BE636496A - - Google Patents

Description

  

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  Portect4onnmonts with steam retorming hence of hydrocarbon.
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 The present invention relates to a continuous process of reforming
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 water vapor from hydroearburits to produce Cas containing appreciable amounts of methane.



  According to the patent 632,913p a gas containing appreciable amounts of methane can $ tr obtained by reforming a
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 liquid or gaseous hydrocarbon containing at least two atoms of
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 carbon per molecule and boiling below 350 "Ce using 4th
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 Water vapor, in a ratio between 1.3 and 5.5 moles per
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 atcue of carbon from the hydrocarbon, over a catalyst at a temperature of 550 to 50 d and under a pressure of at least 7.03 kg / cm2
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 at the Manometer, the conditions of water vapor ratio, temperature

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 tu ,, n and: (1 ';;

   pressure being chosen taking into account other vk.! "luu, .to'1 te.lJ.e8 than the dimensions of the installation and oataly- 3'111J1." ..1..The space speed, so that the equivalent content (the gas lnthwl produced is at least 10% and preferably at least 15% by volume, and has a space speed compatible with these variables and low enough to ensure a
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 aion * - * at least 92> by volume and preferably at least 91> by volume of J.JL1mentatlon hydrocarbonée
An advantage of such a process is that it gives Industrial * gases containing methane and suitable as

  base for gases
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 fuels, U1. contain a reduced amount, and in preferred conditions substantially zero, of liquid hydrocarbon untreated when tem hydrocarbons are used. This result is achieved in a single stage with a high thermal efficiency,

     with a high use of the hydrocarbon and under ion conditions
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 preferred without oil being found in the gas produced at the temperatures and pressures for such a process and for the process according to the invention are the values measured at the outlet of the catalytic bed The methane equivalent content
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 is the quantity of methane which would have the same calorific value as the actual quantity of methane and fatty hydrocarbons <tup4 "'present and is expressed as a percentage of the total effective volume of the gas

    product. Thus, for each fraction of higher gaseous hydrocarbons representing x%, the methane equivalent content is y
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 -5g <u to x Hx / Hy where Hx is the calorific value of the fraction and Hy. The calorific value of methane.

   The values of y for eh * that fraction and. The methane content are then added up * Space velocities for normally liquid hydrocarbons are given in liquid hourly space velocities, i.e. in vo-
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 iume a'hyarooarbide Liquid per volume of catalyst per hour * For normally gaseous hydrocarbons,

   space speed is given
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 noe analogously but the liquid volume is that of an equivalent weight of a petroleum ether having an average molecular weight
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 from 0

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To obtain the high values of methane equivalent in order to produce a gas which only needs to be modified to a small or no extent to obtain town gas, it is necessary in the cited process to use a relatively low temperature. bass., by
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 example from 575 to 650 "<8, and to avoid sensible non-transformation of the feed hydrocarbons it is necessary to use relatively low space velocities, for example less than about 1.0 and often less than. 0,

  5 volume of liquid feed per volume of catalyst per hour.



   The object of the present invention is to enable the production of gas containing greater amounts of methane at higher space velocities in the primary reforming apparatus, with virtually no overall non-transformation of the feed.
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 hfdrocRbOn6., which makes it possible to transform larger quantities of feed for a primary reforming apparatus of determined size.
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 The next:

  J. the object is therefore a continuous process of r.rorm1l '. to the water vapor of a liquid or gaseous hydrocarbon containing in hand two carbon atoms per molecule and boiling below
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 of 35OBC and preferably in the range of 30 k 2200C under atmoOphdrlqu4 $ pressure using water vapor during a stage of y $ <br)!) ing primary, on a reforming catalyst at mt vapor a t.np6rAturt of at least 65,000 and preferably at least 68,090 om Use a space velocity of at least 0.5 v / v / hour and preferably of at least 1,

  0 volume / volume / hour then during a secondary reforming stage on a catalyst which may or may not be the same as this reforming catalyst
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 ming h the water vapor, we a pressure of at least 7.03 kg / c'a2 at the manometer and at a temperature of 450 to 750 * C, and preferably from 500 to 68090 under vapor ratio conditions of water, temperature and pressure, chosen by taking account of other variables such as the dimensions of the installation and the space life,

   such that the methane equivalent content of the gas produced is

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 at least 20% and preferably at least 25% by volume the spatial speeds in the primary and secondary reforming stages and the dimensions of the secondary reforming reactor 'both webs and hydrocarbon (with the exception of methane ) entering the reaction
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 The secondary rm1nc element undergoes reforming therein at a rate of at least 9556 1 volume of the total hydrocarbon feed, In general,

   the methane equivalent content of the gases
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 From the primary reform reactor is relatively small and a certain quantity of unchanged feed hydrocarbon can advantageously be present, it being understood that under the conditions $
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 of use of the secondary raforjoing reactor it is substantially completely transformed, ie at most% reg * tent unchanged on the basis of the initial amount of feed.



   When a normally liquid feed, for example direct light petroleum distillate is used it is preferable
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 to cause conditions in the secondary roformlno reactor such that at least 99% by volume and preferably at least 9ge8% by volume of the feed are transformed, given that the unchanged feed condenses otherwise of the product gaseous and normally preferred to avoid recycling which is ** during
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 possible.

   In the case of normally 4 & better feeds than liquefied petroleum gases, up to 5% of the changed feed is usefully present in the product because the calorific power is thus increased, but a non-transformation
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 Sensitive, ie greater than 9%, should be avoided. However, in some cases it may advantageously be tolerated non-transformation up to 5% wt, for example when the hydrocarbon of The feed contains aromatic compounds, * as contained in a light direct petroleum distillate, which undergo reforming less easily, the unchanged feed then containing a high proportion of aromatic compounds and thus constituting an interesting by-product. However,

  it is better that non-processing is normally minimized.

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   By "non-processing" is meant that the hydrocarbon feed, if normally liquid, appears as a normally liquid hydrocarbon in the gas products, the proportions of its constituents being able to be varied, but to the extent where it is still normally liquidated, it is considered not to have suffered. the transformation.

   In the case of normally gaseous hydrocarbons, the more precise definition must be applied; thus, if butane is reformed and 5% butane appears in the gaseous products, the non-transformation is 5% regardless of the amount of ethane or propane from the butane.



   In general, the methane equivalent content increases with the decrease in the water vapor ratio and with the increase in pressure (unless otherwise indicated, the water vapor ratio is defined here as being the molar ratio of the water vapor). total quantity of water vapor used per carbon atom of the total hydrocarbon feed; therefore jump in the case below where the gas from the secondary reforming reactor is recycled, this ratio of water vapor, together with temperature and pressure, determines the proportion of methane in the gas produced).



  In the secondary reforming reactor, it is therefore preferred to use ,. temperatures from 500 to 600 C and above all from 550 to 675 * C, as well as pressures of at least 10.55 kg per cm2 at a manometer and above all, to obtain high levels of methane equivalent, from 17.56 to 42 , 18 kg / cm2 at the manometer and water vapor ratios of 1.3 to 4.0 and especially from 1.5 to 3.5. It should be appreciated that the preferred temperatures vary with the amount of pressure and water vapor ratio used.

   Thus, to obtain a gas containing 30 to 35% methane using a water vapor ratio of 2.5 and a pressure of 31.64 kg / cm2 at the gauge, the temperature is usually 650 to 675 * vs.



   If the primary reforming reactor is operating under conditions such that at most $% of the feed is not there,

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 space velocity over the catalyst in the retoteuy "" 1Aire is limited only by considerations. *.

