BE546437A - - Google Patents

Description

       

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   COMPANY: METALLGESELLSCHAFT AKTIENGESELLSCHAFT, residing in FRANCFORT s / M. (Germany).



     (Representative: E. LAGUESSE-HAMAL).



   PROCESS FOR THE CATALYTIC REFINING OF HYDROCAR-
BURES.



  (having been the subject of patent applications filed in Germany on March 26, 1955 (resells 23 to 25) and April 7, 1955 (resales 26 to 30) - declaration by the applicant).



  Letter of amendment attached to be valid as of right, dated April 23, 1956: It would be appropriate to add, on page 19, line 1, thus conceived: "of high boiling point, for example of phenyl oxide.



  This "the following correction: instead of phenyl oxide it should read: diphenyl ether.



  The line should read as follows: "High boiling, eg diphenyl ether. This"

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The present invention relates to a process for the catalytic refining of hydrocarbons or fractions thereof in the presence of hydrogen while employing catalysts stable to sulfur. These hydrocarbons or hydrocarbon fractions are present for example during coking, carbonization.

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 EMI3.1
 incomplete or gas6ificatioti, tc :: coal j, 1 '-: 3 1iGni tr': J, oil shale or barter l: Ol. ') u8tlbLn .: aoliduu', Il au:; 3i. when processing coabuntiblos J Lqu3 3c.s, such ctur: 1 .: -> 6tro- le, tar, oil do c; oJ.) fh'lHL or other cor.nfu: t: it3: L. ; '.: 1.d.- lar.

   For the truitoiaont according to the l.nvcil!; II) 1 ', for example come into consideration coma hydrocarbons, 1,) r; bcn: -; ols, mineral spirits, diesel oils, medium oils, or their fractions, and other hydrocarbons, preferably those boiling up to 3600 or higher, for example 500. Catalytic hydrogenation destroys the toxicity of organic sulfur, nitrogen and oxygen compounds, resinigens and other similar impurities, which are contained in hydrocarbons.

   The object of the invention is to use, with a view to this catalytic hydrogenation, gases containing hydrogen, such as lighting gas, coking gas, incomplete combustion gas, water gas, gases which occur during the refining, regeneration or stabilization of oils and other liquid fuels, end of synthesis gas or circuit gas, or other similar gases, which, in addition to hydrogen, contain as main constituents carbon monoxide, metha-
 EMI3.2
 ne or other hydrocarbons # Y;

  .es with low boiling point, in particular gaseous hydrocarbons, and where appropriate carbon dioxide, nitrogen, water vapor, or two or more of these materials, and which allow the catalytic hydrogenation to be carried out in such a way that the formation, unavoidable up to now, of deposits and encrustation in vaporizers, heat exchangers, heaters, pipes are eliminated or at least reduced very appreciably. and other installations used, as well as on the catalysts.



   Another object of the invention is to drive the

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 process so that the catalysts used last for several months. Next, the invention aims to give the gases used for the catalytic hydraugenation, either before or during the catalytic refining, properties which * make the gases particularly suitable for refining.



   Another object of the invention is to produce a portion of the hydrogen necessary for catalytic refining during the practice of the process itself, by converting the carbon monoxide present in the gas containing hydrogen; for the conversion, the same catalyst should be used which was used for the catalytic refining, the conversion and the catalytic refining can take place simultaneously. The following description, the plans and the claims reflect still further objects of the invention.



   According to the invention, it is passed over or through a catalyst, at a suitable temperature of approximately between 50 and 500, preferably 150-450 C or 200-400 C, before it or they are brought into contact with them. hydrocarbons to be catalytically refined, lighting gas, coking gas, incomplete carbonization gas, water gas, der. . which occur during refining or regeneration or other processing is analogous to oils or other liquid fuels, synthesis gases or flue gases from synthesis, which use hydrogen or gases containing hydrogen, for example from synthesis, Fischer-Tropsch, or other gas containing hydrogen.

   In this way, undesirable substances contained in the gas, such as resinogens, oxygen, nitrogen or other oxidizing materials, as well as the organic compounds of nitrogen, oxygen are rendered harmless. or sulfur. The same effect can be achieved by introducing steam into the catalytic refining, or the effect of the water can thereby be improved.

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 EMI5.1
 trait Plaçât catalyL # dou gai :.



  Leu cases are]) -. C, C:, .tatl3.G trait or bare S. (S "1.i.jy. 1.1., Ef., ('P .. - culiùxvucut aux c, t .: ly ;; turs: trLl. = â uu, c ti '. <jL eu ri' (;,:, that after this pre-treatment they uout: ": c.l1l !! iu over raffina- Strictly speaking. They can be introduced into the process of hydrogenation of the hydrocarbons: - in various places, either alone, or 0.1 m³lcL11gc with a, j of circu- lated. We can for example send them in the vaporizer for the hydrocarbons or also before the reactor only or at an appropriate place in the reactor. Thus, for example, after the preparatory treatment, by passing them through the hydrocarbons to be refined, if necessary adding the circulating gas to them. in circuit in the catalytic refining, and they are completely or partially vaporized.

   The mixture of hydrocarbons to be refined and gas containing hydrogen then passes, through heat exchangers and heaters, into the reactor intended for the hydrogenating refining of hydrocarbons, and from this it passes into the devices which separate refined hydrocarbons, gas which can then be used again for refining, preferably after removal of a partial stream.



   Thanks to the preparation according to the invention of the gas containing hydrogen, the undesirable beers mentioned above are transformed into harmless compounds by thermal and catalytic transformation, and thus a disturbance of the hydrogenating refining is avoided. due to the formation of deposits in vaporizers and heat exchangers or on the catalyst itself as well as in the connecting pipes.



   The working temperatures are as a rule approximately between 50 ° C. and the reaction temperature of the subsequent catalytic refining; one works for example at temperatures between 160 and 240 C or 160-450 C. The working pressure and the gas velocity are regulated in such a way

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 correspondingly, the intensity of the hydrogenation increasing with the working pressure and changing in a manner inversely proportional to the gas speed.

   The temperature of the catalyst, the working pressure and the speed of the gas should be chosen in such a way that, when treating gas containing carbon dioxide, there is no conversion of carbon dioxide to carbon dioxide. methane The treatment, in accordance with the invention, of the fresh gas takes place under the condition that the treated gas, admitted into a solution of sulfuric acid and formaldehyde (30 parts by volume of sulfuric acid at 66 degrees for a 40% formaldehyde part by volume) only gives a slight brownish color after a few minutes. There is no difficulty in determining experimentally the treatment temperature, the treatment time and the amount of catalyst.



