FR2542005A1 - PROCESS FOR TREATING PETROLEUM AND OIL RESIDUES TO PRODUCE MORE HYDROGENIC PRODUCTS - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR TRANSFORMING CARBON STARTING MATERIALS. THE STARTING MATERIAL IN THE PRESENCE OF WATER IN THE FORM OF STEAM AND A CATALYST 8 CONSTITUTES AN ALKALINE METAL SULPHIDE AND A SCISSION CATALYST WHICH IS A COMPOSITION, IN A REACTOR 10 OF A FIRST STAGE. CATALYTIC, WHETHER OR NOT SUPPORTED AND INCLUDING A FIRST SOLUTION OF A METAL ALKALIN HYDROXIDE DISSOLVED IN METHANOL, ETHANOL, PROPANOL-1, BUTANOL-1 OR THEIR MIXTURES OR A SECOND SOLUTION OF A METAL ALCANOL-ALKALIN HYDROXIDE TO WHICH ARE ADDED ALKALINE METAL HYDROXIDE DISSOLVED IN WATER, THE SOLUTIONS BEING SATURATED WITH HYDROGEN SULFIDE.

Description

PROCESS FOR TREATING PETROLEUM AND PETROLF RESIDUES

  TO PRODUCE MORE HYDROGENIC PRODUCTS

  The invention relates to the treatment of petroleum and petroleum residues; more particularly, the invention relates to the treatment of petroleum and petroleum residues in general, but in particular high boilers residues

  according to ASTM D-1180 and D-1160, or residues

  those which have no boiling point in accordance with these standards or which are destroyed by distillation with the formation of residues

  In addition, the invention relates to an inde-

  during the constituent parts of petroleum or petroleum residues mentioned above, in order to improve the total yields and the space-time rates, including the use of high pressures such as pressures up to N. 55 105 Pa (150 psi) to allow later

  recovery of desirable products.

  In general, there has been a limited attempt, in the prior art, to improve the heavy petroleum fractions of many petroleum components, such as

  residues, have been particularly resistant to

  After extraction of all petroleum components from the tails, such as by steam extraction and the like, or by treating them later, for example by hydrogen transfer reaction, partial coking, coking with water and other, tailings and / or other components have been obtained from them, for example, using a donor solvent.

  of hydrogen, hydrogen from the solvent is transferred

  This increases the viscosity of part of the high-boiling fraction, so that lighter products are obtained. reactions at very high temperatures and in the presence

  or in the absence of hydrogen at high pressure.

254,0005

  Other methods have been used whereby hydrogen obtained by extracting hydrogen from a portion of the highly refractory residues has been used in a parallel stream, with hydrogen being used as the reactant gas and the coked product subsequently used in Other goals or purposes o Excess hydrogen can also be used in the donor solvent system or otherwise in the refining cycle

to improve the residues.

  In U.S. Application No. 140 6049 and published November 18, 1981 in Great Britain as British Patent Application No. 2,075,549 of Applicant No.A, a process for treating petroleum residues with hydrogen has been disclosed wherein residue is brought into contact with steam

  and with alkali metal hydrosulfides or monosulphonates

  and / or their hydrates and mixtures of the foregoing products to hydrocrack, hydrogenate, hydrotreat, denitrogenate and / or demetallize and / or desulfurize the carbonaceous material. According to the process described in this US application, the treatment of petroleum and oil residues have been significantly improved in yield, through-conversion, space-time rate, density (API number), and so on, so that products

improved higher value.

  In applicant's US Pat. Nos. 4,366,044 and 4,366,045 describing various methods relating to the treatment of coal, numerous references of the prior art have also been mentioned. These documents cited in these two patents and as mentioned in these Here, basic information is given concerning the alkaline sulphide chemistry and also include, in part, references relating to the treatment of petroleum or petroleum refining residues. These references show that attempts have been made to improve the residues or treat materials

various carbonates.

3 2542005

  Other prior art documents, based on the literature,

  US patents, have been reported in "Hydro-

  In this list of US patents, mention was made of patents, for example, by Mr. J SATRIAN, Noyes Data Corporation, Park Ridge, New Jersey, USA (1982), for example, p 62-78. following (although these may have been mentioned inter alia in the above-mentioned technique): U.S. Patent No. 3,520,825; 3,775,346; 3,850,840; 4,117,099; 4,119,528 and 4,203,868. prior art does not disclose the present invention which represents a posterior discovery and an invention with respect to the method described in the application for

British Patent No. 2,075,542.

  Other less relevant prior art documents have also been found, for example, in Fuel, Vol. 62, Feb. 1983, the purpose of which is to exclusively study fundamental studies of catalytic carbon and carbon gasification (see Kikuchi et al, " Supported Alkali Catalysts

  for Steam Gasification of Carbonaceous Residues from Petro-

  leum ", ibid), p 228 et al., which describes carbon deposits on supported catalysts, generally allowing for substantial gasification, and which does not mention the role of

  alkali metal sulfides played in these reactions).

  Other prior techniques have been described by Sikonia et al, "Flexibility of Commercially Available UOP Technology for Conversion of Resid to Distillates", AM-81-46 publication of the National Association of Petroleum Refiners (ANRP),

  1981, Washington, DC, USA; Ritter et al; "Recent Develop-

  in Heavy Oil Cracking Catalysts ", publication AM-81-44,

  ANRP, 1981; Bartholic et al; "Utilising Laboratory Equip-

  in New Residual Oil Development ", publication AM-81-45,

ANRP, 1981.

  The method according to the present invention relates to a method

  the use of a boiling bed reactor and catalytic

  and especially a process for the treatment of particularly refractory petroleum residues, for example those boiling above 850 ° F (4550 ° C) and particularly asphaltenes or ORA fractions (mixture of petroleum, resin and asphaltenes). ) from petroleum refining and characterized as boiling above 5380 C (1000 F) and above, according to ASTND-1180 and D-1160. The present invention relates to a more efficient conversion of

  tails or residual products particularly refractory

  res. Another aspect of the invention is to improve the process described briefly above. It is an easier and more advantageous treatment of petroleum or crude oil, such as using a starting material as well as 'a less fully refined oil or oil residues obtained, by oil treatment, substantially no residue remains

  and the starting material is substantially converted to complete

  This result is achieved by the fact that, according to the present invention, a rigorous oil treatment is not applied.

usual residues.

  By particular boiling point, we mean in the present

  description, a boiling point for which the products

  products are practically completely distilled at this boiling point (according to the processes then defined) up to this temperature, and that it remains substantially

  no residue, unless mentioned.

  The process according to the invention is distinguished from the prior art by the fact that particular catalysts,

  preferably in supported form, to transform

  highly refractory oil residuals such as those having a boiling point above 538 ° C (1000 ° F) and usefully converting these residual components into a low-viscosity product, highly desirable, by a process

particularly effective.

  The process according to the invention is further distinguished from the prior art by the fact that the reaction in particular transforms the most refractory components of the residues, such as asphaltenes, while at the same time avoiding adverse effects of the formation of coke that can occur if the process is not carried out correctly, because of

  the discovery of catalyzed thermal decomposition

  In addition, other advantages are obtained by the use of a boiling bed reactor, by carrying out the process continuously and at a high temperature up to 6500.degree. by simultaneously quenching the conversion product to obtain a desired final product in one or more other reactors, in combination with the first reactor. According to the process of the invention, the ORA fractions obtained from residues such as those resulting from the refining of pre-trole or the refining of other carbon sources, are

  advantageously treated by the process according to the invention.

  However, the process is useful for treating asphal-

  such as asphaltenes extracted with solvents, giving improved results, when they are

  treated in one or two stages to split and / or

  this particularly refractory product in one or two stages and thus the total yield obtained a

from a barrel of oil.

  The improved process of the invention is characterized by the ability of the particular catalyst to convert carbon into Ramsbottom or Conradsen into usefully hydrogenated products.

  without affecting, to a notable degree, the process.

  In addition, the process according to the invention relates to combinations

  particularly advantageous catalyst support bases which can be used, for example, in a bed reactor

  boiling and for the preparation of processing products

  in a particularly advantageous manner, without the catalyst carrier combination being modified by unknown metallic constituents which are in the

  oil and which have accumulated in the fractions ORA.

  In addition, it was found that after the first stage of transformation,

  With the active catalysts, a second soaking step can be carried out during which the cleaved product can be conveniently cut with a particularly selected catalyst, in the second reaction step, for

  produce the predetermined and / or highly desired cuts.

  However, the second reaction step is dependent and based on the particular catalyst of the first step, and based on the reaction carried out appropriately in the

reactor of the first stage.

  In addition, the process of the invention also makes it possible to recycle the product which has not reacted correctly in the first reactor and its subsequent conversion into the desired final product. Thus, it has surprisingly been found that one can still

  to improve the process of the invention by carrying out a

  of the various products recovered first

  from the fluidized bed reactor or boiling and frac-

  In one embodiment, it has surprisingly been found that the split-stream process (which is direct for the treatment of the first gaseous or vaporized phase, e.g. for tail products which are obtained by collecting them in another separation device, such as a cyclone, further contributes to the total conversion of the starting material, by this separate treatment of the heavy fractions collected from the bed of This is due, in part, to the use of different combinations of catalysts to avoid certain defects of the catalyst compositions that are used

  to process the very diverse components of the original products

  no or for their recycling In addition, the tail products

  being pretreated to a certain degree (ie those characterized

  the low A p values) benefit from this parallel processing.

  This separate treatment in at least one vapor stream

  A lower fraction, already degraded initially, eg from a boiling bed reactor, gives a large number of advantages. The catalyst movement is about 5.1 to 101.6 cm (2 to 40 inches) per second and

  for 10 to 30 minutes of parking time for

  the particles supplied, and about 43 cm (17 inches) per second for 20 minutes of parking time of the particles fed, on average (the catalyst movement is defined according to the technique of the bed in boiling) Additional boiling is caused by the steam and , by the product

  in the reactor At the same time, this treatment

  This makes it easier to improve feed rates, yields, conversions, types of products, etc. for the top products from the first stage, so that the total flexibility of the process to treat a

  wide variety of feed products is remarkably

  by the parallel processing as mentioned, in par-

  especially the proportions of derived products can be cut to adjust the different feed products with

  the fractions of the different constituents, as well as the

  mixed feeds from source materials

  various which are particularly difficult to treat.

  This aspect of the process where the heavy tail ends can be recycled but without parallel treatment gives striking results, but a contrary improvement was found This kind of process is called a "recycling process" The improved process is called a "parallel process" Thus, a separate treatment without recycling is more advantageous for the total improvement of products and the yields of products which are obtained from a wide range of products.

  variety of heavy oil, petroleum refining

  and the particularly refractory components In fact, the parallel process as described here causes almost

  entirely a complete recovery of all

  oil killers as useful products.

  The variations of the process are characterized as well as their results by the improved products which are obtained from very poor starting materials, the high hydrogen content of the starting materials, the low viscosity and the small molecular size of the split products and the

  the possibility of processing the products by means of

  posterior-conventional

  Since the process of the invention allows a hydrogenation

  important product that improves yields, improves the product, and gives smaller molecules and thus a less viscous product and largely eliminates and / or decreases the presence of Conradsen or Ramsbottom carbon, the

  The final result shows that important results are

  tants in the continuous search for using all the fractions of a refining product which, until now, could not be improved advantageously to such a degree

  that which is obtained by the process.

  The process according to the invention, namely consisting of "process

  "recycling" and "parallel process" is thus particularly

  useful, since the fractions of oil which

  in the prior art, under particularly -severe conditions, can be reacted by means of the catalysts described, in a less severe and direct manner and either according to a recycling process, or

  in a parallel process The tail products are very

  fractures (obtained by the conventional process) constituting a larger part of the total mixture and which are the most difficult to treat, are treated and recycled or, instead

  to be strongly attacked at first, namely by

  boiling and / or recycling of tails, can now

  treated by a parallel treatment with the degree required

  This rigorous treatment for the recycling process or the parallel process is still markedly and significantly less than that required in the prior art, but gives much better results which are characterized by better greater recovery of products and recovery steps of simpler and other products

  particularly important characteristics which are

below.

