EP1445299A1 - Procédé d'obtention d'une charge utilisable dans une unité d'etherification - Google Patents
Procédé d'obtention d'une charge utilisable dans une unité d'etherification Download PDFInfo
- Publication number
- EP1445299A1 EP1445299A1 EP04290069A EP04290069A EP1445299A1 EP 1445299 A1 EP1445299 A1 EP 1445299A1 EP 04290069 A EP04290069 A EP 04290069A EP 04290069 A EP04290069 A EP 04290069A EP 1445299 A1 EP1445299 A1 EP 1445299A1
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- EP
- European Patent Office
- Prior art keywords
- nitrogen
- compounds
- fraction
- hydrocarbons
- metal
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006266 etherification reaction Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 26
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000002825 nitriles Chemical class 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- -1 diene compounds Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005194 fractionation Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 abstract 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 14
- 150000002830 nitrogen compounds Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000686 essence Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 238000001577 simple distillation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- VDMXPMYSWFDBJB-UHFFFAOYSA-N 1-ethoxypentane Chemical compound CCCCCOCC VDMXPMYSWFDBJB-UHFFFAOYSA-N 0.000 description 1
- DBUJFULDVAZULB-UHFFFAOYSA-N 1-methoxypentane Chemical compound CCCCCOC DBUJFULDVAZULB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000861223 Issus Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007514 bases 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2400/02—Gasoline
Definitions
- the present invention relates to a process for obtaining a usable hydrocarbon fraction as charge of an etherification unit and containing a reduced amount of compounds diene, nitrogen and sulfur, from an initial charge of hydrocarbons.
- the present invention finds its application in the treatment of essences with a view to obtaining a fraction comprising olefins containing from 4 to 6 carbon atoms, and having a reduced content of diene compounds, nitriles, nitrogen and sulfur, this fraction can then be used to feed etherification units, by example to produce methyl tertio butyl ethers (MTBE), ethyl tertio butyl ethers (ETBE), tertio amyl methyl ether (TAME) or tertio amyl ethyl ether (TAEE)
- MTBE methyl tertio butyl ethers
- ETBE ethyl tertio butyl ethers
- TAME tertio amyl methyl ether
- TEE tertio amyl ethyl ether
- the activity of the acid catalysts generally used in the units etherification can be greatly reduced due to the presence in the cut to be treated of unwanted compounds.
- the diolefins (dienes) can be the source of deposition of polymer on the catalyst, and the nitriles cause a gradual deactivation of the catalyst.
- certain compounds such as light sulfides and amines have a certain basicity and can also gradually degrade the activity of acid catalysts.
- Patent application WO 96/00714 provides a method for reducing the content of pollutants present in the charges for etherification units, by selective hydrogenation.
- the pollutants removed by this process are nitriles and diolefins.
- the diolefins are in initially hydrogenated to olefins, then the nitriles are hydrogenated to amines.
- the catalyst used in this step is a catalyst comprising cobalt. Amines being basic compounds, these are then easily extracted by washing with water. This process therefore also requires the implementation of a washing step in order to remove the compounds nitrogen in the form of amines and therefore has the aforementioned drawback of the reprocessing of washing solutions.
- the present invention provides an economical and simple to implement means for remove, at least partially, dienes, nitrile nitrogen compounds and light sulfur compounds present in the original gasoline.
- the process implemented according to the invention comprises at least two stages: a first stage of selective hydrogenation of the entire initial hydrocarbon charge and a second stage of fractionation of said hydrogenated charge.
- said hydrocarbon fraction has a higher cutting or boiling point which is less than 100 ° C, preferably less than 80 ° C and very preferably less than 60 ° C.
- This step is intended to at least partially eliminate the diolefins present in the initial hydrocarbon charge, such as preferably a petrol cut.
- Diolefins are gum precursors which polymerize in etherification reactors and limit their lifespan as well as nitrogenous nitrile compounds (the formula of which is given below). It was indeed found by the applicant that under the conditions mentioned in the rest of the description, said nitriles are transformed into heavy nitrogen compounds which respond positively to the measurement of basic nitrogen.
