Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/049—The hydrotreatment being a hydrocracking

Definitions

• the present invention relates to an integrated process for the conversion of feedstocks containing coal into liquid products . It is known that the direct liquefaction of coal is based on hydrogenating treatment which leads to an increase in the hydrogen/carbon ratio from 0-7-0.8 to values higher than a unit and typical of hydrocarbon mixtures of a petroleum origin. This is a partial demolition, under hydrogenating conditions, of the organic structure of coal. Together with the liquid products, gases and solids are also formed in quantities which vary in relation to the feedstock treated, the operating conditions and type of process .
• Liquefaction is generally based on an essentially thermal reaction which, causes the formation of radicals which are stabilized by hydrogen which has the function of preventing their back-grading to give large less reactive molecules, and on a catalytic hydrogenation which reduces the molecular complexity by splitting the bonds between various carbon atoms and other carbon atoms, oxygen, nitrogen and sulfur.
• These two reactions can be carried out in a single step or in two separate steps. The result however is the breakage of the more complex hydrocarbon structures, accompanied by the reduction, or in appropriate cases, by the elimination of oxygen, nitrogen and sulfur in the form of water, ammonia and hydrogen sul- fide.
• the reactions are carried out in the presence of a solvent, normally produced in the process itself.
• the solvent has an essential role in the transformation, as it is capable of extracting products rich in hydrogen and dissolving the complex molecules which are formed due to the effect of heat and is also capable of facilitating the reaction with hydrogen as transferor and donator.
• the ideal solvent must therefore have a high solvent capacity (and therefore consist of a strongly aromatic structure by affinity with the type of solute) and good hydrogen donor characteristics (and must therefore be easy to hydrogenate and also easily release the hydrogen received to the coal) .
• Products can be obtained from the liquefaction proc- esses which vary from refined coal, still solid at room temperature, with a low content of sulfur and ashes, to light liquid products such as gasoline.
• thermal and catalytic in particular the first liquefaction step can be carried out with a low severity, by effecting the transformation of coal in a liquid extract, with low gas productions due to the low entity of hydrocracking reactions
• thermal and catalytic in particular the first liquefaction step can be carried out with a low severity, by effecting the transformation of coal in a liquid extract, with low gas productions due to the low entity of hydrocracking reactions
• the extract is subjected to a subsequent hydrocracking step under controlled catalytic conditions, to lighten the products.
• the overall advantage derives from a better use of the hydrogen, with a lower overall consumption and a higher process flexibility, resulting in a greater possibility of choice in the spectra of products.
• the coal liquids obtained must be heavily reprocessed with treatment units ad hoc (hydrocracking effected with conventional technologies) , as they are extremely aromatic, rich in nitrogen, sulfur and with a high density, to generate distillates having commercial characteristics . It has now been found that by subjecting these liquids obtained from the liquefaction of coal to certain further conversion processes by means of hydrogenating treatment already used for the conversion of heavy crude oils or distillation residues, the conversion yields to DAO distillates can be maximized.
• the hydrogenating processes for the conversion of heavy crude oils or distillation residues consist in treating the feedstock in the presence of hydrogen and suitable catalysts.
• the hydroconversion technologies currently on the mar- ket use fixed bed or ebullated bed reactors and adopt catalysts consisting of one or more transition metals (Mo, W, Ni, Co, etc.) supported on silica/alumina (or an equivalent material) .
• Fixed bed technologies have considerable problems in treating particularly heavy feedstocks containing high percentages of hetero-atoms, metals and asphaltenes, as these contaminants cause a rapid deactivation of the catalyst.
• Ebullated bed technologies were developed and commercialized for treating these feedstocks, which give inter- esting performances but are complex and costly.
• Hydro-treatment technologies operating with catalysts in dispersed phase may constitute an attractive solution to the drawbacks which arise in the use of fixed bed or ebullated bed technologies.
• Slurry processes in fact, combine the advantage of a wide flexibility with respect to the feedstock with high performances in terms of conversion and upgrading, proving to be, at least in principle, simpler from a technological point of view.
• Slurry technologies are characterized by the presence of particles of catalyst having very small average dimensions and which are efficaciously dispersed in the medium; for this reason, hydrogenation processes are easier and more efficient in all points of the reactor.
