EP1217061B1 - Procédé de traitement d'une charge Hydrocarbonée comprenant une étape d'hydrotraitement en lit fixe à contre-courant - Google Patents
Procédé de traitement d'une charge Hydrocarbonée comprenant une étape d'hydrotraitement en lit fixe à contre-courant Download PDFInfo
- Publication number
- EP1217061B1 EP1217061B1 EP01403141A EP01403141A EP1217061B1 EP 1217061 B1 EP1217061 B1 EP 1217061B1 EP 01403141 A EP01403141 A EP 01403141A EP 01403141 A EP01403141 A EP 01403141A EP 1217061 B1 EP1217061 B1 EP 1217061B1
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- EP
- European Patent Office
- Prior art keywords
- solid particles
- process according
- metal
- catalyst
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 30
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 26
- 239000003054 catalyst Substances 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 49
- 239000007787 solid Substances 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 43
- 230000003197 catalytic effect Effects 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 23
- 239000011707 mineral Substances 0.000 claims description 23
- 229910000510 noble metal Inorganic materials 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- -1 silica-aluminas Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000008240 homogeneous mixture Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052717 sulfur Inorganic materials 0.000 description 22
- 239000011593 sulfur Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 150000002736 metal compounds Chemical class 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910008423 Si—B Inorganic materials 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 229910017305 Mo—Si Inorganic materials 0.000 description 2
- 229910008938 W—Si Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000287107 Passer Species 0.000 description 1
- 229910006367 Si—P Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
Definitions
- the present invention relates to the hydrotreatment (HDT) of hydrocarbon fractions for produce hydrocarbon fractions with a low content of sulfur, nitrogen and compounds aromatic compounds which can be used in particular in the field of motor fuels for internal combustion.
- hydrocarbon fractions include jet fuel, fuel diesel and kerosene.
- the invention finds more particularly its application during processes of transformation of a middle distillate and more particularly of a diesel fuel cut to produce a fuel with a high cetane number, deflavored and desulfurized.
- the invention can also be applied to the hydrotreatment of products more alone or in admixture with diluents, for example hydrocarbon fractions atmospheric or vacuum distillations in the course of operations hydrodemetallation (HDM), hydrodesulfurization (HDS) or hydrodenitrogenation (HDN).
- hydrodemetallation HDM
- hydrodesulfurization HDS
- hydrodenitrogenation HDN
- the present method can thus be implemented both to improve the characteristics of the finished products in terms of specifications required to achieve product quality and standards of pollution (sulfur and aromatic content in particular) prepare charges for refinery processing or conversion units (visbreaking, coking or catalytic cracking for vacuum distillate, isomerization or reforming for a naphtha for example) using impurity-sensitive catalysts (eg sulfur for metal catalysts, nitrogen for acid catalysts and metals in general).
- impurity-sensitive catalysts eg sulfur for metal catalysts, nitrogen for acid catalysts and metals in general.
- Class II diesel fuel must not contain more than 50 ppm of sulfur and more than 10% by volume of Class I and more than 10 ppm of sulfur and 5% by volume of aromatics.
- Class III diesel fuel must contain less than 500 ppm of sulfur and less than 25% by volume of aromatic compounds. Limits similar are also to be respected for the sale of this type of fuel in California.
- the method according to the present invention relates in a more general context any process in which a fixed bed is used in a reactor during a catalytic process and wherein a liquid charge and a gaseous reactant are injected into the reactor from else of the bed and flow against the current in said bed.
- the The process finds its application in the field of hydrotreating of petroleum fractions.
- the main constraint related to this type of device is the possible existence of a congestion phenomenon limiting the possible flow of each of the phases being able to pass through the catalytic bed.
- the risk is thus for the strong gas pressures most often required for hydrotreatment phase training liquid by the gas phase circulating against the current.
- a flow against the current can not be reasonably envisaged that if one minimizes the losses of charges within the catalytic bed. It is known that small catalyst causes a great loss of load.
- the increase in the classical dimensions of supported catalyst generally adopted for fixed beds (0.5 to 10 mm) seems a priori necessary.
- a larger size of the catalyst grains results in a decreased catalytic activity within the reaction bed due to diffusion intraparticular limited charge in large particles.
- the object of the present invention is a method making it possible to limit the associated pressure losses. for the use in a fixed-bed reactor of a flow of countercurrent fluids during a catalytic process of hydrotreatment while maintaining a catalytic activity acceptable within the mixture of particles used.
- one of the objects of the invention is to preserve a catalytic activity reasonable within the bed while minimizing losses.