   However, t 11 sensible amounts of a11aen- ## Mit passed (or and an extra hydroarbon "4 \; dtqu6 hereafter) the space velocity in lr 5 (> cmd * ir, based on l 'power supply not #, -> # >>,}, f' !! 'd4t 111Ju! .d9 power supply not transformed * secondary reforming ilysetir per hour, is v> "" ,, "C not greater than 1 , 05 wl \ 1lDe / .. olu # eheurl in! #> -R <- "; \ lll (3'l ta tlona les ,, olne reactives (for example those
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 1- 1- dO Sensitive quantities of aromatic compost and / or glue? - "'J'lVln.t: ... i' high bulllt1on) or 1 1.3 voluate / volume / hour av-e 'f' 1.1 imentatlons more reactive. Such as diatillat 1, ¯.,: 111 , .. df \ petroleum containing a small proportion of 008. posais: t ". '; ëln \ .1: {11S and liquefied gas * petroleum.

   At 650 ° C, the space speed is preferably no more than 0.7 rviu.ve/rc.t.na/ hour or 1.0 olUJle / 'folwne / hour. respectiv * mvit 1 to 600 * C, la vt t, t 5 '- pt \ tia1. is preferably not greater than z volume / tolu 41 / h (, 1L't. 'eu can reach 0.5 volume / voluae / hour rtspec t1 vet len t.



  {; '. .; i3 &) n ;! are linear)!), and with spatial velocities cor- r!: Sl) Onç1Hn.tcs for lower or intermediate temperatures, ïtt. t t '.: $' :: maximum spatial allowed at the secondary stage depends, a; "^! '1t'" 111,; mt. the reactivity of the feed hydrocarbon,
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 .. # 'dt¯.' activity of the catalyst as well as the dimension and. r .. (the catalyst particle.

   The values * indicated t, I H cur a catalyst such as that used in the example, the relatively small *, for example in pellets of AH dt t be. For more "particles1 * of catalyst S7j-, A- ne and / or less active catalysts, the preferred spa tisJ.E i \ t .. \ tr1 speeds are a little lower than the values in: î.U \ l1:! - 'f "r, carbide escaping the traneforaation in the reaction - {## "i- fI): o: n1ng primary is often of a less reactive species t,,." 1!;:: quent, of the two axial space velocities indicated *,

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 the value iilft: h: l t''t1't Ov uk '2 !. 61Ú "intermediate can be appro-
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 prayed.
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  The contents. t "'Jld' hd N1..h. ' n ethane tend to increase when the vi iUf1H (: t and qupnd equilibrium is approached. The proportion <i "vt '.!":' '.' :: t of untransformed feed for a dn: H ., t; l1. ix *., i .n; .t;,. '! 1,1 d.1:', 8ugl1lOf, t8 rapidly below a t av * tJ * feiAir - ... .t i.ction <u lu space velocity, activity, iit: eatalbi'i. w 'of lihydrocarbonso ce tte teupérattii-e ag: i <snfco with) ## ".! tS3u spatial.



  For the stage of J't '!))' ULh 'pl'I, main', we prefer that the water vapor ratio /: \.) 1 \ mprtet between the limits indicated and more nrttcu11Qre.r, ffl1t Í.1! 1r 1.8 ot 3.0. Other kids loaned
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 rees are given below for the indicated catalysts used
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 in either stage of primary reforming, the water vapor ratio cannot be very low if one wants to avoid the formation of cat'bJ \ f. Lt- oropensiûn the formation of carbon also depends on the temperature At for the catalyst of example 1 reaches its maximum mm at approximately 700-.800 "C (at approximately 700 * C all 7ex3 kg / cja2 ot fi approximately 00i} C under 142.18 kg / cm2 on a pressure gauge).



  For these saUna values the minimum possible water vapor ratio is about i 3 tuai? m, practically the water vapor ratio is chosen nO! '.' J1a.lell, {Hlt '1 \ ni "fi 1 e \, u' greater than this minimum ratio due to! tuctun \ ', 1 .. (",,:. 1 (t", dt! L1eni;, t1oI \ of the various gases.
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  Lu oafcJtiyj'f.w \, r> - "" \ r '1e method of the invention this one oh.'u y .'- p # Il' #. * # - '## #: # frac t. :. ire containing a m6t, EL.4: IRté: r ns' -.- '' ',:;' 1 ': 1. dOR.It' p of a compound which and ;! t.r .. "{1'1)", "#. ' : - and / or which made alkaline in i io) 1. \) t.!,.: m. \ '! I1'-L "'". '. # -.; v'.; = fdrm an oarbonate, a bleupta # '. ". * '' '1 year a3uulnste in a * quantity ... "- J" ",,'! ## 1 st" <'ids Followed byK20, zij In': ',' "4, ', 1,'. -: '1 ".in'! 1.8 in weight 81 the rr! 'Ra ...' t8.:r. ., 4t.-U. , - v ... ', I. ;; - "t -i'-tc ,, \ ')! I" J, 6; if it contained 10 /; da jt jioa, or 41 '\ f:.; iàitti3'c CH'rtft1)' \ f'lill \, '"calculated

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 based on a linear relationship between these variables for other silica contents, as indicated in patent applications oa 441o nxu.62bta, 8156/62 and 188187/62.

   Using these catalyst $ them
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 their preferred forms, the lower water vapor ratios in
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 the. range of J, 3 A 2 "5 can be used my exaggerated deposit of
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 carbon and with these catalysts we obtain the opttau8 production of this methane. working at> 50-650uC with a water vapor ratio of ix3 to 2.0 under a pressure of 17.58 to 42.18 kg / C) t2 to mono "
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 metre.
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 other suitable catalysts are
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 (at;

   nickel catalysts on refractory material which contains
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 contain less than 5 and preferably no more than 2% of silica according to British Patent No. 916,216, preferably using the vapor boosters of.) to high, namely from 2.5 to 5.5 and preferably from 3 to 4. Preferably, such a catalyst contains at least or of a compound of metal "ciujnj, calculated in equivalent of K2u $ which is capable of being converted into the oxide on heating and / or which is, 1. flax in aqueous solution and the water vapor ratio is e.g.

   ple ae 2 to bzz
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 (b) these rhodium catalysts on refractory material in working rim preferably with a water vapor ratio located in the
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 range from 2 to 4 according to the British patent application ne> 24901611 (Ci of catalysts platinum, palladium, rhén1u #, osmium or iridium on refractal material.

   preferably using a water vapor ratio in the range 2 to 4 according to English patent applications J9bU7ll and .09 '/ 6 and, (a) according to UK patent application No. 26997 / 62, aatUf ""
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 nickel / group metal or platinum on refractory material
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 containing (14) preferably a total alkaline or alkaline earth *
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 as described above for the preferred catalyst, this catalyst is **
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 also holding 0.01 to U.5, and preferably 1.1 to or w / w / wt of the platinum group, and using preferably a 41st water vapor ratio in the range of 1.5 to 3.5 *

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The refractory material can be, for example, magnesia and alumina and / or aluminum silicate (for example kaolin)

     and / or a hydraulic binder such as aluminous cement.



   In general, the above catalysts offer resistance to carbon formation and their use is particularly preferred at the primary reforming stage. If the hydrooarbond * feed has been substantially completely transformed * in the reactor. primary reforming, the secondary reforming catalyst should not have such a high resistance *, to carbon formation and ordinary refractory nickel catalysts can be used- However, if the Unchanged argument reaches the reforming reactor secondary,

   it is preferred to use therein one of the above catalysts having a reduced tendency for carbon formation.