   It is not necessary to operate under pressure. The process is also carried out satisfactorily under normal pressure or even under reduced pressure. This is why, according to the process according to the invention, it is also possible to treat the gas before its compression, for example at the pressure at which it arrives from the gasifier or from a network gas pipe, therefore at a pressure lower than that at which the catalytic refining is carried out, and only then to bring it to the pressure necessary for the catalytic refining, which is usually greater than atmospheric pressure, and is placed for example between 20 and 100 atm.

   Or, the gas can be treated according to the process of the invention after the first or another stage of compression, when its pressure is raised in several stages to the pressure necessary for catalytic refining.



   The process according to the invention has the further advantage that the catalyst can be operated with very different yields. The hourly load imposed on it may be

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 reduced to less than 10 Nm3 of gas per m3 of catalyst.



   However, this load can also be significantly increased, for example to bring it up to 1000-8000 Nm3 of gas and even more, for example 12,000 to 13,000 Nm3; per m3 of catalyst and per hour. The catalyst can, for example, be arranged in elongated cylindrical containers to which the necessary heat can be supplied respectively indirectly removed, for example. The process can advantageously be carried out by introducing the gas into the catalyst at a temperature lower than the reaction temperature, so that it is only in the catalyst that it reaches the reaction temperature.



   If a supply of heat to the catalyst is necessary, this supply can be obtained by heat exchange with the exhaust gas, if necessary with additional sources of heat. It is also possible to have recourse to other methods of heating: for example by supplying oxygen to the fresh gas on the catalyst, it is possible to cause combustion and thereby heat the gas. In this case, the catalyst can also be used in the form of a vortex or in the state of suspension.



   The fresh gas can be added to the Hydrocarbon vapors coming from the evaporator, or optionally to the mixture of these vapors with boiled gas, and the resulting mixture is passed through the catalyst, by means of which s The treatment of the fresh gas is carried out according to the invention. This method is particularly suitable if the temperature of the mixture is kept sufficiently below the temperature of the hydrogenating refining, for example approximately between 180 and 200 C.



  In this case, the catalyst is heated indirectly, for example by means of gas from the hydrogen refining reactor. However, and also simultaneously, the mixture of gas and vapor which goes to the reactor is heated. The heat from the catalytic hydrogenating refining can also be used for other

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 for the purposes of the process according to the invention, for example as follows: the new gas is passed, alone or mixed with circuit gas, through a catalyst operating as a heat exchanger with vapors coming from the refining reactor catalytic converter, and then passed through the vaporizer for hydrocarbons.



   As a catalyst for the preparation according to the invention, fresh gas for hydrogenating refining can be used, for example metal oxides and / or sulphides of metals of the 6th and 6th groups of the periodic system. Particularly well suited are known hydrogenation catalysts based on the use of tungsten, molybdenum, vanadium, cobalt, chromium, nickel and iron, which also contain zinc, magnesium or oxide compounds. analogues, and, which can be deposited on supports, such as active carbon, silica gel, alumina. These catalysts can also contain two of the metals mentioned above or even more.



   Sulfur-stable catalysts employed for the pressurized refining of hydrocarbons by resolution or by hydrogenation have been found to be particularly advantageous. Good results have also been obtained with alkalinized ferrous catalysts such as have already been employed for the catalytic conversion of organic sulfur compounds in synthesis gases.



   Molybdenum acid deposited on alumina is used, for example, as catalyst, the molybdic acid concentrations being of the order of about 10%. Another very active catalyst for treating the fresh gas according to the invention can be obtained, for example, by intimately mixing 70 parts by weight of an aluminum hydroxide, having the structure of bayerite - the product which is produced. can be obtained commercially - which serves as the main order of support in the catalyst, with 18 parts by weight of molybdic acid, 8 parts by weight of hydroxide of

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 cobalt and 4 parts by weight of graphite. By compression, this mixture is brought to the state of small cylinders. The catalysts can be used for the process in the form of their oxides.

   The metal oxides then gradually pass through the process stream partly in the sulphurous state and partly in the metallic state, under the influence of hydrogen or hydrogen sulphide either present or formed by splitting. of organic sulfur compounds. However, nothing prevents the catalysts from being sulphurized or reduced in a known manner before their use, and from using them in sulphurous and / or metallic form.



     It has been found that precipitation catalysts are also suitable; they are produced, for example, by precipitating aluminum salts in common with a salt or a mixture of salts of the metals mentioned above, for example in the presence of a carrier substance. Or we impregnate d. alumina or another carrier substance of one or more of said metal salts, and these are brought to the oxide form, for example by heating.



   The catalyst used in the hydrogenating refining can also be used with advantage for the process according to the invention, which in this case also offers the advantage of being a particularly inexpensive catalyst.



   For the process according to the invention, it is possible to use starting gases with different contents of hydrogen and of carbon monoxide. Particularly advantageous have been found to be a partial pressure of hydrogen below 25 atm and a partial pressure of hydrogen and carbon monoxide of up to 40 atm. approximately, that of carbon monoxide should preferably be between 0.1 and 15 atm.



    The gases which exit from the carbonization chambers of the

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 Coke ovens of usual construction towards the end of the carbonization time. These gases can be further improved if, in the latter part of the carbonization period, methane or gases containing methane, such as lighting gas or gas, are passed through red-heated coke. natural gas, or part of the gas passing in accordance with the invention in circuit by catalytic refining, or circuit gases or at the end of synthesis, which work with gas rich in hydrogen, for example those of the Fischer synthesis -Tropsch.



   Advantages similar to those obtained by the catalytic hydrogenating pretreatment of the gas can also be achieved if water vapor is passed through the process, for example in the pretreatment of the gases and / or in the process. through the catalyst which is used for the catalytic refining of hydrocarbons. It is surprising to note that the refining is not even adversely influenced by the presence of water vapor, but on the contrary favored. There is also no deterioration of the contact; As a rule, a stable sulfur contact is used for refining.

   A preparatory treatment of the gas loaded with hydrogen newly introduced into the process is then no longer absolutely necessary, especially not when the newly supplied gas is admitted into the catalyst for the hydrogenating refining at a suitable location, for example at a greater or lesser distance behind the entry of the hydrocarbons to be refined or of their mixture with the circulating gas in the hydrogenating refining reactor.



   The addition of water vapor still provides the advantage that the carbon separations are suppressed on contact, even if the refining takes place at relatively high temperatures, for example ranging from more than 400 to about 500 C. It is also carried out. a saving of hydrogen necessary for hydrogenating refining by

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 following the addition of water vapor and a reduction in the octane number during the hydrogenating refining is avoided. In some cases, the number of octanes is even improved. The amounts of water vapor required by the invention are about 5 to 50% by volume, based on the fresh gas entering the process.

   It is advantageous to use approximately 15 to 35% by volume. If working with circuit gas, it is recommended to use slightly higher quantities of water vapor, relative to the fresh gas. The working pressures can be chosen as mentioned above. Water vapor can be introduced into the process at different places. It can be added to the gas entering the reactor in which the catalytic refining of the hydrocarbons takes place.