• the formation coke is greatly reduced and the upgrading of the feedstock is high.
• the catalyst can be introduced as a powder with sufficiently reduced dimensions or as an oil-soluble precursor.
• the active form of the catalyst (generally the metal sulfide) is formed in situ by the thermal decomposition of the compound used, during the reaction itself or after suitable pretreatment .
• the metal constituents of the dispersed catalysts are generally one or more transition metals (preferably Mo, W, Ni, Co or Ru) .
• Molybdenum and tungsten have much more sat- isfactory performances than nickel, cobalt or ruthenium and even more so than vanadium and iron (N. Panariti et al . , Appl. Catal. A: Gen. 2000, 204, 203).
• the catalyst leaving the reactor can be recovered by separation from the product obtained from the hydro- treatment (preferably from the bottom of the distillation column downstream of the reactor) by the conventional meth- ods such as decanting, centrifugation or filtration (US- 3240718; US-4762812). Part of the catalyst can be recycled to the hydrogenation process without any further treatment.
• the catalyst recovered using the known hydro-treatment techniques normally has a reduced activity with respect to the fresh catalyst so that a suitable regenera- tion step is necessary in order to restore the catalytic activity and recycle at least part of said catalyst to the hydro-treatment reactor.
• said recovery procedures of the catalyst are costly and also extremely complex from a technological point of view. All the hydroconversion processes described above allow more or less high conversion levels to be reached depending on the feedstock and type of technology used, but generating a non-converted residue at the limit of stabil- ity, which we will call tar, which, from case to case, can vary from 15 to 85% of the initial feedstock.
• This product is used for producing fuel oil, bitumens or it can be used as a feedstock in gasification processes.
• the application described is particularly suitable when the heavy fractions of complex hydrocarbon mixtures produced from the process (at the bottom of the distillation column) must be used as feedstock for catalytic cracking plants, both Hydrocracking (HC) and Fluid Bed Catalytic Cracking (FCC) .
• HC Hydrocracking
• FCC Fluid Bed Catalytic Cracking
• HT catalytic hydrogenation unit
• SDA extractive process
• deasphalted oils to be produced with a reduced content of contaminants (metals, sulfur, nitrogen, carbonaceous residue) , and which are therefore easier to treat in catalytic cracking processes.
• Another aspect to be considered, however, is that the naphtha and gas oil produced directly from the hydro- treatment unit still contain many contaminants (sulfur, nitrogen ...
• the integrated process, object of the present invention for the conversion of feedstocks containing coal into liquid products by the joint use of at least the following seven process units: coal liquefaction (CL) , flash or dis- tillation of the product obtained from the liquefaction
• the coal contained in the feedstock to be subjected to the liquefaction step can be as such or optionally benefi- ciated by means of the known coal beneficiation treatment techniques .
• the feedstock containing coal is preferably a feedstock substantially consisting of coal.
• the suitable hydrogenation catalyst present in the liquefaction step (CL) can be at least partially recovered, recycled from the units downstream of said step (for example by means of the stream containing asphaltenes obtained in the deasphalting step (SDA) or by part of the distilla- tion residue (tar) or liquid leaving the flash unit (D) , containing catalyst in dispersed phase, rich in metal sul- fides produced by the demetallation of the feedstock and possibly coke.
• the feedstock essentially consisting of coal is pref- erably slurrified in a hydrocarbon matrix which can come from the units downstream of the liquefaction step (CL) : preferably part of the stream containing asphaltenes, as well as the dispersed catalyst used in the hydro-treatment step (HT) , obtained in the deasphalting step (SDA) and/or part of the stream consisting of deasphalted oil (DAO) obtained in the deasphalting step (SDA) .
• CL liquefaction step
• HT dispersed catalyst used in the hydro-treatment step
• DAO deasphalted oil
• a further stream can be optionally separated, as distillate, which can be optionally added, either partly or totally, to the lighter fractions separated in the distillation or flash unit (D) .
• the direct liquefaction of the stream containing coal can be effected by adopting one of the various known coal liquefaction processes.