     The "particles" of the catalyst can be in any customary size, for example all in the form of rings or pellets. However, it is preferred that each particle has a specific surface area: volume ratio equivalent to that of a pellet. straight cylindrical, the length and diameter of which fall within the range of 3 to 12 mm, and preferably 4 to 9 mm, especially for the secondary reforming stage. Using tablets or other shapes "particles" with an equivalent specific surface,

     the activity and life of the catalyst increases and it is possible to use somewhat higher space speeds for longer.



   The hydrocarbon feed mixture may contain appreciable amounts of unsaturated constituents, particularly if it is a normally gaseous feed mixture. However, the presence of unsaturated material tends to increase the formation of carbon, it is preferable to choose mixtures containing less than 25% and preferably less than 15% of unsaturated compounds. It is advantageous that the hydrocarbon feed mixture does not contain more than 10 p.p.m by weight of sulfur.

   From loaned. nence, as the specifications for town gas usually require

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 u> N, '# - ii.uiu' in ÏL? B less than 1.5 popes in? otu, ui., .. ": '' ## *> '<# ** #! we contain less than 5 p.pen An weight of #outra ,!. <,;> c ': un a, 1 t 3 ci?: n3, .ngee of feed' t, ydx0ar i5lt.x, .¯ f, n, û # at * - - ',. #' # <"'Fi, tt t #. 'i1s9T1Xk: no, intur6, where, the formation of carbon Jmt et # <uait ## .s xÏ "2tt ït quickly reactive gases 1 t." r !. . j: <- "'' i- 3 a ^ 'aif ^: to Avoid cracking at bass M', p'r '' - r-: '. #. #> *' ''. ^ .rziques.i3 , is advantageous. 1 "u, I, = ,. . ## vft (. fin n r. A ... of relatively low water, psx srezp de on j i .. #,;:. f ij slow heating resulting from the presence of larger quantities of steam d 'water.



   Since the reaction in the secondary reforming reactor is generally exothermic, it is advantageous to remove heat therefrom by passing a coolant through the reactor.
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 catalytic bed without it coming into contact with the catalyst, for example by retoldlssement tubes, the heat obtained can be used to heat the gases admitted into the reform reactor
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 primary m3.ng and / or to generate and / or superheat water vapor for the process.

   The primary reforming reactor can receive heat for the endothermic reaction which takes place therein, using similar heat exchange devices. A resulting advantage is that the secondary reforming reactor is in operation. generally easier to build than the primary reforming reactor.



     According to a variant of the process with cooling, there is
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 a stage da rafrcàii.sa nrxt eritre the stages of primary reforming and 8f: e'.1m1a1re,. so that the gases entering the reactor of 1 "- torm1rf sc'3f t.3.i 'fie t"' l .. \! 'entered at a t <*; aprature of 50 to 695 ° C and that the reaction 1 + r ;. z. who. a lipu in the reactor <± # refor- 'mini secondai,? - not containing any cooling device 111 ter does not reach a * 1.1 -. ip, ratare greater than 700.C, the. The natural temperature losses of the secondary reforming reac * <mr and el! vat heat. the tcrrre.r; has gases in this return reactor. secondary ming being s: onn:, srs by the c} .aleU1 'of the reaction.:

  10. thermal.

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 The gases entering the secondary refojmtng reactor are cooled to 500-650 ° C in the wheat prayer. The pressure and the report
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 of water vapor are rules to give a gas having the characteristics
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 desired ticks, as indicated above.



  The catalyst used in the two reforming stages can be any catalyst among those [which has been cited; however, it is preferred that it has a sulfur content and can be obtained.
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 by activating a catalyst containing more sulfur than is de-
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 sire at 75 ° C or more (eg at 800 ° C using hydrogen and preferably also a water generator. This is particularly the case in the case of catalysts in the reforming reactor.
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 eondaire whose upstream end may be
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 relativenixt bass.

   Further, in order to increase the activity of a nickel analyzer for use in the secondary reforming reactor beyond these relatively low temperatures, it is preferred that the es
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 the analyzer contains more nickel; for example 25 to 35% ,, and
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 prefer this about 30 / S of nickel instead of the usual 15-20%.



  Many procedures allow the pre-cooling stage to be executed slowly. A heat exchanger can be used.
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 and the heat removed can be used to generate steam
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 of water or heat the feed gases admitted to the primary reforming reactor or to any other wire. As a variant, the gas produced is recycled to the secondary ifforaing reactor after condensation of the vapor from water of the produced enz and cooling of this
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 latest; this has the effect of reducing the water vapor ratio
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 global at rf stage ''. ') h'. rocondnire and increase the quantity! de Muthane produces ** t; # j "'t-), ##; tu r and tme pressure dotermln eni Simultax; e,:> a3t, e rtyt; s <4 *> w tt <? * water at AtFie of primary reforming can be used;

   t High turn avoid the formation * of Qrbçzle "pax" example '1 3:; H, tt Hr - hintt'tu f - Iitrt- 2.5 and 3.5 without limitation of the teike, 4r d-i final gas product.



  For example, the 1-af 1 cbit Jt- vz4p (, itir d 'ftu at the primary reforming stage can be from 2.5 to 0 and if the recycle rate and the condensation of 1r water value of the gaseous product may have value *
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 such that the water vapor ratio is reduced in the reactor

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 secondary reforming to a value between 1.2 and 2.5.



   Another variation of the above process is to divide the secondary reforming reactor into stages upstream of each of which the recycle gas is introduced, which ensures that the gases entering the secondary reforming reactor are cooled to temperature. desired and allows for further cooling in the secondary reforming reactor, removing heat from the exothermic reaction and maintaining the temperature in the secondary reforming reactor within a more narrowly defined range than would be possible in the absence of control devices. cooling in the secondary reforming reactor.



   In yet another variant of the process, advantage is taken of the endothermic nature of the reaction between the water vapor and the hydrocarbon to collect at least part of the heat given off by the exothermic reaction of secondary reforming. the primary reforming reactor can operate under conditions such as, as already indicated, that unchanged hydrocarbon is present in the gas produced;

   however, preferably the gases produced in the primary reforming reactor and additional hydrocarbon (addition) are admitted to the secondary reforming reactor. Advantageously, a certain quantity of hydrocarbon is allowed to pass through the reactor. unchanged state by the primary reforming reactor and additional hydrocarbon is introduced into the secondary reforming reactor in order to carry out the adjustment.



   A subject of the present invention is therefore also a continuous process for the steam reforming of a liquid or gaseous hydrocarbon containing at least two carbon atonies per molecule and boiling below 350 ° C., and preferably in the interval of
30 to 220 C at atmospheric pressure, using water vapor, part of the hydrocarbon being admitted to a primary reforming reactor on a reforming catalyst with water vapor at a temperature of 'at least 650 and preferably at least 680 C using a space velocity of at least 0.5 volume / volume / hour and preferably at least 1.0 volume / volume / hour,

     the gases produced being admitted! with additional hydrocarbon in a re-reactor

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 secondary forcing on a steam reforming catalyst which may or may not be Identical to that! of the primary reforming reactor, under a pressure of at least 7.03 kg / om2 at a manometer and at a temperature of 450 to 680 C, and preferably 500 to 650 C under the water vapor ratio conditions, temperature and pressure, chosen taking into account other variables such as the dimensions of the installation and the space speed, such that the methane equivalent content of the gas produced is at least
20%, and preferably at least 25%, by volume,

  and the space velocities at the primary and secondary reforming stages as well as the dimensions of the secondary reforming reactor having values such that the hydrocarbon entering the secondary reforming reactor undergoes reforming therein at a rate of at least 95% by volume of the total hydrocarbon feed.



   The additional hydrocarbon introduced into the secondary reforming reactor is preferably a liquid or gaseous hydrocarbon as defined suitable for the primary reforming stage and may or may not be the same as that hydrocarbon.



