ZA200603668B - Integrated process for the conversion of feedstocks containing coal into liquid products - Google Patents
Integrated process for the conversion of feedstocks containing coal into liquid products Download PDFInfo
- Publication number
- ZA200603668B ZA200603668B ZA200603668A ZA200603668A ZA200603668B ZA 200603668 B ZA200603668 B ZA 200603668B ZA 200603668 A ZA200603668 A ZA 200603668A ZA 200603668 A ZA200603668 A ZA 200603668A ZA 200603668 B ZA200603668 B ZA 200603668B
- Authority
- ZA
- South Africa
- Prior art keywords
- process according
- stream
- coal
- solvent
- hydro
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 97
- 230000008569 process Effects 0.000 title claims description 91
- 239000003245 coal Substances 0.000 title claims description 82
- 238000006243 chemical reaction Methods 0.000 title claims description 40
- 239000012263 liquid product Substances 0.000 title claims description 7
- 238000011282 treatment Methods 0.000 claims description 113
- 239000003054 catalyst Substances 0.000 claims description 98
- 239000002904 solvent Substances 0.000 claims description 65
- 238000004821 distillation Methods 0.000 claims description 63
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 50
- 239000003921 oil Substances 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims description 25
- 238000011010 flushing procedure Methods 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 17
- 239000011269 tar Substances 0.000 claims description 17
- 239000000571 coke Substances 0.000 claims description 16
- 239000002956 ash Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000010779 crude oil Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000003849 aromatic solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000295 fuel oil Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007324 demetalation reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000727 fraction Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 206010016825 Flushing Diseases 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 150000003738 xylenes Chemical class 0.000 claims 1
- 239000012071 phase Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 235000001508 sulfur Nutrition 0.000 description 15
- 229960005349 sulfur Drugs 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000004064 recycling Methods 0.000 description 11
- 238000004517 catalytic hydrocracking Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229960005419 nitrogen Drugs 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000007775 late Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
INTEGRATED PROCESS FOR THE CONVERSION OF FEEDSTOCKS CON-
TAINING COAL INTO LIQUID PRODUCTS
The present invention relates to an integrated process for the conversion of feedstocks containing coal into lig- uid products.
Tt 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 petro- leum origin.
This is a partial demolition, under hydrogenating con- ditions, 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, nitro- gen 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 sol- vent has an essential role in the transformation, as it is capable of extracting products rich in hydrogen and dis- solving the complex molecules which are formed due to the effect of heat and is also capable of facilitating the re- action 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 af- finity 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. In the former case, there are higher energy performances and weight yields; as the severity of the hydrogenation increases, when hydro- cracking reactions become increasingly more significant, the quality of the liquid product improves but the yields decrease.
The approaches so far pursued for the liquefaction of coal to medium/light products can be synthetically and schematically represented by the following process lines: e high severity liquefaction in a single step; eo liquefaction with several steps having various degrees of severity.
In the former case, the thermal and catalytic reac- tions take place in a single reactor, in a condition which is a compromise between the different optimum conditions for the two reactions: a severe hydrocracking is normally effected, obtaining products which can be distilled with great advantage in the delicate and onerous separation be- tween liquids and non-reacted solids, which can take place by vacuum flash.
One of the disadvantages, however, is represented by a high production of gas, an undesired product, with a conse- quently considerable hydrogen consumption.
Using a multi-step scheme, it is possible to operate under optimum conditions for the single reactors, 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 reac- tions); but as most of the products cannot be distilled, it is necessary to resort to a more complex solid/liquid sepa- ration of vacuum distillation, such as treatment with an © anti-solvent or filtration.
Finally, after the solid/liquid separation, the ex- tract is subjected to a subsequent hydrocracking step undex 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.
Regardless of whether the liquefaction of coal is car- ried out in one or more steps, 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 commer- cial characteristics.
Tt has now been found that by subjecting these licuids 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 dis- tillation residues, the conversion yields to DAO distil- lates can be maximized.
The hydrogenating processes for the conversion of heavy crude oils or distillation residues consist in treat- ing 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 cata- lysts 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 per- centages of hetero-atoms, metals and asphaltenes, as these contaminants cause a rapid deactivation of the catalyst.
Ebullated bed technologies were developed and commer- cialized 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 ebul- lated 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 dimen- sions 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 suffi- ciently reduced dimensions or as an oil-soluble precursor.
In the latter case, the active form of the catalyst (gener- ally the metal sulfide) is formed in situ by the thermal decomposition of the compound used, during the reaction it- self 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).
Although the use of dispersed catalysts solves most of the problems listed for the technologies described above, it also has disadvantages mainly linked to the life cycle of the catalyst itself and the quality of the products ob- tained.
The conditions for the use of these catalysts (type of precursors, concentration, etc.) is in fact of great impor- tance both from an economical point of view and also with respect to environmental impact.
The catalyst can be used at a low concentration (a few hundreds of ppm) in a “once-through” configuration, but in this case, the upgrading of the reaction products is gener- ally insufficient (A. Delbianco et al., Chemtech, November 1995, 35). When operating with extremely active catalysts (for example molybdenum) and with higher concentrations of catalyst (thousands of ppm of metal), the quality of the product obtained becomes much better but the catalyst must be recycled.
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, however, normally has a reduced activity with 26 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. Furthermore, said recovery proce- dures of the catalyst are costly and also extremely complex from a technological point of view.
All the hydroconversion processes described above al- low more or less high conversion levels to be reached de- pending 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.
Tn order to increase the overall conversion level of cracking processes of residues, schemes have been proposed which envisage the recycling of more or less significant amounts of tar to the cracking unit. In the case of hydro- conversion processes with dispersed catalysts in slurry phase, the recycling of the tar also allows the recovery of the catalyst, to the extent that the same applicants have _ described, in patent application IT-95A001095, a process with allows the recycling of the recovered catalyst to the hydro-treatment reactor without the necessity of a further regeneration step, and at the same time obtaining a good- quality product without the production of residue (zero residue refinery).