- This step also makes it possible to transform light sulfur compounds such as mercaptans, sulphides and CS2, whose boiling point is generally lower to that of thiophene, into heavier sulfur compounds whose boiling point is higher than that of thiophene.
- Said selective hydrogenation stage generally takes place in the presence of a catalyst comprising at least one metal from group VIII of the periodic table, preferably chosen from the group formed by platinum, palladium and nickel, and a support. Without leaving the within the framework of the invention, cobalt may also be chosen from said group.
- a catalyst comprising 1 to 20% by weight of nickel deposited on an inert support, such that for example alumina, silica, silica-alumina, a nickel aluminate or a support containing at least 50% alumina.
- Another metal from group VIB of the classification periodic can be associated with this group VIII metal to form a bimetallic catalyst, such as for example molybdenum or tungsten. This group VIB metal is preferably deposited at a level of 1% by weight to 20% by weight on the support.
- the choice of operating conditions is particularly important according to the invention. We will operate most generally under pressure in the presence of a small amount of hydrogen compared to the stoichiometric value necessary to hydrogenate the diolefins.
- hydrogen and the charge to be treated are injected in updrafts or downdrafts in a reactor preferably with a fixed catalyst bed.
- the temperature is most generally between 50 and 300 ° C, and preferably between 80 and 250 ° C, and very preferably between 120 and 210 ° C.
- the pressure is chosen as sufficient to maintain more than 80%, and preferably more 95% by weight of the gasoline to be treated in liquid form in the reactor; she is the most generally between 0.4 to 5 MPa, limits included, and preferably greater than 1 MPa.
- Advantageous pressure is between 1 to 4 MPa, limits included.
- the space speed is, in these conditions of the order of 1 to 12 h -1 , preferably of the order of 2 to 10 h -1 .
- the initial hydrocarbon charge such as a petrol cut can contain up to a few% weight of diolefins.
- the diolefin content is most often reduced to less than 5000 ppm, preferably less than 2500 ppm, or even less than 1500 ppm.
- step a) takes place in a reactor catalytic hydrogenation which includes a catalytic reaction zone crossed by the total charge and the quantity of hydrogen necessary to carry out the desired reactions.
- the nitrogen compounds originating from stage a) are boiling point compounds higher than those of hydrocarbons comprising 5 carbon atoms. In addition these compounds react to the basic nitrogen measurement according to the ASTM4739 method.
- Step b) consists of a separation of the nitrogen compounds by distillation.
- the effluents from from step a) are split to produce at least two cuts, including a slight fraction comprising the majority of hydrocarbons, and mainly olefins with 4 or 5 atoms of carbon and free of nitrogen compounds, and a heavy fraction concentrating the hydrocarbons heavy and the nitrogen compounds weighed down during step a).
- this preferred embodiment further allows at least partial removal of the compounds sulfur of said light fraction.
- the content of nitrogen compounds in the light fraction of gasoline from step b) contains generally less than 20 ppm of nitrogen, preferably less than 10 ppm of nitrogen, and very preferably less than 5 ppm of nitrogen.
- the content of light sulfur compounds in the light fraction of petrol is generally less than 200 ppm, preferably less than 100 ppm, and very preferably 50 ppm lower sulfur.
- the light essence corresponding to the PI-55 cut concentrates most of the olefins light (C4 and C5). It therefore constitutes the etherification charge. This fraction includes 15 ppm nitrogen, 92 ppm sulfur and an AVM (maleic acid value) of 6.5, which corresponds to nearly 0.8% by weight of diolefins. This gasoline treated on an acid etherification catalyst would result in premature deactivation of it.
- Example below is in accordance with the present invention.
- the initial charge used is similar to that of Example 1.
- step a After a first selective hydrogenation treatment in a first step a), the gasoline produced (essence B) is distilled in three sections (step b)).
- Step a) is carried out as follows: the gasoline A is treated on a fixed bed reactor loaded with HR845® catalyst based on nickel and molybdenum sold by the company Axens, in the presence of hydrogen. The reaction is carried out at 165 ° C, under a pressure of 20 bar (2MPa) and a space speed of 4 h -1 . The H 2 / charge ratio expressed in liters of hydrogen per liter of charge is 6. The gasoline thus produced during step a) is gasoline B, the characteristics of which are given in table 2.