   The space velocity of the unchanged hydrocarbon admitted to the secondary reforming reactor is governed by temperature and reactivity, as already indicated.



   It is advantageous to allow a sufficient quantity of hydrocarbon to escape processing in the primary reforming reactor and / or to add a sufficient quantity of additional hydrocarbon to the gases from the primary reforming reactor to substantially absorb the substance completely. 'excess heat released by the exothermic reactions which take place in the secondary reforming reactor * This amounts to saying, if we take into account the natural thenoic losses of the installation,

  that the temperature in the secondary reforming reactor is reduced to the substance desired by allowing the endothermic reactions to take place in this reactor and by collecting excess heat from the reaction rather than by resorting to deliberate cooling of the reactor. Thus, in Examples 3 and 4, the temperature at the outlet of the secondary bed is governed by the amount of light distillate

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 j0U 1: 9.81, produced in the primary reactor.



  # ¯. t such a case, one can use for the secondary stage "tl t .. this very simple steam refonoing whose device! # 'c'a * .- t.; P': 1tf '1. NU' are reduced to minimum, which allows son- i, s: r5 :. # '- n .i °, ¯ = inf! lhtion. 131 as desired, however, the roactew titi- * # *' "'L' Pf; secondary can work in a t en, en- drer im 1.:-r 'j ...: ft; â,. *> sr cu require a high heat input. 11 \ ;; 1: 'i 1,, 1' hvdr; f: 't \ 1-1./1' ('primary unchanged and / or da..j.flllnta- t1m \ $' ': 0 ,. 1. <, 3, â.,> That ...); 1 at.L: a. ::, and tf. even in this case the reactor of r, efcs:,. R ", = ¯ts, â $> could be simpler in construction and less expensive than the primary reforn.ing reactor.

   It is generally necessary to use a tubular furnace as a primary reforming reactor, because of the heat transfer required to sustain the endothermic reaction. The degree of heat transfer in the secondary reforming reactor, in the case where heat is to be transferred, is much smaller and therefore much simpler and less expensive equipment can be used, for example a simple vessel. Packed with a catalyst including, if desired, interior cooling tubes. An installation according to the invention enables better use of the expensive primary reforming installation than in the absence of a secondary reforming reactor.



   The method according to the invention is interesting for
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 production of gas to be used as fuel, cam.na an important constituent of town gas or in some cases as town gas
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 directly. Thus, the gas produced can be er.riched with methane, by addition of methane or liquefied natural gas or other? gaseous hydrocarbons to bring its calorific value to If, value: tsir'.1 per fXMtple at 3560 - 53AO kaal /! 3 (1 <city gts in England generally has a calorific value of 3780 to 4450:, c, 7; lm ).

   Such an enrichment may follow a conter81on stage during which carbon monoxide is transformed by reaction of water vapor into CO + H2, for example on

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      an iron oxide catalyst, and the CO2 can be washed out by conventional methods. Such a conversion step and such removal of the CO2 may be sufficient to raise the calorific power to the desired level, and if the methane equivalent content is high, for example 25 to 30%, it is sufficient simply to remove all or part of the CO2 from the gas produced.

   Finally, if the methane equivalent content is greater than 30%, it is possible to use the gas as the main constituent of a town gas, with little or no modifications, and by working under optimum conditions. my temperature, pressure and water vapor ratio, we get such a gas. Thus, under optimum conditions, it is possible to transform a hydrocarbon feed mixture continuously with little or no modification into a town gas, with an acceptable thermal efficiency without having to carry out a subsequent purification, for example, separating the unchanged feed mixture.



   To transform the produced gas or to modify it into town gas, to adjust the calorific value, combustion rate and density of the gas to the values prescribed for town gas, ethylene or hydrogen can be added or to prefer that carbon dioxide can be removed to increase the rate of combustion; and hydrogen can be added and / or CO2 removed to adjust density (or Wobbe number) and calorific value. The calorific value can also be increased by adding methane or another gaseous hydrocarbon, or even by injecting a liquid hydrocarbon into the hot product gases to fuel them.



   It is preferable to produce a gas containing 5% or less of carbon monoxide and in general such gas can be obtained by working below the dormant temperature an equilibrium proportion of 5% of carbon monoxide. carbon monoxide in the gases produced under the pressure and with the ratio of water vapor that one uses. These temperatures for various pressures and diver? water vapor ratios

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 are groomed in Table VI which follows the examples, The difference between the temperature chosen and the equilibrium temperature which is higher depends on the difference between the CO content and the value of glue at equilibrium in the conditions used, and this must be taken into account.

   Thus, it emerges from this table that by judiciously choosing the water vapor ratios in the packing from 1.5 to 3.5 and the temperatures in the range of 500-675 C as well as the pressures in the range of 12.65 to 42.18 kg / cm2 at the pressure gauge in the secondary reforming reactor, suitable results are obtained. By combining this condition, and the desire to produce high quantities.,.

   of methane at advantageous spatial velocities in order to obtain a gas suitable as town gas or capable of being easily transformed into town gas without however requiring a close adjustment of the supply flow rate of the installation, it is preferable that the ratio of water vapor is between 1.8 and 3.0, the temperature between 550 and 675 C and the pressure between 17.58 and 42.18 kg / cm2 on the manometer.



   In the following examples, the calorific value, the density, the Wobbe number and the combustion rate factor are calculated from the content of saturated hydrocarbons expressed as methane and the content of unsaturated hydrocarbons expressed as ethylene.



  In most cases, the methane equivalent content of the produced gas is about 1 to 3% higher than the total hydrocarbon content, due to the presence of ethane, propane, butanes, etc., and the power actual calorific value and the Wobbe index are actually a little higher than the values shown. In all the examples, the installation comprises a tubular primary reforming reactor heated in a gas oven, the catalyst being in the heated tube, followed by a simple tubular secondary reforming reactor, the tube of which is well insulated and can be heated by electricity for the running of the process.

 <Desc / Clms Page number 17>

 
 EMI17.1
 



  JEMEMU A direct light distillate of petroleum boiling between 30 and
 EMI17.2
 176 ° C and substantially free from olefins and acetylenes having a sulfur content of less than 5% p.rd. and of which at least 50% distilled at or before 130 C is passed with water vapor over a catalyst composition prepared according to the British patent application
 EMI17.3
 No. 18187/62 and heated to a temperature of 600 to 800 ° C to decrease the solubility and leaching of the alkali or alkaline earth metal compounds under the conditions of steam reforming.

   The catalyst is prepared according to the general indications of British Patent Application No. 20652/60, Example 2, according to which nickel carbonate is precipitated from a solution of nickel nitrate using an excess of Na2CO3, kaolin and magnesia are dispersed in the precipitate, the
 EMI17.4
 Mix, we dry it at 410.0 Cr we grind it, we mix it with "Ciment Fondu", we pellet it, we! impregnated with a solution of caustic potash and dried to give a catalyst having
 EMI17.5
 the SiO composition. 14e2%; A120 3252 CaO 11%; MgO 1), 5 × 8 × 0 z2%; i S03 0.3 Fe 5%;

   N19 2008%; f K20 8.0% and showing a loss of 1.8% on calcination at 900 ° C, which corresponds to a K20 content of 8.9% on the basis of the weight of the au. very constituents after calcination at .00 Ce. The catalyst is then heated to i (30 ° C. for 8 hours. The catalyst is all in the form of rings with a length of 16.5 mm, with a diameter.
 EMI17.6
 16.7mm outer and 6.6mm inner diameter.



