reintroduce residual cz of orc.quago, or add natural gr.z heated to high,: n: 1pro.- ture, or gr,:; residual of rr.i'i'1nF'.go, or of In vr.pcur d 'or.u'.



  The addition of small quantities of hydrogen is 0géowent t.vr,: 1tr'.gouso. The pressures employed may be too much or less or of the order of 20, 50, 70, 100 o.tn. or more.



  The present invention is particularly suitable for 1.?. production of increased hydrocarbons, xts pnr trr; it-ù- act thermal, in particular naked hydrogen, by ôxoùiììp1S for the hydrcnr; tior destructive or 10 craqurgc of natiëres of'.rbo: 1é;:; sr: , nf ;; rcnt td asphalt, such as products from the pressurized extraction of coal or turbo, as well as tars, crude oils based on asphalt, zt cussi (Ls rich residues are asphalts pro- coming from a cracking or from a hydrogenation under pressure To this day, dr'ns the trdtor.1ont thoroiquo of asphalt or substances containing more than 5%, cffc.ctu6 i:; Jnc
 EMI19.3
 

 <Desc / Clms Page number 20>

 
 EMI20.1
 hydrogen is present, ot especially when op0rr.it 1'.U uoycn do cr-tC ', lys, -, urs 6.i SP "' JS0S 1 d.:ui:Llr .:

   d ^ nS 1 t,: mcointo due rosaotian, it so produced freqiàim # cnt dos disturbances, by oxouplc. deposits on the c, .trlysGur, or back,) l1, g,) rgononts in the recipiont fli r, -, cticr¯ cu the tubes, if. although in such cases it was f ", rt difficult to 'continuously offccting 10 trni t'Jt10nt thort1i que do these:.' ii ', tièrcs ready: lièr.s. L', 5;: iplci des ont ,,,. lysours uixtos followed 1 pr6sont.3 invGnti ::! 1 pcr ... at dtcp 'ror s ^ 11s diffioult0 do f çan continues. Let us create such mc; tièr3s prec'Lièrcs .sih. ^, Ltic; uos and when they are treated = ru mycn of hydrogen eu do on C.nt.Ilt.; nt en. ". ïiplC7.Gr ^ rvn ,, i- tr.gouscl: lont dos prossi 1s -ÙD plus do 2Ù9 at: n. , pfll IXJ.Jp1C from 400 to 800 atn., amounting to r, 1x need up to 1000 r'.t'LL. or more.



  Dr.ns da such trnit-lDnts en nploicr. "Do prÓf0r ::; nc0 dos ti <i- p = 3r <, tLtrns greater than 430 C., one in particular ccnpriscs on- trc 450 ot 550 C., pr, r cxi;.; p1o3 do 475 to 500 C., trndis that in use do prefer # zca a rate: l 'rliïl (mtr, tiol1 11o = vE r. in order to avoid a d6dublcn.; nt in tr, bloi. These therapeutic. Rii ".. tièrcs pronièrcs Cl1tnnt fio l'rsphr: .ltc will preferably be heated in stages.

   If the steps are multiple there may be some success in employing specific GTs and conditions such as those in the first step of the heat treatment on obtains a product containing approximately 35 &60; oily hydrochloride boiling at temperatures below 325 ° C. next 1. li nsphnlte content. mr.tière pr8ü1ièrej 1:,. trr.nsformntion complémenkiro can be carried out r.lors in -rastitLl ": 1t ;; ià c5? clc the substances boiling at nux tempêr ^ tur'3s higher than 025oc; or one Iss trd t'nt drns one or more str .pos operating newollas. For c, -. 1 ('. we can use d3s tm: llx, rturos ot pressures 1 -

 <Desc / Clms Page number 21>

 increasing.

   Mixtures of catalysts particularly suitable for the heat treatment of prominent materials rich in asphalts or giving rise to asphalt are those in which both component (a) which is more weakly hydrogenating and component (b) which is more strongly hydrogenating are a sulfide or a thionic salt of said metals, or in which component (a) consists of one or more metal sulfides while component (b) is present in the form of one or more metal oxides.

   When treating asphalt-containing raw materials the activity of these catalysts is not deteriorated, or only to a very small extent, by the high molecular weight asphalt or resinous substances; on the other hand, gas formation in the presence of catalysts is very low and the yield of interesting products comprising fuels stable to detonation at high cn content. volatile aromatic hydrocarbons is therefore elovated.



  When treating by heat with hydrogen or when cracking very rich raw materials, asphalt, the proportion of component (b) strongly hydrogenating must not be less than 10 parts per 90 parts per weight of component (a) weakly hydrogenating.



   When volatile substances are produced from coal extraction products by dosing hydrogenation using catalysts according to the present invention, part of the products which escape otherwise than vapor from the chamber. reaction can be added to a fresh feed of raw material to be treated, and from the remainder a good fuel oil can be obtained or the solid constituents are removed. Qunnt to those of the constituents of

 <Desc / Clms Page number 22>

 products which escape in the vapor state and whose boiling point is higher than that of gasoline, they are preferably added to the fuel oil.



   The present invention is particularly advantageous for the production of non-detonating or anti-detonating fuels or of mixtures of hydrocarbons rich in aromatic hydrocarbons by heat treatment of carbonaceous materials.



     Thus, particularly good results are obtained in the presence of said catalysts when they are employed in the destructive flavoring hydrogenation of oily hydrocarbons, for example medium oils or detonating species; likewise, in the production of non-detonating fuels by reforming, the catalysts of the present invention find an interesting field of application.



     The valuable properties of the catalysts employed according to the present invention are also manifested when they are employed in dehydrogenation treatments.



  As raw materials for dehydrogenation, gasolines or their fractions will be considered in the first place, but also less volatile fractions of mineral oils, tars or the products of exhaustion under pressure or of the destructive hydrogenation of coal, like pc.r for example moyonnos oils or heavy oils, etc.

   Said catalysts, in particular mixtures of sulfuras in the desired proportions, will also be used advantageously in the dehydrogenation of armoatic hydrocarbons, for example hydro-toluenos, hydro-naphthalenes or higher hydrogenated cyclic compounds. as we can

 <Desc / Clms Page number 23>

 obtained by hydrogenating under suitable conditions the coals or gourons, in particular the coal.



   This dehydrogenation can be carried out in the. liquid or gas phase at temperatures of 200 to 700 C., if necessary there is the presence of un vapor or gas such as nitrogen, anhydride, carbon dioxide, but above all in the presence of hydrogen. This is carried out under normal or subordinate pressure, but preferably under high pressure, for example 20, 50, 200 atm. or more. In this reaction the catalyst is either permanently placed in the reaction chamber or added in a finely divided state to the raw material.