This process comprises the following steps: * mixing of the heavy crude oil or distillation residue with a suitable hydrogenation catalyst and sending of the mixture obtained to a hydro-treatment reactor introducing hydrogen or a mixture of hydrogen and H,S therein; e sending of the stream containing the hydro-treatment re- action product and the catalyst in dispersed phase to a distillation zone in which the most volatile fractions are separated (naphtha and gas oil); es sending of the high-boiling fraction obtained in the dis- : tillation step to a deasphalting step, and consequent formation of two streams, one consisting of deasphalted oil (Da0), the other consisting of asphaltenes, catalyst in dispersed phase and possibly coke and enriched with the metals coming from the initial feedstock; e recycling of at least 60%, preferably at least 80% of the stream consisting of asphaltenes, catalyst in dispersed phase and possibly coke, rich in metals, to the hydro- treatment zone. . It was subsequently found, as described in patent ap- plication IT-MI2001A-001438, that, in the case of the up- grading of heavy crude oils or bitumens from oil sands to complex hydrocarbon mixtures to be used as raw material for further conversion processes to distillates, it may be con-
venient to use different process configurations with re- spect to that described above.
The process described in patent application IT-
MI2001A-001438 for the conversion of heavy feedstocks by the joint use of the following three process units: hy- droconversion with catalysts in slurry phase (HT), dis- tillation or flash (D), deasphalting (SDA), is character- ized in that the three units operate on mixed streams consisting of fresh feedstock and recycled streams, using the following steps: e sending of at least one fraction of the heavy feedstock to a deasphalting section (SDA) in the presence of sol- vents obtaining two streams, one consisting of deasphalted oil (DAO), the other of asphaltenes; e mixing of the asphaltenes with the remaining fraction of heavy feedstock not sent to the deasphalting section and with a suitable hydrogenation catalyst and sending of the mixture obtained to a hydro-treatment reactor (HT) intro- ducing hydrogen or a mixture of hydrogen and H,S therein; eo sending of the stream containing the hydro-treatment re- action product and the catalyst in dispersed phase to one or more distillation or flash steps (D) whereby the most volatile fractions are separated, among which the gases produced in the hydro-treatment reaction, naphtha and gas oil;
* recycling of at least 60% by weight, preferably at least 80%, more preferably at least 95%, of the distillation residue (tar) or liquid leaving the flash unit, contain- ing catalyst in dispersed phase, rich in metallic sul- fides produced by the demetallation of the feedstock and possibly coke and various kinds of carbonaceous residues, to the deasphalting zone.
It is generally necessary to effect a flushing on the asphaltene stream leaving the deasphalting section (SDA) to ensure that all these elements do not accumulate too much in the hydro-treatment reactor and, in the case of the de- activation of the catalyst, to allow part of the catalyst to be removed, which is replaced with fresh catalyst. This however is generally not the case as the catalyst maintains its activity for a long period of time; considering that it is in any case necessary to effect a flushing for the rea- sons described above, some of the catalyst must obviously be used up even, it is far from being completely deacti- vated. Furthermore, although the volumes of flushing stream (0.5-4% with respect to the feedstock) are quite limited compared with other hydro-treatment technologies, there are still considerable problems relating to their use or dis- posal.
The application described is particularly suitable when the heavy fractions of complex hydrocarbon mixtures produced from the process (at the bottom of the distilla- tion column) must be used as feedstock for catalytic crack- ing plants, both Hydrocracking (HC) and Fluid Bed Catalytic
Cracking (FCC).
The combined action of a catalytic hydrogenation unit (HT) with an extractive process (SDA) does in fact allow deasphalted oils to be produced with a reduced content of contaminants (metals, sulfur, nitrogen, carbonaceous resi- due), and which are therefore easier to treat in catalytic cracking processes.
Another aspect to be considered, however, is that the naphtha and gas o0il produced directly from the hydro- treatment unit still contain many contaminants (sulfur, ni- trogen ...) and must in any case be reprocessed to obtain end-products.
The integrated process, object of the present inven- tion, 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 (F), extraction with a solvent to remove the ashes (SDAsh), distillation to separate the solvent (RS), hydroconversion with catalysts in slurry phase (HT), distillation or flash of the product obtained from the hydroconversion (D), deasphalting with a solvent (SDA),
is characterized in that it comprises the following steps:
® sending the feedstock containing coal to one or more di- rect coal liquefaction steps (CL) in the presence of a suitable hydrogenation catalyst;
ee sending the stream containing the product obtained from the coal liquefaction reaction to one or more flash or dis- tillation steps (F) obtaining a gaseous stream and a liquid stream;
e sending the liquid stream to an extraction step with a solvent (SDAsh) whereby an insoluble stream is obtained, consisting of the mineral matter present in the feedstock and non-reacted coal and a liquid stream consisting of the liquefied coal obtained and the solvent used; e sending the liquid stream consisting of the liquefied coal and the solvent used to one or more distillation steps in order to substantially separate the solvent contained in the liquid stream, which is recycled to the extraction step with a solvent (SDAsh); mixing the liquid stream substantially consisting of the liquefied coal and at least part of the stream containing asphaltenes obtained in the deasphalting unit with a suit- able hydrogenation catalyst and’ sending the mixture ob- tained to a hydro-treatment reactor (HT) introducing hydro- gen or a mixture of hydrogen and H;S therein; ¢ sending the stream containing the reaction product of the hydro-treatment and the catalyst in dispersed phase to one or more distillation or flash steps (D) whereby the differ- ent fractions coming from the hydro-treatment reaction are separated; eo sending at least part of the distillation residue (tar) or liguid leaving the flash unit, containing the catalyst in dispersed phase, rich in metal sulfides produced by the demetallation of the feedstock and optionally coke, to the deasphalting zone (SDA) in the presence of solvents, op- tionally also fed by at least one fraction of the liquid stream substantially consisting of the liquefied coal, ob- taining two streams, one consisting of deasphalted oil (DAO), the other containing asphaltenes.
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 feed- stock 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 exan- ple 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) ob- tained in the deasphalting step (SDA).
Tn the distillation step (RS) of the liquid stream consisting of liquefied coal and the solvent used, a fur- ther 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.
It may be advisable to effect the direct liquefaction of the stream containing coal by mixing said stream with an aromatic solvent, in a quantity ranging from 20 to 80% with respect to the coal, and with a suitable catalyst in dis- persed phase, operating at a temperature ranging from 360 to 440°C, at a hydrogen pressure ranging from 3 to 30 MPa and with residence times less than or equal to 4 h.