- An intermediate zone of stripping placed between the two reactors allows the evacuation of the lightest compounds resulting from the hydrodesulfurization reaction (H2S, NH3, etc.).
- H2S hydrodesulfurization reaction
- One of the advantages of a two-step process thus lies in the possibility of using in the second reactor a catalyst more specifically dedicated to the hydrogenation of aromatic nuclei (whose reactivity is the weakest) without any problem of deactivation of it by H2S. This technology is for example described in US Patent 5,114,562.
- the reactors have necessarily the highest diameters possible and the low linear velocities of fluids in reactors requires distribution systems within these same very efficient reactors.
- the exothermicity of the reaction makes it difficult to control the temperature along the reactor and most often imposes a management strategy temperatures and the injection of a cooling gas still called by the specialists of this quench gas field directly into the reactor between the catalytic beds, usually followed by redistribution of the reaction fluids.
- a co-current flow of the reagents causes the deposition of molecules of sulfur or coke which obstructs the entry of the pores of the catalyst, in the upper part of the fixed beds.
- the present invention relates to a process for treating a hydrocarbon feedstock containing sulfur compounds, nitrogen compounds and aromatic compounds comprising at least one hydrotreatment stage in which at least one countercurrent chamber is circulated.
- liquid fraction of said hydrocarbon feedstock and hydrogen through at least one fixed bed of solid particles, said solid particle fixed bed (s) comprising a substantially homogeneous mixture of S1 solid particles having an average diameter of 0.5 to 5 mm and S2 solid particles whose average diameter is greater than the average diameter of the solid particles S1.
- at least a part of at least one of said particles S1 or S2 is catalytic and comprises a mineral support.
- the mean diameter of the particles S1 will be between 0.5 and 2 mm and very preferably between 1 and 2 mm.
- the solid particles S2 will advantageously have an average diameter of at least 1.1 times that of the solid particles S1.
- the average diameter of the particles S 2 will generally be between about 1.1 and 10 times, more preferably between 1.5 and 5 times and very preferably between 2 and 4 times the average diameter of the solid particles S 1.
- At least a portion and preferably all the particles S1 are catalytic and at least a portion and preferably all the particles S2 are inert.
- at least a portion of the particles (inert or catalytic) is meant at least 20%, preferably at least 50% and most preferably at least 80% of the particles.
- the ratio of the volume occupied in the bed by said catalytic solid particles to the volume occupied in the bed by said inert solid particles is between 0.1 and 5, preferably between 0.3 and 2.
- the solid particles S1 have a geometric shape different from that of the solid particles S2.
- the inert solid particles may be in the form of beads and / or rings and / or stool.
- the inert solid particles may be ring-shaped and / or saddle-shaped solids and included in the group consisting of Raschig rings, Lessing rings, Pall and Hy-Pak rings, rings. spiraled, stool Berl, Intalox stool.
- the catalytic solid particles are advantageously in the form of extrudates and / or beads and / or pellets. According to a particular and advantageous embodiment of the process of the invention, the catalytic solid particles will be in the form of extrudates and the inert solid particles will be in the form of beads.
- said catalytic solid particles comprise at least partly a hydrotreatment catalyst comprising on a mineral support at least one metal or a group VIB metal compound preferably selected from the group consisting of molybdenum and tungsten and at least one non-noble metal or a non-noble group VIII metal compound preferably selected from the group consisting of nickel, cobalt and iron.
- said catalytic solid particles comprise at least partly a hydrotreatment catalyst comprising on a mineral support at least one noble metal or a group VIII noble metal compound, advantageously at least one metal or one compound of noble metal selected from the group consisting of palladium and platinum, alone or in mixture.
- the support of said catalyst is chosen from the group formed by alumina, silica, silica-aluminas, zeolites and mixtures of at least two of these mineral compounds.
- any additional device of known perfection of the prior art can be included within the scope of the present invention without leaving it, for example additional stripping and / or recycling of gases comprising hydrogen and hydrogen sulfide from any one of the three preceding steps.
- the gaseous effluent formed in the stripping stage containing gaseous hydrocarbons under the conditions of said stripping zone, hydrogen and hydrogen sulfide can be advantageously cooled to a temperature sufficient to form a liquid fraction of hydrocarbons that are sent to the stripping zone and a gaseous fraction depleted in hydrocarbons that is sent to an elimination zone of the hydrogen sulfide it contains and from which is recovered from the purified hydrogen.
- the catalyst of step a) comprises at least one metal or a metal compound selected from the group consisting of molybdenum and tungsten and at least one metal or metal compound selected from the group consisting of nickel, cobalt and iron.