  In addition, the process according to the invention can be applied to other products such as Gilsonite (also known as uintahite, a black glossy asphalt from Utah), pitches (natural products and / or or refined), tars such as tars found in California, (natural) asphalts such as those from Trinidad lakes and the type found in Utah and other products found in the United States. nature or that are obtained

  after refining treatments that allow concentration

  remove oils, resins and asphaltenes from the tailings; oil sludge in refineries whose oil is often not distilled, tailings from coal gasification plants, for example solvent extraction products of coal or products extracted from coal; coal such as those described by Satrien (mentioned above) p 206 or distilled shale oil tail fractions; heavy tailings from the Lurgi gasification process that are produced when the SASOL process is carried out in South Africa; diluted coking products obtained during the bottoms distillation of these products; both hard and soft resins and asphaltenes It is inappropriate to mix these starting materials, but this can be done for the purpose of experimenting with the actual reaction conditions. By heavy crude oils is meant crude oils having an index At Pl less than about 22 including

  the crude oils having much lower numbers A p.

  The combination method as described herein is such that the more volatile fractions of petroleum and similar hydrocarbons can be treated in a direct manner, but heavier tails ie heavier components, particularly the more refractory components. , are treated

  more preferably by a recycling process or process

  parallel, depending on the severity of the treatment required.

  For example, starting materials that require more severe treatment are better treated by the parallel process. In the future, the process is more suitable for

  starting material is chosen in such a way as not to

  the total yields obtained by the reactor of the first diversion and to improve the products obtained at the tail by a recycling treatment or a treatment with

  parallel to improve total returns.

  Although the "parallel process" has been described in relation to

  parallel treatment with two chain reaction pathways or two parallel parallel treatment, other parallel and

  the refractories obtained from the second reaction train

  or the second stream can be reacted without recycling. ill

  According to a result of the combination of steps described above,

  above, the invention provides time-space velocities

  high yields on an absolute basis, yields

  respective parallel steps or combined yields.

  An example of a parallel processing is such that a product

  obtained from a very heavy fraction of mixed tails

  Particularly refractory products yielded final products having a K factor of about 11.71, ie high paraffinic products, which are obtained with great ease at the top of the first reactor and subsequently treated, for example to reduce the bromine index

and others.

  The following description with reference to the accompanying drawings

  of non-limiting example will allow to understand how

  the invention can be practiced.

  FIG. 1 shows a recycling process in a boiling bed reactor and FIG. 2 schematically shows a continuous process by which materials from various sources are transformed into

  useful products by a parallel process.

  As shown in FIG. 1, the reactor of the first stage is a boiling bed reactor 11 comprising a reaction vessel 11 provided with a trap funnel 15 at the top and a pump 14 for recirculating the fluid products 8 from the reactor. The catalyst 9 which is in supported dispersed form is boiling with the fluid 8 A fluid 8 from the reaction comprising the catalyst 9 can be circulated by pumping the fluid into the reactor and reintroduced appropriately by the In a traditional way, the circulating fluid

  can be introduced at the top, but we can make the introduc-

  elsewhere in the reactor at one or more locations.

  On a larger scale, and as close approximation to a boiling bed reactor, it is possible to use a stirred tank, provided that the supported catalyst is placed in one or more boxes or baskets such as envelopes consisting of of stainless steel grid, the latter being fixed to a suitable frame driven by an external motor. By varying the speed of rotation, for example 20 to 180 revolutions per minute, preferably from 50 to 150 revolutions per minute, obtains reactions that are approximately nearly those obtained in a boiling bed reactor Finally, it is important that the fluid contact with the catalyst and the steam is effected

to get the desired result.

  Circular fluidized bed reactors where the supported catalyst circulates with the fluid or bed reactors

  In the same way, a reaction

  fixed bed with a rising and falling fluid can

be used for the invention.

  A preheated feedstock such as asphaltenes or an ORA cut is introduced via a pipe 12 continuously. Steam 13 can be introduced with the starting material or it can also be introduced into the reactor.

  through the fluid from the bottom of the reactor 10.

  The lighter viscosity fluids obtained are fed through a tube or pipe with a large diameter 15 a and cooled by

  appropriately if necessary-in a tremor zone

  page 16, then introduced into a second reactor 17 Although there is shown in the figure a single reactor, it is also possible to use a plurality of reactors in series or in parallel These reactors can be fixed catalyst bed, or reactors gas phase or vapor column is used where the catalyst is supported on trays

25420 O 5

  17 in the traditional way You can use other

  well known for this purpose, such as trickle-bed reactors and others. The tails from the second

  reaction stage are collected in the assembly area

  18 They are classified as tails ne1 These tails

  may be put into circulation wholly or partly

  in the boiling reactor with the fluid collected by the line 15 at the bottom of the funnel of the boiling bed. If necessary, a pump 14 may be used for this purpose. It is also possible to extract and recover a part of the product. for further treatment A feed fraction from reactor 17 of the second step can be refluxed by a reflux generator 19 and the products can be derived from the reflux generator, the gaseous products therefrom are treated in a second reactor such as that shown in 17, but not shown here D are all reactors called second stage reactors to distinguish them from the reactor 10 of the first stage where the splitting of the starting material is carried out, It is possible to: treat the products from the reactor of the second stage and

  other gaseous products, in another reactor or by bar-

  botage in a suitable bath to remove all the components

  unwanted nutrients such as hydrogen sulphide This can be done in a container 20 in which it has dissolved

potassium hydroxide.

  Then the gaseous products are recovered in a manner traditionally

nel the.

  As shown in FIG. 2, the reactor of the first step 110 is a boiling bed reactor. It can also be a basket-type or stirred-cage reactor or a fluidized bed reactor. For example, shaking cages or baskets have not been shown here However, because the boiling-bed and stirred-cage or stirred-basket reactors are very similar in their behavior and results, they are considered to be

the mimes.

  The reactor 110 comprises a reaction vessel 111 with trap means such as a funnel 115 located at the top and a pump 114 for recirculating the fluids 108 undergoing the reaction. The starting or fluid product 108 may be petroleum or hydrocarbons. light petroleum residues boiling at a temperature below about 4540 C (850 F) but may be also ORA (petroleum, resin, asphaltene) boiling above this temperature, ie above 5660 C (+ 1050 'F), i.e., having no boiling point A catalyst 109 which is in dispersed and supported form is boiled with the fluid 108 A screen 109 has prevented the catalyst from rising with However, the fluid undergoing the reaction, including the catalyst, may or may not flow by pumping into the reactor, by means of the pump 114, since the catalyst may remain suspended in the fluid, ( for the circulating fluidized bed reactors)

  o only a liquid phase with no catalytic

  It can be sucked into the funnel 115 As shown in FIG. 2, the boiling fluid pumped by the pump 114 can be introduced anywhere in the reactor, although preferably it is introduced near the bottom or

at the bottom of it.

  To the feed product 108, of the type mentioned above, is added by a single introduction opening, steam and / or water 113 or can be provided openings

  for each of these products, arranged circum-

  ferentially around the container 111 The components

  petroleum fractures, having a longer time of parking

  undergo the catalyzed reaction and are trained by

  the outlet pipe 115 a This pipe reaches directly

  in a cyclone 116 which separates the vapor phase products from the liquid phase products and / or the entrained products and the products obtained with the steam from the boiling bed. More than one cyclone 116 can be used Bottoms 112 cyclone are processed in a separate parallel processing line. Products at the top of cyclones 116 can be quenched in a quench zone 116a as shown in the figure and then reacted immediately in a reaction vessel 117.

  may not be abruptly cooled before introduction.

  duction in the reaction vessel 117 because the soaking

  can take place in the latter The reasons for which

  the sudden cooling will be explained

below.

  After introduction into the container 117, a suitable catalyst, as described below, supported or unsupported, is suspended, as shown schematically, on trays 117a or by other means. The gaseous or liquid stream still produces a lighter and a heavier fraction or the gaseous stream can be hydrogenated. These bottoms can be removed to get into a vessel 118 and then treated in a conventional manner or as described below. , can be treated separately in a

  another parallel processing line.

  Although not shown in the drawings, additional reaction vessels can be provided in

  the same derivation, of the kind of the container.

  Final delivery of gases from the reflux condenser 119 or other condensers (not shown) can be done in a conventional manner such as by cooling and / or low temperature cooling and / or pressure condensation, and is not necessary to

describe these methods.

  It has been found advantageous that gaseous products

  from the initial treatment, after treatment in the reci-

  Still further, the temperature of the reaction vessel 117 can be further treated at a temperature of about C to about 240 ° C. in a reaction vessel of the kind shown in FIG.

  appropriately and appropriately to collect these products.

  Tails 112a, from the reaction and separated for example in cyclones 116, are generally the compounds

  the most refractory of oil or petroleum products.

  These products 112 have, although-thought to have been reactivated

  partially in the reactor 110 (for example as

  characterized by the improved A P1 index) are treated

  in a first line of parallel processing.

  Since these bottoms have reacted to a certain degree due to the presence of the catalyst 109 in suspension in the boiling bed, the rear reaction is preferably carried out with another specific catalyst suitably modified, if necessary, to suit the reaction. particular product. This second stream thus forms the tails 112a which are fed into the reaction vessel 130, at the same time as the steam and this feed jointly undergoes a catalytic treatment of the still hot product. The feed 112 has been more easily hydrogenated. and thus we achieve superior improvements to obtain compounds a

  lighter viscosity of heavier oil fractions.

  It is advantageous to treat feed products 112a with a different catalytic composition in the presence of steam in the same proportions as the steam supplied to the feed.

  first reactor 111. It has been found that

  The various lytic compounds are more advantageous in the later reactions, unlike the catalysts which were originally used in the boiling-bed reactor and designated 109. The use of a different catalyst is due to the partial reaction of the compounds. more

  Refractory in the container 111 The catalyst composition

  different for the treatment of tail fractions is described below. Since the reaction vessel 130 can always be followed by another reaction vessel (not shown), the overhead products recovered in the reflux column 133 from the reaction vessel 130 can be reprocessed.

  reflux column 133 can be cleaned in the recirculation

  The reaction vessel 130 can be used in the same manner as the reaction reactor 117, i.e. as a reactor, to remove the undesired components, for example H 2 S, and the gaseous products are then recovered and reused. a rising or falling flow, with a supported or unsupported catalyst, suspended in a bed or

  on trays 130a, or as a fixed bed catalyst.

  A liquid catalyst, such as molten, hydrous, molten, liquid sulfides at the temperature at which it is preferable, as previously described in US Pat. No. 4,366,044, may also be used in

following reactors.

  If it is not desired a subsequent reduction in the molecular size of the distilled product at the top from the first reactor 110, the distilled product can be hydrotreated.

  head in vapor phase reactors, immediately, when

  from the cyclone 116 separating the tails (the heavy product, partially reacted or recycled and unprocessed), the

head distillate that is produced.

  The quenching in the cooler 116 avoids the recondensation of the separated compounds. The hydrogen treatment is favored by the absence of the heavier fractions (removed by the cyclone 116). By definition, the treatment with hydrogen is done by no cracking either thermal or catalytic and includes the addition

of hydrogen to a molecule.

  Since the hydrogenation reaction is exothermic, the

  cooler 1 * 16 previously described helps to control the temperature and avoids damaging the product if we meet

excessive temperatures.

  Fixed bed reactors can be used for this treatment

  hydrogen, or catalytic reactors can be used.

  However, presently, the catalytic reactor

  liquid appears to be more effective at lower temperatures than

  at 280 ° C., because of the solidification of the catalyst above 28 ° C., which is a result of interconversion of the hydrates. Fixed bed reactors are less efficient

  the degree of hydrogenation obtained in liquid reactors.

  of. If now the product of arrival is described as being typically a fraction ORA, that is to say a fraction of oil, resin, asphaltene, it is in fact a product

  which boils at atmospheric pressure 2 a higher temperature than

  re at 5380 C (1 OOOCF) Although this is a description

  the fact that the quantity of oil, resin and

  asphalten is not necessarily known it is a measure

  easy for the most refractory compound in an oil.

  It is known that asphaltenes can be solvent-extracted from petroleum residues or ORA fractions to allow the subsequent treatment of the petroleum and resin residue Asphaltenes, of course, are particularly refractory to a subsequent treatment such as by catalysts or other means and thus constitute a fraction that can

* only be effectively burned or coked by means of

  dice of the prior art to evacuate all possible hydrogen

of this product.

  A practical characterization of asphaltene is that it is this part of the asphalt or bitumen that is soluble in carbon disulfide, but insoluble in paraffins,

  for example heptane, paraffin oil or in ether.

  Resins of the ORA fraction can be extracted by propane Bitumens are also soluble in carbon disulphide Carbenes, which are constituents of bitumen,

  are insoluble in carbon tetrachloride but

  carbon disulphide In addition, the constituent

  oily or bituminous is also called malthene or malt

  These products are soluble in petrol.