   Another particularly advantageous application of the present invention is the production of aromatic hydrocarbons or of mixtures of hydrocarbons rich in aromatic hydrocarbons by treating carbonaceous materials at elevated temperatures by desclcylation or by isomerization, preferably in the presence of carbonaceous materials. 'extra hydrogen (hydroformation). In such isomerizations, straight chain hydrocarbons can be converted to branched-chain hydrocarbons. As to the dealkylation, it will be carried out in a manner analogous to the dehydrogenation described above and is manifested by the elimination of side chains of the higher homologs of benzene or of polynuclear compounds.

   Said catalysts can also be used to release the radicals placed at the end, or in its vicinity, dos molecules of hydrocarbons with a long open chain, in which case it will also be advantageous to operate with additional hydrogen. For these dealkylations and isomerizations, the components of the constituent (b) will be metal oxides before gousting.

 <Desc / Clms Page number 24>

 
 EMI24.1
 



  Many of these recelions often take place side by side with e8to, It slast revealed particularly 1, vr, nt ... joL1x d'om-
 EMI24.2
 ployor, as raw materials for the. hydro production
 EMI24.3
 volatile aromatic carbides or non-detonating gasolines according to the present invention, the constituents poor in hydrogen obtained by segregation of a mixture of rich constituents or hydrogen ot of constituents poor in hydrogen r, u by means of selective solvents, COE1 : "Sulfurous nihy arid, l '. ^, Nilino, nor: ni.lc hydrocarbons; aint gr.zeux to liquefied etr, and mr.ints r.utrs.



  Lc, present invention is é-x; 1é-iiiznt useful for rW.ctions such as 1 <n trw.nsformft7.a11 of cresol on phenol r.L1 medium do gF'.z h5drogsnc.nts, in which case 1 ;; rér.cticn 'principal;.: 10 sc unrolls confOrmaii10nt ..U type d: -, reccctio: 1 following: OH3-06114-0H + H2 = C6H50H + OH4.



  An I: '. Utrc application w.nt'ouso dz In introduces ost le. reduction of phenols to hydroc: rburcs ^ roma.-
 EMI24.4
 corresponding tiquos.
 EMI24.5
 



  In order to reduce the oxhydril groups of phenols, the raw materials are fried, pr: r 'Y.,: Lj,) l of the crude cresol or dos fractions of Tar rnfcrm (t of phenol, on said catalysts, in particular sulphides, preferably in the vapor, there is only hydrogen under a pressure of 20 mps. vs. tm. or more, preferably from 100 to 200 r.tm. or more, at Ó.82 tor.l'pr.-t'rcs do .350 to 50000. or 'sometimes higher, ordin ^ .ir,:; ucr ¯t from 400 to 475 C. We obtain do this Bin.nière neutral oils which contain 70 to 90% of hydrocarbons ..rot: lr; 'iqu,:, S such q llt ... benzene or lc toluene.



  In a way Mi '-. Lcue end can obtain hydr <, c ..; rbL1rcs from coniposés crg'niQu; s sulfur, 1' = z <#tl or dos

 <Desc / Clms Page number 25>

   halogens.



   In the course of one and the same operation, it is possible to take advantage of the different specific properties of a concentrated catalyst employed according to the present invention and of a mixed catalyst composed in the proportions indicated and deposited on a support by splitting the materials. first in the presence of said mixtures of catalysts deposited on supports and by carrying out, before or after this splitting, a heat treatment, either of the raw materials or of the products as the case may be, in the presence of said mixtures of catalysts without. supports.

   The advantages of the operation comprising the use of supports, that is to say the achievement of a massive doubling of volatile substances, are thus combined with those which provide an operation carried out without supports, which residing in a virtually complete elimination of phenols.



   The products formed in the doubling step of said multi-stage process can, before additional heavy treatment, be freed from hydrocarbons boiling in the gasoline zone. When the treatment is absent of supports ost the second stage of the process, it is advantageous, before treating them additionally, not to eliminate products of the first and according to the bosoins that the constituents boiling at temperatures below 160 or 180 C., in order to achieve a reduction of all phenols present in light oils boiling above the indicated temperatures.



   The oils not converted to gasoline in the second stage can be reintroduced in a more consistent manner, ie either in the first or in the second stage. It is generally more advantageous

 <Desc / Clms Page number 26>

 to carry out the reintroduction in the stage where one operates by using supports, because the oils to be returned to the cycle are already free of phenol and are more strongly doubled in said stage. The two catalyst spaces can, if desired, be permanently placed one after the other in the same reaction vessel.

   The doubling will take place in both stages preferably in the presence of hydrogen, advantageously under high pressure, for example at 20, 50, 300 atm. or higher, and at temperatures between about 350 and 600 C., particularly between 400 and 550 C. The pressure, temperature and feed rate may be the same or different in gentle stages.



   It is often preferable to subject the raw material, before its treatment according to the present invention, that is to say before the first step referred to in the previous paragraph, to a preliminary hydrogenation in the pre-phase of a process. strongly hydrogenating catalyst, except tungsten disulphide alone, for example to remove diolefins, asphalts or the like. For cola, a smaller reaction vessel is advantageously employed than in subsequent main reactions. In the preliminary hydrogenation the temperature will usually be kept cooler, for example in the region between about 200 and 350 C.



   In this way, a high yield is obtained by squeezing rich aromatic hydrocarbons such as benzene, toluene, ethyl bonzene, xylene and the higher homologs. These can be isolated from the mixture, usefully after having enriched by fractional distillation :, au A

 <Desc / Clms Page number 27>

 by means of selective solvents or by azeotropic distillation.



  With a view to segregating the selective solvents, liquefied gaseous hydrocarbons can be added under normal conditions, such as, for example, ethane or propane, or the aromatic hydrocarbons can first be extracted by means of. do selective solvents ot then treat the solutior: using liquefied hydrocarbons in order to perfect it. rectification. the present invention is also very useful for refining impure liquid or fusible hydrocarbons with hydrogen.

   Such refining can consist in transforming by hydrogenation the constituents capable of forming "gums" or of its resin or comprise a complete transformation. These operations are often referred to as "refining hydrogenation".



   Such a refining hydrogenation is usually carried out at temperatures between 300 and 500 ° C. and often under a high pressure of hydrogen, under conditions such that no appreciable splitting occurs. .



     As raw materials for the refining hydrogenation, crude lubricating oils or fractions containing or other mixtures containing oxygenated, nitrated or sulphurous compounds or unsaturated compounds having the tendency to polymerize to form a substance can be used. resins, such as crude gasoline, for example cracking gasoline or gasoline obtained by carbonization at low temperature, as well as crude benzol, mineral oils, tar and medium oils or the heavy oils which are drawn, then the crude paraffin wax, the lignite wax n

 <Desc / Clms Page number 28>

 brute,

   used lubricating oil, crude naphthalene and other crude or impure polycyclic hydrocarbons. The raw materials should generally be free of asphalt or contain little; in principle, they should not contain more than 5%.