   The water vapor separated from the gas charged with hydrogen can also be fed into the reactor. In many cases, it is convenient to mix the water vapor already with the fresh gas containing hydrogen entering the process, and to send the water vapor together with the fresh gas to the process stage. preparatory treatment of gas, already described. Here too, the presence of water vapor is advantageous: the water vapor in particular protects the catalyst of the preparatory treatment from premature wear, which would otherwise be caused in many cases over time by soot separation. or deposit formation on the catalyst.



  When adding steam to the pretreatment, the gas is also even more suitable for the subsequent catalytic refining. There is still some increase in the hydrogen content of the gas by converting part of the vapor with carbon monoxide into hydrogen and carbon dioxide. By the preparatory treatment of the fresh gas introduced into the process, a cooling of the gas is avoided which could lead to a separation of water vapor, if the gas

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 prepared went to hydrogenating refining without increasing pressure. If the preparatory treatment takes place at a lower pressure than the hydrogenating refining, it is advantageous, before the compression, to wash off the carbonic acid.

   In the case of preparation in two or more stages of the new gas used in the process, the water vapor can be added either before the first stage, or also only before one of the following stages.



   The addition of steam provides the additional advantage that it is possible to operate at relatively high reaction temperatures, which may for example include 380-400 C and above. This also applies to the preparation of the gas con-. firmly to the main patent, than to even hydrogenating refining.



   It is not necessary to have recourse to a preliminary purification of the new gas used in the process, aimed at the elimination of the sulfur compounds and other similar impurities.



   The apparatus shown schematically and by way of example in FIG. 1 can be used, for example, for the process.



   The fraction of hydrocarbon to be refined, for example benzol, flows from the collecting tank 1 through line 2 to pump 3, and is discharged by the latter, through line 4; and the preheater 5 as well as the line 6, in the vaporizer which is maintained at the desired vaporization temperature by means of the heating system 8 designed in known manner. The vapors leave the vaporizer 7 through line 9 and are brought to the reaction temperature in heat exchangers 10 and 11. It is at this temperature that they enter, through line 13 into the contact furnace. 14 used for the hydrogenating refining, furnace in which the catalyst 15 is disposed on a gas permeable support 16.

   The vapors leave the contact furnace via line 17, pass through the exchangers

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 thermals 11 and 10 and thereof, s.- ent, through line 18, in condenser 19, where the refined product is fluidized; it exits via line 20 and passes through separator 21.



   The refined product is withdrawn in 22.



   Part of the benzol or other substance is withdrawn from the vaporizer 7 via line 23 and cooler 24, in order to lead it via line 25, for example, to a tar distillation or other distillation apparatus. This part is, for example, distilled in the distillation of tar from a gas plant or from a coking plant, mixed with the tar coming from these plants.

     Or- then distilled off the low boiling point constituents from the part withdrawn from the visor 7 with the low boiling point constituents of the tar, and the resulting mixture of low boiling point hydrocarbons can be subjected to the refining according to the invention, for example to the refining of benzol, while the constituents with a high boiling point pass into the residue of the distillation and can be upgraded with the latter.



   The gas charged with hydrogen necessary for the catalytic refining can be taken from line 26, for example via line 27, and incorporated into the benzol or other substance which passes through line 4. It then arrives with the latter in the vaporizer 7 passing through the heat exchanger 5. However, it can also be introduced directly into the vaporizer 7 via the line 28, if necessary mixed with the circuit gas. . The circuit gas coming from the separator 21 passes into the vaporizer via the preheater 29 and the line 30. A part of the circuit gas is subtracted at 31, so that said circuit gas always retains the same composition.



   If we introduced the gas charged with hydrogen directly

 <Desc / Clms Page number 14>

 
 EMI14.1
 in the process of raf "* 'u-lyUqae i - # coriftky it so would form in dci> .ui- -j # /! - # .-- r #' # i-ut. 10 oc ii. '. tiperaturos ooïaprlsec onfc; -î 1 ....- '"' '" vî.ooi ,,'! ' n ': .. cj chaoïmous. It s' <mH-. -. 1-, pi- i -: - n cV -îToxuti.- 1- l'iiia- ... Il.' -voked by, '.,.,. 1. ()' "atm at the beginning of eajî. 'elé? e on p. 1. ' r, Joars H, 5 at. and more. At the end of a souiaia- approximately, 1.- éek "-souro LJaormiquco,
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 that are in the aoii? of tz ..; "! 1) 61 ', j, .tu, e jn.- -e.'3.UiiC: Cx- a': 3, i:. = .., and which are constituted by tûbalc, are fouled by goldfinch deposits :, ce uai i3 ';;, ;; at the stop c'e installation.

   In the vaporisât- '3 qui' pont vr e - :. or'1: etr designed and conducted according to the 1, n'8v..1o, 3? Jleiia a'3 .t1 930.224 and 930.225, there are deposits which , .1 "'.:;. F',:, ¯¯.a 1 passed (the material to be vaporized and çrc impede vaporioction.



  According to the invention, the new gas is driven by ¯1 ° .d in a preheater 32, advantageously;: ';' 93: '38 compr (':,:; i01: l at the pressure at which The refining takes place .... 'c,: lrtiqtr :, or at a lower pressure. From: hauff811: i.', ;; il: .. ;;:.>. "::: 313 through line 33 into container 34 resistant to t71'G 'S.'i.s'9'I which can be heated in known manner. 9 "Jh"') '1 10 100 liters of mass is required. of contact for 100 ill3 of new gas per hour under a pressure of 35 atm. by ",.:", .. iI..i! '! ..' ;: in 34. The new gas is brought to the optimum co-contact reaction temperature, by indirect heating.

   The contact, consisting for example of a mixture of 8-molybdic acid, cobalt hydroxide, aluxarae and ;; rp'rEr is carried out at a temperature of between 100 and 4:00 "C approximately, preferably between 180 and 350 C, by ē'3ùlp: "'e \?. , '200 G
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 approximately, depending on the nature of the new gas.
 EMI14.4
 The gas leaving the contact has by r :: '\:' J1l1plo the composition
 EMI14.5
 next :

   

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 EMI15.1
 Co2 + ll,: 3:, 0 N H CuHm ........... 0, ')
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<tb> O2 <SEP> ............ <SEP> O
<tb> CO <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 12.4
<tb>
<tb> H2 <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 55.8
<tb>
<tb> CH4 <SEP> ............ <SEP> 24.7
<tb>
<tb> N2 <SEP> ........... <SEP> 4.6
<tb>
 
It contains about 0.1 g of hydrogen sulphide per m3n, but it is free from all other substances which can react with the resinigens contained in the hydrocarbons to be refined.