  Maltenes are soluble compounds in pentane and

  asphaltenes are compounds that are insoluble in pentane.

  In another broader and wider sense, asphalt

  such as petrolatum, mineral tar, gul-

  rock tar, Trinidad tar, petroleum tar and natural hydrocarbon mixtures such as amorphous solid or semi-soiids fractions produced by oxidation of

  Residual petroleum are included in the definition above.

  Moreover, there is no agreement on the exact definition of these compounds such as maltenes or asphaltenes, mixtures which are often reported as being one or other of the constituents in the prior art. , the

  solvents used and the techniques of extraction and

  In this respect, asphaltenes extracted with solvents such as asphaltenes extracted with carabonium disulphide, precipitated from heptane, are not considered as constituents of the final product. pure as they have no particular melting point but only softening points softening points of

  asphaltenes up to 204 C (400 F) and above

  As a result, a practical measure to define the ORA fraction is to define it as a product boiling at 538 C (1000 F) and above, although this temperature limit is arbitrary and lower temperatures such as 482 C (900 F) can be chosen because the entire

  material can not be extracted properly.

  From now on, a temperature below 427 C (8000 F) will be

  simply erases a tractable composition less easily.

  For example, an asphaltene extracted by a solvent with a high softening point has a softening temperature

  approximately 132 C (270 F), a density at 15.6 C (60 F) of approximately

  The viscosity at 135 C (275 F) is 1.026 and thus the viscosity is 3.957 stokes or 395.700 c St '(centistokes).

  (The stokes are obtained by dividing the poises by densi-

  The viscosity at 149 C (300 F) of the same asphaltene at the softening point is 877 poise with a density at 149 C (300 F) of 1.016 and 86 000 c Sto. The viscosity at 163 C ( 325 F) for this asphaltene is 261.5 poises and the density at 169 C (335 F) is

1,006 which gives 26,000 ST.

  The analysis of the above solvent extracted asphaltene is given in the following table:

ANALYSIS OF ASPHALTENE

  Metals Carbon 84.59% Fe 360 pp m Hydrogen 8.80% Ni 147 pp m Nitrogen 0, 82% V 490 pp m Sulfur 5.52% Na 497 pp m Ash 0.27% K 4 pp m Moisture 0.0 % Heat capacity of Oxygen asphaltene 18.6 J Total 100.00% Although the above asphaltenes may be considered representative, many other asphaltenes, depending on the source from which they originate, may have

different characteristics.

  Based on the above analysis of the products, it is seen that these products have a considerable content of metals. This content varies according to the source of the material and can be up to 6,000 parts per million (ppm) of vanadium. , but typically about 600 ppm nickel and

  other constituents may also be present up to

  As a result, these metals also affect the possibility of treating the residue by conventional methods of treating petroleum residues.

  On the basis of various analyzes, the typical hydrogen content

  that the ORA fraction may be in the range of about 13.5% to 7% and less by weight, but again this is not a precise characteristic In a boiling oil residue above 538 C (1000 F), the hydrogen content is about 12.5% and lower A considerable percentage of "11" carbon fiber has also been found (as Conradsen carbon), for example up to 45% by weight. free carbon is defined as carbua ne Conradsen or carbon Ramsbottom, but these analyzes are not identical because the different methods used to define the "free" carbon that in fact may not be "free" In the fraction ORA, the Conradsen carbon can be up to 40 and more%, by weight In any case, the residue

  carbon can be converted according to the method described here.

  Cracking, whether thermal or catalytic, produces smaller molecules than those present in the original Lii product being cracked. A smaller molecule will have a boiling point at a lower temperature than a larger molecule. the hydrogen treatment does not produce cracking (and thus gives smaller molecules) The temperature range of the boiling point

  appears to be approximately the same before and after

  by hydrogen. The hydrogen treatment is effective for example in the hydrogenation of paraffinic olefins in the product by hydrogenation of said olefins and triolefins either to monoolefins or to paraffins. Aromatic carbides are also converted to naphthenes by treatment with hydrogen Real paraffins appear as

  not reacting during treatment with hydro-

  gene. The treatment with hydrogen can also reduce the sulfur and nitrogen content of the product. However, if the asphaltenes, which contain more nitrogen, have not been previously cracked, the nitrogen of said asphaltenes is not capable of

  disappear by treatment with hydrogen The degree of

  removal of sulfur and removal of nitrogen is equivalent to hydrogen treatment of an unsaturated bond (when

  hydrogen is not present at the position at which the hy-

  must be inserted into the molecule) These atoms of

  sulfur and nitrogen, in an exposed position in the structure

  the chemical nature of the product, and the nitrogen and sulfur atoms that can be replaced by hydrogen, in a thermodynamically favorable exchange, with the formation of ammonia and hydrogen sulphide and the formation of more saturated molecules of the product, are the sulfur and nitrogen compounds that

  can be removed by hydrogen treatment.

  The bromine index is a measure of the degree of unsaturation of the product. The lowest-unsaturated product fractions have the highest bromine values. The hydrogen treatment of the product causes the bromine index to acceptable level, for example a bromine number of 40 to 50 for the product having an initial boiling point at 204 ° C (400 F) (product obtained by distillation in

  this interval by the methods described above).

  As mentioned above, the tail products 31 can take a separate parallel path and can be used as feedstock, but these

  can also be recycled because the post-reaction

  However, if the tail products 31 are difficult to process, by another derivation, they can be subjected to yet another treatment stream of the type shown for the product.

  120 a, and in particular shown in Figure 2.

  As long as most of the overhead products from the reaction vessel 11 are treated with only one direct passage therethrough, the bottom fractions 112a as collected in cyclone 116 or in the

  118 are products but in a

  smaller portion, depending on the composition of the petroleum constituents These tail products can thus be processed in smaller containers, depending on the proportion of the components of the petroleum products to be processed. Thus, various mixtures of petroleum can be processed.

  now be usefully treated, which depends on the

  The size of the reactor 130 should be in proportion to the tail constituents in the oil such as those boiling at a temperature of 3580 ° C.

(l OOOF) and above.

  Steam is introduced into the reactors 110 and 130, the amount of steam used being at a rate that depends on

  to a certain extent the product that is thought to be obtained.

  The vapor can be about 50 up to 100 and 130% of the recovered product by weight. The steam can also be given on a base defining a lower limit, ie such that the coking does not occur to a significant degree due to the absence of steam but which does not occur in the reactors 110 or 130 if the steam is present in insufficient quantity Thus as the lower limit, the amount of vapor introduced may be such that any significant coking is avoided in the reactors 110, 117 , 130, etc. Additional steam can be fed in the same way into the reactors 117, 130, etc. The vapor is a

  low pressure, preferably it is recovered steam.

  The temperature in the reactor can generally be up to 650 C, although a more advantageous reaction temperature

  less than 4500 C, and even less than 425% C Cepen-

  temperature in the reaction vessels

  for example 117, etc., can be lower and lower temperatures seem to give a more

  hydrogen, which is characterized by a lower bromine

  However, the treatment of more refractory compounds in reactor 130 may require the same temperature as

in the reactor 110.

  The rapid cooling can be carried out at a temperature of 390 ° C. and below. The third-stage reactor, which is not shown, can have a temperature as low as in a range of 170 ° C. and less, ie less than 125 ° C. C (but without vapor condensation) Lower temperatures are preferable because the hydrogenation is exothermic

  and most of the hydrogenation is done in the reactions

  downstream, while most of the cracking is done in reactor 110, and to a lesser degree in

the reactor 130.

  The pressure in the vessel 111 and downstream thereof can be maintained at atmospheric pressure. Although pressures below the atmospheric pressure are possible, they are not as effective if the pressure is between about 7 days. 5 Pa (100 psi) or less than 25.8 10 5 Pa can be used), the reactions appear to be improved when pressures between 4.2 IO 5 Pa (60 psi) and less than 10.5 are used. 1 05 Pa (150 psi) is an interval that is the best for unknown reasons Steam condensation should be avoided at higher pressures Although the exact reason is unknown and V is not known do not understand the conversion, it seems that there is a better hydrogenation in this

  interval, but the increase in pressure is less

  that because it requires more complicated equipment and

  1 r a bigger investment in money.

  In addition, instead of using cyclone separation as described with reference to the drawings, for example using one or more cyclones 116, other separation means can be used to recover the products.

  liquids and / or entrained and thus to treat

  Such other means may be separat-

  centrifugal equipment, disposal drums, and others.

  With regard to the materials which can be subjected to the treatment, it is a question of varied oil coming from any sources and having any viscosity. These oils, as long as they are suitably liquid at the treatment temperature, can These residues are characterized as products which have a boiling fraction within about 4540 C (85 O'F) However, their constituents or reaction products (from reactor 110) which boil below 454 C (850 F) are treated better in a parallel circuit such as

described below.

  Subsequent treatment in the second parallel reaction circuit can give products of better and improved viscosity, having a higher hydrogen content and a better chemical structure (eg products having a high paraffin content with high K values, or polycyclic aromatic compounds which can always be further processed to produce unsubstituted olefinic cyclic compounds and linear or branched paraffinic products) Thus the gaseous products obtained by carrying out the process according to the invention and the conversion of the unsaturated products to more saturated products constitute a refinement to the process previously described. By treating the products of this process with hydrogen, in order to reduce the bromine number and further reduce the nitrogen and sulfur content of these products, it is necessary to keep the mind that hydrogen treatment at room temperature lower does not mean "crack" the product has a

  significant degree and thus does not mean to form molecules

  The hydrogen treatment of the product makes it more difficult to improve subsequently, ie, by cracking (as determined by a range of boiling points at the end of the boiling point). lower temperature due to the formation of smaller average molecular sizes),

  to the apparent inability of this process 1 to crack paraffi-

  The treatment with hydrogen must therefore be the final phase of the process and should not be used until the desired molecular size has been obtained by the "cracking" of the process. vacuum residues are initially cracked into smaller size molecules under less severe conditions, and then the refractory residues, i.e. the feed stream 112a, are treated under more severe appropriate conditions which do not affect the products. of the main stream The product

  resulting in a range of boiling points at room temperature

  The reduction of the sulfur and nitrogen content of the top product accompanies this reduction in size

  molecular, with respect to the feed product.

  The resulting smaller molecules that form the

  "cracked" products do not contain high amounts of nitrogen such as the feedstock Nitrogen is normally concentrated in the "heavy asphalt" tails of the petroleum residues. methylene group in the porphyrin structure of the asphaltenes and are thus usually separated in the parallel reaction path Therefore, the metals and the nitrogen remain in the unreacted central porphyrin structure of the asphaltenes and are either not present or

  present in a very limited quantity in the product

  of the vacuum residue containing the asphaltenes which have been concentrated in relation to the

  asphaltenes of the crude product which forms said residue under vacuum.

  Metals and nitrogen are more concentrated in the tails

  1, namely 112a, which do not form the product

  The sulfur content is not necessarily concentrated in the asphalten portion of the crude oil or residue. The resin portion of the residue may contain up to 5 X

by weight of sulfur.

  With regard to catalysts which are sometimes also called

  reagents, they are used in the form that these cat-

  lysers give the desired results, namely a separa-

  and / or splitting of the bonds in the first reactor and the reactors of the parallel paths 28 -

  following or a hydrogenation ultimately desired.

  States are obtained by treating appropriately and severely

  re, but not too harsh, the products treated first

  with the catalysts described below, and these are referred to

  With reference to the results obtained, the pretreated refractory compounds (in the reactor 110) are suitably treated in the parallel path in a severe manner. Mixtures of these catalysts can be as highly desirable for the oils and their residues or for the mixtures. oil based on various fractions of oil.

  A catalyst allowing the severe treatment in the reaction

  110 is called catalyst A and is prepared as follows: one mole of potassium hydroxide is dissolved either in ethanol or methanol, preferably in ethanol, or

  in an ethanol-methanol mixture, or less advantageously

  because of the lower solubility, in the propa-

  nol-1 or butanol-1 The solubility of the catalyst is less than

  in these last two and in larger quantities

  alkanol must be used and therefore

  The alkanols can be absolute alkanols, although they can be 95% ethanol. Potassium hydroxide is dissolved in this solution and then reacted with hydrogen sulphide which is bubbled through.

  the solution After complete saturation, the catalytic mixture

  The alcohol-alcohol is recovered and the alcohol is removed by vacuum suction. Leresidu is the catalyst For a mixture of solvents, for example, one mole of potassium hydroxide is dissolved in 200 μl of ethanol and 130 ml. of methanol Granules having the quality of analytical reagent of potassium hydroxide (approximately 86% KOH), absolute ethanol or 95% ethanol and absolute methanol As

  mentioned above, the proportions of an ethanol-

  methanol may vary The solution is evaporated under vacuum

  until no residual alkanol remains.

  lysers seem to be the best for separation and especially for scission of refractory compounds and therefore are used in adequate proportions (or

  only) with others to obtain the desired split.