   The catalyst is used in two reforming reactors under a pressure of 21.09 kg / cm2 at a gauge, the secondary reforming reactor containing a volume of catalyst equal to 2.4 times the volume of catalyst of the primary reforming reactor.



  The primary reforming stage is carried out at 750 C with * a space velocity of 0.7 v / v / hour, and the secondary reforming stage is carried out with a space velocity of 0.29 v / v / hour, over the basis of an identical feed, but with a very low space speed on the basis of feed hydrocarbons.

 <Desc / Clms Page number 18>

 
 EMI18.1
 ..: which are only present in very small quantities * 'J,'. ' > t 1> analysis of the gas produced in the re * reactor, #! # <* irr are pp <'6f'tes in table I, the product of:'. ,, 1 3 in g pr..na.r having the following composition 60.9:. c> 3o K 1 ".4, '2 and 13 t2 of saturated hydrocarbons including! -ï \ n, u <.e.;. scraane. The water vapor ratio is 3.0.
 EMI18.2
 



  *, ## * '? *; , '"dt: it:' The tests 2 to 5, after correction convmiw1 {'1 calorific value satisfy the British Cas Croup Spsoif.Cvit-' '<G and the gases produced? in test 4a, o' e8t ...- ie li7 gas 3t leqeai 4 u'barrasse by washing part of the C02 meets all the requirements for a town gas specification G4 at 4450 kcal / m3.



   TABLE I
 EMI18.3
 
<tb> Es- <SEP> Temperature <SEP> Analysis <SEP> of <SEP> gases <SEP> in <SEP> Capacity <SEP> Index <SEP> Speed
<tb>
 
 EMI18.4
 lai At the outlet% volume volume / hour calori- Wobbe 4th com ne of cath- by grg AI tic process, lyric bastion of H Co Co Bydro- kcal / m3 of reactor of z2 z2 carbu- Weaver reforming res secondais r (? Ja
 EMI18.5
 
mangy <tb>
<tb>
<tb>
<tb>
<tb> (prin-
<tb>
<tb>
<tb>
<tb> cipale-
<tb>
<tb>
<tb>
<tb> ment)
<tb>
 
 EMI18.6
 1,680 52.8 4.8 19.2 $ 21 2 3,680 819 38.9 2,615 48.2 $ 4 2 2OeO 27.6 3,930 850 35 # 1 3,555 46.9 3e5 20.0 29.6 4,050 850 34sO
 EMI18.7
 
<tb> 4 <SEP> 530 <SEP> 46.2 <SEP> 3.5 <SEP> 20.0 <SEP> 30.3 <SEP> 4080 <SEP> 855 <SEP> 31.1
<tb>
<tb> 5 <SEP> 500 <SEP> 46.7 <SEP> 4.5 <SEP> 19.3 <SEP> 29.4 <SEP> 4050 <SEP> 854 <SEP> 34.1
<tb>
 
 EMI18.8
 ira Product t'e 5os3 3.8 13.0 32.9 4450? 42 36,

  4 gold Rai ajn% -s 513 dtd <'-.Ï <- cc.



  EXAMPLE 2
The example is repeated, the main difference being a substantial cooling between the stages. The other differences
 EMI18.9
 are that the pressure is) 1.64 kgf c.n2 at the manometer, the water vapor ratio of 2.0, the space velocity in both stages of 0.5;

 <Desc / Clms Page number 19>

 the two catalytic beds comprise 50 liters of a catalyst similar to that used in Example 1 but in the form of pellets having a length and a diameter of 8.7 mm in the primary reforming reaction and a length and a diameter of 5.4 mm in the secondary reforming reactor.

   The product from the primary refor.ning reactor contains 61.5% H2; CO 6.2%, CO2 18.6%; CH4 13.5% and unsaturated compounds 0.2%. Table II shows the temperature at the outlet of the secondary reforming reactor, the gas analysis, the calorific value, the density, etc. The cooler is such that the gases eojrtant from the primary reactor at 750 C are brought to a temperature) of 640 to 700 C. CO2 is removed by washing the gaseous products at a rate of 5% volume / volume and the values calculated for the calorific value, the density, the Wobbe index and the combustion rate factor take this purification into account.

   The products of ± tests 3 to 10 correspond to the Gas Group 04 requirements and the products of tests 1 and 2 satisfy the Gas Group 05 requirements after suitable correction of the calorific value.

 <Desc / Clms Page number 20>

 
 EMI20.1
 



  TA B LE AU II
 EMI20.2
 Test Temperature at Gas Analysis Density Power Index Speed factor secondary reactor Analysis of gsz calorifica- tion Wobbe 'terse of secondary comreactor ûaire ¯ ¯ J ± é Wesver Input Output E2 CO C02 Bydrocnr- Hytiroeerbures k 1 / jft3 Wever
 EMI20.3
 
<tb> bures <SEP> no
<tb>
 
 EMI20.4
 saturated saturated ¯¯¯¯¯¯ ¯¯¯¯ 1 672 476 7.8 17.0 27.6 0 4230 0.467 693 38.1
 EMI20.5
 
<tb> 2 <SEP> 674 <SEP> 48.4 <SEP> 6.4 <SEP> 16.8 <SEP> 28.4 <SEP> 0 <SEP> 4250 <SEP> 0.478 <SEP> 691 <SEP > 37.8
<tb> 3 <SEP> 662 <SEP> 44.4 <SEP> 6.2 <SEP> 17.4 <SEP> 31.6 <SEP> 0.4 <SEP> 4490 <SEP> 0.481 <SEP> 725 <SEP> 33.6
<tb> 4 <SEP> 660 <SEP> 45.8 <SEP> 5.8 <SEP> 17.6 <SEP> 30.6 <SEP> 0.2 <SEP> 4410 <SEP> 0.479 <SEP> 718 <SEP> 35.5
<tb>
 
 EMI20.6
 5,650 40y 6.6 18.4 34.8 0.2 4650 0.514 727 z1.7 6 642 637 43.8 5.6 17.8 32.6 0.2 4520 0,

  486,728 in
 EMI20.7
 
<tb> 7 <SEP> 642 <SEP> 632 <SEP> 42.2 <SEP> 5.6 <SEP> 17.8 <SEP> 34.2 <SEP> 0.2 <SEP> 4630 <SEP> 0.494 <SEP> 739 <SEP> 31.9
<tb> 8 <SEP> 642 <SEP> 640 <SEP> 45.0 <SEP> 5.8 <SEP> 18.0 <SEP> 31.2 <SEP> 0 <SEP> 4420 <SEP> 0.482 <SEP > 715 <SEP> 34.9
<tb> 9 <SEP> 632 <SEP> 43.2 <SEP> 3.8 <SEP> 18.4 <SEP> 34.4 <SEP> 0.2 <SEP> 4600 <SEP> 0.485 <SEP> 742 <SEP> 33.1
<tb> 10 <SEP> 620 <SEP> 42.6 <SEP> 5.0 <SEP> 18.0 <SEP> 34.0 <SEP> 0.4 <SEP> 4620 <SEP> 0.491 <SEP> 725 <SEP> 32.9
<tb> 11 <SEP> 692 <SEP> 44.4 <SEP> 6.2 <SEP> 17.6 <SEP> 31.6 <SEP> 0.2 <SEP> 4400 <SEP> 0.483 <SEP> 718 <SEP> 34.5
<tb> 12 <SEP> 670 <SEP> 43.4 <SEP> 6.0 <SEP> 17.6 <SEP> 32.6 <SEP> 0.4 <SEP> 4530 <SEP> 0.486 <SEP> 723 <SEP> 33.9
<tb>
 

 <Desc / Clms Page number 21>

    EXAMPLE,?..