   In the refining hydrogenation according to the present invention, the raw materials are passed along with hydrogen, usually under a pressure greater than 50 atm., For example 150 to 600 atm. or more, for example 1000 atm., at a temperature for example 300 to 450 ° C., on the catalyst according to the present invention, the conditions ot in particular the feed rates then being adjusted so that it is not There is practically no duplication of the molecule or it does not occur insensibly.



  In some cases, for example in the refining hydrogenation of crude benzol, relatively low pressures, for example of the order of 40 atm, can be employed. However, in some cases the boiling curve of the product compared to that of the raw material can be lowered, for example if phenols are present or as impurities, because these are reduced to the corresponding aromatic hydrocarbons. .

   When refining relatively high boiling products such as lubricating oils and the like, it is generally not possible to avoid slight doubling. However, care must be taken that. the reaction conditions are chosen so that the formation of silvery products is less than 20%, in particular that of products boiling at temperatures below 325 C.



   For refining hydrogenation the catalyst is usually contained in the ground in the reaction vessel.

 <Desc / Clms Page number 29>

 



  It can, however, be added to the finely divided art and in high concentrations, for example in proportions greater than 5% by weight of the raw material.



   When using raw materials with a high boiling point or with a high content of asphalt, it is sometimes advisable to add thinners such as hydrogenated polynuclear compounds, for example tetra- or decahydro-naphthalene, medium tar huilos, ctoo
The refining hydrogenation by means of catalysts according to the present invention can be employed in a particularly advantageous manner as a preliminary treatment prior to an alteration or a destructive hydrogenation, for example by means of catalysts according to the. present invention or other catalysts,

   For example, the tungsten disulphide deposited on the "Terrana", because the roundness is thus increased, the liquid products obtained in the transformation itself, the quantity of gaseous products formed is reduced and the contamination of the gas is avoided. catalyst. Thus, gasolines which have previously been treated by refining hydrogenation or presumably catalysts according to the present invention are valuable raw materials for the so-called reforming treatment.

   that is, a treatment in which their octane number is improved by heating at high temperatures, or for flavoring destructive hydrogenation. Medium oils which have undergone a refining hydrogenation are suitable for transformation into gasoline and heavy oils which have been treated in the same way are of interest for the production of lubricating oils or for heavy transformation in medium oils or gasolines by stripping or by destructive hydrogenation, or both for said production ot 1 ± dito transformation.

 <Desc / Clms Page number 30>

 
 EMI30.1
 When dealing with medium oils that have undergone a.
 EMI30.2
 refining hydrogenation followed the pr3s ..: nt:

  .. invention, for example due to mo oils; = .: r.:ms obtained ..11UG8 by hydroGsl1 "tiol1 of coal, it turned out to be avf'ntr-geux at '= .n tr nsforner 55 to 40 1 on gasoline back tdupérr tur .sd 'iiviroii 420 to 440 C. and to split ;; vca òrùis, tion of 6EonCJ 108' reaction products boiling at do higher t:.; yérr, tur:; s than c.llc -ci, the operation "- stoffactunnt of nr; fr: .ca on pr6s: nc8 dr c. ''. t'.lysurs following the present invention deposited on dos supports.



  Lr. The present invention is Gg; 'l: Jm.) It is very useful for improving or producing: .. for hydroforming low-volume hydrocarbons as well as lubricating oils.



  The. present invention can be successfully employed dr.ns li tr: -, i thermal hydroc: .rburos riohos in hydrogen cie-
 EMI30.3
 lr, ngés back hydrocarbons or bituminous substances
 EMI30.4
 poor one hydrogen, for example d.-ns tr 11sforl ': l, tion d: o.rburr.nts detonants in inàétonants errbur-nts, for ex, [, lp10 of ossencos obtained in f, -is-nt blush back oxides of the carbon rivoc the hydrogen, lo ca 0oh6rl \ 'C under a pressure appreciably l1ormr.l,), in mlc.n; o n.voc small quantities of tars,
 EMI30.5
 extracts obtained under pressure, etc.
 EMI30.6
 



  Los ot ".tr.lys.:; Urs following the present invention can be used for the extraction under pressure of coal in the presence of hydrogen, usually in small proportions, or
 EMI30.7
 we are absent.
 EMI30.8
 



  These catalysts can be successfully used in the thermal tritonent of carbonated materials such as oily hydrocarbons by means of soft oily hydrocarbons, but oo propane, etc.
 EMI30.9
 



  These catalysts can also be used for

 <Desc / Clms Page number 31>

 produce interesting hydrocarbons from liquid, semi-solid or meltable distillable carbonaceous materials which contain asphaltic substances, in which case said raw materials, preferably those which have not undergone heat treatment at temperatures above 800 C., in particular the products of a destructive distillation of solid carbonaceous materials, will be treated in the liquid phase by means of hydrogenating gases in the presence of said oatalyzers in high concentration, with a feed rate of 0.2 to 1, 5 kg., Usefully 0.3 to 0.8 kg. per hour and per liter of reaction space, under a pressure of at least 50 atm.

   and at a temperature between 270 and 420 C., preferably less than 400 C., and especially when the operation is carried out in the presence of strongly hydrogenating catalysts during a substantial fraction of the treatment at temperatures not exceeding 380 C. , preferably between 300 and 380 0., these conditions then being coordinated so that the content of asphaltic substances, particularly of asphalts, is reduced by at least 90% in continuous operation, so that less is produced again. of 5% or, better, less than 2.5% of gaseous hydrocarbons calculated as carbon relative to the carbon of the raw material and less than 20% of products boiling at temperatures below 350 C.,

   after which the reaction conditions can be made more stringent.



   The following examples will better show how the present invention can be implemented, but it should be understood that the latter is not limited to said examples. The parts are by weight unless otherwise indicated.



   Example 1: Pass at a temperature of 495 C. the same tomps as hydrogen under a pressure of 250 atm.

 <Desc / Clms Page number 32>

 a medium oil boiling in the zone between 200 and 325 ° C., obtained by the destructive hydrogenation of coal, on a catalyst consisting of a lutine mixture of 90 parts of ferrous sulphide and 10 parts of tungsten disulphide. The feeding rate is 0.5 kg. per liter of reaction space and per hour.



   A product is thus obtained which contains, in addition to 40% gasoline, 60% dean oil. Return this to the reaction vessel. Gasoline is free from phenols and sulfur, has an octane number of 8 ± and is an excellent detonation stable fuel that can also be used to improve other gasolines. 12% toluene can be obtained from this gasoline by distillation.