  In the first stage of the reactions, the catalyst may not be supported, but more advantageously for the first stage and the later stages, it is deposited on supports and calcined. Referring now to the catalyst supports which are employed, these are used most of the time to obtain an increased surface area. The catalyst supports are spinels, such as chromite spinels (Cr 2 O) and more preferentially porous metals, namely stainless steel of the genus AISI and others This latter is obtained by sintering powder metal particles, of very small uniform size, or is produced in the form of a thin plate obtained by exhaustion of the exhaustible compounds in the thin metal plate (for example 3 mm). which consequently forms intercommunication passages Other metal supports are obtained by sintering very fine wires, about 0.2 to 5 mm thick, and in one blow These are, for example, 2 to 5 mm in length. Other carriers are alumina with pore sizes ranging from 1 to 5 mm. 50 to 250 10 '0 n and even up to 100010 i m but these need to be

  protected as explained below, although the

  in the reactors is less dependent on the characteristics

  of the support, the treatment in the first stage reactor according to the invention is better when it is carried out

  with a strong inert support such as metal

  porous cells which have a pore size, for example up to 3500 A and above, ie the metal is made up of% metal and 90% pore by volume although the metal

  can go up to about 25% in volume.

  In all reactions, the catalyst is allowed to react without atmospheric oxygen and thus in the absence of oxygen. Similarly, the deposition of the catalyst on the support is carried out in the absence of oxygen as well as for the evaporation of the volatile compounds. of the support. The catalyst and the carrier, when the volatile compounds have been removed, are heated to a suitable temperature of between 320 ° C. and 450 ° C. or even up to 560 ° C. The catalyst adheres firmly to the support and can thus be used in a reactor. rotating cage (also called rotating basket) a boiling bed reactor or a fluidized bed. If the support is unduly attacked by the catalyst, such as alumina in the reactor of the first step, the following method is then used: The catalyst mentioned above is evaporated to be completely dried, dissolved

  in the glycerol, and the glycerol-catalyst mixture is deposited

  For example, other carriers which are less resistant to attack by the catalyst, such as molecular sieve supports, are treated in the same manner. Preferably, these molecular sieves may be of the genus Y and X, for example. Example Y Lo 82 with a low sodium content (they come from Union Carbide, Danbury, CT or comparable carriers come from fobil Oil, New York NY). However, molecular sieves function as catalyst supports, namely increase the Area

catalyst contact.

  The glycerol = catalyst mixture after deposition on the support is then progressively heated to for example 560 ° C and

  the volatile compounds are evaporated.

  It is also possible to deposit the glycerol first, to heat it to about 200 ° C., then to deposit the catalyst on it (after the support has been cooled), and then to heat the mixture.

desired temperature.

  The reaction in the first reactor may be at a temperature of

  ture and can range from about 3200 C to about

  450 ° C, although temperatures up to 560 ° C have been used.

  even up to 650 ° C For asphaltenes, the interval

  the preferred temperature is from about 3600 C to about 430 C; it seems that the interval 390 C to 425 'C is a very

good interval.

  Because for these catalysts the reaction must always

  be carried out in the presence of steam to facilitate the

  generation, hydrocracking, etc., the steam is used in a ratio which is at least about 27% by weight, based on the weight of the feed product such as the ORA fraction, the crude oil, the residues, etc., loaded into In contrast, the amount of water charged as steam at the reaction temperature can be increased or decreased depending on the degree of hydrogenation desired (which can also take place in the first reactor at a higher temperature).

  certain degree) If one seeks to obtain more hydrogen

  tion, more steam is introduced, but preferably the

  The vapor must not exceed about 85% by weight of the material.

  to be treated, although 130% by weight can be used with respect to the hydrogenated product to be obtained, namely withdrawn (if a gaseous fraction is produced, then it is converted into a liquid equivalent) On another basis, the amount of water used is determined by subtracting the hydrogen content of the product to be processed from the

  hydrogen of the desired product, on a weight basis and in

  tiplying the quantity by 9 (because the water is 1/9 by weight of

  preferably up to 30% excess is injected

in the first reactor.

  If no water is introduced into the reactor, for example in the form of steam, or if the introduction is stopped for one reason or another, then coking can be done, so the carbon is deposited or formed by a somewhat catalytic thermal cracking process 9 but in this

  In this case, the catalyst acts as a thermal cracking catalyst.

  more advantageous (because the cracking

  catalytic thermal is performed at a much lower temperature, for example 320 ° C), but much less efficient than when it operates in the presence of steam

  as a hydrogenation and / or separation catalyst.

  Ai-nsi, as mentioned earlier, a slight coking can also take place in a lower limit although

less desirable.

  Intermittent or insufficient introduction of steam can also cause the production of particularly heavy products in the reactor 110 It is important that the steam is introduced all the time, in a correct manner in the reactor and dispersed completely (without interruption time).

  in the introduction of steam and / or reagent).

  Nevertheless, it should be mentioned that excessive amounts of steam also prevent the reaction being carried out in an appropriate manner, which would unduly

partially converted.

  If carbon is deposited for one reason or another, typical

  it is deposited on hot spots such as the walls of the heated reactor or the catalyst support By

  therefore, the reactor 10 preferably operates in a manner

  Re-adiabatic carbon deposits on the catalysts can be avoided, ie converted into useful products by exposure to steam for a period of time, without introduction of the additional product, after which the catalyst can be used again and can

  to be used for the production of groups of products

  The intermittent introduction of hydrogen sulfide or sulfur may be useful in general and for low sulfur starting materials, for example, crude crude oils. In addition, it has been found that if the temperature, as with the above-mentioned catalyst, has increased by about 320 ° C. to 420 ° C., depending on the composition of the starting material (for example its asphaltene composition), reaction

  exothermic reaction may take place, for example an exotic reaction

  The thermal reaction takes place at 440 ° C. The exothermic reaction can reach temperatures up to 600 ° C., but depends

  also the amount of vapor that is introduced.

  The higher vapor temperature tends to produce lighter carbonaceous products. Excessive temperatures are undesired and lower temperatures are preferred. In the reactor of the second step in Figure 1, 17, or referenced at 117 on the 2, in which the rear reactions take place, the products of the first reactor are advantageously rapidly cooled to about 250 C and in the presence of a catalyst, generally at temperatures

  between 250 C and 390 Co The quality of the product is.

  increased when the process is carried out at temperatures up to about 430 ° C, preferably 425 ° C, but the

  conversion apparently does not increase after 390 Co The cooling

  Sudden quenching in the cooler 16a is done at a rate such that the vapor does not condense and does not interfere with the reaction The light tails, of course, which are

  hydrogenated products are not condensed.

  The catalyst in the second reactor 17 or 117 is also

  preferably a supported catalyst but it can be a catalyst.

  Unsupported catalyst and allows the treatment of steam or gaseous products. A typical catalyst for this second reaction step, namely in reactor 17 or 117, is a less severe catalyst B. This catalyst is produced by dissolving a technical or analytical species. a hydroxide

  of potassium which is approximately a potassium hydroxide

  86% sium in ethanol or absolute methanol or 95%

  (preferably ethanol) and saturated with hydrogen sulphide

  but without boiling the alkanol, collecting and trapping all the evaporated alkanol in a container in avalo Other containers in which the reaction takes place can be arranged downstream to trap the hydrogen sulfide When the last container containing KOH shows a reaction, the reaction is stopped in the containers in avalo If the reaction is carried out in other reactors 17 or

  1175, namely in second-stage reactors, advances

  The effects of the process reside in the combination obtained by the abrupt and immediate cooling of the reactants from the first stage reactor to about 300 ° C, but preferably 250 ° C, in the presence of the catalyst and then carrying out these reactions of the raw materials. Step in the second step For this purpose, it has been found particularly advantageous that the catalyst is supported on a suitable support. These supports may be the same as those used in the first step, but in any case these supports must be inert under the reaction conditions. in the particular reactor, for example Figure 1, 17, or Figure 2, 117 and 130 o These reactors 17 or 117 of the second stage can be used as reactors bed

  fluidized bed (circulating fluidized bed, partially circulating bed)

  The reactor 30 may also be a boiling bed reactor or a fluidized bed 2 reactor.

or circulating fluidized bed.

  It has also been found that it is suitable for the second stage reactors, for example 17 or 117, to use commercially readily available carriers such as fixed zeolite alumina aluminasilicates, ie molecular sieve type, with sodium or potassium in zeolite exchanged with ammonia Type X and Y zeolites (10 and 13) are well suited. Type Y molecular sieve zeolites are preferable; of these, low molecular weight sodimum sieves are particularly suitable (ie, less than about 1.0% Na 2 O). The molar ratio of silica to alumina of these products is about 3 to about 1, about 5 to 1, etc .; Na 20 is about 0.2 wt.%. These products are commercially available as spherical powders,

  of cylindrical and other extrudates, etco, of suitable size

  such as 3 mm for extrudates or spheres Although these appear to be poisoned or destroyed by alkali metals, when used in the process described above, these supports are useful despite the fact that alkaline sulfide reagents described above are deposited. These supports can also be used in the

  reactor 10 of the first step.

  Other suitable zeolites are potassium-type ELZ-L zeolite as described in US Pat. No. 3,216,789 and silicates as described in US Pat. No. 4,061,724. The latter has a pore size of about Other carriers are those described in British Pat. No. 1,178,186, namely zeolite having a low sodium content of less than 0.7% by weight, for example ELZ-6 or ELZ-6. E 6 or E 8 or El O Other supports are mordenites and erionites with a very low sodium content obtained

  by exchange of ammonia and the calcined genus Molecular sieves

  Such caps of the above type are very low sodium type Y carriers, for example 0.15% by weight, ammonia-exchanged and sold under the trademark LZ-Y 82 from companies such as Linde Division. In any case, the stability and shelf life of these molecular sieves used as carriers are tested under reaction conditions and are established for the purposes of the present invention. use in the reactor of the second stage. The preparation process for the supports of the second step is as follows: Exchanged zeolite extrudates with a low sodium-amonimum content, such as powders, or having cylindrical shapes, in the form of stools,

  stars, rings, spheres, etc., of powders or extrusions

  dats having a size of about 3.17 mm to 3.97 mm or 4.76 mm, with glycerol or other polyhydroxyalkane compounds, such as partially reacted polyhydroxy compounds including up to hexahydric alkanes, impregnating

  first these forms in a reactor that is kept closed.

  Then, for example when using glycerol, by heating and removal of the decomposition compounds of these powders or forms, from ambient temperature up to 265 to 280 ° C and even up to 5600 C, an appropriate but unknown reaction takes place The support having thus reacted is then sis screened, drained, and cooled in a closed container hermetically if the temperature has been brought to 560 C.

  When it is cool, the medium described above is then

  impregnated with a reactive catalyst of the general formula K 2 S 5 (empirical); this catalyst is acceptable but is not critical for cleavage Although the catalyst is designated by empirical formula, a particular method of preparation determines the behavior of the catalyst accordingly, although various catalysts can be presented by the same formula ( Empirical), very different properties have been observed and different starting materials have been treated to produce different products. This catalyst, which is designated as catalyst C, is obtained by dissolving 6 moles of KOH in 4 1/2 to 7 1 / 2 moles of water without

  external supply of heat and then with a small

  alkanol, for example 2 to 2.5 ml of methanol or ethanol.

  These are added per mole of KO 2 O. Then 4 moles of elemental sulfur are added to the above solution which is exothermically reacted. Next, an appropriate amount of sulfur is added to adjust the catalyst to the desired sulfur level by addition of additional sulfur to form empirical sulfide, namely from K 2 S but K 251.1 to K 252.5,

  up to K 2 S 55 which is useful, depending on the

  desired products To obtain more gas in the

  product, less saturated species are used in the process.

  To obtain more liquid in the product, we use

  varieties more saturated with sulfur.

  Another catalyst, catalyst D, is prepared as follows

  dissolves one mole of KOH in 1.0 mole of water with vigorous stirring.

