EP2640811B1 - Procédé de désulfuration de gazole à consommation d'hydrogène réduite - Google Patents
Procédé de désulfuration de gazole à consommation d'hydrogène réduite Download PDFInfo
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- EP2640811B1 EP2640811B1 EP11807796.5A EP11807796A EP2640811B1 EP 2640811 B1 EP2640811 B1 EP 2640811B1 EP 11807796 A EP11807796 A EP 11807796A EP 2640811 B1 EP2640811 B1 EP 2640811B1
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- sulfur
- ppm
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- diesel
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- 238000000034 method Methods 0.000 title claims description 67
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 31
- 239000001257 hydrogen Substances 0.000 title claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 29
- 238000006477 desulfuration reaction Methods 0.000 title claims description 12
- 230000023556 desulfurization Effects 0.000 title claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 82
- 229910052717 sulfur Inorganic materials 0.000 claims description 82
- 239000011593 sulfur Substances 0.000 claims description 81
- 238000001179 sorption measurement Methods 0.000 claims description 37
- 239000003463 adsorbent Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 7
- 229910003294 NiMo Inorganic materials 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 31
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 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
- 239000012467 final product Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 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 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- 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
- C10G67/06—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 a sorption process as the refining step in the absence of hydrogen
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- the present disclosure relates to desulfurization of diesel and in particular to a novel process for deep desulfurization of diesel with reduced hydrogen consumption. More particularly the present disclosure pertains to an integrated process comprising diesel hydro de-sulfurisation (DHDS) or diesel hydrotreatrnent (DHDT) with reduced severity, to desulfurize high sulfur-containing (1 -2%) diesel stream to a much lower level of sulfur content of 350 ppm in the treated diesel stream, followed by an adsorption procedure for effecting deep desulfurization to reduce overall sulfur content to less than 10 ppm with reduced hydrogen consumption, as compared to high severity DHDS or DHDT procedures followed in the prior art.
- DHDS diesel hydro de-sulfurisation
- DHDT diesel hydrotreatrnent
- the residual sulfur below 500 ppm in diesel is mostly refractory sulfur. Removal of the refractory sulfur of the diesel through conventional hydrotreating requires severe operating conditions like higher pressure, lower 'Liquid Hourly Space Velocity (LHSV)', higher consumption of hydrogen, and use of highly active and expensive catalyst systems.
- LHSV Liquid Hourly Space Velocity
- the present invention provides a novel process to utilize a reactive adsorbent for reducing refractory sulfur present in diesel from 350 to less than 10 ppm.
- the process developed in the present invention can be utilized in the downstream of existing DHDS/DHDT units.
- the hydrogen consumption is significantly low, since it is consumed only for saturation of olefinic bond generated by cleavage of the sulfur from the sulfur compounds.
- the combination will result in reduced hydrogen consumption at refineries.
- the DHDS procedure employs catalytic hydrogenation to upgrade the quality of diesel so as to conform to the environmental norms by mainly removing sulfur and nitrogen. In addition, this procedure brings about saturation of olefins and aromatic compounds.
- Catalysts are formulated by combining varying amounts of nickel or cobalt with molybdenum oxides on an aluminium base. Important operating parameters of this procedure are, inter alia, temperature, pressure, nature of catalyst, feed flow rate, feed characteristics, etc.
- the catalysts used therein are meant for carrying out reaction under less severe/drastic condition and at a faster rate.
- US publication US20070261994A1 discloses a method for producing a super-low sulfur gas oil blending component or a super-low sulfur gas oil composition having a sulfur content of less than 5 ppm, under relatively mild conditions, without greatly increasing the hydrogen consumption and without remarkably decreasing the aromatic content.
- the hydrogen consumption reduction is not clearly specified.
- the composition of the catalyst used is different.
- the present invention uses a process of splitting the treated diesel between two fractions, which is not present in this US publication.
- US patent 6,551,501B1 discloses a combined process for improved hydrotreating of diesel fuels, in which the feed to be hydrotreated is pretreated with a selective adsorbent prior to the hydrotreating step to remove polar materials, especially nitrogen containing compounds (N-compounds).
- both the hydrotreatrnent and adsorption process are used to reduce the sulfur content in the fuel; however, the reduction of sulfur content in two publications is different.
- the splitting of hydrocarbon and reduction of hydrogen consumption is not mentioned.
- PCT application WO2008122706A2 discloses an improved method for deep desulphurisation of a gasoil comprising a catalytic hyrodesulphurisation unit preceded by an absorption unit for nitrogen compounds inhibiting the hydrodesulphurisation reaction.
- the present invention uses either DHDT or DHD S process followed by adsorption process for sulfur removal.
- the type of catalyst, reduction of hydrogen consumption and reduction of severity are not mentioned in the PCT publication.