The aromatic solvent used preferably comes, at least partially, from one or more of the following recycled streams: eo part of the stream consisting of deasphalted oil (DAO) produced in the deasphalting step (SDA) ; } e at least part of the stream containing asphaltenes, as well as the dispersed catalyst used in the hydro- treatment step (HT), produced in the deasphalting step (SDA) ; se part of the medium and heavy fractions (medium and heavy distillates) obtained in the distillation or flash unit (D) ; eo part of the solvent separated in the distillation unit (RS) downstream of the ash removal step (sbhash) ; eo part of the additional stream separated, as distillate in the distillation unit (RS) downstream of the ash removal step (SDash).
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.
With respect to the general process, it is also possi- ble to add a heavy feedstock, selected from heavy crude oils, distillation residues, heavy oils coming from cata- lytic 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 lique- fied coal to be sent to the hydro-treatment step (HT).
A secondary post-treatment hydrogenating section of the C,-500°C fraction, preferably of the Cs-350°C fraction, deriving from the high pressure separating sections situ- ated upstream of the distillation, can be present in addi- tion to the steps forming the integrated process.
In this case, the stream containing the hydro- treatment reaction product and the catalyst in dispersed phase, before being sent to one ox 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 pres- sure separation step can be sent to a hydro-treatment sec- tion producing a lighter fraction containing Ci1-C4 gas and
H,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;-500°C, preferably Cs-350°C, fraction exploits the availability of this fraction to- gether with hydrogen at a relatively high pressure, which is approximately that of the hydro-treatment reactor, al- lowing the following advantages to be obtained: e the production, starting from oil feedstocks extremely rich in sulfur, of fuels in line with the strictest specifications on the sulfur content (<10-50 ppm of sul- fur) and improved with respect to other characteristics of diesel gas oil such as density, the content of pol- yaromatic hydrocarbons and the cetane number; e the distillates produced do not suffer from problems of stability.
The hydrogenating post-treatment on a fixed bed con- sists in the preliminary separation of the reaction efflu- ent of the hydro-treatment reactor (HT) using one or more separators operating at a high pressure and high tempera- ture. Whereas the heavy part, extracted at the bottom, is sent to the main distillation unit, the part extracted at the head, a Cz-500°C, preferably Cs-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 o0il 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 o0il 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, pref- erably from 280 to 420°C; the temperature is generally in relation to the desulfuration level required. The space ve- locity is another important variable in controlling the quality of the product obtained: it can range from 0.1 to 5 h™!, preferably from 0.2 to 2 ht.
The quantity of hydrogen mixed with the feedstock is fed at a flow-rate ranging from 100 to 5000 Nms3/m3, pref- erably from 300 to 1000 Nmz/ms.
A further secondary post-treatment section of the flushing stream can be optionally present, alone or possi- bly 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.
In this case, 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 sol- vent can be subsequently removed.
The possible treatment section of the flushing efflu- ent, preferably in a quantity ranging from 0.5 to 10% by volume with respect to the fresh feedstock, consists of a de-oiling step with a solvent (toluene or gas 0il 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: e to the pool fuel oil, as such or after being separated from the solvent and/or after the addition of a suitable fluxing agent; e and/or to the hydro-treatment reactor (HT) as such.
In specific cases, 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 ox metals contained in the transition catalyst (for example molybdenum) (with re- spect 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: eo the entity of the flushing fraction is strongly reduced; e most of the flushing fraction is upgraded to fuel oil by separating the metals and coke; eo the fraction of fresh catalyst to be added to the primary hydro-treatment feedstock is reduced as at least part of the molybdenum extracted from the selective recovery treatment is recycled.
The Qeoiling step consists in the treatment of the " flushing stream, which represents a minimum fraction of the asphaltene stream coming from the deasphalting section (spa) 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 liguid phase, leaving the metallic sulfides, coke and more refrac- tory carbonaceous residues (insoluble toluene or similar products), in solid phase.
Considering that the components of a metallic nature can become pyrophoric when they are very dry, it is advis- able to operate in an inert atmosphere, containing as lit- tle oxygen and humidity as possible. various 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 0il coming from the FCC unit or. Thermal Gas oil coming from the Visbreaker/Thermal
Cracker unit, can be mentioned.
Within certain limits, the operating rate is facili- tated by increases in the temperature and the reaction time but an excessive increase is unadvisable for economic rea- sons.
The operating temperatures depend on the solvent used and on the pressure conditions adopted; temperatures rang- ing from 80 to 150°C, however, are recommended; the reac- tion 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.
Once the mixing phase between the solvent and flushing stream has been completed, the effluent maintained under stirring is sent to a separation section of the liquid phase from the solid phase.
This operation can be one of those typically used in industrial practice such as decanting, centrifugation or filtration.
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.
Alternatively, 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.
It has been found, in fact, that by adding a heavy feedstock but without metals such as, for example, part of the Deasphalted Oil (DAO) coming from the deasphalting unit of the plant itself, to the above solid phase, and mixing said system with acidulated water (typically with an inor- ganic acid), almost all of the molybdenum is maintained in the organic phase, whereas substantial quantities of other metals migrate towards the aqueous phase. The two phases can be easily separated and the organic phase can then be advantageously recycled to the hydro-treatment reactor.
The solid phase is dispersed in a sufficient quantity of organic phase (for example deasphalted oil coming from the same process) to which acidulated water is added.
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.
As far as the general process conditions are con- cerned, reference should be made to what is already speci- fied in patent applications IT-MI2001A-001438 and IT- 95A001095.
According to what is described in patent application
IT-952001095, all the heavy feedstock can be mixed with a suitable hydrogenation catalyst and sent to the hydro- treatment reactor (HT), whereas at least 60%, preferably at least 80% of the stream containing asphaltenes, which also contains catalyst in dispersed phase and possibly coke and is enriched with metal coming from the initial feedstock,
can be recycled to the hydro-treatment zone.
According to what is described in patent application
IT-MI2001A-001438, 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.
According to what is described in patent application
IT-MI20012-001438, at least most of the stream containing asphaltenes, which essentially consists of said asphalte- nes, 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. when only part of the distillation residue (tar) or liquid leaving the flash unit is recycled to the deasphalt- ing zone (SDA), at least part of the remaining quantity of said distillation or flash residue can be sent to the hy- dro-treatment reactor, optionally together with at least part of the stream containing asphaltenes coming from the deasphalting section (SDA).