  Then 2 ml of ethanol or ethanol are added immediately after KOH is dissolved. Immediately afterwards, 2/3 mole of elemental sulfur is added and allowed to react vigorously.

  a desired empirical sulfur content by adding quan-

  appropriate amounts of sulfur with stirring, i.e., mole of 2/3 mole of sulfide adds 0.5 empirical sulfur content of K 2 S; 1/4 of 2/3 of mol of dissolved sulfur gives K 251.5; 1/2 of 2/3 of mole gives K 252.0 etc. including other appropriate fractions Thus the catalyst can be

  in the range of K 1251.1 to K 252.5 'or even up to 1 K 25.

  Species with a lower sulfur content, for example

  K 251.5 are catalysts of good cleavage when mixed with Catalyst A and it is a good catalyst in general for a less severe treatment of oils.

  Catalyst is also a catalyst for hydrogenation.

  lyseur A is usually mixed with from 3 to 25% but

  ference less than 10% by weight to the catalyst Do When the catalyst was thus prepared, it was evaporated

  under vacuum in a coulanteo mud Then it is poured on the ex-

  cooled trudate treated with glycerol, as described above.

  above (ie if the carrier was heated to 3000 C or higher), and under a very low vacuum, stirred and aspirated until drying Then the catalyst is then put on grid when it is dried and immediately introduced into the second stage reactor which has been purged of oxygen from the air when it is used as a hydrogenation catalyst

  Another method for protecting the medium if the medium

  Glycerol is heated between 2600 C at a decomposition point (indicated by an appreciable slowing down of a liquid condensate which is collected), consists in adding the

  catalyst sludge described above and the container is

  covered and heated up to at least 440 ° C, including up to 560 ° C In any case, the catalyst is calcined above the temperature at which the catalyst is used in the process o Another method is to mix glycerol D for example about 88 ml of glycerol, about 1 mole (based on t ()

  of catalyst in solution or by mixing the catalysts

  The catalyst-glycerol mixture is heated to evaporate the vapor and / or the alcohol which leaves the catalyst glycerol solution. The temperature is brought to 190.degree. C. for this purpose. The mixture is then poured onto the support and with stirring brought to at least 4500 ° C. and even up to 560 ° C. This supported catalyst gives a very unpleasant odor. It can be prepared under well isolated conditions. first stage reactor having

  the capacity of 3.78-1 in connection with a second reactor

  up to about 2/3 mole of supported catalyst (K base) is charged to the second reactor.

* can be loaded in the reactor of the second stage a cata-

  K 251.5 (empirical) lyser supported on alumina.

  Another catalyst, catalyst E, is an unsupported or supported catalyst capable of decreasing the molecular size of the product in a first stage reactor (or used in another second stage reaction). Catalyst E is obtained by adding dried KHS powder or sludge, the addition being given in moles or percentages by weight (relative to the desired product size) to any of which

  reactive mixtures A, B, C or D mentioned above.

  Any forms of supported or unsupported catalysts may be used. 1/5 to 1/3 mole

  molar base of K from KHS to, for example, K 2 S sulphide

  e) or K 2 Si, 5 (empirical), and the molecular size of the

  product is rendered inferior by these additions of KHS.

  When the process is carried out with supported catalysts

  in the reactor of the second stage, adjustments can be made

  For example, K 2 Si, l or K 251.5 gives more hydrogenation, and K 252 gives larger molecules (and thus more distillate and less gas). These reactions are carried out in a temperature range of 1130 C a

  440 C Similar adjustments can be made to the cata-

  lyser in other reactors, for example when using

  more than a single reactor 17 or 117 of the second stage.

  In any case, the reaction of the first step is however carried out with the mentioned reagent to achieve the desired degree of separation or cleavage of the non-treatable refractory constituents forming the initial material, for example crude oil residues, the ORA fraction and in particular Asphaltenes In parallel processing, these difficult to work compounds that have not yet reacted are then

  catalytically treated to obtain the desired degree of

  The combination of the total process in the subsequent stages

  which are the second, third, fourth, etc., steps, depends on the particular reaction of the first step and the present part of the constituents not having

  reacted and is thus interdependent.

  The amount of catalyst deposited on the support is about 4 moles of catalyst (K base) at about 0.5 mole or as low as 0.1 mole (K base) for 500 ml of carrier on a

  other base, but a base which is not identical, the quantity

  The amount of catalyst is about 20 g per 300 microns of support, but can be in the range of 3 g or 5 g of reagent per 100 ml of carrier to about 25 g to 300 g for

mid support.

  The vanadium metal can be completely removed from the petroleum product and the heavier product can contain essentially all the vanadium. If it is in contact with the supported catalysts present, the vanadium is analyzed in a very small amount or not detectable in the tails. NO 2, namely the product 18 The removal of nickel is

  favored if a little reagent is present in hydro-

  Sulphide There is no reaction between alkali metal sulfides and nickeli sulphides but there is a solubility reaction when alkali metal hydrosulfide and nickel sulphides are present Nickel (and iron) form ferrite-like complexes with alkali metal sulfide hydrosulfides These complexes are immediately hydrolysed in liquid water to form the

  precipitates of iron or nickel hydroxide in liquid water

  of, the vanadium complex with the catalyst is strongly

  soluble in water and stable in water Iron is normal-

  contained in the residue, after the determinations of the distillation intervals, in an amount of between 3 and ppm, but the quantity also depends on the amounts in

the initial step.

  In general, the catalysts for the second and subsequent step reactions are hydrosulfides and sulfides, i.e., monosulfides and polysulfides of Group IA elements of the periodic table other than hydrogen prepared from of the alkanol solution mentioned above Although for the purpose proposed, sodium, potassium, rubidium and lithium may be used,

  the most advantageous elements are sodium and potassium.

  Of these two elements, potassium is preferred. Although rubidium compounds appear to be acceptable, rubidium, as well as lithium, is not advantageous from a cost point of view. However, for the reactor of the first stage, it is possible to use rubidium very advantageously in

  a mixture of rubidium, potassium and sodium in the proportions

  14% rubidium sulphide, 26% sulphide

  of potassium and 60% of sodium sulphide, for example

  different varieties of these on the basis of the elemen-

  by weight O Report intervals for mixtures

  The above are 11.5 2.5: 3.5, 4.5, respectively, but these compositions should be prepared in the manner mentioned for the catalyst preparation process A. The catalysts used are preferably used as the catalyst.

  hydrates but a small part of the catalyst is

  preferably in the form of an alkanolate (hydrate analogue), ie up to about 15% but preferably less than 10%

  or even less than 5% by weight of alkali metal thionates

  The hydrates (and alkanolates) of these compounds are very complex and undergo a large number of transitions during the initial reaction and under the reaction conditions they undergo.

  Mixed alkanolates are needed to obtain

  Outstanding Achievements No attempt has been made to elucidate the nature of these transition structures or actual structures under the reaction conditions for sulphides, hydrates, alkanolates, thionates, or their mixtures. It is sufficient, however, to indicate that the The catalyst introduced may be a mixture of a plurality of hydrates and / or alkanolates or a eutectic mixture of various hydrates and / or alkanolates, but in any case the particular separation catalyst may be used for the refractory compounds. Similarly, during the reaction, there is a conversion between the sulfur-containing forms of the sulfides 9 and no attempt has been made to characterize this conversion. However, as mentioned above, the starting material of the first stage contains fairly large quantities of refractory components, ie asphaltebene of various sizes, resin and oil such as oil sludge namely containing more than 50% by weight and up to b, but including With 95% of a fraction boiling above 538 ° C., the reaction of the first step requires at least a portion of the specific catalyst, for example catalyst A as defined above.

  refractory decreases in the starting material, it is necessary

  To use less catalyst A similarly for the starting material 12a, it is recommended to use

  the analyzer Ao can also be added to other composi-

  catalytic losses, depending on the linkage split

  sirée (as characterized by the number API, viscosity, etco), the composition seeming to undergo a better link splitting or a better cleavage without excessive production of gazo For tails no 1, namely the supply steam

  12a, the preferred reaction vessel is a reaction vessel

  Boiling bed lionel or cage reactor or stirred basket, fluidized bed reactor and fixed bed reactor

  Another catalyst for the feed stream 12a is a catalyst.

  lyser B containing 5% by weight (based on l (elemental

  KHS) introduced into the catalyst or replaced in the same proportions including up to 95 plump catalyst A

  general, the order of catalysts for the separation of

  The cleavage of the refractory compounds is as follows: Cat A lyseur A (prepared with the haemol); cat al yseur A (prepared

  with the met hanol); Catalyst A (prepared with methanol

  ethanol); Catalyst A + B (50% or more mixture of

  A on the basis of moles K); catalyst D; Catalyst E (about 1/3 mole of KHS added); Finally, by increasing the amount of KHS additions to the catalysts, the capacity to crack is increased. The order of the catalysts for the hydrogenation is the following 1/2 catalyst A + KOH on the molar base, then one adds

  the other half of A (very exothermic hydrogenation reaction

  than); Catalyst C mixture with KHS (based on degree

  desired cleavage); catalyst B + A (50 Do or more cat-

  lyser B on the molar basis of K), and catalyst B. It should be recalled that in the discussion above, the nature

  refractory materials of carbon source and their

  sants is the one that was given for the prior art by

  comparison, the present process is carried out at temperatures

  lower res and lower pressures and is capable

  to transform all the refractory materials of the prior art

  with significant advantages and great ease.

  However, carbon source materials and their components

  In this case, the paraffins are more refractory while the asphaltenes and the aromatics are not more refractory. the invention lies in the fact that it is possible to treat,

  in an appropriate order, and according to this process, with

  suitable compounds, all the compounds of these carbonaceous materials as characterized above by obtaining yields hitherto impossible when these sources of

carbonaceous materials.

  The following description, with reference to the examples annexed to

  non-limitative title will make it possible to understand how the invention

tion can be put into practice.

Example 1

  An asphaltene having a high softening point 1320 C (2700 F) as described below is treated and solvent extracted with the following reagent to obtain product A.

  The catalyst or reagent is the catalyst A described above

  When the product from the asphaltenes treated in the first stage is reacted in a second stage, the product is identified under the reference B.

  the second step is the same as the first step.

  All catalytic compositions are not supported.

  Product Distillate Distillate de p art A B Residue mix A + B from A + B

316 C

(600 F)

  Density, Aq q 159 ', 6 C (60 * F) Cino viscosity p 9898 C, c St (210 F) Carbon content remaining% weight Aniline point 9 o C FIA vol% Aromatic Saturated olefins Bromine number Carbon,% weight Hydrogen, wt% Nitrogen, wt.% Sulfur, wt.% Ash 9% wt. Moisture, wt.% Oxygen, wt.% Nickel, ppm (wt) Vanadium, ppm (wt) Iron, 9 wt. Insoluble heptane (IP method) 4, 6 39, 5 31.3 0, 94 0.920 44.6 8.7 58.0 71.5 84.24 8, 50 0.75 6.19 None * Softening point 132 C (270 F) o Aromatics and olefins are not clearly separated in

  probably due to heavy tails above 3160 C (600 F).

28.5

83, 77

12, 52

09 10

2, 3 1

  0.905 Ln 84.81 9, 95 0, 58 4.946 0.20 Nil the column ru Ln ir 1 j

  The table above clearly indicates the improvement

  maple obtained for the viscosity as well as for the density

  products, the increase in the content of hydro-

  gene and the considerable displacement of the metals present in the last fractions. The following examples show the results obtained. The starting material consists of solvent extracted asphaltene of the kind mentioned above and characterized in

Example 1

  All tests are done as a trial

  Continuous 9 in a stirred reactor The stirred reactor has an internal volume of 15.3 cm in diameter (6.24 inches) and a height of 25.4 cm (10 inches). The stirred reactor is provided with

  stirrer and steamer.

  A steam generator, connected directly to the water supply, forms steam at a pressure of 2.8 l (40 psi). The steam passes through pipes having an internal diameter.

  9.2 mm (3/8 inch) of the agitator and is at atmospheric pressure

  However, the reactor can operate from 0.5 to about 5.10 Pa (0.5 to about 5 atm) or even more as previously mentioned. The bubbler has a diameter of about 8.6 cm ( 3.5 inches) and features a series of barb holes Gttage, all the holes leading upward steaming The bubbler eur is

located at the bottom of the reactor.

  The reactor is equipped with an agitator when a catalyst is used.

  unsupported lyser The motor is mounted directly

  top of the reactor A seal seals the area where the agitator bar passes into the reactor The agitator consists of two circular curved blades forming a

  The agitator can be replaced by baskets

J

  catalyst supported as mentioned above.