- WO 2004/050800 concerns a method for desulphuration, denitrogenation and/or dearomatization of a hydrocarbon feed containing sulphur compounds of the benzoand/or dibenzothiophene type, nitrogen compounds of indole and/or carbazole type and polyaromatic compounds, comprising a step which consists in adsorbing the feed in an adsorption column containing an adsorbent including a n electron acceptor based complexing agent; recovering a desulphurized, denitrogenated and/or dearomatizedand adsorption effluent and stopping the adsorption of the feed on the column.
- the invention is applicable to final desulphuration of a diesel fuel.
- US 2006/0131 217 describes a process for desulphurizing a gas oil type hydrocarbon cut by adsorption to obtain a desulphurized effluent containing less than 10 ppm by weight in a yield of more than 95% by weight.
- Said process comprises a step for simulated moving bed adsorption of sulphurcontaining compounds in the feed, a raffinate distillation step and an extract distillation step.
- the present invention is defined in claim 1.
- the present invention provides splitting of treated diesel containing about 350 ppm of refractory sulfur into two cuts viz Initial boiling point (IBP) 140-150°C - 280/300°C and 280/300°C to Final boiling point (FBP).
- the 280/300°C-IBP cut contains preferably less than 10 ppm sulfur which can be blended into diesel stream without any further treatment and the 280/300°C-FBP cut containing about 500-600 ppm of refractory sulfur can be desulfurized using novel adsorption process capable of bringing down sulfur content of diesel to less than 10 ppm.
- the process in accordance with this invention can be utilized in the downstream of existing DHDS/DHDT units.
- the present invention shows consumption of hydrogen is significantly low as compared to the prior art, because hydrogen is consumed only for bringing about saturation of olefinic bonds generated by cleavage of sulfur from the sulfur-containing compounds.
- the present invention discloses a novel process for desulfurization of diesel with reduced hydrogen consumption, which comprises hydrotreating high sulfur-containing diesel stream (1.0 -2.0% by wt. of S) over a NiMo catalyst to reduce sulfur-contentto a level of 350 ppm, followed by subjecting the treated diesel stream to an adsorption procedure to bring down sulfur content to less than 10 ppm.
- high sulfur diesel stream containing about 1.0-2.0 wt% sulfur can be hydrodesulfurized to a level of 350 ppm sulfur product utilizing conventional DHDS or DHDT process with subsequent processing by an adsorption process to reduce sulfur content below 10 ppm.
- treated diesel containing about 350 ppm of refractory sulfur is split into two cuts viz. IBP(140-150°C) -280/300°C and 280/300°C to FBP.
- the 280/300°C-IBP cut contains less than 10 ppm sulfur. This cut can be blended into diesel stream without any further treatment.
- the 280/300°C-FBP cut containing about 500-600 ppm of refractory sulfur canbe desulfurized using an adsorption process.
- the adsorption process comprises two numbers of fixed bed reactors, which are being operated in swing mode of adsorption and regeneration.
- 280/300°C-FBP cut along with hydrogen is contacted with the adsorbent in down or up flow mode at 350 - 400°C, 15 - 30 bar, hydrogen to hydrocarbon ratio of 100 - 400 Nm 3 /m 3 , liquid hourly space velocity of0.5 -2.0 h- 1 depending on the sulfur contents of feed.
- the sulfur compounds are chemically adsorbed on the adsorbent followed by cleavage of the sulfur atom form the sulfur compound.
- the hydrocarbon molecule of the sulfur compound is released back into the hydrocarbon stream.
- the presence of hydrogen during the adsorption also prevents deactivation of adsorbent due to coking.
- the treated diesel contains less than 10 ppm sulfur which can be blended with other cut to produce diesel pool containing less than 10 ppm sulfur. After reaching the breakthrough point, the adsorbent is regenerated at 350 - 500°C.
- Regeneration of adsorbent is accomplished in situ by controlled oxidation of the adsorbed carbon and sulfur with lean air followed by activation with hydrogen.
- the cycle time will vary from 4 to 10 days depending on feed sulfur and boiling range.
- the adsorbent has higher strength and thermal stability compared to hydrotreating catalyst.
- the regenerability studies for the adsorbent has been conducted in pilot plant for 6 months (25 cycles) and there was no loss of activity and physical properties, hence the life of the adsorbent is expected to be similar to that of hydrotreating catalyst systems.
- Adsorbent The adsorbent used in the process is disclosed in prior art ( US 2007/0023325 ) which is comprised of a base component, a reactive component, and booster.
- the base component of adsorbent is a porous material, which provides extrudibility and strength. Such materials include alumina, clay, magnesia, titania or a mixture of two or more such materials.
- the reactive component of the adsorbent is a spinel oxide and prepared through solid-state reaction of the individual metal oxides. This component is responsible for detaching the sulfur atom from the sulfur compounds.