   In this example, a light distillate such as that admitted in
 EMI21.1
 the primary reforming reactor is injected into the gas from the primary reforming regulator at a rate of 5 or 10 liters per hour (the quantity admitted in the primary reforming reactor being 25 liters per hour. same as the one
 EMI21.2
 used in Example 2 and the water vapor ratio in the ref r ".ing IJriJtlfdre reactor is to '(5 but the overall efju vapor ratio is 2.1 or 1.8 cause of injection 1. The general speed in the primary reforming reactor is 0.5 but 0.6 or 0.7 c in the secondary reforming reactor.



  The pressure is 31 64. kg / cm2 individually in the primary re-feed reactor and the temperature is 750 ° C. at the outlet of the bed as above. As in 1 exrr Ze 2, 5% of the Cu2 are eliminated and the results are given in the Tebleau III. The products of tests 1, 3, 5 and 6 correspond to the requirements of the Wobbe Group 04 and those of the test 2 correspond to the requirements of the Wobbe Group
 EMI21.3
 05, while those of the e5sj 4 meet Group requirements
Wobbe 03.

 <Desc / Clms Page number 22>

 



    TABLE III
 EMI22.1
 ²! "F" '!. 6i5till-.t 1 / ger #> &; .. 'r> ture Gas analysis J' .- "; <" fulliz at reft) t.-: \. 1 reactor "',,'" 1, -. "'iûing secondsir *?'.-conijr¯. ##. ####. ####### - Tii '*'. ## - 'vr.t * Output H2 CO C0; Hydroc>% - r- Eyrnc,!, -. ': t / .. fce-. bur <' s es- b1.11 "':

  S nnn
 EMI22.2
 
<tb> saturated <SEP> tuffs
<tb>
 
 EMI22.3
 4xs 584 660 45.6 5.8 18.0 30.4 0.2 4390 0. 712 35.4 2 5.1 588 67? 45.2 6.6 18.2 30.0 0 433C- 0, i? 6 6? 9 35.3 --5- 50 620 667 43.8 6.6 17eg 31.6 0.2 i4 * 3 - , Í.'1 71? 34.3 4 10.2 580 644 40.47.2 16.0 ¯3O O, L 4330, 493 773 32.0 5 10.2 604 652 42.2 6.4 17.6 33.4 0.4 4eiO 0.4q6 736 33.1 6 10.2 605 658 42.0 6.8 17.4 33.4 0.4 46 <5 4Q7 737 33.1

 <Desc / Clms Page number 23>

 EXAMPLE 4
In this example,

   a light distillate such as that admitted into the primait reforming reactor is injected into the gas produced in the primary reforming reactor at a rate of 18 to 20 liters / hour while the quantity admitted into the primary reforming reactor is 60 liters per hour to obtain in the primary reforming reactor a space velocity of 1.2 volume / volume / hour * - and in the secondary reforming reactor of 1.6 volume / volume / hour.

   The water vapor ratio in the primary reforming reactor is 2.5 in runs 1 to 4 and in the secondary reforming reactor about 1.9. In runs 5 to 8, the water vapor ratio in the primary reforming reactor is 2.0 and in the secondary reforming reactor 1.5. Furthermore, the example is carried out under the same conditions as Examples 2 and 3.

   As above, $ 5 by volume of CO2 is removed and the results are given in Table IV as for the other examples. The products generally meet the requirements of Gaa Group G4.

 <Desc / Clms Page number 24>

 



    @ WATER TABLE IV.
 EMI24.1
 
<tb>



  Test <SEP> Distillate <SEP> light <SEP> Temperature <SEP> Analysis <SEP> of <SEP> gases <SEP> Power <SEP> Density <SEP> Index <SEP> Factor <SEP> of <SEP>
<tb> sai <SEP> Distillate <SEP> light <SEP> Temperature <SEP> calori- <SEP> Wobbe <SEP> speed <SEP> of
<tb>
 
 EMI24.2
 .ïting secondary secondary ¯ ################## calculates fc3La Input output Dp CG C02 Hydro- Hydre- iCC8l.Îm .;

   Tighten
 EMI24.3
 
<tb> carbides <SEP> carbides <SEP> acal / m3
<tb> grazed <SEP> no
<tb> saturated
<tb>
 
 EMI24.4
 T "1872 620 660 46.8 7.6 17jO 28.4 0.2 4300 0.471 703 36" Q
 EMI24.5
 
<tb> 2 <SEP> 18.7 <SEP> 630 <SEP> 662 <SEP> 47.0 <SEP> 7.4 <SEP> 16.8 <SEP> 28.4 <SEP> 0.4 <SEP > 4325 <SEP> 0.468 <SEP> 710 <SEP> 37.0
<tb> 3 <SEP> 19.1 <SEP> 630 <SEP> 665 <SEP> 46.8 <SEP> 7.6 <SEP> 16.6 <SEP> 28.8 <SEP> 0.2 <SEP > 4334 <SEP> 0.467 <SEP> 712 <SEP> 36.9
<tb>
 
 EMI24.6
 4 3.9 0 625 665 47.2 7.4 17.0 28.4 0 4270 0.467 702 37.1
 EMI24.7
 
<tb> 5 <SEP> 20.0 <SEP> 662 <SEP> 648 <SEP> 46.4 <SEP> 8.4 <SEP> 16.0 <SEP> 29.0 <SEP> 0.2 <SEP > 4360 <SEP> 0.467 <SEP> 717 <SEP> 36.8
<tb> 6 <SEP> 20.0 <SEP> 675 <SEP> .655 <SEP> 46.4 <SEP> 8.8 <SEP> 16.0 <SEP> 28.6 <SEP> 0.2 < SEP> 4334 <SEP> 0.468 <SEP> 712 <SEP> 36.9
<tb> 7 <SEP> 20.1 <SEP> 680 <SEP> 690 <SEP> 45.0 <SEP> 8.8 <SEP> 15,

  2 <SEP> 30.6 <SEP> 0.4 <SEP> 4510 <SEP> 0.468 <SEP> 741 <SEP> 35.8
<tb> 8 <SEP> 20.0 <SEP> 683 <SEP> 696 <SEP> 44.6 <SEP> 9.0 <SEP> 14.6 <SEP> 31.4 <SEP> 0.4 <SEP > 4570 <SEP> 0.465 <SEP> 754 <SEP> 35.5
<tb>
 

 <Desc / Clms Page number 25>

 EXAMPLE 5.



   In this example, no light distilla is injected between stages, male the primary reforming reactor is running
 EMI25.1
 At a temperature of 65000 R the exit -from the bed instead of 750 ° C. as in the other examples. The prjesslon is 31.64 kg / OM2 at the pressure gauge. The light distillate is admitted into the primary reforming reactor at a rate of 50 liters / hour (space speed
1.0 volume / volume / hour) and about 2; liters / hour (ie 4%) of this quantity pass without undergoing reforming. The water vapor ratios at the primary and secondary reforming stages are 2.5.

   The gases from the primary reforming) enter the secondary reforming reactor at 650-665 * 0 and leave it at 620-
630 C final product gases not containing unchanged distillate. In both tests, a gas is obtained which satisfies the
 EMI25.2
 Oas Group Op requirements after removal of 5. ± of C02. The results)! (Are given in table Y.