   While untreated coke oven gas produces a blackish color in a few seconds in the presence of a solution of sulfuric acid and formaldehyde, said solution only becomes slightly brown when passed through for several seconds. minutes the gas treated according to the invention.



   The separation of elemental sulfur as well as the formation of resin and carbon deposits in the vaporizer and heating systems are avoided according to the invention by removing harmful constituents from the fresh gas.



   Even when the refining takes place in the liquid phase or in a mixture of liquid or gaseous hydrocarbons, all harmful scale and deposits are prevented by the process according to the invention. In this case, it is advantageous to react the liquid hydrocarbons to be refined or their mixture with gaseous hydrocarbons, against the current of the gas containing hydrogen. The duration of the refining is significantly reduced and its intensity increases. The mixture of gas laden with hydrogen and of hydrocarbon vapors, leaving the hydrogenating refining, can be treated with a second sulfur-stable catalyst of the same nature.

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   The reactor 14 shown schematically in FIG. 1 is constituted, for example, in main order, by an outer casing resistant to pressure and an inner casing, in which the catalyst is placed in a fixed position on a sieve bottom.

   The inner casing is provided in such a way as to protect the pressure-resistant casing, such that the latter impedes overheating temperatures and that any corrosion can only occur in the inner casing. The space between the outer casing which can be insulated internally or externally. and the inner shell is in communication with the gas chamber of the reactor, such that the inner shell is not subject to pressure and can be designed with a low wall thickness.

   However, the reactor can also be built without an inner shell. The outer shell of the reactor should then be provided with a coating of a known corrosion-resistant material, replacing the inner shell. On the top, the reactor is closed with a cover. On this cover, a heater can optionally be provided, which is filled with metallic bodies, for example rings, balls or the like.



  Around this heater, - fits an induction coil which, if necessary, can be switched on and then cause heating. The gas / vapor mixture arriving at the reaction enters, heated, through a pipe in the contact furnace and is further heated to the reaction temperature under the effect of induced and eddy currents. It then travels through the contact layer, in which the decomposition of sulfur compounds, nitrogen, oxygen, resinogens, etc. takes place ... The gas heats up here to around 10 to 50 C and leaves clean of the contact oven. The reactor is surrounded by a heat insulating layer.

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  The starting material to be refined, & MGur, <j on e Cfiai. : y., ut pass through the catalyst with the ay.n == nGticaxz cu ri = i: = t, 'p, -i. temperature conditioned by the amount I tu 1, =: h-'F.¯rxwtsn = c .., by the reaction, without the rtzf'f.l.i '' = G 'a, (' j. ': f =, (UI; the refined product is of lesser value. d .: large quantity of heat developed by the reaction, they copy that the reaction temperature inside the gas in the catalyst is relatively low, otherwise it will be relatively high.



   Since the process according to the invention is not dependent on maintaining low reaction temperatures, it is also possible to use starting materials which have a relatively high boiling point, for example gas oils, cooking oils. grease, heating oils or the like.



   The height of the catalyst column in the reactor can be adjusted to about 3-15m. In many cases, it is convenient to subdivide the catalyst column into two or more layers, since the mechanical strength of the catalyst is insufficient when it is provided in a single layer of great height. It is also advantageous to work at relatively high speeds, for example from 2 or 3 m / sec to about 15 m / sec. These passage speeds mainly contribute to the catalyst being traversed and heated uniformly, so that no local overheating occurs, even if a relatively large catalyst cross section is chosen, for example in the case where the catalyst is placed in a shaft furnace without the subdivision referred to.

   Subdividing the catalyst column horizontally into two or more layers also reduces the danger of overheating.



   Vapors or gases, for example ga; circuit or

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 Fresh gas or gases containing hydrocarbons, located in one or more places of the catalyst column in the process according to the invention, can be introduced between two layers. The temperature of these gases and / or vapors may be higher or lower than the reaction temperature at which the treated gas / vapor mixture passes through the space between two layers.



   In the first case, the gases or vapors introduced then serve to bring heat to the reaction while in the second case they lower the reaction time at which the mixed gas / vapor treated passes into the next layer. In addition to this temperature control, it is possible to obtain activation of the reaction by increasing the concentration of hydrogen and / or of carbon monoxide, for example by means of the supply of fresh gas between the layers of catalyst. Similar effects are obtained by the introduction of water vapor between the layers at one or more places in the catalyst column, in correlation with a transformation of water vapor and oxide. carbon to hydrogen.



   In certain cases, it may be advantageous to carry out a slight addition of oxygen or air before the various layers or before part of them.



   As already stated. the reaction temperatures can vary within fairly wide limits; in general, they are situated between approximately 300 and 500 C. They can be regulated by heat exchange with the gas / vapor mixture coming from the reaction and possibly by additional heating.

   If the gas / vapor mixture leaves the catalyst at relatively high temperatures and if in the catalyst column there is a fairly large temperature rise, of 100% for example, it is possible, even in the event of heat exchange between the gas / vapor mixture entering and leaving the reactor, easily adjust to the desired temperature, if the exchange is not carried out

 <Desc / Clms Page number 19>

 heat only part of the gas leaving the reactor and if the heat of the other part is used for other uses in the process itself or outside it.



   According to the invention, the catalyst column is subdivided: the number of layers thus formed can vary within the limits of about 2-20. The choice of this number in the different cases is conditioned by the fact that the mechanical properties of the catalyst are not overloaded and that adequate reaction conditions are created, particularly from the point of view of temperature and flow rate; The quantities of gas used can also be taken into consideration, roughly as follows: the number of layers of catalyst will be greater if large quantities of gas are kept in the circuit.



   If cold gas is introduced between the layers, then more gas should be admitted for small amounts of circuit gas and less for large amounts.



   To increase the gas velocity, it is necessary to work with quantities of circuit gas of about 500-15. 000 m3n of gas per tonne of starting material used.



   If, during the reaction, large amounts of heat are released, it may be beneficial to cool the catalyst.



  For example, the catalyst can then be provided in vertical tubes which are traversed on the outside by a boiling cooling agent. Vapors of the coolant are removed from the chamber of said coolant and condensed by recovering heat therefrom, and the condensation product can be returned to the chamber.



   Placement of the catalyst in the tubes or in a closed column is also suitable for maintaining the catalyst at a uniform temperature. The tubes of the contact chamber subdivided in the horizontal plane are then surrounded by a liquid at the point

 <Desc / Clms Page number 20>

   high boiling point, for example phenyl oxide. This phase determines a heat equilibrium between the different parts of the catalyst when they take on unequal temperatures as a result of different reaction rates.



   If, in the process according to the invention, one works with the addition of water vapor, the latter can already be added to the new gas charged with incoming hydrogen; in the process, and then goes with this gas in the catalytic preparation for the refining of hydrocarbons. In preparation and refining, water vapor is the source of a noticeable reduction in hydrogen consumption. In addition, it causes an advantageous temperature equilibrium in the catalyst, which takes place mainly during the catalytic refining of hydrogenating hydrocarbons.