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 concentration of the catalyst, defined on the ba- sis of the concentration of the metal or metals present in the hydroconversion reactor, ranges from 300 to 20,000 ppm, preferably from 1,000 to 10,000 ppm.
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 re- duced 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 reac- tor can be recycled to the subsequent reactors.
The deasphalting step, effected by means of an extrac- tion 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.
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 treat- ment.
Depending on the characteristics of the crude oil (metal content, sulfur and nitrogen content, carbonaceous residue), the feeding to the whole process can be advanta- geously varied by sending the heavy residue alternately ei- ther to the deasphalting unit or to the hydro-treatment unit, or contemporaneously to the two units, modulating: e the ratio between the heavy residue to be sent to the hy- dro-treatment section (fresh feedstock) and that to be sent for deasphalting; said ratio preferably varies from 0.01 to 100, more preferably from 0.1 to 10, even more preferably from 1 to 5; e the recycling ratio between fresh feedstock and tar to be sent to the deasphalting section; said ratio preferably varies from 0.01 to 100, more preferably from 0.1 to 10; e the recycling ratio between fresh feedstock and. asphalte- nes to be sent to the hydro-treatment section; said ratio can vary in relation to the variations in the previous ratios; e the recycling ratio between tar and asphaltenes to be sent to the hydro-treatment section; said ratio 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).
Depending on the type of crude oil, 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 mix- tures 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).
The combined action of a catalytic hydrogenation unit (HT) with an extractive process (SDA) allows 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, af- ter being preferably slurrified in a hydrocarbon matrix, a suitable solvent (2) and an appropriate hydrogenation cata- lyst (3) are sent to the direct liquefaction unit (CL), into which hydrogen or hydrogen and H,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 extrac- tion unit (SDAsh), from a further liquid stream (11).
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 hy- drogen and H,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) con- taining the dispersed catalyst and coke.
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 to- tally added (25) to the liquid stream (11) consisting of liquefied coal and optionally partially recycled (26) to the feedstock substantially consisting of coal (1).
Some examples are provided hereunder for a better il-
lustration of the invention, but should in no way be con- sidered as limiting the scope of the invention itself.
EXAMPLE 1
The following experiment was effected, following the scheme represented in Figure 1.
Liquefaction step ¢ Reactor: 30 cc made of steel equipped with a capillary stirring system and the possibility of reintegrating the hydrogen. eo Feedstock: 5.0 g of Columbian coal El Cerrejon (Table 1) ® Solvent: 5.0 g of hydro-treated DAO e Catalyst: 200 ppm of Mo (introduced as hydro-soluble pre- cursor) e Temperature: 400°C +e Residence time: 2 h e Pressure: 15 MPa
The coal liquefaction step was carried out according to the operating conditions indicated above. When the test had been completed, the quenching of the reaction was ef- fected; the autoclave was depressurized and the gases col- lected in a sampling bag for gas chromatographic analysis.
The non-gaseous products present in the reactor were recov- ered with THF and filtered on 0.5 pm Teflon filters to eliminate the THF-insoluble components consisting of the inorganic material (ashes), the non-reacted organic frac-
tion and the catalyst.
The conversion was calculated according to the follow- ing equation:
Conversion = (coalpas—IOM)/ (coalnar)*100
In the formula specified above, the weight of coal is given on the basis of maf (moisture and ash free), i.e. the total weight of coal was subtracted from the ash and water part.
IOM (insoluble organic matter) refers to the part of THF- insoluble products recovered at the end of the reaction from which the ash and water part was subtracted.
Hydro-treatment step of liquids from coal: e Reactor: 30 cc made of steel equipped with a capillary stirring system and the possibility of reintegrating the hydrogen. e Feedstock: 10 g of liquids from coal produced from the liquefaction step e Catalyst: 3000 ppm of No (introduced as hydro-soluble precursor) e Temperature: 415°C eo Residence time: 4 h e Pressure: 16 MPa
When the test had been completed, the quenching of the reaction was effected; the autoclave was depressurized and the gases collected in a sampling bag for gas chroma- tographic analysis. The non-gaseous products present in the reactor were recovered with THF and filtered on 0.5 pm Tef- lon filters to separate the THF-insoluble components con- sisting of the catalyst, metal sulfides and possible traces of coke produced. The THF-soluble fraction was then treated with an excess of n-pentane to precipitate the Cs asphalte- nes and produce a DAO (Deasphalted 0il) to be analyzed by means of GC SIM-DIST for the determination of the distil- lates, or quantifying the yields to: - naphtha (PI-170°QC) - atmospheric gas oil (170-350°C) - vacuum gas oil (350-~500°C) - vacuum residue (500°C+)
Experimental results
The data relating to the liquefaction step and subse- quent hydrogenating treatment are indicated in Table 2.
Table 1: coal characterization
COAL Humidity | Volatiles | Ash | C H N S (W%) (W%) (W%) | (Wo) | (W%) | (W%) | (WY)
El Cerrejon Co- 5.25 35.46 471 | 73.7 | 5.35 | 1.41 | 0.61 lumbia
Co - 34 -
Table 2: results of the liquefaction and hydro-treatment test
TEST Conv, | THFI | ASFCs |Cy-C4 Cs- 170- 350- | 500°C+ woe) | woe) | (we) | (wo) 170°C | 350°C | 500°C (W%) (W%) (W%) (W%) lll step
ERR EEE treatment step
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 mo- lybdenum 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 (W%) | (W%)| (W%) (W%) step
EXAMPLE 3 .
Following the scheme represented in Figure 1, the fol- lowing experiment was effected.
Liquefaction step e Reactor: 3000 cc made of steel equipped with a magnetic stirring system and the possibility of reintegrating the hydrogen. eo Feedstock: 250 g of coal (Table 1) ee Solvent: 250 g of LCO (Light Cycle 0il) e Catalyst: 500 ppm of Mo(introduced as hydro-soluble pre- cursor) e Temperature: 415°C e Residence time: 4 h eo Pressure: 16 MPa
When the test had been completed, the quenching of the reaction was effected; the autoclave was depressurized and the gases collected in a sampling bag for gas chroma- tographic analysis.
The product was recovered from the reactor and sub-
jected to filtration to separate the THF-insoluble compo- nents consisting of the inorganic material (ashes), from the non-reacted organic fraction and the catalyst.