  Four baskets containing the supported catalyst are mounted on the agitator shaft. L-es baskets and the agitator shaft have a total diameter of almost 15.8 cm (6.25 inches). height of 15.2 cm (6 inches) and have a thickness of about 1.27 cm (1/2 inch) The basket

  unmounted is a 1.27 cm deep rectangle.

  At the top of the reactor is the gasket through which the agitator shaft rotates, a riser pipe which allows the reactor head distillate to exit, a pressure relief line which includes a valve which

  opens above 2.1} 10 Pa (30 psi) and sucks the

  The pressure relief device is also used to

  fill the reactor with the soluble starting material.

  Two thermocouples are usually located at the top of the reactor A thermocouple measures the temperature of the lower half of the reactor and the upper thermocouple measures the

  temperature of the upper half of the reactor.

  The riser consists of a pipe having a height of about 33 cm (9 inches) and has an internal diameter

about 3/4 inch (1.9 cm).

  The reactor of the second stage is a tubular reactor

  having an internal diameter of 3.8 cm (1.5 inches) and has a length

  30 cm (12 inches) The capacity of the reactor is

  347.5 ml This reactor is equipped with three heaters enrob-

  A thermocouple controls each of the heaters by

  controllers that are mounted in a mobile way.

  The gases and vapors that pass into the reactor of the second stage upstream are then brought downstream by a

  40 cm (16 inch) glass bubble condenser

it is not cooled by water.

  The first condenser is mounted vertically and the bottom of the condenser supports a collecting balloon of 500 Me The balloon

  is normally maintained at 2400 C by an immersion heater.

  The bottom of the flask has a shut-off valve for the collected product. A second condenser comes from the balloon above and is parallel to the first condenser The second condenser is not cooled by water The second condenser is also a

  glass condenser with bubble cooling airs.

  The downwardly inclined tube from the second condenser is connected to a water-cooled condenser. This water-cooled condenser is mounted vertically and has a length of about 45.8 cm (18 inches); it adapts to the top of an unheated 500 ml flask which has a stop cock at the bottom A vertical parallel water cooled condenser follows the second device of this flask Another water-cooled condenser is adapted directly above this

condenser.

  The water cooled condenser at the top is equipped with a 30.4 cm (12 inch) long pipe which tilts upwards. This pipe has a diameter of between 1.3 cm and 1.9 cm. cm (1/2 inch and 3/4 inch) This line is connected to a

ice cream refrigerant.

  Ice refrigerant is a double-walled container used

  usually used to trap vapors before they can enter a vacuum pump The central container contains a water-ice mixture while the gases and

  vapors pass through the outer section of the container.

  Gases and vapors enter the bottom of the container and exit to the top of the container The bottom of the container contains a collector of 500 m I The collector is equipped with a tap

stop to remove the product.

  The remaining gases and vapors are sent to the other refrigeration

  rant, similar to ice refrigerant This refrigerant is

  cooled by a mixture of carbon dioxide and propane

  solid nol-2 Then the product is collected again in a 50 ml container under the refrigerant and this container is

equipped with a tap.

  The remaining gases and vapors are then washed in a

  Potassium hydroxide solution The solution contains 6 moles of KOH dissolved in 360 ml of water The gases are then

  measured by passing through a wet meter.

  After this measurement, samples are collected periodically

  lons and unrecovered gases are sent to the hood.

  For the following tests, 1300 g of solid asphaltene were weighed and crushed to a suitable size for loading into the reactor. The protected liquid or solid catalyst

  oxygen is then added to the reactor, previously

  purged, for example with helium.

  reactor about 40 g of catalyst A anhydrous theoretically.

  The second reactor is loaded, again with the same precau-

  The second reactor is initially heated to remove the water content of both the zeolite carrier and the catalyst.

catalyst.

  When the water content of the internal space of the second reactor has been reduced by raising the temperature of the second reactor

  above 3000 C, the first reactor being heated.

  Solvent extracted asphaltenes having melting points of either 93 ° C (2000 ° F) or 204 ° C (4000 ° F) are used.

  melting point determines the particular shape of the asphalt-

  nes. After the correct temperature for melting the asphaltenes is reached in the first reactor, the agitator is rotated. Normally the agitator initially operates.

  at approximately 30 b 60 rpm.

  Steam is introduced normally when the first reaction

  At this time, the reaction

  second stage must have reached or reached

at 424 C.

read

  Normally, helium is bubbled across the bar.

  kicker before 1 introduction of steam into the device

  in order to keep the bubbler holes open and the

  without oxygen, the approximate helium is bubbled

200 m I / min

Example I

  The size of 1 300 g of solvent-extracted asphaltenes is reduced so that they can pass through the 2.54 cm (1 inch) aperture at the top of the reactor. The asphalts are not heated but are charged in the reactor in soluble form After the charge, one makes babotter in the reactor of heliumo

  The catalyst used is another kind of catalyst A pre-

  prepared as follows to the initial KOH solution described above.

  Finally, a solution of one mole of KOH dissolved in 30 cc of H 2 O is added and then the mixture is saturated with hydrogen sulphide solution. The solution separates into two layers of about one-third for the top layer. two thirds for the lower layer The layers are separated and dried and then the two portions are remixed The mixture can be in the same proportions as those obtained (as in this example), where the proportions of the two catalysts can vary. can also be mixed, dissolved or dispersed to be deposited on a support In theoretically anhydrous condition, the weight of the

  charged catalyst is approximately 40 g.

  The reactor of the second stage is loaded with a catalyst

  supported on zeolite during assembly of the

  The reactor of the second stage contains approximately

  300 g of support and catalyst. This support is zeolite L 2 -Y 82 and the catalyst is the catalyst D, bk K 2 Sl, 5 (empirical) to promote the hydrogenation of the cleaved product. The starting process requires that the second reactor is brought to at least 1750 C before the first reactor

be heated.

  Then the reactor is heated in the first stage Only half of the bottom of the reactor is heated, half of the top of the reactor is not heated to 220 ° C., a small amount of steam is added to the reactor by the bubbler

the bottom.

  At approximately 3200 C, in the bottom of the reactor of the first stage, then begins the slow but calm production

  hydrocarbon product, which condenses in the flask.

  However, this product is much heavier than the product obtained at temperatures in the range of 390 ° C to

4240 C.

  When the bottom of the reactor of the first stage reaches 3600 C, there is a considerable improvement in the production rate of the

  The reaction becomes exothermic and rises rapidly

  This temperature is maintained during this time at the bottom of the reactor. The top of the reactor reaches 3600 C. The temperatures of the reactors of the second stage are in the range of 2200.degree. C. to 4600.degree. C. When the reactor contents of the first stage are in contact with the agitator, the process takes place uniformly at about 4150 C in the reactor of the first stage and with variations between 440 and 460 C in the reactor of the second stage. The amount of steam is estimated at approximately 20 mi

  of water transformed into steam per minute At the end of the reaction

  the top and bottom temperatures in the reactor

  from the first stage can go up to 440 'C.

  Catalyst A mentioned above (as described above)

  above), gives almost no gas passing through the wet meter The amount of gas is less than

6 liters.

  The volume of product consists of the tails N O 2 e collected under the condensers cooled by water This product when combined with the product collected under the ice-water trap totals 458 g This product has a number A Pl

of 23 (density e 15.60 C 0.9158).

  Tails No. 1 total 33 g and have a density of 0.96587 (A P1 index 15), e 15.6 o C (60-F) Tails N O 1 are

  collected under air-cooled condensers -

  The amount of tails collected under the cooled trap b

  dry ice-propanol-2 are 44 vq in the calibrated trap.

  However, when they are collected, only 26 ml are obtained because of the vaporization of these light tails. The density A p1 of these light tails is 81 e 10 'C (density eo C = 0.6553). evaporation, this

  density is relatively imprecise.

  An extraordinarily light coke is formed and forms layers 5 cm (2 inches) thick in the reactor Ce

  coke has a volume of 1800 ml but has a weight of 513 g.

  The dead space under the stirrer causes a reaction of coke-

  delayed faction under the real reaction zone.

Example III

  This example is done in a similar way to that of

  example 11 except that a different form is used.

  catalyst and a faster starting heating of the

reactor of the first stage.

  Catalyst A for this example is a single layer catalyst and does not require layer separation during the drying phase which is made for the catalyst used in Example I above. The maintained temperature of this reaction is 420.degree. During the 42 minutes of this reaction, after reaching the process temperature (about 420 ° C), the catalyst, approximately 40 g on a theoretically anhydrous basis, transforms the following tails from 1,300 g of a feedstock. asphaltenes extracted with solvents initialso

  (a) Tails No. 1, collected under refrigerated condensers

  from air, total 29 g of a hydrocarbon having a density A P1 of 11.5 (density 0.9895 15.60 C-60 F) o

  (b) Naked tails 2, collected under cool condensers

  water and ice water condensers, total 398 g of hydrocarbons, having a density A P1 of 29 (density e, 60 C-600 F = 0, 8816) oc) Tails No. 5, collected under dry ice refrigerant ice-propanol-2, total 43 ml with a density of 83 b ambient temperature A large part of tails n 5 are lost by determining the density AP Io d) A total of 135 l of gas is produced The gases are measured after alkaline hydroxide washing of gases and vapors (after cold dry ice-2-propanol siege) 0 These gases are not collected for analysis, but the similar average reaction analysis produces approximately 5% (percent by volume) of non-hydrocarbon gas, such as

  hydrogen, carbon monoxide and carbon dioxide

  The remaining hydrocarbon gases have a molecular weight

  on this basis a total weight of 280 g of hydro-

  carbides may be mentioned as being the gas obtained, e) The same light coke as that formed in Example II was observed in the reactor according to this reaction.

coke is 489 g.

The weighted weights are

Tails na 1: 29.0 g.

Tails No. 2 398.0 g.

  Tails No. 5 g 41.5 g (cold trap) o

Gas g 280.0 g.

Coke: 489.0 g

Total 1,238.0 g.

  Recorded g 95.23% (conversion of tails n 1, 2, 5

  gas / feedstock feed = 57.57%).

  For both examples I and XIX, the supported catalyst of the second reactor is completely cleaned and without bitumen, carbon, etc. The total of the products counted obtained by Example II is 1,045.7 / 1,300 = 80,42. o Conversion, namely the

  tails naked 1, 2, 5 l gas = 532.7 / 1 300 = 40.97%.

  The main difference between the two examples is that in

  In Example III, much more gas is produced.

* In these two examples, the tails are completely separated from the water, condensed from the steam and there is no

emulsion that forms.

Example IV

  In this example, a mixture of catalysts is used.

  about 2/3 of the catalyst that is described in the example

  pI, but not separated, 1/3 of the catalyst of Example III (base K) The various proportions can be varied, including the proportions of the catalyst layers in

  Example II The catalyst is unsupported and is approximately

  40 g on a theoretically anhydrous basis. The reactor reaches a temperature of 420 ° C. during this reaction. The products obtained during this reaction are: Tail # 1: Tail # 2: Tail # 5: Total Coke Gas Counted, 8 g (density 0.9793 15.6 C or A P13) o

  309.5 g (density 0.86 15.6 C or A P1 33).

28.0 g

  276.4 g (133 1 X 0.95 / 22.4 X 49 = 276.4 g).

473.0 g.

1,282.7 g.

  = 1,282.7 / 1,300 = 98.67% o Conversion (tail n 1, 2, 5 + gas = 809.7 g / 1300 g) =

62.28%.

  It is apparent that the formation of coke comes from the 480 cc space under the agitator and a little bit of this space is

also under the bubbler.

Example V

  The main difference between this example and the previous examples is the use of a supported catalyst in place of an unsupported catalyst which is added before the start of the reaction. The catalyst is supported on stainless steel in the form of four-basket agglomerated grid The stainless steel is 3 mm (1/8 inch) thick and has been cut into 3 mm (1/8 inch) strips that have been crossed at sizes of 4.7 mmi. of

  support is therefore 3 mm X 3 mm X 4.7 mm

  This is the same catalyst used in Example II. The supported catalyst is placed in baskets of 0.6 cm × 6.1 cm × 15.2 cm, four baskets being used and the

  baskets being supported and stirred by the agitator tree.

  The baskets follow the agitator A grid holds the supported catalyst in place and the baskets formed by the

  Grids of wires are supported on a frame.

  With the same catalyst as in Example II (and considering

  the amount of gas produced decreases from 135 1 to 90 1 Most of this gas

  is produced during the end of the reaction when the temperature

  rises to 4400 C. The speed of the agitator which rotates the baskets is initially 60 rev / min and later in the reaction is

increased to 120 rpm.