• the extraction step with a solvent (SDAsh) to remove the ashes is preferably effected at a temperature ranging from 150 to 350°C and at a pressure ranging from 20 to 60 atm in the presence of a suitable aromatic solvent.
• a heavy feedstock selected from heavy crude oils, distillation residues, heavy oils coming from catalytic treatment, thermal tars, bitumens from oil sands, various types of coals and/or other high-boiling feedstocks of a hydrocarbon origin known as black oils, to the feed- stock consisting of coal to be sent to the liquefaction unit (CL) and/or to the liquid stream consisting of liquefied coal to be sent to the hydro-treatment step (HT) .
• a heavy feedstock selected from heavy crude oils, distillation residues, heavy oils coming from catalytic treatment, thermal tars, bitumens from oil sands, various types of coals and/or other high-boiling feedstocks of a hydrocarbon origin known as black oils
• a secondary post-treatment hydrogenating section of the C 2 -500°C fraction, preferably of the C 5 -350°C fraction, deriving from the high pressure separating sections situated upstream of the distillation, can be present in addition to the steps forming the integrated process .
• the stream containing the hydro- treatment reaction product and the catalyst in dispersed phase, before being sent to one or more distillation or flash steps, is subjected to a separation pre-step effected at a high pressure in order to obtain a light fraction and a heavy fraction, said heavy fraction alone being sent to said distillation step(s) (D) .
• the light fraction obtained by means of the high pressure separation step can be sent to a hydro-treatment section producing a lighter fraction containing C 1 -C 4 gas and H 2 S and a heavier fraction containing hydro-treated naphtha and gas oil.
• the insertion of the secondary post-treatment hydro- genating section of the C 2 -500°C, preferably C 5 -350°C, fraction exploits the availability of this fraction together with hydrogen at a relatively high pressure, which is approximately that of the hydro-treatment reactor, al- lowing the following advantages to be obtained:
• the heavy part, extracted at the bottom is sent to the main distillation unit, the part extracted at the head, a C 2 -500°C, preferably C 5 -350°C, fraction, is sent to a secondary treatment section in the presence of hydrogen, available at a high pressure, wherein the reactor is a fixed bed reactor and contains a typical desulfura- tion/dearomatization catalyst, in order to obtain a product having a much lower sulfur content and also lower levels of nitrogen, a lower overall density and, at the same time, as far as the gas oil fraction is concerned, an increased cetane number.
• the hydro-treatment section normally consists of one or more reactors in series; the product of this system can be further fractionated by distillation to obtain a totally desulfurated naphtha and a diesel gas oil according to specification as fuel.
• the fixed bed hydro-desulfuration step generally uses typical fixed bed catalysts for the hydro-desulfuration of gas oils; said catalyst, or possibly also a mixture of catalysts or a series of reactors with several catalysts having different properties, causes a heavy refining of the light fraction, significantly reducing the sulfur and ni- trogen content, increasing the hydrogenation degree of the feedstock, consequently reducing the density and increasing the cetane number of the gas oil fraction, at the same time reducing the formation of coke.
• the catalyst generally consists of an amorphous part based on alumina, silica, silico-alumina and mixtures of different mineral oxides on which a hydro-desulfurating component combined with a hydrogenating agent, is deposited (with various methods) .
• Catalysts based on molybdenum or tungsten, with the addition of nickel and/or cobalt depos- ited on an amorphous mineral carrier are typical catalysts for this type of operation.
• the post-treatment hydrogenating reaction is carried out at an absolute pressure slightly lower than that of the primary hydro-treatment step, generally ranging from 7 to 14 MPa, preferably from 9 to 12 MPa; the hydro- desulfuration temperature ranges from 250 to 500°C, preferably from 280 to 420°C; the temperature is generally in relation to the desulfuration level required.
• the space velocity is another important variable in controlling the quality of the product obtained: it can range from 0.1 to 5 h "1 , preferably from 0.2 to 2 h -1 .
• the quantity of hydrogen mixed with the feedstock is fed at a flow-rate ranging from 100 to 5000 Nm 3 /m 3 , preferably from 300 to 1000 Nm 3 /m 3 .