The liquefaction step was repeated several times in order to obtain a quantity of liquid sufficient for the subsequent hydro-treatment tests.
Reference is made to the data indicated in Tables 2 and 3 for the results in terms of coal conversion.
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 distilla- tion.
Hydro-treatment step
The hydro-treatment reaction was effected under the conditions specified in Example 1, using the product ob- tained 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 C3; DAO produced was then sepa- rated and recovered. 8 consecutive hydro-treatment tests were effected, using for each test a feedstock consisting of 350°C+ residue obtained from the coal liquefaction and
Cs asphaltenes obtained from the previous hydro-treatment step and subsequent deasphalting, containing the catalyst,
, v so as to allow the complete recycling of the catalyst added during the first test. At each step, a quantity of residue from coal liquids was added, so as to continuously operate on the same quantity of total feedstock (approx. 300 g).
The ratio between the quantity of coal liquids and quantity of recycled product reached under these operating conditions was 1:1.
The data relating to the outgoing streams after the last recycling (weight % with respect to the liquid feed- stock introduced) are provided hereunder: * Gas: 7% e Naphtha (Cs-170°C): 8% + Atmospheric gas oil (AGO 170-350°C): 19% * Deasphalted oil (VGO + DAO): 66%
In the example indicated it was not necessary to ef- fect a flushing of the recycled stream.
Units which are used in this specification and which are not in accordance with the metric system may be converted to the metric system with the aid of the following conver- sion factor: 1 atm = 101.325 kPa - 3 8 -
AMENDED SHEET 8.03.07
Claims (53)
1. An integrated process 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 distillation of the prod- uct obtained from the liquefaction (F), extraction with a solvent to remove the ashes (SDAsh), distilla- tion to separate the solvent (RS), hydroconversion with catalysts in slurry phase (HT), distillation or flash of the product obtained from the hydroconversion (D), deasphalting with a solvent (SDa), characterized in that it comprises the following steps: ¢ sending the feedstock containing coal to one or more direct coal liquefaction steps (CL) in the presence of a suitable hydrogenation catalyst; eo sending the stream containing the product obtained from the coal liquefaction reaction to one or more flash or distillation steps (F) obtaining a gaseous stream and a liquid stream; e sending the liquid stream to an extraction step with a solvent (SDAsh) whereby an insoluble stream is ob- tained, consisting of the mineral matter present in the feedstock and non-reacted coal and a liquid stream consisting of the liquefied coal obtained and the sol-
vent used; e sending the liquid stream consisting of the lique- fied coal and the solvent used to one or more distil- lation steps in order to substantially separate the solvent contained in the liquid stream, which is recy- cled to the extraction step with a solvent (SDAsh); e mixing the liquid stream substantially consisting of the liquefied coal and at least part of the stream con- taining asphaltenes obtained in the deasphalting unit i0 with a suitable hydrogenation catalyst and sending the mixture obtained to a hydro-treatment reactor (HT) in- troducing hydrogen or a mixture of hydrogen and H,S therein; e sending the stream containing the reaction product of the hydro~treatment and the catalyst in dispersed phase to one or more distillation or flash steps (D) whereby the different fractions coming from the hydro-treatment reaction are separated; es sending at least part of the distillation residue (tar) or liquid leaving the flash unit, containing the catalyst in dispersed phase, rich in metal sulphides produced by the demetallation of the feedstock and op- tionally coke, to the deasphalting zone (Spa) in the presence of solvents, optionally also fed by at least one fraction of the liquid stream substantially con- - AD -
sisting of the liquefied coal, obtaining two streams, one consisting of deasphalted oil (DAO), the other con- taining asphaltenes.
2. The process according to claim 1, wherein the feed- stock containing coal essentially consists of coal.
3. The process according to claim 1, wherein the suitable hydrogenation catalyst present in the liquefaction step (CL) is at least partially recovered from the units downstream of said step.
4. The process according to claim 2, wherein the feed- stock essentially consisting of coal is slurrified in a hydrocarbon matrix.
5. The process according to claim 4, wherein the hydro- carbon matrix comes from the units downstream of the liquefaction step (CL).
6. The process according to claim 5, wherein the hydro- carbon matrix is part of the stream containing asphal- tenes, as well as the dispersed catalyst used in the hydro-treatment step (HT), obtained in the deasphalt- ing step (SDA) and/or part of the stream consisting of deasphalted oil (DAO) obtained in the deasphalting step (SDA).
7. The process according to claim 1, wherein the direct liquefaction of the stream containing coal is effected by mixing said stream with an aromatic solvent in a quantity ranging from 20 to 80% with respect to the coal, and with a suitable catalyst in dispersed phase, operating at a temperature ranging from 360 to 440°C, at a hydrogen pressure ranging from 3 to 30 MPa and with residence times lower than or equal to 4 h.
8. The process according to claim 1, wherein part of the stream containing asphaltenes, as well as the catalyst used in the hydro-treatment step (HT), obtained in the deasphalting step (SDA) is added to the feedstock con- taining coal to be sent to the liquefaction unit (CL) as solvent.
9. The process according to claim 1, wherein part of the stream consisting of deasphalted oil (DAO) obtained in the deasphalting step (SDA) is added to the feedstock containing coal to be sent to the liquefaction unit (CL) as solvent.
10. The process according to claim 1, wherein a part of the medium and heavy fractions (medium and heavy distillates) obtained in the distillation or flash unit (D) is added to the feedstock containing coal to be sent to the liquefaction unit (CL) as solvent.
11. The process according to claim 1, wherein part of the solvent separated in the distillation step (RS) is added to the feedstock containing coal to be sent to the liquefaction unit (CL) as solvent.
12. The process according to claim 1, wherein in the dis- tillation step (RS) of the liquid stream consisting of liquefied coal and the solvent used, a further stream is separated as distillate.
13. The process according to claim 12, wherein part of the further stream separated, as distillate, in the dis- tillation step (RS) is added to the feedstock contain- ing cecal to be sent to the liquefaction unit (CL) as solvent.
14. The process according to claim 1, wherein the direct liquefaction of the stream containing coal is effected by mixing said stream with an aromatic solvent in a quantity ranging from 20 to 80% with respect to the coal, and with a suitable catalyst in dispersed phase, operating at a temperature ranging from 360 to 440°C, a hydrogen pressure ranging from 3 to 30 MPa and with residence times lower than or equal to 4 h.