- the catalyst of step a) advantageously comprises at least one element selected from the group consisting of silicon, phosphorus and boron or one or more compounds of this or these elements.
- the support of the catalysts employed in step a) and in step c) are chosen independently of one another in the group formed by alumina, silica, silica-aluminas and zeolites. and mixtures of at least two of these mineral compounds.
- said solid particles will be charged into said chamber according to any technique known to those skilled in the art using a means to obtain within the chamber a dense and homogeneous mixture solid particles.
- any of the devices described in patents FR 2,721,900, EP-B1-482,991 or EP-B1-470,142 of the applicant or one of the devices disclosed in patents GB 2,168,330, US 4,443,707 or EP-B1-769,462, may be used.
- the operating conditions of the steps a) and c) are selected according to the characteristics of the load which may be a diesel cut straight-run distillation, diesel fuel cut from catalytic cracking or diesel fuel from the coking or visbreaking of residues or a mixture of two or more of these cuts. They are usually chosen in order to obtain a product at the leaving step a) containing less than 100 ppm sulfur and less than 200 ppm nitrogen, preferably less than 100 ppm nitrogen and most often less than 50 ppm nitrogen and the conditions of step c) are chosen so as to obtain a product, on leaving said step c), containing less than 20% by volume of aromatic compounds.
- the conditions of step a) comprise a temperature from 260 ° C to 450 ° C, a total pressure of 2 MPa to 20 MPa and an overall hourly space velocity of liquid charge of 0.1 to 4 and that of step b) a temperature of 100 ° C to 400 ° C, a total pressure of 3 MPa at 15 MPa.
- the catalyst employed in step a) contains on a mineral support at least one metal or Group VIB metal compound of the periodic table of elements in a quantity in weight of metal relative to the weight of the finished catalyst usually about 0.5 to 40%, at least one non-noble metal or non-noble metal group VIII compound said periodic classification in an amount expressed by weight of metal with respect to catalyst weight usually finished from 0.1 to 30%.
- the catalyst used will also contain at least one element selected from the group consisting of silicon, phosphorus and boron or compounds of this or these elements.
- the catalyst will contain example of phosphorus or at least one phosphorus compound in quantity expressed by weight phosphorus pentoxide relative to the support weight of 0.001 to 20%.
- the catalyst will comprise boron or at least one compound boron preferably in an amount expressed by weight of boron trioxide relative to carrier weight from 0.001 to 10%.
- the catalyst will comprise silicon or at least one silicon compound preferably in a quantity expressed by weight of silica relative to the weight of the support of 0.001 to 10%.
- the amount of metal or the Group VIB metal compound expressed in weight of metal per the weight of the finished catalyst will preferably be from 2 to 30% and most often from 5% to 25% and that of the metal or Group VIII metal compound will be preferably from 0.5 to 15% and most often from 1 to 10%.
- step a1) When you want to stay in a relatively low pressure range while wishing to obtain excellent results it is possible to perform a first step a1) in conditions to reduce the sulfur content of the product to a value of 500 800 ppm then send this product to a subsequent step a2) in which the conditions will be chosen to reduce the sulfur content to below 100 ppm, preferably less than 50 ppm and the product resulting from this step a2) is then sent to step b).
- the conditions of step a2) are softer than when for a given load one operates in a single step a) since the product sent in this step a2) already has a greatly reduced sulfur content.
- the catalyst of step a1) may be a conventional catalyst of the art prior art such as that described in the text of patent applications in the name of the Applicant FR-A-2197966 and FR-A-2538813 and that of step a2) is that described above for step a). It would not be outside the scope of the present invention using the same catalyst in steps a1) and a2).
- the mineral support of the catalyst is preferably chosen from group formed by alumina, silica, silica-aluminas, zeolites and mixtures of minus two of these mineral compounds.
- Alumina is very commonly used.
- the catalyst of these steps a), a1), a2) comprise at least one metal or metal compound selected from the group consisting of molybdenum and tungsten and at least one metal or metal compound selected from the group formed by nickel, cobalt and iron. Most often this catalyst contains molybdenum or a molybdenum compound and at least one metal or metal compound selected from group formed by nickel and cobalt.
- the catalyst of these steps a), a1), a2) will include boron or at least one boron compound.
- the catalyst will include for example silicon or a silicon compound, or a combination of silicon and boron or compounds of each of these elements possibly associated with phosphorus or composed of phosphorus.
- the proportions by weight of boron, silicon and phosphorus with respect to support will be the same as those already stated.