The results obtained are

  Gas: 187.0 g (90 1 of gas X 0.95 / 22.4 X 49 = 187.0).

Tail # 1: 407.0 g.

Tail # 2: 368.0 g.

  Tail # 5: 43.0g O Coke 199.95gt Total 1 20495gb The initial product load of solvent-extracted Snes asphalt is 1290g. 1,204.5g / 1,290g = 93% Conversion = tails n 1, 2 and 5 + gas / l 290

= 77990 A

  The number A Pl of tails No. 2 and No. 5 combined is 32.0 e, 6 OC (600 F) o The tails were divided between the part which is liquid at 200 C and that which is not liquid at C The liquid part has a calculated number A Pl of 5 and

  this part constitutes 228 g of the 407 g of the tails n 1 total

  the, ie 56.03% The remainder appears to be light forms

  Degradation of Snes asphalt extracts by solvent

  recalculate this low conversion on the

  quide 2000 C of tails no. 1 gives a conversion of 64% O

  In all these conversions and in the estimates

  lows, the gas produced is calculated to be 95% hydro-

  carbide, of a hydrocarbon having an average molecular weight

of 49.

  It is obvious that when the feedstock feed is under the bubbler, a competitive process takes place which involves catalytic thermal cracking at lower temperature with an improved threshold for thermal cracking, a

  know when steam is not present with the catalyst

  When the catalyst is supported, there is no

  If the steam, the initial product, the asphaltene and the catalyst are in intimate contact with each other If there is not enough steam or no steam reaches the asphaltrate starting material then the reactions are favored thermal cracking reactions

  catalytically, although then the reaction takes place at a time

  lower temperature than normal thermal cracking, at a

  At about 10 times faster than normal thermal cracking, catalytic hydrogenation hydrocracking is much more desirable because of high yields, high speeds, the composition of desirable products that can be adjusted, and According to Example II mentioned above, a mixed residual starting material containing different types of

  residues referred to as FHC-353.

  The analysis for the starting material is as follows: Weight% cuts at 538 C (1000 F) 8.6% Number A P 6.6 6.6 Density at 15.6 C 1.0243 Sulfur% e by weight 3 91 Nitrogen% by weight 0.478 Hydrogen% by weight 10.35 Carbon% by weight 84.72 Oxygen% by weight 0.471 Total elements 99.9% Oils% by weight 29.6% Resins% by weight 57.8 Asphaltnes by weight 12 6 Recovered% by weight 100% Carbon Ramsbotton% by weight 21a Metals Vanadium 228 ppm Nickel 52 ppm q Iron 14 ppm Sodium 4 ppm Viscosity 1430 c Jl 100 C 250 ccr 135 C Pour point 54 C (130 F The residual product is heated gradually so as not to cause coking until the mixed residue can be pumped or reaches the reaction temperature

  approximately 425 ° C., the reaction being carried out at this temperature.

  The total feed product sample is 15.650 g and 98.1% of the feedstock feed is recovered, based on the various feedstocks.

condensates obtained.

  The boiling point of this residual feed product is re-determined according to ASTM D-1160 and D-1180, for

  a sample of 200 ml of starting material according to the procedure

  described and we obtain the following results (which are

  reported by the temperatures observed during the determination

  nation). Sample m I recovered r 6 cup 6 r 6 Temperature C at the top of the column 3.30 Crucible temperature C Corrected temperature

(D-1160; D 1180)

  1 030 1 050 1 090 Pressure (mm Hg) 4.2 4.2 4 ', 6 4.2 4.2 4.2 4.2 4.2 4, 2 4.2 2.0 2.0 2 , 2.0 2.0 Pressure (Pa) 552.3 552.3 604.9 552.3 552.3 552, 3552.3 o) o 552.3 552.3 552.3 131.5 r ' This product is converted into a stirred basket reactor comprising a supported catalyst. The carrier is a Union Carbide, Danbury, C To zeolite Y-82 'in the form of carbon extrudates.

  3.2 mm (1/8 inch), for example, flat elements.

  The analyzer has an empirical formula of K 251.5, namely, is prepared as catalyst D above 9 with 5% by weight of catalyst A added thereto The amount of catalysts

  is 20.16 g for 220 ml of the support described.

  The initial conversion of the product with regard to the first

  duit (product located at the top of reactor 110) is 71% (for a combined product with the exception of highly volatile materials that are trapped in a cold trap with dry ice and isopropanol and gases) o This conversion does not include no

  the material distilled in the starting material recovered

  at 566 C (1,050 F) o The top products and tails recovered are counted and constitute 98.1% of the feedstock load, the remainder apparently being gaseous and volatile distillates. A sample of 1,392 g containing 7 g of water from the products at the top of reactors 110 and 117, a

  with the exception of the condensates mentioned above,

  next Initial boiling point at 182 C (360 F) 71.6 g or 5, 24% by weight Boiling point, initial 182 to 343 C (360 F to 650 F) 203.4 g or 14.89 % by weight O Initial boiling point 343 C to 538 C (650 F to 1000 F)

1084.1 g or 79.36% by weight.

  Total distilled: 1,359,1 go The cautious 2 t of actors 110 and 117 has an initial boiling point of 1820 C (3600 F), a product which has the following characteristics:

next es -

  Index A Pl -D r-n if e Viscosity 6 Ash content Nitrogen content Sulfur content 54 5

0.7608 to 15.50 C (60 F)

  0.72 i St at 37.80 C (1000 r) 0.568 c S-t at 65.50 C (1500 F) 09009% D by weight

0, 05 -0

1 5? O?, 0

  boiling point of 1820 C to 3380 C (3600 F to 6400 F) has the following characteristics lndice A Pl Density 6 Water Pour point Viscosity Sou eng Ash 34, 2

0.8540 to 15.50 C (600 F)

0.002% by weight

29, OC (200 F)

  2.57 c St at 37.80 C (1000 F) 1.61 e Si at 71.10 C (1600 F)

2.18%

  0.01% by weight The fraction boiling at 33 Bc C (6500 F) at the end point has the

following features -

  index A Pl Density Pour point Vi S cosi ty Carbon content Hydrogen Nitrogen content Carbon CONRADSON

1721 8

0.9478 to 15.50 C (600 F)

  46.1 ° C (-1150 ° F) 37.534 ° C at 65.50 ° C (1500 ° F) 12.905 ° C at 98.80 ° C (2100 ° F), 10% by weight, 55% by weight 0, 26 wt.% By weight 2.56 wt.% The residue recovered 6 re, ie remaining after the 566 C (1050 F) step is reached: Vanadium Iron Sodium Potassium Nickel, 6 ppm 48, 6 ppm 8.2 ppm 22.3 ppm 0.48 ppm For the oil fraction evaporated under vacuum, ie the fraction mentioned above, the characteristics are as follows: Initial boiling point at 345 ° C (652 ° C) F) and recovery as follows:%%%

40%

%%%%

90%

  End point to a to to -a to to

389 C

417 C

4430 C

470 C

4790 C

4980 C

509 C

524 C

548 C

565 C

(7320 F)

(782 F)

(830 F)

(878 F)

(894 F)

(928 F)

(948 F)

(976 F)

(1 018 OF)

(1050 O F)

And 94.4% recovery.

  K-factor for completely processed head products

  in the reactor 110 and for a fraction of boiling points

  tion 3430 C (6500 F) (hydrogenation being performed as

final stage) is 11.71.

  The tails from the first-stage reactor 110

  The catalyst for product 112a is a catalyst A supported on steel grids having a size of 3 mm × 6.1 mm × 4.6 mm. (1/8 inch X 1/4 inch X 3/16 inch) of a total volume of cc which contains 15.7 g of catalyst. The total sample has a weight of 1,286 g. A total of 750-7 is recovered. g (which also includes the 8 g of products from the dry ice trap but does not include gases) Approximately 29% of product FHC-353 is recovered as a bottoms product. : carbon 84.78 "by weight hydrogen: 8.74% by weight ash 0.98 t by weight sulfur 4.64% by weight

CONRADSON carbon 40.57% by weight.

  About 58.4% of the product is converted For a continuous process, a higher conversion is obtained, but in this case, the dead space in the reactor located under the cage or under the rotating basket does not make it possible to obtain a complete reaction space, and the maintenance in the

  binding prevents the reaction from being complete.

  The combined recovered products have the following characteristics: Carbon 82.24 wt.% Hydrogen 11.95 wt.% Oxygen 0.64 wt.% Water 2.8 wt.% Boiling fraction 1 82 t EC 343 C (360 ~ 650-F) as Characteristics, according to the A-index, 27.2 ° C (260 ° C (15 ° F)) viscosity 8.533 c St at 3 BOC (1000 F) 4.028 c St at 660 ° C (1,000 ° F) at 7 ° O 0, 17% by weight water 2.8% by weight The fraction boiling at 6500 ° C boiling point with the following characteristics: Index A P Density Flow point Viscosity 6 Carb on e Hydrogen Oxyghne Carbon Conradson Azot e Vanadium Iron Sodium Pot assium Nickel 17.4

0, 944

+ 950 F (350 C>

  21.54 c If at (15 D O F) 660 C 79989 e St at (210 "F) 990 C

84.7% ID

11.27% -

  0.66 Do 2.2% by weight 0.27% by weight 3.5 ppm 7.96 ppm 1.6 ppm, 3 ppm 0.45 ppm

Residue distilled -

  Carbon Hydrogen O xygen Sodium, 22 "O by weight 11.06" O by weight 0.49 by weight 3.07 ppm Vanadium Nickel Iron Potassium Nil 0.344 ppm 4.6 ppm 27 4 ppm The product having a d boiling above 343 C (650 F) (from product 112a) has the following distillation characteristics at a feed of 191 g from which 163 g are removed at the head; it is a 175 ml sample at 15 60 C (600 F). The recovered fractions are as follows:% ', O%

40%

%%

85%

to è

3430 C (6500 F)

4120 C (7750 F)

4430 C (8300 F)

465th C (870 F)

486 C (907 F)

5540 C (1 i 030 * F)

565 'C (1 O D 50 F)

  This residual distillation product has the characteristics

  the following: A Pl index of 20.0 to 15.60 C (60 F) and 16.4

  In addition, the low metal content and the relatively high A p value mean that this residue is a good starting material, for example a catalytic cracking starting material. Although the residue constitutes approximately 15%, it can constitute the tails of the reaction vessel, for example 130, and these can be subjected to a subsequent treatment, for example another parallel passage 9, namely the same as for the product. Analysis of the residual product in the reaction vessel is carbon 83.99% by weight hydrogen 6.88% by weight

Z 542005

  oxygen: 2.9% by weight water: 0.5% by weight

  On the basis of a total conversion of 58.37

  péré divided by the weight of the initial product with result

  calculated from 83%), (recycling of bottoms 112 has

  from the reactor 108) and the top products of the reactor but not counting for them the separated liquids in the dry ice trap nor the gases recovered from the

  products at the top of the 110 reactor and the

  supposed distillable fats (still assumed in the product

  FHC-353, distilling at a temperature below 5650 C-

  1 0500 F), the total transformation is 87.9% W; however, if gaseous products and products recovered from

  dry ice trap are counted on a molar weight basis

  mean angle of 49 and the converted volume being counted by weight, including the actual distillate content SHC-353,

  then the actual recovery is even higher.

  The yields of the above examples were-calculated on

  a basis for making the interpretation of these returns consistent

  with the usual practice The transformation over a space-time velocity can also be calculated, namely the starting material treated per unit of volume of catalysts

  for this starting material for a given unit of time.

  Yields are usually calculated on the basis of the total amount of starting materials used and processed

  with a fraction of compounds boiling to a boiling point

  less than 5660 C (1 0500 F) including Points

  are determined by the methods described above.

  These are the usual methods used in the petroleum industry. According to the practice of the petroleum industry, the limit of 5660 C (1050-9 F) is used to describe highly refractory raw materials or products.

  distillation using traditional methods.

  2542 d 005 Yields can also be based on a proportion of the compounds transformed into products with a lower viscosity such as a degree on the basis of the API product. The residues such as those collected in cyclones 116 and used as products of feed 11a are it's 11 $ s in the returns as additional products to the

  initial quantity of starting materials processed and recovered

  The residue from vessel 130 boiling at or above 5660 C (10500 F) is then subtracted from all the collected material provided that this residue is not removed.

later treated.