   Example 2: To pass at a temperature of 500 C. in time that hydrogen under a pressure of 220 atm. an average oil obtained by the destructive hydrogenation of a lignite from central Allomagna over a catalyst consisting of an intimate mixture of 85% manganous sulfura and 15 parts of molybdenum bisulfide. The feed rate is 0.5 kg. per liter of catalytic space and per hour.



   The product thus obtained contains 50% gasoline having an octane number of 75 ot convcnant among others for los aviation engines with high compression ratio.



   Example 3: Firstly, pass crude heavy benzol, in order to refine it, at the same time as hydrogen under a prossion of. 200 atm. and at a temperature of 200 ° C. on pieces of agglomerated tungsten disulphide, then at a temperature of 490 ° C. on a catalyst consisting of an intimate mixture of 90 parts of ferrous sulphide and 10 parts of tungsten disulphide. L feeding rate

 <Desc / Clms Page number 33>

 is 0.75 kg. per liter of catalytic space ot per hour.



   A product is thus obtained containing 60% of constituents boiling at temperatures below 185 ° C. and containing 5% benzene, 15% toluene and 15% xylene. The remainder consists of less volatile aromatic hydrocarbons which are very suitable as solvents for varnishes and as anti-knock agents for gasolines.



   Example 4; Pass under a pressure of about 200 atm. and at a temperature of 500 ° C. together with hydrogen on a catalyst permanently placed in the reaction vessel and consisting of an intimate mixture of 85 parts of ferrous sulphide and 15 parts of molybdic acid a medium oil obtained by destructive hydrogenation of coal. A product is obtained comprising 37% gasoline, about half of which consists of aromatic hydrocarbons and whose octane number is dE) 86. The average oil which has not been transformed into gasoline will be reintroduced. in the reaction vessel.



     Example 5: Heat in a coil an average oil boiling at Tompéroturcs between 200 and 325 C. and obtained by destructive hydrogenation of the coal, hydrogenate it preliminarily in a stable container at high pressures at a Turkish temperature of 240 C. under a pressure do 250 atm. the presence of tungsten disulphide and the subjection to a destructive hydrogenation split in a reaction vessel whose internal volume is four times that of the first vessel stable at high pressures, the operation is carried out at a temperature about 502 C.

   under the same pressure as the glue used for the preliminary hydrogenation. For the second operation, we omploierr. a cataly-

 <Desc / Clms Page number 34>

 will be composed of 80 parts of the activated carbon which will have
 EMI34.1
 mcnti.ircm. ^, nt activated prr trnitered naked avg steam to a :, tOi1l1) err.ttu'o. of 800 0. and on which we rurr. deposited an intimate tnela.ngo of li parts of ferrous sulphide and d ,, 8 pnrti, as of bisulphur of tungsten. Li t <^. Ur, feed ast dc 0.5 kg. of medium oil pnr liter of space cn, t-, 1d-tiqaz and prr hour.



   We obtain a product composed of 60% gasoline
 EMI34.2
 (final boiling point: 200 C.) and 40 fl of medium oil. 8.5% benzene and 11.0% toluene can be isolated from this essence.



   Example 6: Intimately mix 85 parts of Forroux sulphide with 15 parts of tungsten disulphide and
 EMI34.3
 r.ggloraéror under pressure mixes it.ng8 in pills. By crimping pass over co-catalyst at a t ,, ripérrturc of 450 C. under a hydrogen pressure of 200 atm. the vrpours of a raw cresol taken from there. coal, a product containing 99% neutral oil is obtained. Gllo contains 66 ci of aromatic hydrocarbons, mainly toluene.

   Instead of the said stripper, it is also possible to use an intimate mixture of wood sulphide and of tungsten disulphide obtained by subjecting a mixture of 87 parts of metal oxide and 13 parts of tungsten disulphide to a treatment. medium of hydrogen sulfide at a
 EMI34.4
 tompérnturc do 40000, Lo t ^ .blca.u ci -. ^. near gives the results obtained by this way of operating, including those obtained under identical conditions elsewhere)
1) using tungsten disulphide alone,
2) by means of ferrous sulphide (FoS) alone and
 EMI34.5
 3j using a mixture of 85% tungsten disulphide and 15% forroux sulphide (FeS).

 <Desc / Clms Page number 35>

 
 EMI35.1
 



  Cc.tnlysour WS Fn8 85% do WS 2 15% dù WS a 15 de FcS 85% do'FoS Poura <-ntr.go 100 80 '.98 99
 EMI35.2
 
neutral oil <tb> <SEP>
<tb>
 
 EMI35.3
 TJn0Ur cn hydro- 3 27 5 66 carbides ar o nat 1 -
 EMI35.4
 
<tb> ques <SEP> do <SEP> l'huila
<tb>
<tb> noutre <SEP> (%)
<tb>
 This table highlights the specific action remar-
 EMI35.5
 Quablomunt powerful catalyst mixture following the advance in the formation of aromatic hydrocarbons.



  EXOMPIC 7: Thoroughly mix iron oxide with 1 μl of tungsten; metallic üt transform oC mixture into sulphides by prsa3r on it do. hydrogen sulphide at a tompératur of 39000. By using this catalyst in the treatment of a raw cresol obtained from coal and drns los m3!: under conditions ru3 according to oxo <npls 6 we obtain a product comprising 97 % neutral oil ronformrnt 50% hydro.- enrburas nromntigi-ics. If the ferrous sulphide obtained by sulphurizing the oxide is used without a tungsten junction, a product is obtained in which the neutral oil contains only 27% of aromatic hydrocarbons.
 EMI35.6
 



  Exomplo 8; Convert into fine turnings which are then treated with hydrogen sulphide at a temperature of 4530 °. A special steel containing 22.7% tungsten, 0.5%
 EMI35.7
 molybdenum, il, 1% nickel and lt4 vanadium. On the sulphide captalyscure thus obtained, pass hydrogen under a pressure of 900 atm, ot at a temperature of 50 C. in a minimum time quo, and crude xylenols obtained from a liquefaction product

 <Desc / Clms Page number 36>

 coal. The final product comprises 90% neutral oils containing 65% aromatic hydrocarbons.



     Example 9: Heating to a temperature of 490 C. a catalyst composed of 80 parts of ferrous sulphide and 20 parts of tungstic acid and permanently placed in a tube stable at high pressures. On this catalyst pass at the same time as hydrogen under a pressure of 250 atm. raw cresol vapors; a product is obtained comprising 95% neutral oil. This contains 60% aromatic hydrocarbons.



   Example 10: Preheat in a coil a medium oil boiling at temperatures between 200 and 325 C. obtained by destructive hydrogenation of coal, hydrogenate it preliminary at a temperature of 250 C. under a pressure of 260 atm. in the presence of tungsten disulphide and subject it to a destructive doubling hydrogenation in a reaction vessel whose volume is four times greater than that of the first vessel, the operation being carried out at a temperature of 502 C. and under the same pressure - sion quo glue used for preliminary hydrogenation.