    Example 1.



   This example represents an embodiment of the invention applied to the catalytic refining of benzol recovered in a coking plant.



   In FIG. 2, which shows schematically and by way of example an installation particularly suitable for the process, 51 shows the pipe, through which the gas containing hydrogen comes from the coke oven. The gas then passes through a tar separator 52, where the components which can be condensed are removed from the gas. Through line 53 these arrive at tank 54 and from there to tar distillation 55. Here the tar is broken down into "tar benzol" and / or similar fractions as well as pitch. The fractions to be refined, for example the benzol of tar, pass through 1; line 56 in the storage tank 57; the residue is emptied through line 58, for example in the form of pitch.



   On leaving the tar separator, the gas is conveyed via line 61 to the ammonia scrubber 62. From there, it continues

 <Desc / Clms Page number 21>

 via line 63 to the oil scrubber 64. Here, the valuable constituents still contained in the gas and to. refine, for example gaseous benzol ", which pass with the washing agent charged through line 65 to extractor 66.



     From this, the regenerated washing oil returns through line 67 to the scrubber, while the benzol passes through line
68 in the tank 69 and by the line 70 in the collecting tank 71, which also receives by the line 72 the tar benzol coming from 57. The gas to be removed from the oil washing can be further purified in the apparatus 74 and 75 in a known manner as well as by desulphurization and be stored or delivered as network gas or lighting gas.



   To fully understand the meaning of the invention, for example for its application to the refining of benzol, it should be noted that a gas plant which supplies 17,000 m3n of gas per hour, at the same time produces 500 kgs of crude benzol, which have a content of about 0.5% of total sulfur.



   From the collecting tank 71, the crude benzol passes through the line Si into the vaporizer 82. In this one takes place the vaporization under the admission of about 130 m 3 of new gas per hour, which comes through the line 87 of the. gas plant of the plant, from which it is withdrawn through line 83, for example, compressed at 84 and admitted through line 85 into an installation
86, where, in order to be freed of its undesirable constituents, such oxides of nitrogen, oxygen, resinigens or other impurities of the same nature, it passes at temperatures between 50 and 400 C approximately over a contact stable with sulfur, which may for example have the same known composition as that used for catalytic refining.

   Via line 87, the gas then passes into vaporizer 82, which operates at temperatures
 EMI21.1
 Pastures of 150-250 C, of 1S0-OOo crumple, for example 180 C. Here, the raw benzol is vaporized in the gas stream

 <Desc / Clms Page number 22>

 constituted by fresh gas and circuit gas until a residue is obtained, which may be of the order of magnitude of 1-10%.



  Through line 88, the residue passes into reservoir 89; it can be treated in the tar or gas treatment plant of the same plant. For example, in the diagram shown in the drawing, it arrives through line 90 in the tar distillation 55, where the constituents contained in the residue are also separated, with a boiling point below approximately 200-220 C. , to be returned with the tar benzol to the refining plant. Mixed with fresh gas and circuit gas, the benzol vapors leave the vaporizer 82 via line 91 and arrive, via one or more heat exchangers 92, at the reactor 93.

   They enter for example therein at a temperature of 340 C and leave it at a temperature of 360 C, to be brought for condensation, via line 94, heat exchanger 92 and line 95, in cooler 96 , from where the product of condensation passes into the storage tank 97 and from which the gas is discharged through the line 98. Part of the gas can be returned by means of the pump 99 to the vaporizer through the line 100; the remainder can return to the gas purification, being conveyed in the pipe 101, for example by means of the pump 103.



  In the reactor, it is also possible, via line 102, to add water vapor to the benzol to be refined.



   In accordance with the invention, the reactor is designed in the form of an internally and externally insulated vessel. There is 1.5 m3 of catalyst in a layer 10 m high. In the reactor, the reaction temperature increases by, for example, 20 from the gas inlet above to the gas outlet below. This increase can also be more or less strong depending on the nature of the gas available.

 <Desc / Clms Page number 23>

 or the raw material and depending on the starting reaction temperature. It turns out that, in the case of this mode of working, the refined crude benzol has a sulfur content of less than 0.001% by weight, and that the yield of refined product is about 98% by weight. .



   The plant should operate in such a way that the refined product is under operating pressure. It can then be expanded to normal pressure in a column, where it is completely free from hydrogen sulphide or most of it, and other low boiling point constituents, for example at low boiling point. boiling lower than that of benzol. The remains of hydrogen sulfide, which may still be found in the refined product, can be removed therefrom, for example by washing with dilute sodium hydroxide solution and / or water. This washing plant can be very small and in many cases also be neglected, since the refined product often already leaves the column in sufficient purity.



   In this facility, 491 kgs of refined product were produced per hour. The quantity of circuit gas in this case included 500 m3n / h, the quantity of residual gas 120 m3n / h, which contained 10 kgs of benzine. These 10 kgs were recovered by washing with oil and thus returned to refining.

   The table below indicates the compositions of the lighting gas prepared for refining, of the lighting gas after the treatment in 86, and of the residual gas, which leaves the installation:
 EMI23.1
 
<tb> Lighting <SEP> gas <SEP> After <SEP> purification <SEP> Residual <SEP> gas
<tb>
<tb>
<tb>
<tb>
<tb> New <SEP> gas' <SEP> Residual <SEP> gas
<tb>
<tb>
<tb>
<tb>
<tb> CO2 <SEP> 2.6 <SEP> 2.8 <SEP> 9.6
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> H2S <SEP> - <SEP> - <SEP> 1.4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> CnHm <SEP> 1.9 <SEP> 0.5 <SEP> 0.4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> O2 <SEP> 0.5 <SEP> - <SEP> -
<tb>
 
 EMI23.2
 Go u 9 7 9 6 2 g2 52.4 52.0 40.1
 EMI23.3
 
<tb> CH4 <SEP> 24.8 <SEP> 26.7 <SEP> 37.7
<tb> N2 <SEP> 8,1 <SEP> 8,4 <SEP> 8,

  5
<tb>
 

 <Desc / Clms Page number 24>

 
The following example shows how the process according to the invention is designed when working with the addition of water vapor instead of applying the catalytic treatment of the fresh gas beforehand.



    Example 2:
For the process, it is then appropriate to use the installation shown schematically and by way of example in FIG. 3.



   It is through line 201 that the hydrogen-laden gas to be used for refining is supplied to compressor 202, where it is compressed. Refining should take place at pressures above 1 atm. , with advantage of 20 to 100 atm.