- the catalyst employed in step c) contains on a mineral support at least one metal noble or noble metal compound of Group VIII of the Periodic Table of Elements in an amount expressed by weight of metal relative to the weight of the finished catalyst of 0.01 to 20% and preferably at least one halogen.
- the mineral support of the employed catalyst in step c) is chosen independently of the support used for the catalyst of step a). Most often the catalyst of step c) comprises at least one metal or a compound of noble metal selected from the group consisting of palladium and platinum.
- the inorganic support of the catalyst employed in step c) is usually selected from group formed by alumina, silica, silica-aluminas, zeolites and mixtures of minus two of these mineral compounds.
- This support will preferably comprise at least one halogen selected from the group consisting of chlorine, fluorine, iodine and bromine and preferably in the group formed by chlorine and fluorine. In an advantageous embodiment, this support will include chlorine and fluorine.
- the amount of halogen will most often be from 0.5 to 5% by weight relative to the weight of the support.
- the most support often used is alumina.
- Halogen is usually introduced onto the support from corresponding acid halides and platinum or palladium from aqueous solutions of their salts or compounds such as, for example, hexachloroplatinic acid in the case of platinum.
- the amount of metal of this catalyst of step c) will preferably be from 0.01 to 10%, from 0.01 to 5% and most often from 0.03 to 3% expressed by weight of metal relative to the weight of the finished catalyst.
- a diesel fuel cut is obtained from a mixture of a straight-run diesel (GOSR) and a catalytic cracked gas oil (LCO).
- the mixture is desulfurized on a conventional desulfurization unit and then stripped in a first step.
- a catalyst sold by the company Procatalyse under the reference HR 448 and containing nickel and molybdenum is placed in a 1 liter reactor (1). After activation of the catalyst by sulfurization, the unit is maintained under a pressure of 5 MPa and at a temperature of 340 ° C.
- the diesel fuel charge is injected with a VHV of 1.5 h -1 .
- Step 2 is carried out in a pilot unit which is disposed in one liter of catalyst sold by the company Procatalyse under the reference LD402 and operating against the flow of fluids at a pressure of 5 MPa and a temperature of 300 ° C.
- the unit charge flows in a downward flow as the hydrogen flows upwards in the reactor. A congestion phenomenon is observed and most of the injected charge is caused by the gas flow and does not pass through the reactor.
- Desulfurized and stripped gas oil from the first step described in Example 1 is available.
- the 2nd step is carried out in a pilot unit operating against the flow of fluids.
- the unit charge flows in a downward flow as the hydrogen flows upwards in the reactor.
- the LD402 catalyst is not loaded as such in the unit, but is diluted with alumina beads of 5 mm diameter (and average diameter).
- the mixture is constituted in volume by half of LD402 catalyst and half of alumina beads. This unit is charged with 1 liter of substantially homogeneous mixture of catalyst and alumina beads.
- the present process can be applied to desulfurization, denaturalization and desaromatisation of diesel coupes, kerosene cuts, distillates empty of a refining unit or white oils.
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0016824A FR2818283B1 (fr) | 2000-12-20 | 2000-12-20 | Procede de traitement d'une charge hydrocarbonee comprenant une etape d'hydrotraitement en lit fixe a contre-courant |
FR0016824 | 2000-12-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1217061A1 EP1217061A1 (fr) | 2002-06-26 |
EP1217061B1 true EP1217061B1 (fr) | 2005-11-30 |
Family
ID=8858041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01403141A Expired - Lifetime EP1217061B1 (fr) | 2000-12-20 | 2001-12-06 | Procédé de traitement d'une charge Hydrocarbonée comprenant une étape d'hydrotraitement en lit fixe à contre-courant |
Country Status (6)
Country | Link |
---|---|
US (1) | US6645371B2 (ja) |
EP (1) | EP1217061B1 (ja) |
JP (1) | JP4304653B2 (ja) |
DE (1) | DE60115372T2 (ja) |