• a further secondary post-treatment section of the flushing stream can be optionally present, alone or possibly together with the post-treatment hydrogenating section, in addition to the steps forming the integrated process.
• Said further secondary post-treatment section consists in the post-treatment of the flushing stream in order to significantly reduce its entity and allow at least part of the catalyst, still active, to be recycled to the hydro- treatment reactor .
• the fraction of stream containing as- phaltenes, coming from the deasphalting section (SDA), called flushing stream is sent to a treatment section with a suitable solvent for the separation of the product into a solid fraction and a liquid fraction from which said solvent can be subsequently removed.
• the possible treatment section of the flushing effluent consists of a de-oiling step with a solvent (toluene or gas oil or other streams rich in aromatic compounds) and a separation of the solid fraction from the liquid fraction. At least part of said liquid fraction can be fed:
• the solvent and fluxing agent can coincide.
• the solid fraction can be disposed of as such or, more advantageously, it can be sent to a selective recovery treatment of the transition metal or metals contained in the transition catalyst (for example molybdenum) (with respect to the other metals present in the starting residue, nickel and vanadium) with the optional recycling of the stream rich in transition metal (molybdenum) to the hydro- treatment reactor (HT) .
• This composite treatment has the following advantages with respect to a traditional process:
• the deoiling step consists in the treatment of the flushing stream, which represents a minimum fraction of the asphaltene stream coming from the deasphalting section (SDA) at the primary hydro-treatment plant of the heavy feedstock, with a solvent which is capable of bringing the highest possible quantity of organic compounds to liquid phase, leaving the metallic sulfides, coke and more refractory carbonaceous residues (insoluble toluene or similar products) , in solid phase.
• SDA deasphalting section
• solvents can be advantageously used in this deoiling step; among these, aromatic solvents such as tolu- ene and/or xylene blends, hydrocarbon feedstocks available in the plant, such as the gas oil produced therein, or in refineries, such as Light Cycle Oil coming from the FCC unit or Thermal Gas oil coming from the Visbreaker/Thermal Cracker unit, can be mentioned.
• aromatic solvents such as tolu- ene and/or xylene blends
• hydrocarbon feedstocks available in the plant such as the gas oil produced therein, or in refineries, such as Light Cycle Oil coming from the FCC unit or Thermal Gas oil coming from the Visbreaker/Thermal Cracker unit, can be mentioned.
• the operating rate is facilitated by increases in the temperature and the reaction time but an excessive increase is unadvisable for economic reasons .
• the operating temperatures depend on the solvent used and on the pressure conditions adopted; temperatures ranging from 80 to 150°C, however, are recommended; the reaction times can vary from 0.1 to 12 h, preferably from 0.5 to 4 h.
• the volumetric ratio solvent/flushing stream is also an important variable to be taken into consideration; it can vary from 1 to 10 (v/v) , preferably from 1 to 5, more preferably from 1.5 to 3.5.
• the liquid phase can then be sent to a stripping and recovery phase of the solvent, which is recycled to the first treatment step (de-oiling) of the flushing stream.
• the heavy fraction which remains, can be advantageously used in refineries as a stream practically free of metals and with a relatively low sulfur content. If the treatment operation is effected with a gas oil, for example, part of said gas oil can be left in the heavy product to bring it within the specification of pool fuel oil.
• the liquid phase can be recycled to the hydrogenation reactor.
• the solid part can be disposed of as such or it can be subjected to additional treatment to selectively recover the catalyst (molybdenum) to be recycled to the hydro- treatment reactor.
• the ratio between aqueous phase and organic phase can vary from 0.3 to 3; the pH of the aqueous phase can vary from 0.5 to 4 , preferably from 1 to 3.
• Various kinds of heavy feedstocks can be treated: they can be selected from heavy crude oils, bitumens from oil sands, various types of coals, distillation residues, heavy oils coming from catalytic treatment, for example heavy cy- cle oils from catalytic cracking treatment, bottom products from hydroconversion treatment, thermal tars (coming for example from visbreaking or similar thermal processes), and any other high-boiling feedstock of a hydrocarbon origin generally known in the art as black oils .