  The compressed gas arrives, advantageously without cooling, through line 203 in heat exchanger 204, which it exits through line 205. To the gas containing hydrogen is added through line 206 with vapor from the gas. water in a proportion of 5 to 50% by volume, for example 30% by volume. However, the gas can also be charged with water vapor in a known manner, by streaming water, when it is at an elevated temperature, for example after having been heated to about 100-300, for example 170 C. The mixture steam and hydrogen-laden gas then enters the vaporizer 207 which, at its upper part 208, is filled with Raschig rings and, at 209, is equipped with a heating system.

   In this vaporizer 207 is fed, if necessary after preheating, the product to be refined, for example benzine or benzol, stored in the tank 210, and this by the line 211, the pump 212 and the line 213. A a small part of the material to be refined, for example crude benzine, is withdrawn in 215 via the siphon 214. The mixture of gas charged with hydrogen, water vapor and benzine vapor, coming from the vaporizer 207 is brought through line 216 to the subsequent heating stage,

 <Desc / Clms Page number 25>

 which can take place for example in heat exchangers
217 and 218 and the heater 219.

   From heat exchanger 217, the gases pass through line 239 into the heat exchanger
218,. And from the latter via line 220 in the heater
219, where they are almost brought to the reaction temperature; then, through line 221, they pass into the contact furnace
222 which is filled with the sulfur stable catalyst 223. The catalyst can be placed in a known manner on a sieve 224.



  Instead of the reactor 222 similar to a shaft furnace, shown on the plan, it is also possible to use a reactor of any other known construction mode. In the reactor 222, the hydrogenating refining takes place during the passage through the contact, for example from top to bottom, of the gas / vapor mixture. The gas charged with hydrogen, water vapor and vapors of benzine or the like, leave the reactor through line 225 and, against the current of the mixture going towards the reactor, give up to said mixture heat in the reactor. the heat exchangers 217 and 218.



  They first enter heat exchanger 218, exit through line 226, pass through heat exchanger 217 and, from there, through line 227, into heat exchanger 204. The charged gas mixture of hydrogen, water vapor and benzine vapors, already cooled to a temperature of about 1200 for example, leaves the heat exchanger and, through line 228, passes into cooler 229, in which the water vapor and the benzine vapor are condensed by cooling to room temperature. This cooler can optionally be subjected to a runoff of fresh water to avoid separations of ammonium carbonate. The cooling water enters the cooler at 230 and leaves it at 231.



   Gas charged with hydrogen, water and refined benzine or

 <Desc / Clms Page number 26>

 other body, pass through line 232 into separator 233 from where the refined product is removed in 234 and water in 235.



   The refined product contains small amounts of hydrogen sulphide as well as dissolved ammonia, and, with a view to their removal, it is passed through a column, in which the dissolved gases are extracted at the top or washed with diluted detergent and water. The hydrogen-laden gas is withdrawn from the system at 236 and admitted to the gas production installation which supplies the hydrogen-laden gas entering the process, for example before the production of benzine from this installation, in order to recover the benzine. However, it is also possible to recover the refined product contained in this residual gas in a known manner, for example by adsorption with activated carbon, cooling or washing with a washing oil.



   Part of the residual gas coming from the installation 236 can be put back into circuit, for example before the compressor 202 or before the heat exchanger 204.



   If the process is practiced with a view to the hydrogenerating refining of liquid hydrocarbons or of hydrocarbon fractions, these, preferably after preheating, which optionally takes place in the presence of gas charged with hydrogen and / or water vapor, for example at a temperature close to the reaction temperature of the reactor 222, are introduced into said reactor, for example bypassing the vaporizer, and passing through the heat exchangers 217 and 218 and the heater 219. The gas charged with hydrogen, coming from the heat exchanger 204, after mixing the water vapor, can be brought immediately to the heat exchanger 217 or to the reactor, for example in its central part , where it is brought into contact with the liquid material to be refined.



   When gasifying a flaming coal with low binding power with oxygen and water vapor,

 <Desc / Clms Page number 27>

 under a pressure of 20 atm., for the production of network gas, tar, tar oil and gasoline gas are collected as by-products. These materials are recovered in a known manner from the pressurized gas produced by the gasification; gaseous benzine, for example, is recovered by treating the gas with washing oil. The tar and the tar oil are jointly subjected to a distillation in which, among other things, a fraction extending from the start of boiling up to a temperature of about 2iO C.

   This fraction of light oil, which contains approximately
25% by volume of phenols, can be dephenolated in a known manner, for example by extraction with hot water or with an alkali solution. This dephenolation is not however absolutely necessary because the phenols, even if they are contained in rather large quantities in the starting material, are transformed into hydrocarbons during the hydrogenating refining. The gaseous benzine and the fraction of light oils, where appropriate dephenolated, are pooled and subjected to catalytic refining for the production of a motor fuel of a specific type.

   The mixture has, for example, the following composition:
 EMI27.1
 
<tb> Density <SEP> to <SEP> 20 C <SEP> 0.813
<tb>
<tb> Sulfur <SEP>% <SEP> in <SEP> weight <SEP> 0.65
<tb>
<tb> Acid <SEP> oils <SEP>% <SEP> in <SEP> volume <SEP> 2
<tb>
<tb> Start <SEP> boiling <SEP> 64 C
<tb>
<tb> 5 <SEP>% <SEP> en <SEP> volume <SEP> 71 C
<tb>
<tb> 15 <SEP>% <SEP> "<SEP> 93 C
<tb> 25 <SEP>% <SEP> "<SEP> 100 C
<tb>
<tb> 35 <SEP>% <SEP> "<SEP> 107 C
<tb>
<tb>
<tb> 45 <SEP>% <SEP> "<SEP> ii6 C
<tb>
<tb> 55 <SEP>% <SEP> "<SEP> 128 C
<tb>
<tb> 65 <SEP>% <SEP> "<SEP> 143 C
<tb>
 

 <Desc / Clms Page number 28>

 
 EMI28.1
 
<tb> 75 <SEP>% <SEP> in <SEP> volume <SEP> 160 C
<tb>
<tb> 85 <SEP>% <SEP> "<SEP> 180 C
<tb>
<tb> 95 <SEP>% <SEP> "<SEP> 203 C
<tb>
<tb> End <SEP> of boiling <SEP> 210 C
<tb>
<tb> Loss <SEP> boiling <SEP> '

  <SEP> 2.4 <SEP>%
<tb>
 
The refining loss includes 39 kgs / 1000 kgs of crude benzine. The refined product has the following composition:
 EMI28.2
 