  ARRAY, Y '
 EMI25.3
 te- Toapdruture imn1tygmeà Ana voité Pou- Dansi- Indi- Fac $ ai to the reactor N3 CO --C02 Hydra-, veto site * ce tur ne .SMCAAM ... car- car- calo- Wobbe do aï * 6or * burtis bure . t'1fi- vi- tr4o tie .11 t .. not que tee ria satu- ke4v te re lu coa-
 EMI25.4
 
<tb> bustian
<tb> from
<tb>
 
 EMI25.5
 #MMM. i ... ifri. luciniiuu .... i.ui.1 .¯; r: j ....,. ,, .., ni..uiiiiii l "1 aHMa.

     i "1 650 626 50 S, 8 18 2 26pOi 0 4070 0.458 678 39.0 2 665 625 5le2 5.0 18.4 25.4 0 4040 0.451 67639.7 ¯¯¯¯¯¯¯¯¯¯¯¯, , ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
 EMI25.6
 
<tb>
<tb>
 

 <Desc / Clms Page number 26>

 TABLE VI
 EMI26.1
 , '' '' <Temperature Ratio of t (qu111br8 j.fira; '.;' '' 1- 'vkippiir for 5 $ of CO in OC of water
 EMI26.2
 
<tb> 13.25 <SEP> 2.0 <SEP> 615
<tb>
<tb>
<tb>
<tb> 2.0 <SEP> 633
<tb>
<tb>
<tb>
<tb> "<SEP> 4.0 <SEP> 647
<tb>
<tb>
<tb>
<tb> "<SEP> 5.0 <SEP> 655
<tb>
<tb>
<tb>
<tb> 20 <SEP> 2.0 <SEP> 635
<tb>
<tb>
<tb>
<tb> "<SEP>, 5 <SEP> 643
<tb>
<tb>
<tb> "<SEP> 3.0 <SEP> 649
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 25 <SEP> 2.0 <SEP> 647
<tb>
<tb>
<tb>
<tb> "<SEP> 2.5 <SEP> 652
<tb>
<tb>
<tb>
<tb> "<SEP> 3.0 <SEP> 657
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 30 <SEP> 2.0 <SEP> 62
<tb>
<tb>
<tb>
<tb> "<SEP> 2,

  5 <SEP> 662
<tb>
<tb>
<tb>
<tb> 3.0 <SEP> 668
<tb>
 CLAIMS
 EMI26.3
 1. Continuous reforming process 1 the tau value of a liquid or gaseous hydrocarbon containing at least two trump cards! of
 EMI26.4
 carbon per molecule and boiling below 350,000 using de vauar d * aaa. donates a primary reforaing stage on an etttly U? due reror1n & to water vapor at a temperature of at least po'C using a space velocity of at least 0.5 volutne / voluiae / heuft) then in a secondary reforming stage on a catalyst all one (pressio * id # au -, àoino 7,, or kg / em2 a toiiperatur:

   of 450 pressure at ioinp 7.0? / c'J12 and at a temperature of 450 to 750 C. under conditions of water vapor ratio, temperature ** pull t pressure, chosen taking into account other variables such as the dimensions of the installation and space speed,
 EMI26.5
 such as l. methane equivalent content of the g4y produced is at least 20% by volume, the space velocities in the primary and secondary reforming stages as well as the dimensions of the
 EMI26.6
 secondary reforaing reactor being such that the hydrocarbons (except or. of '! 1 \ t: tane) entering the secondary reforaing reactor undergo reor.aing therein at a rate of at: tolu. 95 "in volume

** ATTENTION ** end of DESC field can contain start of CLMS **.

 

Claims (1)