  For this destructive hydrogenation, an intimate mixture of 80 parts of ferrous sulphide and 20 parts of tungsten disulphide will be carried out as a catalyst. The product thus obtained contains 30% gasoline (final boiling point: 200 C.). Remove this by distillation and subject the remaining oil to destructive hydrogenation in a second reaction vessel operating at a temperature of 505 ° C. and a pressure of 260 amt.

   For co-final treatment, a catalyst composed of 80 parts of activated carbon prepared by treating with a :; temperature-, 800 C. by means of va-

 <Desc / Clms Page number 37>

 
 EMI37.1
 First, water from the small lignite coke on which an intimate mixture of 12 parts of ferrous sulphide and 8 parts of molybdenum sulphide will have been deposited.



   The product obtained contains 56% gasoline (final boiling point: 200 C.). The untransformed medium oil will be reintroduced, in the second destructive hydrogenation stage.



     Mix the essences from the gentle stages ot
 EMI37.2
 the natural hydrocarbons are extracted from a mixture of sulfur dioxide and propylene at a temperature of -.80 C. Frnctionn ;; 1 'before distillation of the aromatic hydroonrburcs thus obtained; Thus, for 100 Dr-rti-s of osonc08 m01cngc, 8 pcrtics of bonzèn are collected, and 11 parts of toluene.



  Example; 11: OHotor predc, blom0nt dnns un coil a ,,} huil.J l1loy, nnc? Ao11i11.11't --ux tomp6r, -. Turkish between 300 ot 5 C. that llr; -. obtained by destructive hydrogenation from :; the. coal ot In subject to a preliminary hydrogenation dr; ns a container stnblo with high prossions in the presence of tungsten disulphide, at a tompérr., turo de; NJ5 C. and under a Prussian hydrogen 0 of 250 atm. Fniro ans140 pass the products to you in a second
 EMI37.3
 high pressures where one los trr.:itexa by hydrogen at a temperature of 505 C. and under a pressure of 250 atm.

   The second container contains a fixed gold.tr'3.ys'jur composed of 80 parts of an activated carbon prepared for motivation by means of steam.
 EMI37.4
 of water at a temperature of 800 0., 12 parts of ferrous sulphide and 8 parts of tungsten disulphide. Remove by distillation from the products obtained the constituents which boil.
 EMI37.5
 slow at temperatures below 1? OeG, and which are prnti-

 <Desc / Clms Page number 38>

   completely free from phenols.

   Submit the rest to a hydrogen
 EMI38.1
 destructive nation in a second str.pe in the presence of a CP.tr'.lyseur composed of an intimate ucl-nge of 80 parts of ferrous sulphide and 20 parts of tungsten disulphide, the ope- ration carried out at a temperature of 505 C. and under a
 EMI38.2
 hydrogen pressure of 250 ^ ton. There is thus a further doubling with the formation of esbeuoe and a premature complete reduction of the phenols. Drive out the distilled pcr gasoline and reintroduce the medium oil dr: .ne 1st step Mix the gasoline fractions obtained at the
 EMI38.3
 two stages and extracting therefrom the rrom '"' tic or medium hydrocrrbons of a mixture of liquid sulfur dioxide and propa.ne at a temperature of -8t1 C.

   To fractionate the hydrocarbons thus obtained by distillation; For 100 parts of the gasoline mixture, 8 parts of benzene and 11 parts of toluene are collected.



   Example 12: Bring to a temperature of 510 C. d: -. Ns
 EMI38.4
 , a cooler operating with gr2 at the same time as hydrogen at a pressure of 250 atm., a medium oil obtained by the dostructive hydrogenation of lignite and introduce
 EMI38.5
 . This in6l, -, ngo dr.ns the br.s of a vertical reaction vessel in the form of a tower *. This is rourplï ^ ux 8/10 of a cr t ^: lys our composed of 80 pr.rtios of Gul fnrc. ferrous and 20 pr: rtios of molybdenum disulphide. The remaining 2/10 d 1'osp..cc c ^ .t;: lytic at 1 ^ P, -rtiO superior to the container are filled with a cr.trlytiqua mixture composed of 80 parts of decolorrtnto 1 .OctivatedJ jour.nt the role of; support and 12 parts of ferrous sulphide and 8 parts of tungsten sulphide.

   This gives a product of rG: -. Ction (,, orûjrcn - ,. nt 52% hydroc? -Rburos boiling rux toal-D6rtturcs less than 180 0.

 <Desc / Clms Page number 39>

 
 EMI39.1
 The constituents of the boiling reaction product
 EMI39.2
 at temperatures above 180 or 20üoC. new raw material will be reintroduced at will from the reaction vessel. A mixture is obtained containing benzene, toluene and xylene, which can be used CD1ino carburants stable to detonation and from which it is possible to isolate all of its homologues * x < Jt, itl ;, 1 :.

   F, .- irc; pn.sscr on mm0 t.:mps quo of the hydrogen under a prossion of 600 c.tme et at a tc:; mp6rntura do 435 C. a residue dc cr.qun.go bou1l1r.nt ux tcmpér ^ turos above 325 C., derived from a crude oil which ripples 13% r'.sphr.lt3, on an o!: '. tr:'. lysJur coripos6 of 90% do sulphide for- raiix and do 10% tungsten disulphide. A product is obtained which contains 12% of stable gasoline. detonation, 33 ô of Diosol 1-oil has an oéténno index of 50 and a freezing point of -20 C. These constituents which boil at temperatures above 325 C. and which contain less than 1 o of spheroid, they are reintroduced into the reaction vessel at the same time as new quantities of pre-mixed liquid.



  Exompic 14: Fa.irc pass the same time as hydrogen under a pressure of 250 atm. ot at a ti3mp6rf-.turc do 40 G. uahuïla average boiling ^ ux temperatures between 200 and 3ZOQ0. renfar.r: nt 2S% of phenols and obtained by destructive hydrogenation of 14, coal on a catalyst
 EMI39.3
 constituted by an intimate mixture of 80 parts of formed sulphide
 EMI39.4
 roux ot 20 parts of tungsten disulphide. 37% gasoline (formed :, principzl..ruont by reduction of phenols) is obtained with an eye number of 73.

   As to the medium oil, practically free from phenols, it should be passed on m0m; time "

 <Desc / Clms Page number 40>

 as hydrogen at a pressure of 250 atm. and at a temperature of 4070. on a catalyst composed of 10% tungsten disulphide deposited on "Terrana" bleaching earth previously treated with hydrofluoric acid. 70% gasoline is obtained with an octane number of 80. Mix the gasolines obtained in the two above-mentioned stages; we then obtain a gasoline with an octane number of 77.