15. The process according to claim 1, wherein the extrac- tion step with a solvent to remove the ashes is ef- fected at a temperature ranging from 150 to 350°C and a pressure ranging from 20 to 60 atm (2.03 to 6.08 MPa) in the presence of a suitable aromatic solvent.
16. The process according to claim 1, wherein a heavy feedstock, selected from heavy crude oils, distilla- tion residues, heavy oils coming from catalytic treat- - 43 - AMENDED SHEET 8.03.07 ment, thermal tars, bitumens from oil sands, various types of coals and/or other high-boiling feedstocks of a hydrocarbon origin known as black oils, is added to the feedstock consisting of coal to be sent to the liquefaction unit (CL).
17. The process according to claim 1, wherein a heavy feedstock, selected from heavy crude oils, distilla- tion residues, heavy oils coming from catalytic treat- ment, thermal tars, bitumens from oil sands, various types of coals and/or other high-boiling feedstocks of a hydrocarbon origin known as black oils, is added to the liquid stream consisting of liquefied coal to be sent to the hydro-treatment step (HT).
18. The process according to claim 1, wherein before being sent to one or more distillation or flash steps (D), the stream containing the hydro-treatment reaction product and the catalyst in dispersed phase, is sub- jected to a separation pre-step effected at high pres- sure in order to obtain a light fraction and a heavy fraction, said heavy fraction alone being sent to said distillation step(s) (D).
19. The process according to claim 18, wherein the light fraction obtained by means of the high pressure sepa- ration step is sent to a secondary post-treatment hy- drogenating section producing a lighter fraction con-
taining C;-Cs gas and HS and a heavier fraction con- taining hydro-treated naphtha and gas oil.
20. The process according to claim 19, wherein the post- treatment hydrogenating reaction is effected at a pressure ranging from 7 to 14 MPa.
21. The process according to claim 1, wherein all the liquid stream substantially consisting of liquefied coal is mixed with a suitable hydrogenation catalyst and sent to the hydro-treatment reactor (HT), whereas at least 60% of the stream containing asphaltenes, which also contains catalyst in dispersed phase and possibly coke and is enriched with metals coming from the initial feedstock, is recycled to the hydro- treatment zone.
22. The process according to claim 21, wherein at least 80% of the stream containing asphaltenes is recycled .. to the hydro-treatment zone.
23. The process according to claim 1, wherein the liquid stream substantially consisting of liquefied coal and ‘ at least most of the stream containing asphaltenes, which also contains catalyst in dispersed phase and possibly coke, are mixed with a suitable hydrogenation catalyst and sent to the hydro-treatment reactor (HT).
24. The process according to claim 1, wherein part of the distillation residue (tar) or liquid leaving the flash unit (D) is sent to the deasphalting zone (SDA) and at least part of the remaining part of said distillation or flash residue is sent to the hydro-treatment reac-
tor.
25. The process according to claim 24, wherein at least part of the remaining quantity of the distillation or flash residue (D) is sent to the hydro-treatment reac- tor together with at least part of the stream contain- ing asphaltenes coming from the deasphalting section (SDA) .
. 26. The process according to claim 1, wherein at least 80% by weight of the distillation residue is sent to the deasphalting zone (SDA).
27. The process according to claim 26, wherein at least 95% by weight of the distillation residue is sent to the deasphalting zone (SDA).
28. The process according to claim 1, wherein at least part of the remaining quantity of distillation residue (tar), not sent to the deasphalting zone is recycled to the hydro-treatment section (HT).
29. The process according to claim 1, wherein the distil- lation steps are carried out at a reduced pressure ranging from 0.0001 to 0.5 MPa.
30. The process according to claim 29, wherein the distil- lation steps are carried out at a reduced pressure _ 46 -
ranging from 0.001 to 0.3 MPa.
31. The process according to claim 1, wherein the hydro- treatment step is carried out at a temperature ranging from 370 to 480°C and at a pressure ranging from 3 to 30 MPa. :
32. The process according to claim 31, wherein the hydro- treatment step is carried out at a temperature ranging from 380 to 440°C and at a pressure ranging from 10 to 20 MPa.
33. The process according to claim 1, wherein the deasphalting step is carried out at temperature rang- ing from 40 to 200°C and at a pressure ranging from
0.1 to 7 MPa.
34. The process according to claim 1, wherein the deasphalting solvent is a light paraffin with from 3 to 7 carbon atoms.
35. The process according to claim 1, wherein the deasphalting step (SDA) is carried out under subcriti- cal or supercritical conditions with one or more steps.
36. The process according to claim 1, wherein the stream consisting of deasphalted oil (DAO) is fractionated by means of conventional distillation.
37. The process according to claim 1, wherein the stream consisting of deasphalted oil (DAO) is mixed with the products separated in the distillation step after be- ing condensed.
38. The process according to claim 1, wherein the hydro- genation catalyst derives from a decomposable precur- sor or a preformed compound based on one or more transition metals.
39. The process according to claim 38, wherein the transi- tion metal is molybdenum.
40. The process according to claim 1, wherein the concen- tration of the catalyst in the hydroconversion reac- tor, defined on the basis of the concentration of the metal or metals present, ranges from 300 to 20,000 ppm.
41. The process according to claim 40, wherein the concen- tration of the catalyst in the hydroconversion reactor ' ranges from 1,000 to 10,000 ppm.
42. The process according to claim 1, wherein a fraction of the stream containing asphaltenes, 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 frac- tion and a liquid fraction from which said solvent can be subsequently separated.
43. The process according to claim 42, wherein the flush- ing stream is in a quantity ranging from 0.5 to 10% by _ 4 8 —- AMENDED SHEET 8.03.07 volume with respect to the fresh feedstock.
44, The process according to claim 43, wherein at least part of the liquid fraction deriving from the treat- ment section of the flushing stream is sent as such or after being separated from the solvent and/or after the addition of a suitable fluxing agent to the Fuel Oil fraction.
45. The process according to claim 44, wherein at least part of the liquid fraction deriving from the treat- ment section of the flushing stream is recycled to the hydro-treatment reactor (HT) and/or at least part of the liquid fraction deriving from the treatment sec- tion of the flushing stream is recycled to the coal liquefaction unit (CL).