<tb> Density <SEP> to <SEP> 20 C <SEP> 0.795
<tb>
<tb> Sulfur <SEP>% <SEP> in <SEP> weight <SEP> 0.034
<tb>
<tb> Acid <SEP> oils <SEP>% <SEP> in <SEP> volume <SEP> 0
<tb>
<tb> Start <SEP> boiling <SEP> 61 C
<tb>
<tb> 5 <SEP>% <SEP> en <SEP> volume <SEP> 74 C
<tb>
<tb> 15 <SEP>% <SEP> "<SEP> 84 C
<tb>
<tb> 25 <SEP>% <SEP> "<SEP> 92 C
<tb>
<tb> 35 <SEP>% <SEP> "<SEP> 97 C
<tb>
<tb> 45 <SEP>% <SEP> "<SEP> 105 C
<tb>
<tb> 55 <SEP>% <SEP> "<SEP> 113 C
<tb>
<tb> 65 <SEP>% <SEP> "<SEP> 125 C
<tb>
<tb> 75 <SEP>% <SEP> "<SEP> 143 C
<tb>
<tb> 85 <SEP>% <SEP> "<SEP> 158 C
<tb>
<tb> 95 <SEP>% <SEP> "<SEP> 193 C
<tb>
<tb> End <SEP> boiling <SEP> 203 C
<tb>
<tb> Loss <SEP> boiling <SEP> 3,

  2 <SEP>% <SEP>
<tb>
 
Since it still contains hydrogen sulfide as well as ammonia, it is carried through a column, in which the dissolved gases are removed by extraction at the top or washed with sodium hydroxide solution and water. , and then dried. In most cases, it is no longer necessary to further process the refined product. In the case of difficult hydrocarbons, particularly benzines, it can often happen that the refined product is not completely stable to light.

   Thanks to an easy complementary treatment, by

 <Desc / Clms Page number 29>

 example washing with dilute sulfuric acid and / or treatment with bleaching earth, alumina, silica gel, activated carbon, or the like, in the liquid phase at normal temperature or above high, or in the gas phase, optionally under pressure, however, the desired total light stability can be achieved without difficulty. This treatment, which follows the refining with the sulfur-stable catalyst, can advantageously take place in the presence of the gas charged with hydrogen and / or water vapor.



   However, this additional treatment can also be replaced by a fractionation of the refined hydrocarbons - or fractions of hydrocarbons. In particular, it has been found that, during this fractionation, a light-stable distillation product passes, while the materials causing the colorations remain in the still residue. This can be kept relatively low, for example at only about 1-15% of the refined product subjected to fractionation. The residue from the distillation should be added again to the hydrocarbons or hydrocarbon fractions to be refined.

   In particularly difficult cases, this fractionation and further treatment with dilute sulfuric acid, bleaching earth or the like can be drunk successively - in any sequence.



   The refining of the crude benzine takes place at a pressure, which will advantageously be somewhat higher than the pressure of the network gas. Thus, for example, for a network gas pressure of 20 atm., The pressure in the refining installation will be set at 25 atm. Through line 201, 1,000 m3n of new gas per hour are brought to the compressor 202, which are brought to a temperature of 170-180 C in the heat exchanger 204, which is optionally supplemented by a cooling system. additional heating. To this gas, it is brought by line 205, 250 kgs

 <Desc / Clms Page number 30>

 of water vapor per hour, available at a pressure of
36 atm.

   The hydrogen-laden gas enters at the same time as the water vapor into the vaporizer 207, which is maintained at a temperature of 190-220 C by the heating system 209. Through line 213, it is fed to the vaporizer 1.000 kgs of raw benzine per hour. 15 kgs of vaporization residue per hour are withdrawn via line 215, which can be discharged into the tar, which occurs during the production of gas, for example before its distillation. Leave the vaporizer through the pipe 216.1.000 m3n of gas, 250 kgs of water vapor and 985 kgs of benzine vapor per hour, which are brought together to a temperature close to the reaction temperature. - tion by the heat exchangers 217 and 218 as well as by the heater 219.

   Reactor 222 is filled with a stable sulfur catalyst, based on cobalt, molybdenum and alumina, and is operated at a temperature of about 380-500, eg 400-420. The imposed load of crude benzine comprises approximately 0.1-2 t / m 3 of catalyst per hour, preferably 0.3-1.0 t / m 3 of catalyst per hour. As a catalyst, for example molybdic acid on alumina is used, the molybdic acid concentrations being of the order of approximately 10%.

   A further catalyst of high activity for the treatment according to the invention of fresh gas can be obtained by free ... by intimately mixing 70 parts by weight of a commercially available aluminum hydroxide with texture of bayerite, which serves mainly in the catalyst as a support, with 18 parts by weight of molybdic acid, 8 parts by weight of cobalt hydroxide and 4 parts by weight of graphite. The mixture is formed into small cylinders by compression. After cooling of the gas / vapor mixture leaving the oven, cooling taking place in heat exchange as well as in the cooler 229, it is present in the separator 233,

 <Desc / Clms Page number 31>

 946 kgs of a refined product of benzine.

   Through line 236 1,000 m 3 of gas are withdrawn which are delivered to the gas production plant, for example before washing the benzines after the pressure has been reduced from about 23 to 20 atm. for example. The number of octanes of the crude benzine was determined according to the Research-Method: it was 75 without the addition of tetraethyl lead. It was found that the number of octanes of the refined product - determined by the same method - was 78, while that of a crude product refined under the same conditions without the addition of steam. prior to the invention, was only 68. Benzine refined in the presence of water vapor and gases laden with hydrogen is also much more sensitive to lead.



   The gas withdrawn through line 236 contains carbon monoxide in amounts of about 3-8% by volume. Such an extensive conversion of carbon monoxide during refining is therefore not as necessary as it would have been before refining if it had been refined with gas loaded with carbon monoxide and without the addition of carbon monoxide. water vapour.

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


    

Claims (1)