     ExemDle 15: Pass at the same time as hydrogen under a pressure of 600 atm. a tar containing 50% of constituents boiling at temperatures below 325 C. and obtained by carbonizing at low temperature a lignite from central Germany, on a catalyst consisting of an intimate mixture of 80 ferrous sulfura and 20% bisul - Tungsten fide disposed to remain in the reaction space, the temperature being 400 ° C. at the point of entry into the reaction fluid and 430 ° C. where the reaction products are exiting.

   This gives a product comprising 65% of constituents boiling at temperatures below 325 ° C., 20% of pure paraffin wax and 15% of a lubricating oil having a viscosity index of 50.



     Example 16: Subjecting to uno hydrogenation refining a medium oil obtained by hydrogenation under pressure in the liquid phase of a residue from the cracking of an Iraqi oil, it is passed for this purpose, at the same time as hydrogen under a pressure of 250 atm. ot at a temperature of 350 ° C., on a catalyst composed of 80% of heavy sulphide and of 20% of tungsten bisulphide, the feed rate being such that substantially no spun was formed.

   Passor then under uno pros ,, - ion of 250 atm. and at a temperature of 415 C. the medium oil thus previously treated on a

 <Desc / Clms Page number 41>

 catalyst containing 10% of tungsten disulphide deposited on do the bleaching earth "Terrana" previously treated with means. hydrofluoric gas. The gasoline obtained in this way has an octane number of 69.5.

   We can return to cyolo the untransformed medium oil or that which has been insufficiently,
If, for comparison, the raw material is passed directly over said catalyst without pretreatment according to the present invention, only about half the amount is obtained per unit time. quantity of gasoline indicated above and the gasoline obtained has only an octane number of
62.



     Example 17: Dough into a paste with water a mixture of nickel carbonate and tungstic acid in molecular proportions of 1: 2, dry the paste, grind it and convert it to a mixture of sulphides. by treatment at elevated temperature with hydrogen sulfide. Intimately mix the mixture of nickol and tungsten sulfides thus obtained with Forroux sulfide precipitated in the proportion by weight of 15: 85 parts, agglomerate this new mixture of pills and fill with collos-oi a reaction vessel .



   Over this catalyst, pass at the same time as hydrogen under a pressure of 50 atm and at a temperature of 475 C. the vapors of an ossonco containing 15% of phenols and, in its fraction free from phenols, 31%. naphthenes and 32% aromatic hydrocarbons, said ossonoo resulting from the destructive hydrogenation of coal. There is thus obtained an ossonoo which is practically free of phenols and which contains 15% of naphthenos and 59% of aromatic hydrocarbons.



   The octane number of the product is 88 against 80 for the ma-

 <Desc / Clms Page number 42>

   third first.



     Example 18: From an aqueous solution of ferrous sulphate precipitate sulphide by addition of an aqueous solution of ammonium sulphide. Isolor the precipitate by filtering and drying it by laying it for several hours in a stream of hydrogen at a temperature gradually rising to 400 ° C. Impregnate 90 parts of the sulphide thus obtained with a solution of 14 parts by weight of thio - ammonium tungstate in aqueous ammonium sulphide and dry this product for several hours in a stream of hydrogen at a

    temperature up to 400 ° C. Next, shape the catalyst into pieces of suitable shape and fill a reaction reaction stable at high pressures.



   Over this catalyst pass a temperature of 475 0. in drear time as the hydrogen under a range of 600 atm. a cracking residue containing 5.3% of constituents boiling at temperatures below 325 C. and containing 5% of asphalt in its fraction boiling at temperatures above 325 C.



   The product obtained contains 53% of constituents boiling at temperatures below 325 ° C. and 0.2% of asphalt in the residue.



   Example 19 Having diluted with an average of 100 liters of light gasoline, 100 liters of an average oil boiling at temperatures of 200 to 325 C. and containing phenols, the gasoline will have been obtained by destructively hydrogenating a ligni- in central Germany, treat the whole at a temperature of 20 C. with 200 liters of liquefied sulfur dioxide. 66 liters of moyonno oil thus pass to solution.

   The fraction which has not dissolved constitutes, after one

 <Desc / Clms Page number 43>

 will have eliminated light gasoline and small amounts of dissolved sulfur dioxide, a good diesel oil with a ketene number of 66.5 and which does not give rise to corrosion.



     After having evaporated off the liquid sulfurous anhydride, distill off the constituents which are poor in hydrogen, then heat them together with the hydrogen and subject them to a preliminary treatment with hydrogen in a small container. reaction, operating at a temperature of about 235 ° C., under a pressure of about 250 atm. and in the presence of tungsten disulfide.



   Then subject the products thus obtained to destructive hydrogenation at a temperature of about 502 ° C. and under a pressure of 250 atm. in a reaction vessel having a capacity about 4 times greater than that in which the preliminary treatment was carried out. The catalyst is permanently placed in the reaction space and consists of a mixture of 80 parts of forroux sulfide and 20 parts of tungsten disulfide. The feeding rate is 0.75 kg. per liter of reaction space ot per hour.



   A product is obtained comprising 60% gasoline ot 40% medium oil. From gasoline which is practically free of phenols and sulfur with an octane number of 80.5, 9.5% toluene can be obtained.



     Example 20: Diluor using 80 liters of light gasoline 100 liters of medium oil boiling at temperatures between 190 and 325 C. obtained by cracking under pressure a German crude oil, then treating the whole at uno tcmpératuro do -40 C. with 200 liters of liquefied sulfurous anhydride. It thus passes 28 liters of oil solution

 <Desc / Clms Page number 44>

 average. The undissolved fraotion is a very good diesel oil with an etene index of 73.



   Continue as described in Example 19 with the treatment of the dissolved constituents poor in hydrogen. This gives a product containing 52% gasoline (final boiling point; 200 C.) and 48% medium oil.



     The gasoline has an octane number of 82 and contains 9.5% toluene.



     Example'21: In an aqueous solution of 250 gr. of ferrous sulfate pour while stirring a solution of 33 gr. of ammonium thio-molybdate in 500 cmc. of a 15% aqueous solution of ammonium sulfide. Isolate by filtering the black precipitate of iron sulphide and iron thio-molybdate thus formed, wash it, dry it away from air and heat it to a temperature of 400 C. at the same time as do hydrogen to which 20% hydrogen sulfide will have been added. After rofroi-. The catalyst thus obtained dissolves into pills agglomerate, which contains 80 parts of sulphide and 20 parts of molbdenum sulphide.



   By passing over this catalyst the vapors of an average oil obtained from the residues of cracking of an American asphalt-based petroleum by dostructive hydrogenation in the liquid phase and exhibiting a ketene indicator of 20 ounces than hydrogen at a temperature of 440 C. under a pressure of 250 atm. a diesel oil is obtained with a ketene indicator of 50.