46. The process according to claim 42, wherein the solvent used in the treatment section of the flushing stream is an aromatic solvent or a mixture of gas oils pro- duced in the process itself or available in refiner-
ies.
47. The process according to claim 46, wherein the aro- matic solvent is toluene and/or a mixture of xylenes.
48. The process according to claim 40, wherein the volu- metric ratio solvent/flushing stream varies from 1 to
10.
49. The process according to claim 48, wherein the volu- - 4 9 — AMENDED SHEET 8.03.07 metric ratio solvent/flushing stream varies from 1 to
50. The process according to claim 49, wherein the volu- metric ratio solvent/flushing stream varies from 1.5 to 3.5.
51. The process according to claims 42 and 38, wherein the solid fraction of the product treated is sent to a further selective recovery treatment step of the tran- sition metal or metals contained in the hydrogenation catalyst.
52. The process according to claim 51, wherein the transi- tion metal or metals recovered are recycled to the hy- dro-treatment reactor (HT).
53. An integrated process according to claim 1 substan- tially as herein described with reference to Figure 1. - 50 - AMENDED SHEET 8.03.07
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT002207A ITMI20032207A1 (en) | 2003-11-14 | 2003-11-14 | INTEGRATED PROCEDURE FOR THE CONVERSION OF CHARGES CONTAINING CARBON IN LIQUID PRODUCTS. |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200603668B true ZA200603668B (en) | 2007-09-26 |
Family
ID=34586990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200603668A ZA200603668B (en) | 2003-11-14 | 2004-11-10 | Integrated process for the conversion of feedstocks containing coal into liquid products |
Country Status (8)
Country | Link |
---|---|
US (2) | US20070144944A1 (en) |
EP (1) | EP1730252A1 (en) |
CN (1) | CN100489061C (en) |
AU (1) | AU2004289810B2 (en) |
IT (1) | ITMI20032207A1 (en) |
RU (1) | RU2360944C2 (en) |
WO (1) | WO2005047425A1 (en) |
ZA (1) | ZA200603668B (en) |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7485267B2 (en) * | 2005-07-29 | 2009-02-03 | Chevron U.S.A. Inc. | Process for metals recovery from spent catalyst |
ITMI20061512A1 (en) * | 2006-07-31 | 2008-02-01 | Eni Spa | PROCEDURE FOR THE TOTAL CONVERSION OF HEAVY DUTIES TO DISTILLATES |
ITMI20061511A1 (en) * | 2006-07-31 | 2008-02-01 | Eni Spa | PROCEDURE FOR THE TOTAL CONVERSION TO HEAVY DISTILLATES |
US20080072476A1 (en) * | 2006-08-31 | 2008-03-27 | Kennel Elliot B | Process for producing coal liquids and use of coal liquids in liquid fuels |
US7674369B2 (en) | 2006-12-29 | 2010-03-09 | Chevron U.S.A. Inc. | Process for recovering ultrafine solids from a hydrocarbon liquid |
US8449632B2 (en) | 2007-05-24 | 2013-05-28 | West Virginia University | Sewage material in coal liquefaction |
US8465561B2 (en) | 2007-05-24 | 2013-06-18 | West Virginia University | Hydrogenated vegetable oil in coal liquefaction |
US20120097519A1 (en) | 2007-05-24 | 2012-04-26 | Quantex Research Corporation | System and Method of a Coated Coker |
US8597382B2 (en) | 2007-05-24 | 2013-12-03 | West Virginia University | Rubber material in coal liquefaction |
ITMI20071198A1 (en) * | 2007-06-14 | 2008-12-15 | Eni Spa | IMPROVED PROCEDURE FOR THE HYDROCONVERSION OF HEAVY OILS WITH BULLETS |
US7846404B2 (en) * | 2007-11-28 | 2010-12-07 | Chevron U.S.A. Inc. | Process for separating and recovering base metals from used hydroprocessing catalyst |
US7658895B2 (en) * | 2007-11-28 | 2010-02-09 | Chevron U.S.A. Inc | Process for recovering base metals from spent hydroprocessing catalyst |
US8221710B2 (en) * | 2007-11-28 | 2012-07-17 | Sherritt International Corporation | Recovering metals from complex metal sulfides |
US7837960B2 (en) * | 2007-11-28 | 2010-11-23 | Chevron U.S.A. Inc. | Process for separating and recovering base metals from used hydroprocessing catalyst |
US7964090B2 (en) * | 2008-05-28 | 2011-06-21 | Kellogg Brown & Root Llc | Integrated solvent deasphalting and gasification |
US8123934B2 (en) | 2008-06-18 | 2012-02-28 | Chevron U.S.A., Inc. | System and method for pretreatment of solid carbonaceous material |
US20100122934A1 (en) * | 2008-11-15 | 2010-05-20 | Haizmann Robert S | Integrated Solvent Deasphalting and Slurry Hydrocracking Process |
CN101643660B (en) * | 2009-01-13 | 2012-11-14 | 煤炭科学研究总院 | Coal liquefaction method |
CA2756556A1 (en) * | 2009-03-25 | 2010-09-30 | Chevron U.S.A. Inc. | Process for recovering metals from coal liquefaction residue containing spent catalysts |
US8110090B2 (en) * | 2009-03-25 | 2012-02-07 | Uop Llc | Deasphalting of gas oil from slurry hydrocracking |
US8540870B2 (en) | 2009-06-25 | 2013-09-24 | Uop Llc | Process for separating pitch from slurry hydrocracked vacuum gas oil |
US8202480B2 (en) * | 2009-06-25 | 2012-06-19 | Uop Llc | Apparatus for separating pitch from slurry hydrocracked vacuum gas oil |
US8231775B2 (en) | 2009-06-25 | 2012-07-31 | Uop Llc | Pitch composition |
BRPI1014342A2 (en) * | 2009-06-25 | 2016-04-05 | Uop Llc | process and apparatus for converting heavy hydrocarbon feed into lighter hydrocarbon products. |
US20110120914A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120917A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120915A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
US20110120916A1 (en) * | 2009-11-24 | 2011-05-26 | Chevron U.S.A. Inc. | Hydrogenation of solid carbonaceous materials using mixed catalysts |