ES (1) | ES2256187T3 (ja) |
FR (1) | FR2818283B1 (ja) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4658491B2 (ja) * | 2004-02-26 | 2011-03-23 | Jx日鉱日石エネルギー株式会社 | 環境対応軽油の製造方法 |
US7906013B2 (en) | 2006-12-29 | 2011-03-15 | Uop Llc | Hydrocarbon conversion process |
FR2913024B1 (fr) * | 2007-02-27 | 2012-07-27 | Total France | Procede d'hydrotraitement d'une charge gazole, unite d'hydrotraitement pour la mise en oeuvre dudit procede, et unite d'hydroraffinage correspondante |
US7794588B2 (en) * | 2007-10-15 | 2010-09-14 | Uop Llc | Hydrocarbon conversion process to decrease polyaromatics |
US8999141B2 (en) * | 2008-06-30 | 2015-04-07 | Uop Llc | Three-phase hydroprocessing without a recycle gas compressor |
US9279087B2 (en) | 2008-06-30 | 2016-03-08 | Uop Llc | Multi-staged hydroprocessing process and system |
US8008534B2 (en) * | 2008-06-30 | 2011-08-30 | Uop Llc | Liquid phase hydroprocessing with temperature management |
EP2199371A1 (en) * | 2008-12-15 | 2010-06-23 | Total Raffinage Marketing | Process for aromatic hydrogenation and cetane value increase of middle distillate feedstocks |
US7927975B2 (en) | 2009-02-04 | 2011-04-19 | Micron Technology, Inc. | Semiconductor material manufacture |
US8127938B2 (en) * | 2009-03-31 | 2012-03-06 | Uop Llc | Apparatus and process for treating a hydrocarbon stream |
US8518241B2 (en) * | 2009-06-30 | 2013-08-27 | Uop Llc | Method for multi-staged hydroprocessing |
US8221706B2 (en) * | 2009-06-30 | 2012-07-17 | Uop Llc | Apparatus for multi-staged hydroprocessing |
MX2011009116A (es) | 2011-08-31 | 2013-02-28 | Mexicano Inst Petrol | Proceso de hidroconversion-destilacion de aceites crudos pesados y/o extra-pesados. |
WO2013067323A1 (en) | 2011-11-04 | 2013-05-10 | Saudi Arabian Oil Company | Hydrotreating and aromatic saturation process with integral intermediate hydrogen separation and purification |
US9724639B2 (en) | 2015-08-18 | 2017-08-08 | United Arab Emirates University | System for contacting gases and liquids |
US10118843B2 (en) | 2015-08-18 | 2018-11-06 | United Arab Emirates University | Process for capture of carbon dioxide and desalination |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3147210A (en) * | 1962-03-19 | 1964-09-01 | Union Oil Co | Two stage hydrogenation process |
US3437588A (en) * | 1965-10-08 | 1969-04-08 | Sinclair Research Inc | Process for hydrorefining hydrocarbons with a catalytic mixture of individually-supported active components |
US5589057A (en) * | 1989-07-19 | 1996-12-31 | Chevron U.S.A. Inc. | Method for extending the life of hydroprocessing catalyst |
US5110444A (en) * | 1990-08-03 | 1992-05-05 | Uop | Multi-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
DK170679B1 (da) * | 1992-06-30 | 1995-12-04 | Topsoe Haldor As | Katalysatorleje til anvendelse ved hydrobehandling af carbonhydrider |
US5624547A (en) * | 1993-09-20 | 1997-04-29 | Texaco Inc. | Process for pretreatment of hydrocarbon oil prior to hydrocracking and fluid catalytic cracking |
DK0840772T3 (da) * | 1995-07-13 | 2000-04-10 | Meern Bv Engelhard De | Hydrering af thiofeniske, svovlholdige kulbrinter |
US5837128A (en) * | 1996-01-16 | 1998-11-17 | Amoco Corporation | Method for grading cylindrical catalyst particles in a bed to reduce pressure drop |
JP2000144150A (ja) * | 1998-11-11 | 2000-05-26 | Nippon Mitsubishi Oil Corp | 低硫黄軽油 |
-
2000
- 2000-12-20 FR FR0016824A patent/FR2818283B1/fr not_active Expired - Lifetime
-
2001
- 2001-12-06 DE DE60115372T patent/DE60115372T2/de not_active Expired - Lifetime
- 2001-12-06 EP EP01403141A patent/EP1217061B1/fr not_active Expired - Lifetime
- 2001-12-06 ES ES01403141T patent/ES2256187T3/es not_active Expired - Lifetime
- 2001-12-20 US US10/022,831 patent/US6645371B2/en not_active Expired - Lifetime
- 2001-12-20 JP JP2001387591A patent/JP4304653B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FR2818283B1 (fr) | 2003-02-14 |
JP2002201479A (ja) | 2002-07-19 |
DE60115372D1 (de) | 2006-01-05 |
EP1217061A1 (fr) | 2002-06-26 |
US20020130063A1 (en) | 2002-09-19 |
DE60115372T2 (de) | 2006-07-06 |
ES2256187T3 (es) | 2006-07-16 |
FR2818283A1 (fr) | 2002-06-21 |
US6645371B2 (en) | 2003-11-11 |
JP4304653B2 (ja) | 2009-07-29 |
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