of the total hydrocarbon feed. <Desc / Clms Page number 27> 2.- A method according to claim 1, characterized in that the conditions !! water vapor ratio, temperature and pressure are chosen so that the equivalent content of EMI27.1 ! IÎ! Tlri1'i! or at least 25% by volume. 3. A process according to claim or 2, characterized in that at least 99% by volume of the total hydrocarbon feed is transformed, 4. A process according to claim 3, characterized in that at least 99, 8% by volume of the total hydrocarbon feed is processed. 5.- Process according to one or other of the claims EMI27.2 above characterized in that the temperature at the primary reforiaing stage is at least b01 C. 6. A method according to either of the preceding claims, characterized in that the space velocity at the primary reforming stage is at least 1.0 volume / volume / hour. 7. A method according to either of the preceding claims, characterized in that the water vapor ratio is between 1.3 and 4.0. , 8.- A method according to one or 1 other of the pre- EMI27.3 cideyites, characterized in that the water vapor ratio is between 1.5 and 3.5. 9. A method according to either of the preceding claims, characterized in that the water vapor ratio is EMI27.4 including ï1rL'é; E "(, x 1.8 and 3.0. JO.- i'.cd. s: before one or: The other of the preceding claims, ts c'aytct <ri in that the temperature in the ret <3raing reactor is between 500 and 6800C. 11.- Pr-icAdé according to one or the other of the preceding claims cbd4ratsaycr: .ct = ri :. so that the temperature in the apc '' 'daire reforming reactor is between 550 and 675 ° C. 12.- Process according to one or other of the preceding claims, characterized in that the temperature in the reactor of <Desc / Clms Page number 28> secondary reforming is between 550 and 650 C. 13. A method according to either of the preceding claims, characterized in that the pressure is at least 10.55 kg / cm2 at the pressure gauge. 14.- A method according to either of the preceding claims 4 characterized in that the pressure is between 12.65 and 42.18 kg / cm2 at the manometer. 15-. Process according to either of the preceding claims, characterized in that the pressure is between 17.56 and 42.18 kg / cm2 at the pressure gauge * 16.- Process according to either of the preceding claims, characterized in that the catalyst is a nickel catalyst on refractory material containing an alkali metal compound and / or alkaline earth metal added to the constituents of the catalyst during its preparation in the form of a compound which is converted to the oxide on heating and / or which is alkaline in aqueous solution, in an amount of at least 0.5% calculated by wavelength equivalent weight of potassium. 17.- Process according to claim 16, characterized in that the quantity of alkali metal and / or alkaline earth metal, calculated as equivalent weight of potassium oxide, is at least 1.8% when the catalyst contains 5% silica and 3.6% when it contains 10% silica, or a corresponding amount calculated according to a linear relation between these variables for other contents of alica. 18.- The method of claim 16 or 17, characterized in that the alkali metal compound is added in the form of oxide, hydroxide, carbonate, bicarbonate or organic acid salt of sodium or potassium . 19.0 A process according to any one of the preceding claims, characterized in that the catalyst is a nickel / platinum group metal catalyst on refractory material containing 0.01 to 0.5% by weight of the. platinum group metal. <Desc / Clms Page number 29> EMI29.1 2û.- p¯roc'i "<'i' \ '..': '' ## '# io-. Om Is added to the preceding claims.' Î? I eftri;. '#' <* '# rv-' #} ".'- f *! , 4. ' J'.ßf. "t ÉPjv a catalyst to ttictet *! ur Mr U, 'if r-'ir #': *,>! .t e., o *) 4" not more than 5% by weight ' r; '. "Pr'c-c <' ## ;! '' ut ## / {. #; ': #) - * <mf -.u the other of? claims 1 # J *? / Js '-s --- /> - .: L Vis *' *: ;; cr: or-- [##; F: i.:?. f c3iï -gt a metal catalyst dis s ft> U] i '-: rs R ,,, ï 3t> cr.. r.'. ' '' f'fr.ctair'e. :; -; > ### '#,' # '# "* #' or ', a tÀ tb of claims' ïn -iv '.'-'.-! .. v.-; -.- .; 1' *. # '.-! i1'; # '# î this catalyst particles have;. = j:; <; 1ïif> J.'ti #' ## j <"- t. ' 'r i- rz; 7 secondary a relation sur- f.) t'; '":, l' '! <' - qt, iv '* .. ô v **' î Ji a ') n' ' ', 4still.e straight cylindrical of which 3 and 5 <.- ùlH. \ 6tj <> between 3 and 12 nm. 23. pf <.uc <iiv, saw one or the other of claims 1 h 2 '31 "g.tr'r: T '' and 'er; -c' ;: qui '.', E; .'â ^ ". ':' 'sr ..: fJ'.,, 1J'arC? CÔ'bOtâG contains ui qu at 2 M ef # Cs at? - 'i ki.v Y,' ..; : Lx% Yl:. ' 7 uor- saturated. "2A." Py-.Hi '*' '** 1 4rafw.'tF .'-' arx '' "t ('? Ax or' v re., Y, '. Â claims to 2ÎJ, carautri ** 5 c uf the hydrocarbon feed contains up to $ 1 in uox-in '!' - "': tà ± tï..ïi? ltÂl7i FFiJR'1 8aturÛ3. 25. "? R (<- d <: '###' # '..one *' nu> yC1: .T'êd es claims pro '' .1% S! 9t '.'". i1 notebook #; # * "## '#" ##### s <> #' "not a hydrocarbon .t3d bo-utJLlunt -Y * ïr. o". - .. 'vvoC- iJ6 ¯ f FOO1 *: - '' *, 't¯5,' - # '* ### or' avtre iev ':' It'4Tlnn rï:: '.') Previous W, CAî'av? "'; **; : # # ..> * and- ... g -,. îâ .'a>: â3i: vGxi hydrocaroonée zut a distillate 1 dir. ':; t.!' ¯ "4..a.,. < T. 7 "P''o" -; i ï: '' ï-1 '* ".; n-"' 3u of 1 & 23 characters? 'c ".- #. *?" -v.', à: ", - i 4. r-z hy'Jroc <trbonée is a liquefied gas of p't! '<*". 2 <.- "r'ry1.'slts ';, a: a j'. '!. i. Un-,' or .i di.stc.ti3 of claims pre- Ct8S, t..Kr. .ct.!. ':.' : - - # -! .i>, (. '* alli.6n cation tSi î: 3'QCiI:' bJ1 "it'.t? cor. tJ.Knb tP7t; y3i :: fxt.'Ki" a; .j; - ##. '# \: ju> 1a #} t.' ;, 11: 'i. °': icf; :: unsaturated: gx fig #: a6ii.43: r .a .; aR.!; #! it r-.i t'u:, S; .éL, at; 2, i ..: ia temperature> 1 j lC'é. '. Î.i:.) CkcA: 1? s "C3k: for Jv! .t '- ir I cnct-ir, at busts .kTa: .p :: W attL: 2'c des c' ..'- ttt. t3 ' <Desc / Clms Page number 30> 29.0 Process according to any one of the preceding claims, characterized in that the pressure, the temperature and the water vapor ratio used during the reforming stage are such that the product obtained from this stage contains less than 5% carbon monoxide. 30.- Process according to claim 29, characterized in that the pressure is between 17.56 and 42.18 kg / cm2 on a manometer, the temperature in the secondary reforming reactor is between 550 and 675 * C and the ratio of water vapor is between 1.8 and 3.0. 31.- Continuous process for the production of a gas suitable for coca.ne town gas or easy to transform into town gas by steam reforming of a liquid hydrocarbon boiling in the range of 30 to 220 C, wherein the hydrocarbon is passed with steam, in a steam ratio of 1.8 to 3.0 over at least one of the catalysts defined in claims 16 to 20 in a reactor primary reforming at a temperature of at least 680 "C and with a space velocity of at least 1.0 volume / volume / hour, then on such a catalyst in a secondary reforming reactor at a temperature of 550 to 675 C under a pressure of 17.56 to 42.18 kg / cm2 on a manometer, these variables being chosen taking into account other variables such as the dimensions of the installation and of the catalyst, so that the methane equivalent content of the gas produced is at least 25% by volume and the space speed in the secondary reforming reactor is such that the conversion of the hydrocarbon feed is at least 99.8% by volume. 32.- Process according to either of the preceding claims, characterized in that heat is removed from the secondary reforming reactor by passing a cooling agent through the catalyst bed, but in contact. with the catalyzer. <Desc / Clms Page number 31> their. 33.- process.,. according to one or otter of claims 1 to 31, characterized in that it comprises a cooling between the primary and secondary reforming stages such that the gas entering the secondary reforming reactor is at a temperature of 450 to 695 C and that the exothermic reaction taking place in the secondary reforming reactor, no. provided with device! for interior cooling, does not reach a temperature above 700 C. 34.- Process according to claim 33, characterized in that the gases entering the secondary reforming reactor are cooled beforehand between 500 to 650 c. 35.- The method of claim 33 or 34, characterized in that the gases entering the secondary reforming reactor are cooled beforehand. By mixing them with the gases produced in the secondary reforming reactor, cooled and recycled and including water vapor has been condensed. 36.- Process according to claim 35, characterized in that the initial water vapor ratio and the recycling rate are such that the water vapor ratio is between 2.5 and 4 at the primary reforming stage, 0 and at the secondary reforming stage between 1.2 and 2.5. 37.- Process according to claim 35 or 36, characterized in that the secondary reforming reactor is divided into several stages upstream of each of which the recycle gas is introduced. 38.- Process according to 1) either of the preceding claims, characterized in that unchanged hydrocarbon is present in the gases leaving the primary reforming reactor and / or additional hydrocarbon is added to the gases admitted to the reactor. the secondary reforming reactor. 39.0 Process according to either of the preceding claims, characterized in that a sufficient quantity of hydro- <Desc / Clms Page number 32> EMI32.1 ybuya escapes reforming in the primary rtforaing reactor # ;, My è;! i t u; .n.t1té sufficient hydrocarbon is added to the gases ::, '1;' :. ','. ' return due to primary reforming to absorb in subotance o the heat released by the exothermic reactions ist unwind in the! rector of secondary reforming. 40, - proc6d.f: 'continuous 1'6 (o1 ".:' L1n & u the water vapor of a,. ,, ..t:;, liquida or mange containing at u.olns two atoaee of cartels by flol 'cu "t Ú't boulllarst au-desaoua de 3S0.C, en tub tance son- * Ó.6" t "1i. above' iI! 1C rij / rre / sce to one or the other of exea- -. . &, 1.- Following process. one or the other of the claims. prd- -; -'-- # ¯ .s; .. "ç ... t" t \ ctl: ris6 ('il; l' ..) '0 ± \ additionally increases power, iJ-: if .ae (1tt gas produced by * 'yichi9Bement using methane 04. other gaseous hydrocarbons or fuel the hot gaseous product by ijt-cUïi 4'n liquid hydrocarbon. 42.- Process according to one or other of the claims EMI32.2 previous, characterized in that after the reforming stage at EMI32.3 water vapor, carbon monoxide is transformed into anhydride EMI32.4 carbon by catalytic conversion. 43.- Process according to Puna or other of the preceding claims, characterized in that it comprises a later stage EMI32.5 \ 1 (1 separation of carbon dioxide. 44 ..- The process followed ('one, or the other of the claims before / dente9! T c4tract4rît4 m this or' near the stage of retorming at V8Î) .J. "" The Paa.u .. of 1 '"th J t" r' 'f% ".; hydrogen ce added or C05 f! 5'!:, ,, t!; io / pour. -u,, ** -. # 1 'il , t.HI: Jff of combustion of the product or t) 1 "'"' OT.'1'.tg "" l: 'i, -. # -? #'. + -, # ' # - A5 * 0a? Qbterl11 pll "'1' # -c-'d 1, .t van t one or other of the eveu, 1i.:, T.ton .: 1) f'- .vs. have*. .