• part of the heavy feedstock and at least most of the stream containing asphaltenes which also con- tains catalyst in dispersed phase and possibly coke, are mixed with a suitable hydrogenation catalyst and sent to the hydro-treatment reactor, whereas the remaining part of the quantity of the heavy feedstock is sent to the deasphalting section.
• at least most of the stream containing asphaltenes which essentially consists of said asphaltenes, is mixed with a suitable hydrogenation catalyst and sent to the hydro-treatment reactor, whereas all the heavy feedstock is fed to the deasphalting section.
• the catalysts used can be selected from those obtained from precursors decomposable in-situ (metallic naphthen- ates, metallic derivatives of phosphonic acids, metal- carbonyls, etc.) or from preformed compounds based on one or more transition metals such as Ni, Co, Ru, W and Mo: the latter is preferred due to its high catalytic activity.
• the hydro-treatment step is preferably carried out at a temperature ranging from 370 to 480°C, more preferably from 380 to 440°C, and at a pressure ranging from 3 to 30 MPa, more preferably from 10 to 20 MPa.
• the hydrogen is fed to the reactor, which can operate with both the down-flow and, preferably, up-flow procedure. Said gas can be fed to different sections of the reactor.
• the distillation step is preferably effected at reduced pressure ranging from 0.0001 to 0.5 MPa, preferably from 0.001 to 0.3 MPa.
• the hydro-treatment step can consist of one or more reactors operating within the range of conditions specified above. Part of the distillates produced in the first reactor can be recycled to the subsequent reactors .
• the deasphalting step effected by means of an extraction with a solvent, hydrocarbon or non-hydrocarbon (for example with paraffins or iso-paraffins having from 3 to 6 carbon atoms) , is generally carried out at temperatures ranging from 40 to 200°C and at a pressure ranging from 0.1 to 7 MPa. It can also consist of one or more sections operating with the same solvent or with different solvents; the recovery of the solvent can be effected under subcritical or supercritical conditions with one or more steps, thus allowing a further fractionation between deasphalted oil (DAO) and resins.
• DAO deasphalted oil
• the stream consisting of deasphalted oil (DAO) can be used as such, as synthetic crude oil (syncrude) , optionally mixed with the distillates, or it can be used as feedstock for fluid bed Catalytic Cracking or Hydrocracking treatment .
• DAO deasphalted oil
• synthetic crude oil syncrude
• hydro-treatment unit a hydro-treatment unit
• the ratio between the heavy residue to be sent to the hy- dro-treatment section (fresh feedstock) and that to be sent for deasphalting preferably varies from 0.01 to 100, more preferably from 0.1 to 10, even more preferably from 1 to 5 ;
• the recycling ratio between fresh feedstock and tar to be sent to the deasphalting section preferably varies from 0.01 to 100, more preferably from 0.1 to 10;
• the recycling ratio between tar and asphaltenes to be sent to the hydro-treatment section can vary in relation to the variations in the previous ratios .
• This flexibility is particularly useful for fully ex- ploiting the complementary characteristics of the deasphalting units (discrete nitrogen reduction, and de- aromatization) and hydrogenation units (high removal of metals and sulfur) .
• the stability of the streams in question and quality of the product to be obtained also in relation to the particular treatment downstream
• the fractions of fresh feedstock to be fed to the deasphalting section and hydro-treatment section can be modulated in the best possible way.
• the application described is particularly suitable when the heavy fractions of the complex hydrocarbon mixtures produced by the process (bottom of the distillation column) are to be used as feedstock for catalytic cracking plants, both Hydrocracking (HC) and fluid bed Catalytic Cracking (FCC) .
• HC Hydrocracking
• FCC fluid bed Catalytic Cracking
• HT catalytic hydrogenation unit
• SDA extractive process
• deasphalted oils to be produced with a reduced content of contaminants (metals, sulfur, nitrogen, carbonaceous residue), and which can therefore be more easily treated in the catalytic cracking processes .
• a preferred embodiment of the present invention is provided hereunder with the help of the enclosed figure 1 which, however, should in no way be considered as limiting the scope of the invention itself.