CLAIMS 1 - Process for the hydrogenantalytic refining of hydrocarbons or the like, which are liquid or cold at room temperature, refining taking place at elevated temperature preferably under elevated pressure in the gas phase and / or in the phase liquid, in the presence of lighting gas, coke oven gas, incomplete carbonization gas, natural gas or similar gases containing hydrogen, a process characterized by the fact that these gases, before or during., hydrogenating refining, are freed from materials hindering hydrogenating refining and are made particularly suitable for audit <Desc / Clms Page number 32> treatment, and pass through hydrogenating catalysts at temperatures between about 50 and 500 C, usefully between 150 and 450 C. 2 - Process according to claim 1, characterized in that, with a view to the treatment of the gases, use is made of sulfur-stable catalysts based on mutais of groups 6 and / or 8 of the periodic system, for example those which are or have been used for the subsequent refining of hydrocarbons, and which are preferably based on tungsten, molybdenum, vanadium, cobalt, chromium, nickel or iron. 3 - Process according to claim 1, characterized in that it is used alkaline ferrous catalysts for the '.treatment of gases. 4 - Process according to claims 1 to 3, characterized in that it is mixed with the gases, before, during or after the treatment with hydrogenating catalysts, of the circuit gases which come from the catalytic hydrogenating refining of hydrocarbons or fractions of 'hydrocarbons. 5 - Process according to claims 1 to 4, characterized in that it is added to the hydrocarbons or fractions of hydrocarbons or to their vapors during the vaporization or heating to the reaction temperature, for example before the last stage of heating, gases treated with hydrogenating catalysts. 6 - Process according to claims 1 to 5, characterized in that the gases treated with hydrogenating catalysts are introduced, with or without the addition of circuit gas, into the vaporizer for the hydrocarbons or fractions of hydrocarbons to be refined, or in the reactor, in which the catalytic refining of the hydrocarbons or hydrocarbon fractions takes place. 7 - Process according to claim 4, characterized by the <Desc / Clms Page number 33> EMI33.1 causes that the new gas is passed in a mixture 'i 3f 1., ;; ..' itt, ', 4 sl-- vaporized carbides and possibly4; lu gas de c ::.!: (; '-' 1.i -: .. through the catalyst which is at .la tuoo: ß3 p L -: x -: .'- .. e; = u 3. 'new. 8 - Method according to one of claims 1 to 7, charac- EMI33.2 terized by the fact that we use for the; h. = ii "age Q0- gas charged with hydrogen the heat from the refining ca o, .. T'j.- that subsequent. 9 - Process according to claims i to 7, characterized in that the catalyst for the preparation of the gases is heated indirectly with the gases used for the hydrogenating refining of hydrocarbons or fractions thereof. 10 - Process according to claims 1 to 9, characterized in that the hydrocarbons or fractions thereof to be subjected to the hydrogenating refining are heated to the reaction temperature or to a temperature close to the latter, by way of heat exchange with refined hydrocarbons or hydrocarbon fractions. 11 - Process according to claims i to 10, characterized in that oxygen is added to the gas before or during EMI33.3 owing to their treatment with hydrogenating catalysts, t in the n-sud where in catal ': heating of the gas by partial combustion of the latter occurs. 12 - Process according to claims 1 to it, characterized in that the gases charged with hydrogen are not brought to the EMI33.4 pressure used for the catalytic refining of hy1ro.Jr1 ::,. i.- res or hydrocarbon fractions, only after the treatment with the hydrogenating catalysts, the treatment of the gases with the hydrogenating catalysts can also take place under pressure. , however lower than that of catalytic refining. 13. Method according to claims 1 to 12, characterized in that one works during the treatment of the charged gases <Desc / Clms Page number 34> of hydrogen, with a catalyst in the form of a swirling layer or in the suspended state. 14 - Modification of the process according to claims 1 to 13, characterized in that the departure of the materials hindering the hydrogenating refining from the gases loaded with hydrogen and the particular aptitude of these for hydrogenating refining are caused or improved. by adding water vapor. 15 - Process according to claim 14, characterized in that the water vapor is added in quantities of approximately 5-50% by volume, usefully 15-35% by volume, based on the gas charged with hydrogen entering the process newly. 16 - Process according to claims 14 and 15, characterized in that the water vapor is introduced into the preparatory treatment of the gas or into the refining reactor hydrogenating hydrocarbons or hydrocarbon fractions. 17 - Process according to claims 14 to 16, characterized in that it is used water vapor and unprepared new gas. 18 - Process according to claim 17, characterized in that the new gas not prepared with the addition of circuit gas and water vapor, or separated from the circuit gas and water vapor, is admitted at a location of the raffina- reactor. Hydrogenating ge which, seen in the direction of the flow of the gas / vapor mixture, is located downstream from the point of admission for the hydrocarbons or hydrocarbon fractions to be refined. 19 - Process according to claims 1 to 18, characterized in that the hydrocarbons or hydrocarbon fractions refined by catalytic hydrogenation are fractionated and that the distillation residue is treated in the manner of the distillation of tars or oils of tar, usefully in common with these matters. 20 - Process according to claims 1 to 19, characterized <Desc / Clms Page number 35> by the fact that hydrocarbons or hydrocarbon fractions refined by catalytic hydrogenation are subjected to an easier subsequent treatment with bleaching earth, alumina, silica gel, activated carbon or materials the like, in the liquid phase at normal temperature or higher, or in the gas phase, where appropriate under pressure. 21 - Process according to claim 20, characterized in that the subsequent treatment is carried out with less concentrated sulfuric acid, or that the subsequent treatment is reinforced by this treatment with sulfuric acid. 22 - Process according to claims 1 to 21, characterized in that it is used as a gas containing hydrogen, gas rich in hydrogen. 23 - Process according to claim 22, characterized in that a gas rich in hydrogen withdrawn from the carbonization chambers of a coking plant towards the end of the carbonization period is used. 24 - Process according to claim 23, characterized in that a gas rich in hydrogen is used which has been removed from the carbonization chambers of a coking plant towards the end of the carbonization period, passing through said chambers of the coking plant of,; thane or gases loaded with methane, such as lighting gas or network gas. 25 - Process according to claims 23 and 24, characterized in that a gas rich in hydrogen is used which is drawn from the carbonization chambers of a coking plant towards the end of the carbonization period, in which case, around at the end of said period, the fumes from the catalytic refining of hydrocarbons or the like pass through red-heated coke, either alone or with methane or other gases containing methane. 26 - Process according to claims 1 to 25, characterized in that the gases containing hydrogen are passed <Desc / Clms Page number 36> It is common with hydrocarbons or hydrocarbon fractions by contact furnaces without cooling elements, in which the catalyst is provided in a layer with a height of 3 to 15 m. 27 - Process according to claim 26, characériel in that the flow rate of the mixture of gases charged with hydrogen and hydrocarbons or hydrocarbon fractions in the catalyst is set to more than 0.5 m, preferably from 2 - 15 m / second (volume of gas calculated at normal pressure, at 0 C and at any passage section). 28 - Process according to claims 26 and 27, characterized in that contact furnaces are used, in which the. The catalyst column is subdivided into two or more superimposed layers. 29 - Process according to claims 26 to 28, characterized in that gas charged with hydrogen is introduced between the catalyst layers with or without a mixture of circulating gas, water vapor and / or hydrocarbons or hydrocarbon fractions .. 30 - Process according to Claim 29, characterized in that the agent introduced between the layers has a higher or lower temperature ..the reaction temperature. 31 - Installation for carrying out the method according to claims 26 to 30, characterized by an electric heating system for the gas, or part of it, entering the contact furnace of the hydrogenating refining, system suitable for the furnace of contact, usefully on its cover. 32 - Installation according to claim 31, characterized in that the contact furnace has an outer casing resistant to pressure and an inner casing not subject to pressure. <Desc / Clms Page number 37> 33 - Process according to claims 1 to 30, charac- terized in that, during the catalytic hydrogenating treatment of hydrocarbons or hydrocarbon fractions, which are in the liquid state or in the form of a mixture of liquid and - Fear during refining, the hydrocarbons or hydrocarbon fractions are passed in the reaction against the current of the gas charged with hydrogen.