   Example 22: In an aqueous solution of 246 gr. of chloride of crystallized for pour while stirring a solution of 20 g of tungstic acid in 250 orne. 20% ammonia and then add further amounts of ammonia until

 <Desc / Clms Page number 45>

 complete precipitation of iron. The precipitate of iron hydroxide and iron tungstate obtained is isolated by filtering and transformed into a mixture of sulphides by treatment with hydrogen sulphide at a temperature of 400 C.



   By passing this catalyst at the same time as hydrogen under a pressure of 250 atm. at a temperature of 505 C. the vapors of an average oil boiling at temperatures between 200 and 325 C. and which will have been obtained by destructive hydrogenation of the coal, we obtain 35% gasoline and 65% % average oil which will be further decoupled with formation of gasoline in the reaction vessel.



  The octane number of this gasoline is 88.



   Example 23: Subjecting Rhenish lignite to destructive hydrogenation at a pressure of 600 atm. c. 465 C. under addition of 3% ferrous sulphide.



   Isolate from the product obtained an average oil fraction boiling between 200 and 325 ° C. and direct it with hydrogen at a pressure of 250 atm. and at a temperature of 492 ° C. on a catalyst consisting of 80 parts of ferrous sulphide and 20 parts of tungsten disulphide, the average partial pressure of the oil being 12 atm.



   Subject the reaction product to fractional distillation, thus isolating the fraction boiling between 13-0 and 210 ° C. and reintroducing the upper fractions into the hydrogenation apparatus. The fraction isolated in a yield of 60 µla relative to the average oil is an excellent safety fuel with an octane number of 87.



   This way of operating makes it possible to produce fuels that are particularly suitable for supplying high compression ratio aircraft engines. You can adjust the initial boiling points and

 <Desc / Clms Page number 46>

 end of these gasoline extremely stable to detonation by reintroducing the higher boiling fractions in the apparatus used for the hydrogenation of the medium oil.



  Thus, it is possible to obtain a fuel boiling between 130 and 260 C., between 150 and 200 C. or even between 160 and 215 C .; the proportion of constituents distilling above 180 C. is predominant in these essences.


    

Claims (1)