- the activity booster component of the adsorbent is a bimetallic alloy generated in situ from mixed metal oxides.
- the present disclosure also provides a process for regeneration of adsorbent comprises the steps of controlled oxidation of the adsorbed carbon and sulfur with lean air at a temperature ranging between 350°C and 500°C, and activation with hydrogen wherein the process is carried out in situ.
- Diesel stream containing 1.53 wt% sulfur was hydrodesulfurized using commercial DHDS and DHDT catalyst system in a hydroprocessing micro-reactor unit (MRU).
- MRU hydroprocessing micro-reactor unit
- Table-1 Details of feed/product properties and operating conditions 1.
- Feed/ product properties Feed DHDT Product DHDS Product a) Density @ 15 °C, g/cc 0.8449 0.8107 0.8265 b) Sulfur, ppm 15300 20 30 c) CI (D4737) 50.8 57.9 55.1 4. H2 Consumption, wt% of feed 1.3 1.0
- Diesel stream containing 1.53 wt% sulfur was hydrodesulfurized using highly active commercial DHDS and DHDT catalyst system in a hydroprocessing micro-reactor unit (MRU). The severity of operating parameters was reduced to get 350 ppm sulfur product.
- Table-2 Details of feed/ product properties and operating conditions (350 ppm sulfur product) 1.
- Feed/ product properties Feed DHDT Product DHDS Product a) Density @ 15 °C, g/cc 0.8449 0.8279 0.8283 b) Sulfur, ppm 15300 350 350 c) CI (D4737) 50.8 54.5 54.2 4. H2 Consumption, wt% of feed 0.7 0.7
- the 350 ppm sulfur product was subsequently treated by an adsorption process to reduce total sulfur content below 10 ppm.
- the detailed GC-SCD analysis of 350 and 10 ppm sulfur product diesel is given below in Table-3.
- the GC-SCD Chromatograms of 350 and 10 ppm sulfur product diesel is given below in Figure-2 of the drawings.
- Table-3 GC-SCD of 350 and 10 ppm sulfur Product Diesel S. No.
- the 350 ppm sulfur product diesel from DHDS or DHDT was split into two cuts viz. IBP to 280°C and FBP to 280°C.
- the 280°C IBP cut contains less than 10 ppm sulfur.
- the 280°C-FBP cut containing 530 ppm of refractory sulfur was desulfurized using an adsorption process to reduce sulfur below 10 ppm. The details of various cuts and final product diesel are given below in Table-4.
- Table-4 Details of various cuts and final product diesel Property IBP-280 °C 280°C -FBP (390°C) 280°C -FBP treated by Adsorption process Final Product Diesel Wt fraction 0.35 0.65 0.65 1.00 S,ppm 8 530 6 7 Density, g/cc 0.83 0.8450 0.8450 0.8397
- the liquid product from the separator of DHDS/DHDT is sent to splitter where wild naphtha [150 (-)°C cut] is separated from top of the column, 150-280°C cut from the middle and 280(+)°C cut from bottom is separated. Bottom or bottom along with middle cut is further deep desulfurized using novel adsorption process to reduce total sulfur content below 10 ppm.
- the Adsorption process scheme is given in Figure-4 of the drawings.
- cetane number of the product is not improved.
- cetane number specification is same for Euro-III and Euro-IV diesel, the process is particularly suitable as a finishing step for further treatment of Euro-III diesel after DHDS/DHDT.
- the existing DHDT unit can be operated at lesser severity, just sufficient to meet the cetane requirement, and further sulfur reduction can be achieved by employing the adsorption process. This will result in substantial saving of precious hydrogen. From the data (Table-5), it can be observed that by combining the adsorption process with DHDS or DHDT units saves about 20 to 40% hydrogen consumption respectively. Table-5: Saving of hydrogen by integration of Adsorption process with DHDS or DHDT unit S. No.