  In some cases the yields are based on the treatment of residues with certain boiling points, ie residues boiling at more than 6500 C and below 8500 C or within these limits, and then considering only the fraction convertible by traditional processes (irrespective of the process used for the particular refining) Whereas this basis is not used to evaluate the present process because the present process transforms virtually all residues that were previously non-convertible, it is believed

  that it is better to characterize the products that are re-

  in the first direct stage and the products of the

  first and second parallel stages (if necessary) distil-

  at a temperature below 5660 C (1050 UJF) as additions That is, after the products of the first stage and the products of the second and third parallel steps are added together, including all products from other reaction vessels, for example 117, etc., and including any condensed products,

  etc., and these are combined and distilled

  as above, and residues boiling above 5660 C (1050 'F) are subject to conversion calculations.

  yields are then determined.

  For a better determination, the gaseous hydrocarbon products in the starting material distillable at less than 5660 ° C (1050 F), the low temperature condensables and the gases are included. The gas can be included on a calculated basis such that average molecular weight calculated by volume collected, converted into a percentage by weight for

  give the calculation of all products.

  According to the description above and in accordance with Example VI

  described, it is believed that the particular treatment of fractions divided or separated from crude oil, low boiling point residues up to 455 C (850 F) or residues having high boiling points up to and including above 566 C

  (1050 F) in a direct reaction with the use of

  Low temperatures and low temperatures allow the conversion of almost all oil or oil or other products

  hydrocarbons into usable products if a treatment is

  posterior tails fractions with catalytic

chosen in an appropriate manner.

  So far, important efforts have been made to convert the difficult parts of the residues

  of oil or petroleum in useful compounds but makes them

  In this context, it was recalled that up to 50% of these non-treatable parts had to be subjected to very severe treatment. considerably higher yields and much better end products, high time-space velocities, etco, while poorer starting materials are used to treat the residual product separately or conditions less

  hard, and therefore it is obvious that the present parallel process

  makes a great contribution to continuous research to get useful products from a given volume

oil or its residues.

Claims (16)

  Process for converting carbonaceous starting materials, such as petroleum or residues thereof, and other starting materials having refractory constituents, without the addition of hydrogen gas as a reagent, to obtain products having a low viscosity and / or end products which are more hydrogenated, said conversion being made in the presence of an alkali metal sulfide catalyst, characterized in that O   a) is reacted in a pre-reaction zone in pre-   the presence of added water in the form of steam and a catalyst, at least one carbonaceous starting material such as heavy fuel oil, natural asphalt, natural tar, bitumen, Gilsonite, petroleum mud 9 asphalt solvent extract; pitch or tar derived from coal 9 a petroleum residue; mixtures of oils, resins and asphaltenes; or a petroleum-resin-asphaltene fraction of a distillate having a boiling point up to 455 C (850 F) and above; a distillation residue not having   boiling point without undergoing destructive distillation.   ve; a coal oil extract; a tail fraction   a shale oil treated with a heavy tail of gasification   coal of the 'SASOL' type l o a distillery tail   of a diluted coking product or mixtures of   preceding, said catalyst comprising a sulphate catalyst.   alkali metal and an additional catalyst of at least 5% cleavage of refractory compounds in said starting material 9 for their pre-treatment in   said first reaction zone, said scavenger catalyst   added with the alkali metal sulfide catalyst   process for treating the refractory compounds in said starting material, the scission catalyst being a supported or unsupported catalytic composition and comprising: 1) a first solution of an alkali metal hydroxide dissolved in methanol, ethanol, propanol Or 1-butanol or mixtures of these alkanols, or 2) a second solution of an alkali metal hydroxide-alkanol as defined above, to which is added hydroxide of a metal alkali metal dissolved in water and wherein said alkali metal hydroxide, on a molar basis, is present in said 0.5-1 to 1: 0.5,   said first and said second solution being saturated with hydrogen sulfide so that in each solution (i) a single phase solution is formed or (ii) a two phase solution is formed, said catalytic composition being said one-phase solution of (i), said two-phase solution of (ii), each of the phases of (ii) taken individually, mixtures of the phases of (ii) with each other, a mixture of each of the individual phases of (ii) with the single-phase solution of (i) or a mixture of the two phases of (ii) with each other taken with the single phase of (ii) b) the product is recovered at the top of said first reaction zone, including the gases as vapor or gaseous products, and the tail products 9 are separated off; c) the bottoms are recycled or the bottoms are separated in a parallel stream from the bottom products; products of the first reaction zone, said products being liquid products, entrained liquid products, or refractory components partially processed in said starting materials;   d) is reacted in the presence of steam introduced initially   or separate vapor, the bottoms separated in the presence of said cleavage catalyst (a) and said alkali metal sulphide catalyst, and   e) recovering the products produced in step (d).   2 Process according to claim 1, characterized in that, in step (a) and step (d), the catalysts   are catalysts supported on metals.   3 Process according to claim 1, characterized in that the products of step (c) are recycled instead of to be treated separately.   Process according to Claim 1, characterized in that the reaction products in vapor or gaseous overhead form obtained in step (b) or step (d) are further reacted directly or after cooling in at least one additional reactive zone, for hydrogenation, in the presence of a supported catalyst and added vapor, the supported catalyst consisting of hydrosulphide, sulfide, polysulfide, sulfide hydrate, alkali metal polysulfide hydrate; or their mixture of   bromine index should be reduced in relation to the indi-   it brominates products of step (b) or step (d).   5. Process according to claims 1 and 3, characterized   in that the reaction products of top form   vapor or gas of step (b) are reacted subsequently   directly, or after cooling, in at least   an additional reaction zone, to undergo a hydro-   generation, in the presence of a supported catalyst and steam   added, the supported catalyst consisting of a hydro-   sulfide, sulfide, polysulfide, a hydrate of a sulfide, a hydrate of an alkali metal polysulfide, or a mixture thereof such that the bromine number is reduced relative to the index   bromine products of step (d).   Process according to any one of claims 1   and 5, characterized in that the catalyst in step (a) or step (b) is a supported catalyst and comprises 1 / catalyst A or 2 / catalyst A up to 95 9, based on moles K of the catalyst A, in admixture with the catalysts B, Ca D or E, or their mixture, each of the catalysts being prepared in the following manner: the catalyst A is prepared by dissolving a mole   of potassium hydroxide in ethanol, methanol, a mixture of   ethanol-methanol, 1-propanol or 1-butanol, by reacting the potassium hydroxide solution with hydrogen sulfide which is bubbled into the solution in the solution, recovering the alcohol catalyst mixture and separating said alcohol of said solution; catalyst B is prepared by dissolving a   technical or analytic grade potassium hydroxide   approximately 86% of potassium hydroxide, in   ethanol or methanol and saturated with hydrogen sulphide   in a series of containers by introducing into a first container said hydrogen sulfide, but without boiling the alkanol, by collecting and trapping the alkanol which escapes by exothermic reaction between said potassium hydroxide and the sulfide of hydrogen in a downstream vessel, and stopping the hydrogen sulfide addition reaction when the last vessel containing KO O shows that a reaction takes place in the catalyst C is obtained by dissolving about 6 moles of KOH in about 4 1/2 to 7 1/2 moles of water without providing external heat, and then adding a   low amount of alkanol or about 2 to 2.5 cc of metha-   gold or ethanol per mole of KOH; adding about 4 moles of elemental sulfur; by adding an appropriate amount of sulfur to adjust the catalyst to the desired sulfur level by adding additional sulfur to form the empirical sulfide from about K 251.1 to K 255 the catalyst D is obtained by dissolving one mole of KOH in 10 moles of water, immediately adding 2 ml of methanol or ethanol after KOH is dissolved 2 by adding 2/3 mole of elemental sulfur, adjusting the catalyst to an empirical sulfur content by addition of sulfur with stirring, said catalyst being K 251.1 to 1 <255; the catalyst E is obtained by adding a dry KHS powder or paste to each of the catalysts or catalyst mixtures A, B, C or D, said addition being about 1/5 to 1/3 mol on the molar base from KHS KHS to sulfide 125 (empirical) up to% K 252.5 (empirical), molar base 7 Process according to claim 1, characterized in that the catalyst in step (a) or in step (d) is a supported catalyst and the support is a metal   porous, a spinel of chromite, a z olite or an alumina.   Process according to claim 1, characterized in that the catalyst in step (a) or step (d) is a supported catalyst on a porous metal and said porous metal is a stainless steel having up to 30 of metal by volume. Process according to claim 6, characterized in that the carbonaceous starting material reacted in step (a) is heavy oil or a residue having no boiling point or asphaltane and the supported catalyst   comprises at least 75% by weight of a catalyst A in combination with   with a catalyst D deposited on a catalyst support   Process according to Claim 9, characterized in that the catalyst A contains 5% by weight to 80% by weight and the remainder is the catalyst. The process according to Claim 6, characterized in that in the stage ( d) the catalyst is a catalyst supported by a porous metal, the reaction being carried out at a temperature of 3600 ° C. to 440 ° C. 12 Process according to claim 1, characterized in that the reaction is carried out at a pressure of less than the atmospheric pressure of less than 10.5 105 Pa (150 psi), at a temperature of about 160 C to about 600 C,   in the presence of a catalyst supported by a porous metal.   Process according to Claim 6, characterized in that the catalyst for the rear reaction is a catalyst composition A with KHS as a mixed component   up to 15% by weight, the catalytic product   both being deposited on a porous stainless steel support.   A process wherein the catalyst support for the reactions of claim 1 is protected, said support being a porous metal, a chromite spinel, a   alumina, zeolite or mixed supports.   Process according to Claim 14, characterized in that the catalyst is supported and the carrier is alumina having a pore size of from 6 to 10 m 3, preferably from 10 to 10 m 3 350 to 900 l mm, said alumina being protected from attack by said catalyst by depositing said catalyst in the form of a mixture with glycerol and   by calcining it in the absence of oxygen, or a polyhydric alkanol   with at least 6 carbon atoms, by depositing on said support glycerol or polyhydric alkaonol, by heating said support to 2000 C, by cooling said support, and then depositing said catalyst on the support and then heating said catalyst up to about 560 C   Method according to claim 1, characterized by   the carbon material in the second reaction zone   it is a residue of a first reaction zone re-   collected in a cyclone maintained at 3900 C. 17 Process according to claim 1, characterized in that after recovery of the product from step c, a portion of said liquid product is separated and reacted subsequently in at least one second additional reaction zone (d), and a bottoms product from the reaction zone (d) is reacted in yet another reaction zone.   Process according to Claim 1, characterized in that the reaction in stage (a) and stage (b) is carried out adiabatically at a temperature up to 5600 C.   Process according to claim 1, characterized in that the reaction products of the petroleum residue are reacted in said zones immediately after step (a) with a rapid cooling of the overhead reaction products from step ( a), and at the same time a top reaction product of step (d) is reacted with   again with sudden cooling in a reaction zone   additional for hydrogenation.   Process according to Claim 1, characterized in that the reaction in step (a) or step (d) is carried out with a catalyst supported on a porous metal, in a boiling bed reactor, a bed reactor fixed,   a liquid bed reactor or a fluidized bed reactor.   Process according to Claim 69, characterized in that the reaction in step (a) is carried out in a boiling-bed reactor with the catalyst supported on zeolites, said catalyst consisting of 25% of catalyst A and 75% The method according to claim 6, wherein the reaction in step (d) is carried out in a boiling-bed reactor and the catalyst is supported on a zeolite and the catalyst consists entirely of catalyst. Process according to Claim 6, characterized in that the reaction in step (a) is carried out in a boiling bed reactor or a reactor equipped with rotating baskets, the catalyst being a mixture of catalyst A and catalysts B, C and D or mixtures thereof and the amount of A is from 3 to 95% by weight, said catalyst being supported on a zeolite, a porous metal or a spinell The process according to claim 6, wherein the reaction in step (d) is carried out in a   boiling bed reactor or with tower baskets   and the catalyst is a mixture of Catalyst A and Catalysts B, C and D or mixtures thereof and   A quantity is from 50 to 100% by weight.   Process according to Claim 249, characterized in that the amount of catalyst A is between 50 and 95% by weight.   Process according to Claim 69, characterized in that the products of the reactions of steps (a) and (d)   are reacted again before being hydrogenated.   Process according to claim 26, characterized in that the top products of steps (a) and (d) are hydrogenated with the catalyst A and KUH added thereto, the   Catalyst C with KHS being mixed therewith, the catalysts   B and A, with 50% or more of catalyst K on the molar basis of K, or catalyst B.