• a feedstock (1) substantially consisting of coal, after being preferably slurrified in a hydrocarbon matrix, a suitable solvent (2) and an appropriate hydrogenation catalyst (3) are sent to the direct liquefaction unit (CL) , into which hydrogen or hydrogen and H 2 S (4) are introduced and from which a stream (5) leaves, which is subjected to a flash step (F) in order to obtain a gaseous stream (6) and a carbonaceous liquid stream (7) .
• the carbonaceous liquid stream (7) is fed to the ex- traction unit with a solvent (SDAsh) whereby an insoluble stream (8) is obtained, consisting of the mineral matter present in the feedstock and non-reacted coal and a liquid stream (9) consisting of the liquefied coal obtained and the solvent used, the latter stream (9) being sent in turn to a distillation step (RS) in order to separate the sol- vent (10) contained therein, to be recycled to the extraction unit (SDAsh) , from a further liquid stream (11) .
• a solvent SDAsh
• An additional stream (12) can be optionally separated, as distillate, and possibly added (13) to the lighter frac- tions separated in the distillation or flash unit (D) and/or recycled (14) , as solvent, to the liquefaction unit (CL) .
• the liquid stream (11) consisting of liquefied coal mixed with a suitable hydrogenation catalyst (15) , is fed to a hydro-treatment unit (HT) introducing hydrogen or hydrogen and H 2 S (16) therein, from which a stream (17) is obtained, containing the hydrogenation product and the catalyst in dispersed phase, which is fractionated in a distillation column (D) , from which the lighter fractions are separated (18) together with the distillable products (19), (20) and (21) from the distillation residue (22) containing the dispersed catalyst and coke.
• HT hydro-treatment unit
• Said distillation residue (22), called tar, is sent to the deasphalting unit (SDA) so as to obtain two streams: one (23) consisting of deasphalted oil (DAO), the other (24) consisting of asphaltenes which can be partly or totally added (25) to the liquid stream (11) consisting of liquefied coal and optionally partially recycled (26) to the feedstock substantially consisting of coal (1) .
• DAO deasphalted oil
• asphaltenes which can be partly or totally added
• the liquid stream (11) consisting of liquefied coal and optionally partially recycled (26) to the feedstock substantially consisting of coal (1) .
• Reactor 30 cc made of steel equipped with a capillary stirring system and the possibility of reintegrating the hydrogen.
• Feedstock 10 g of liquids from coal produced from the liquefaction step
• the THF-soluble fraction was then treated with an excess of n-pentane to precipitate the C 5 asphaltenes and produce a DAO (Deasphalted Oil) to be analyzed by means of GC SIM-DIST for the determination of the distillates, or quantifying the yields to: - naphtha (PI-170°C) atmospheric gas oil (170-350°C) - vacuum gas oil (350-500°C) vacuum residue (500°C+)
• EXAMPLE 2 The same procedure is adopted as described in Example 1; 5.0 g of coal are treated together with 5.0 g of DAO solvent, in the presence of a solid mixture containing molybdenum sulfide, metal sulfides and heavy carbonaceous ma- terial .
• the above mixture derives from hydro-treatment tests of heavy hydrocarbon feedstocks and represents part of the bottom of the deasphalting column ("flushing" stream of Figure 1) .
• a quantity of solid mixture is introduced into the reactor, which is such as to obtain a concentra- tion of molybdenum equal to 200 ppm.
• Table 3 indicates the data relating to the coal liquefaction test. Table 3: results of the liquefaction test
• Reactor 3000 cc made of steel equipped with a magnetic stirring system and the possibility of reintegrating the hydrogen.
• Feedstock 250 g of coal (Table 1) • Solvent: 250 g of LCO (Light Cycle Oil)
• Flash step The light fraction (350°C-) consisting of the solvent used in the liquefaction step and the distillates produced by the reaction, were separated by means of batch distillation.
• Hydro-treatment step The hydro-treatment reaction was effected under the conditions specified in Example 1, using the product obtained from the flash step (column bottom, 350°C+ residue) . The gaseous products were separated at the end of the hydrogenation step. The product was then deasphalted by means of liquid propane. The C 3 DAO produced was then separated and recovered.
• Atmospheric gas oil (AGO 170-350°C) : 19%
• VGO + DAO Deasphalted oil

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