Claims (1)
- Procédé de désulfuration de diesel, comprenant les étapes suivantes :- l'hydrotraitement d'un flux de diesel contenant de 1,0 à 2,0 % en poids de soufre sur un catalyseur NiMo ou CoMo pour réduire la teneur en soufre à 350 ppm,- le fractionnement du diesel hydrotraité contenant environ 350 ppm de soufre réfractaire en deux coupes :(i) première coupe avec un point d'ébullition initial (IBP) de 140-150°C à 280-300°C contenant moins de 10 ppm de soufre :(ii) deuxième coupe avec un point d'ébullition final (FBP) de 280-300°C contenant environ 500-600 ppm de soufre réfractaire ; et- la soumission de la seconde coupe traitée à une procédure d'adsorption pour ramener la teneur en soufre à moins de 10 ppm ;
dans lequel la procédure d'adsorption comprend les étapes suivantes :- le fonctionnement de deux réacteurs à lit fixe en mode swing d'adsorption et de régénération, et- la mise en contact de la seconde coupe avec un adsorbant en même temps que de l'hydrogène en mode d'écoulement descendant ou ascendant à une température de 350-400°C, une pression de 15-30 bars, un rapport hydrogène/hydrocarbures de 100-400 Nm3/m3, et une vitesse spatiale horaire du liquide de 0,5 à 2,0 h-1 ;dans lequel les composés soufrés sont adsorbés chimiquement sur l'adsorbant, puis le soufre est clivé du composé soufré et les molécules d'hydrocarbures du composé soufré sont libérées dans le flux d'hydrocarbures ;
dans lequel l'adsorbant est régénéré par oxydation du carbone et du soufre adsorbés avec de l'air à une température comprise entre 350°C et 500°C et activation avec de l'hydrogène, dans lequel le procédé est réalisé in situ,
dans lequel l'adsorbant est constitué d'un composant de base, d'un composant réactif et d'un booster; où le composant de base de l'adsorbant est un matériau poreux qui comprend de l'alumine, de l'argile, de la magnésie, de l'oxyde de titane ou un mélange de deux ou plusieurs de ces matériaux ; le composant réactif de l'adsorbant est un oxyde de spinelle ; et le composant booster d'activité de l'adsorbant est un alliage bimétallique généré in situ à partir d'oxydes métalliques mixtes.
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IN1309KO2010 | 2010-11-19 | ||
PCT/IN2011/000795 WO2012066574A2 (fr) | 2010-11-19 | 2011-11-16 | Procédé de désulfuration de gazole à consommation d'hydrogène réduite |
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EP2640811A2 EP2640811A2 (fr) | 2013-09-25 |
EP2640811B1 true EP2640811B1 (fr) | 2021-07-14 |
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EP11807796.5A Active EP2640811B1 (fr) | 2010-11-19 | 2011-11-16 | Procédé de désulfuration de gazole à consommation d'hydrogène réduite |
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US (1) | US20130270155A1 (fr) |
EP (1) | EP2640811B1 (fr) |
WO (1) | WO2012066574A2 (fr) |
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CN111871339A (zh) * | 2020-07-16 | 2020-11-03 | 南京延长反应技术研究院有限公司 | 一种柴油加氢的反应系统及方法 |
US20220089960A1 (en) * | 2020-09-21 | 2022-03-24 | Indian Oil Corporation Limited | Process and a system for production of multiple grade de-aromatized solvents from hydrocarbon streams |
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EP1057879A3 (fr) | 1999-06-02 | 2001-07-04 | Haldor Topsoe A/S | Procédé combiné pour l'hydrotraitement de carburants diesel |
US20030070965A1 (en) * | 1999-11-01 | 2003-04-17 | Shih Stuart S. | Method for the production of very low sulfur diesel |
FR2847587B1 (fr) * | 2002-11-25 | 2006-03-17 | Inst Francais Du Petrole | Procede de desulfuration, de deazotation et/ou desaromatisation d'une charge hydrocarbonee sur un adsorbant complexant a base d'accepteur d'electrons pi |
FR2878252B1 (fr) * | 2004-11-23 | 2008-08-22 | Inst Francais Du Petrole | Procede de desulfuration d'une coupe hydrocarbonee en lit mobile simule |
KR101355722B1 (ko) | 2004-12-28 | 2014-01-24 | 제이엑스 닛코닛세키에너지주식회사 | 초저황 경유 기재 또는 초저황 경유 조성물의 제조 방법 |
FR2882562B1 (fr) * | 2005-02-25 | 2010-05-14 | Inst Francais Du Petrole | Procede de desulfuration profonde par adsorption d'une coupe hydrocarbonee de type gazole |
US8222180B2 (en) | 2005-08-01 | 2012-07-17 | Indian Oil Corporation Limited | Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof |
FR2913235B1 (fr) | 2007-03-02 | 2011-02-25 | Inst Francais Du Petrole | Procede ameliore de desulfuration et de deazotation d'une coupe hydrocarbonee de type gazole contenant des composes azotes. |
US20100155302A1 (en) * | 2008-12-18 | 2010-06-24 | Kaminsky Mark P | Purification of ultralow sulfur diesel fuel |
-
2011
- 2011-11-16 WO PCT/IN2011/000795 patent/WO2012066574A2/fr active Application Filing
- 2011-11-16 EP EP11807796.5A patent/EP2640811B1/fr active Active
- 2011-11-16 US US13/988,305 patent/US20130270155A1/en not_active Abandoned
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US20130270155A1 (en) | 2013-10-17 |
EP2640811A2 (fr) | 2013-09-25 |
WO2012066574A3 (fr) | 2012-09-27 |
WO2012066574A2 (fr) | 2012-05-24 |
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