-ABSTRACT- 1 Process for producing or improving liquid or fusible hydrocarbons such as gasoline, solvents, diesel oil, fuel oil, lubricating oil or paraffin wax, or gaseous hydrocarbons, by subjecting carbonaceous materials the molecule of which contains more than one carbon atom to a heat treatment involving, in the molecule of the raw material or a part thereof, a disjunction of the carbon-to-carbon bonds or of the bonds between atoms carbon and other elements, or the removal of asphalts or resins or substances giving rise to them, consisting in carrying out the reaction in contact with catalysts comprising a mixture or a chemical compound (or both) of one component (a ) consisting of one or more metals of weakly hydrogenating nature with atomic number between 25 and 30, in the form of preformed sulfur compounds, in particular preformed sulphides, or of phosphorus compounds, in particular of phosphates (phosphorus) <Desc / Clms Page number 47> zinc phato used being always a neutral phosphate), with component (b) consisting of one or more metals having a strongly hydrogenating character and an atomic number of at least 42 and belonging to groups 4 to 7 of the periodic system, or on vanadium, chromo, niokol or cobalt or their compounds, the proportion to weight of component (a) in catalyst being greater than the proportion to weight of component (b). 2 The weight ratio of component (a) to component (b) in the catalyst is at least 51: 49. 3 The weight ratio of component (a) to component (b) in the catalyst is between 55:45 and 99.5: 0.5. 4. The weight ratio of component (a) to component (b) in the catalyst is between 60:40 and 97: 3. The weight ratio of component (c.) To component (b) in the catalyst is between 70:30 and 85:15. The various components of the catalyst are present in a state of intimate admixture with one another. When the metals of component (a) form more than one sulphide, the lower sulphides are used. 8 Lower sulphide is ferrous sulphide. 9 As component (a), ferrous sulphate, copper sulphate, zinc sulphate, manganese sulphate, or sulphites, thiosulphates, mercaptides or thionic sols of said metals * 10 The thionic sol used as constituent (a) is a soil of forest, zinc, manganese or copper of a <Desc / Clms Page number 48> a thioid of a metal of component (b). As component (b) the oxides, hydroxides, sulphides, sulphates, thio-aoids or thionic salts, mercaptides or others, sulphurous compounds, halides, selenides, tilurides, phosphates, carbonates or salts of organic acids of molybdenum, tin, tungsten, rhenium, uranium, chromium, nickel or cobalt. 12 ..- Components (a) and (b) are both used in the form of preformed sulphides. In the preparation of the catalyst, the preformed metal sulphides were obtained by subjecting metals, metal oxides or hydroxides or other suitable metal compounds to a sulphurizing treatment under conditions allowing complete transformation by means of sulphurizing agents. a species of hydrogen sulfide, sulfur, carbon disulfide or mercaptans. In the preparation of the catalyst the preformed metal sulphides were obtained by decomposition of thionic salts. In preparing the catalyst components (a) and (b) are prepared separately and then mixed. 16 The mixture of components (a) and (b) is obtained directly in the chemical preparation of the catalyst. The mixture or compound of components (a) and (b) is obtained by simultaneous chemical transformation of a mixture or a compound of components (a) and (b) or rudiments thereof. 18 The intimate mixture of constituents (a) ot <Desc / Clms Page number 49> (b) is obtained by sulphurizing under energetic conditions a finely divided alloy containing in suitable proportions the base metals of constituents (a) and (b). 19 To prepare the catalytic mixture of preformed sulphides, sulphide of powders, filings or turnsings of molybdenum or tungsten acids. In order to prepare the catalyst mixture, a sol formed by an acido-thionic acid of a metal of component (b) and a base metal of component (a) is decomposed, and is added, before, during or after said decomposition, do new amounts of a constituent or a rudiment of constituent (a). The mixed catalyst or rudiments thereof is prepared by common precipitation from a solution containing in suitable proportions the rudiments of components (a) and (b). The catalyst is prepared by mixing intensively in the prescribed proportion, with a metal sulphide belonging to the group comprising component (a), a mixture of strongly hydrogenating metal sulphides belonging to the group a comprising component (b). ot which will have been prepared by sulfurizing in common the metcux or corresponding metal compounds. The catalyst is prepared by impregnating a metal sulfide belonging to the group comprising the weakly hydrogenating component (b) with a suitably proportioned solution of the strong hydrogenating component (b) or a rudiment thereof. 24 The procedures for preparing a catalytic converter following paragraphs 18 to 23 apply to the <Desc / Clms Page number 50> EMI50.1 preparation of mixtures crtnlytiqiics do constitu;,. nts one f i- b1 (.rJ ..: mt and the rutrc strongly hTdr06Gnf '; nt: .utr; s qu # those d .: s- tinés à serve right through the procedure: finished r, u speak 'ph1. 250 The constitur.nt (,) is a sulphide rJ.0tr.lliquc and the constitunt (b) a metal oxide. 26. We use a cr, tr, 1j "s = ur compound almost OXClllSiv0nlûnt dos constitu.nts (.:" '.) Ot (b) drns 1 &&. proportions specified os (cr.tr'3-ysGur concntr6). 27 The c <^. Tï: lysour s'cmploio deposits on porous surfaces with surf: active oo or meln.ng; vec them (c.t.r.lys:; ur EMI50.2 diluted). EMI50.3 28 Oocmo support we use 'chr.rbon! ". Ctir. Z9 In r.131r: .nf3ù or we coxibin;, i its r'.V' :: C said tr: l0- l-.ngc do constituents ( r.) ot (b) one employs a suitable proportions chosen according to the very high results of sulfur or of h. "'. logenos, or their compounds .. ^. vcc 1 'hydrogen,), l' r.r '", 10n1 ['. quc EMI50.4 or lo carbon. EMI50.5 ZOO The o.t.lysur is placed at d: .ï "urc in the r3Gction enclosure. 31 The c, ". Tr.1Jscur s'-1: iploio under fornù of:.? Or- those of fori1o3 irregular or under that of small cubs, cylinders, pills, ^ .nnc ^ ux, stars, prisses, grids, balls or lncrytliforuos body, these regular forces 5t-, nt obtained pir EMI50.6 agglomeration under pressure. EMI50.7 32 We operate at tcüp6rr: .turos ooriprisos' drns the zone s'6toiid, -it from 180 to 700 C., more particularly from 250 6501> 0. 55 We opbrc under the. pressure nor,:,: -. 10 or under pressures 0lVcl0S of the order of 20, 50,.! 00, 500, 800, 1000 atm. or DU-8. <Desc / Clms Page number 51> EMI51.1 S4 The operation is carried out under the addition of hydrogen or of gn2'yronfcr.lant a sufficient quantity of free hydrogen, at oor.p'risoE temperatures between: 350 and 650 ° C. ot 'under pros- sions greater than 50 atn. 5 The defined process applies, to the destructive hydrogenation of cr.rbons ot more p.nrticulièrcrrcnt. package do: f'.tièros of. ". rbon0os liquids or EMI51.2 fuses. EMI51.3 56 The procedure defined above applies to 0 l 'Q U'-' g 0 7 Lc: procods cxdossus defined applies to trr, i t0ï: thermal lcnt dD carbonaceous rotiëros containing 1 "c, s- phalte. 3 For 1c trit01oht aims at previous per0grr.pho we operate in contact with an or'.to.lysour dnns' which the proportion on weight of the strongly hydrogenc'.nt constituent: (b) is not infriourc at 10 parts per 90 parts of the constituent weak: xent hydrog6nnt (8). '39 The procedure defined above applies to the production of non-detonating or anti-knocking o ('. Rbu.rr.n ts or of rjelangos of hydrocarbons rich in hydrocc.rburos 'r..r01: 1 (' .- ticks by traltcuicnt therniouo de 9r: .tièrcs oarboneos, 40 OO!: l: 1.C; '. 11:'. tièros prc.nièrùS on 0ï.lp1oic los EMI51.4 poor constituents or hydrogen obtained by segregation at EMI51.5 from a skyango of rich constituents we hydrogen ot dc poor constituents cn hydrogen using seloe solvents EMI51.6 tifs. EMI51.7 41 The preoedeonent procedure defined applies to the destructive arourtisanto hydrogenation of oily hydrocarbons such as nuclei oils, .. mno :: or detonating gasolines. <Desc / Clms Page number 52> EMI52.1 42 Lo proc6dJ prjc (. 'Do!: L:' lcnt defined requests d0s4ydroGntion options. 450. Li proceeded pro6djn: '. Iont defined applies to 1n, production of hydroci'.rburcs ^ rol: ^ tiquos or do r.?1.^nges of hydroooxburos rich in hydrocarbons aTozc, tiqucs cn trr.i- tcnt to tcvp5r; turos 1'cves des dobbies Co.rbon00s by dsn.7.coyl.ation or by isolation ".l6ris:; tion, preferable or prosonco of a supplement of hydrogen (hydrofornr.'tion), 44 The above-defined process applied to the reduction of 3-phenols to roo.tiquos corrosive hydrocarbons. 45 We cffoctuc un dÓdcub1cD0nt dos cmtièros preaièros we presonc0 dosdits' t..51Gngos da cr.tr.lyscurs deposited on supports ost, nvc.it or 0.prBS cc dúdoublcr.1011t, on cf- foctuo un trs, itot-i -3nt thorniquo either back: 1f, tièr.) S pro; '. 1i èras either dos products according to 1o co.s, the opcrnticn s'0ffoctucnt cn pr6- sonoo dosdits ¯1 ^ .ngcs do cl "1.trysours S1S suppcrts. 46 We sounot from ^ bcrd los Dtièrcs'pr0Dièros to uno hydrogenation prli ::. In.ur: we recommend a ch, t ^ lyscur with strong effect0QOnt hydrog0nnt, tol that of tungs- tene disulfide soûl, cuvant lo tr ^ .itc.mnt th-irtiiqu-i proprcaont said. 47 t'c pracúd6 pr6cdùql: 10nt defined applies to the hydrogunction r ^ ffinnntc. 48 Lc prcc0è.-: 'pr -:' c, sdOï.1i: lù :: 1t defined applies EMI52.2 in coal pressure mining. EMI52.3 49 The prccd pr0c.,; Dol'.1uont defined applies or trcitc -.- ,. cnt dj "10. tièros c: -: rb :: m6os tollés que les hydroc ^ r- buros huiloux cu tzcyon of hydrocarbons gc, ziax cor.üao le butr, no or 10 ptoprnoo EMI52.4 50 We operate a contact with a c ^ tr: lyscrar cor.lprc- <Desc / Clms Page number 53> EMI53.1 nuent COlJ.! 1l0 conati tunnt (^) du suifuro forroux and COJ: lt11G consti- EMI53.2 killing (b) an oxide or sulphide of molybdenum or tungsten, EMI53.3 14 rr.ppcrt on weight Cu ccnati tUr.nt (r.) Nu constitute (b) tnnt c0t ': ipr.is between 55:, 45 and 99: 1,, 51, We operate without a catalyst consisting of tu by an intino uolango of sulphide fcrroux and disulphide of tungsten dc.ns the proportions set between 8'5; 15 ot '70: 30 <520 As c3 industrial products wcuvcux los hydrocarbons .interest; nts cbtcnus or. r.r ;, 611oréa by 10 the precodormont roc6c16s defined ...