CN101863637B (en) * | 2010-07-05 | 2012-02-01 | 长安大学 | Paving asphalt concrete additive and preparation method thereof |
US8815184B2 (en) | 2010-08-16 | 2014-08-26 | Chevron U.S.A. Inc. | Process for separating and recovering metals |
CN102229810B (en) * | 2011-06-03 | 2013-11-27 | 陕西煤化工技术工程中心有限公司 | Method for extracting thermolysis coal by coal tar |
US9150470B2 (en) | 2012-02-02 | 2015-10-06 | Uop Llc | Process for contacting one or more contaminated hydrocarbons |
CN103789036B (en) * | 2012-10-26 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of inferior heavy oil combinational processing method |
CN103789027B (en) * | 2012-10-26 | 2015-04-29 | 中国石油化工股份有限公司 | Modifying method for heavy oil hydrogenating |
US9580839B2 (en) * | 2012-12-26 | 2017-02-28 | Honeywell Federal Manufacturing & Technologies, Llc | Methods of making carbon fiber from asphaltenes |
WO2014131040A1 (en) * | 2013-02-25 | 2014-08-28 | Foster Wheeler Usa Corporation | Increased production of fuels by integration of vacuum distillation with solvent deasphalting |
CN103254933B (en) * | 2013-05-30 | 2015-05-20 | 神华集团有限责任公司 | Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues |
ITMI20131137A1 (en) | 2013-07-05 | 2015-01-06 | Eni Spa | PROCEDURE FOR REFINING THE CRUDE |
CN103555357B (en) * | 2013-11-04 | 2015-08-19 | 华东理工大学 | The processing method of a kind of coal gentleness liquefaction |
CN103937542B (en) * | 2014-04-14 | 2016-06-29 | 辽宁科技大学 | A kind of analysis method of mink cell focus and Colophonium composition in hydrogenation liquefaction solid residue |
FR3021326B1 (en) * | 2014-05-21 | 2017-12-01 | Ifp Energies Now | METHOD FOR CONVERTING A HEAVY HYDROCARBON LOAD INTEGRATING SELECTIVE DESASPHALTATION BEFORE THE CONVERSION STEP. |
US10400108B2 (en) * | 2016-04-29 | 2019-09-03 | Axens | Carbon black feedstock from direct coal liquefaction |
IT201600122525A1 (en) | 2016-12-02 | 2018-06-02 | Eni Spa | PROCEDURE FOR THE PRODUCTION OF LIPIDS AND OTHER BIOMASS ORGANIC COMPOUNDS |
RU2665484C1 (en) * | 2017-08-25 | 2018-08-30 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method for producing catalyst and method for hydrogening oil-polymeric resins at its presence |
CN108531206B (en) * | 2018-04-03 | 2020-12-29 | 西南石油大学 | High-evolution pyrobitumen high-temperature circulating dissolving device and method |
WO2020121220A1 (en) * | 2018-12-11 | 2020-06-18 | Eni S.P.A. | Process for the selective recovery of transition metals from organic residues |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4354922A (en) * | 1981-03-31 | 1982-10-19 | Mobil Oil Corporation | Processing of heavy hydrocarbon oils |
US4431510A (en) * | 1982-04-01 | 1984-02-14 | Uop Inc. | Process for producing hydrogen-enriched hydrocarbonaceous products from coal |
US4486293A (en) * | 1983-04-25 | 1984-12-04 | Air Products And Chemicals, Inc. | Catalytic coal hydroliquefaction process |
US4874506A (en) * | 1986-06-18 | 1989-10-17 | Hri, Inc. | Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction |
JPH08269459A (en) * | 1995-03-31 | 1996-10-15 | Agency Of Ind Science & Technol | Coal liquefaction method |
ITMI20011438A1 (en) * | 2001-07-06 | 2003-01-06 | Snam Progetti | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES SUCH AS HEAVY FATS AND DISTILLATION RESIDUES |
US8017000B2 (en) * | 2002-12-20 | 2011-09-13 | Eni S.P.A. | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
DK1572839T3 (en) * | 2002-12-20 | 2006-10-23 | Eni Spa | Process for the conversion of heavy raw materials, such as heavy crude oils and distillation residues |
ITMI20042445A1 (en) * | 2004-12-22 | 2005-03-22 | Eni Spa | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES WHICH WEIGHING AND DISTILLATION WASTE |
-
2003
- 2003-11-14 IT IT002207A patent/ITMI20032207A1/en unknown
-
2004
- 2004-11-10 WO PCT/EP2004/012763 patent/WO2005047425A1/en active Application Filing
- 2004-11-10 AU AU2004289810A patent/AU2004289810B2/en not_active Ceased
- 2004-11-10 CN CNB2004800356932A patent/CN100489061C/en not_active Expired - Fee Related
- 2004-11-10 US US10/579,224 patent/US20070144944A1/en not_active Abandoned
- 2004-11-10 EP EP04818390A patent/EP1730252A1/en not_active Withdrawn
- 2004-11-10 RU RU2006115300/04A patent/RU2360944C2/en not_active IP Right Cessation
- 2004-11-10 ZA ZA200603668A patent/ZA200603668B/en unknown
-
2010
- 2010-03-01 US US12/715,122 patent/US20100219104A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1730252A1 (en) | 2006-12-13 |
AU2004289810A1 (en) | 2005-05-26 |
ITMI20032207A1 (en) | 2005-05-15 |
RU2006115300A (en) | 2007-12-20 |
US20070144944A1 (en) | 2007-06-28 |
AU2004289810B2 (en) | 2010-02-11 |
RU2360944C2 (en) | 2009-07-10 |
CN1890350A (en) | 2007-01-03 |
CN100489061C (en) | 2009-05-20 |
WO2005047425A1 (en) | 2005-05-26 |
US20100219104A1 (en) | 2010-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
ZA200603668B (en) | Integrated process for the conversion of feedstocks containing coal into liquid products | |
CA2530894C (en) | Process for the conversion of heavy charges such as heavy crude oils and distillation residues | |
US8123932B2 (en) | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues | |
US8017000B2 (en) | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues | |
CA2530906C (en) | Process for the conversion of heavy charge stocks such as heavy crude oils and distillation residues | |
US8057660B2 (en) | Process for the total conversion of heavy feedstocks to distillates | |
WO2014113285A1 (en) | Conversion of asphaltenic pitch within an ebullated bed residuum hydrocracking process |