- Essence B is then fractionated by distillation into 3 fractions, the cutting points of which are identical to the fractions of Example 1.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
- ladite fraction hydrocarbonée et comprenant une quantité réduite de composés diéniques, azotés et soufrés et
- une fraction lourde contenant les hydrocarbures lourds et la majorité des composés azotés et soufrés issu de l'hydrogénation de l'étape a).
Description
- le brevet US 5,569,790 qui divulgue un procédé visant à éliminer les traces d'acétone, d'acétonitriles ou de propionitriles dans une coupe d'hydrocarbures comprenant 4 à 6 atomes de carbone. Les nitriles sont finalement éliminés par lavage à l'eau. L'eau usée est régénérée avant d'être recyclée vers le procédé.
- le brevet US 5,675,043 qui propose un procédé pour éliminer les composés azotés de type
nitriles d'une coupe d'hydrocarbures par extraction à l'aide d'un solvant de type glycol.
Ces deux procédés présentent cependant l'inconvénient de générer un solution polaire contenant les composés azotés extraits de la coupe hydrocarbure. Cette solution polaire doit être retraitée et régénérée pour être recyclée dans le procédé, ce qui entraíne une complexité accrue de l'unité. - le brevet US 5,300,126 qui divulgue un procédé d'élimination des dioléfines les coupes C4/C5 sont mises en contact avec un diénophile tel que l'anhydride maléique. Les composés azotés basiques et les dioléfines sont extraits après qu'ils aient réagi avec l'anhydride maléique.
- ladite fraction hydrocarbonée et comprenant une quantité réduite de composés diéniques, azotés et soufrés et
- une fraction lourde contenant les hydrocarbures lourds et la majorité des composés azotés et soufrés issu de l'hydrogénation de l'étape a).
Essence A | PI-55 | 55-140 | 140+ | |
Densité | 0,716 | 0,6504 | 0,7382 | 0,842 |
Azote basique (ppm) | 9 | 1 | 1 | 71 |
Azote total (ppm) | 21 | 15 | 13 | 110 |
MAV (mg/g) | 14 | 6,5 | 15,5 | 30 |
IBr | 101 | 130 | 79 | 48 |
S (ppm) | 780 | 92 | 926 | 2563 |
Rendement (%pds) | 100 | 29,59 | 64,27 | 6,14 |
Essence B | PI-55 | 55-140 | 140+ | |
Sp Gr | 0,7166 | 0,6518 | 0,7375 | 0,8474 |
azote basique, ppm | 13 | < 1 | 6 | 173 |
Azote total, ppm | 21 | < 1 | 12 | 230 |
MAV (mg/g) | 0,8 | 0,2 | 7 | 8,1 |
IBr | 98 | 128,7 | 93 | 47 |
S, ppm | 782 | < 1 | 928 | 2719 |
Rendement(%pds) | 100 | 27,4 | 66,7 | 5,4 |
Claims (10)
- Procédé d'obtention d'une fraction hydrocarbonée utilisable comme charge d'une unité d'éthérification et contenant une quantité réduite de composés diéniques, azotés et soufrés, à partir d'une charge initiale d'hydrocarbures comprenant un mélange d'oléfines, de diènes, de nitriles ainsi que de composés soufrés, ledit procédé comprenant au moins les étapes successives suivantes :a) une hydrogénation sélective de ladite charge initiale d'hydrocarbures, en présence d'un catalyseur comprenant au moins un métal du groupe VIII et un autre métal du groupe VIB de la classification périodique,b) un fractionnement par distillation des effluents issus de l'étape a), dans des conditions permettant d'obtenir au moins deux coupes dontladite fraction hydrocarbonée et comprenant une quantité réduite de composés diéniques, azotés et soufrés etune fraction lourde contenant les hydrocarbures lourds et la majorité des composés azotés et soufrés issu de l'hydrogénation de l'étape a).
- Procédé selon la revendication 1 dans lequel le métal du Groupe VIII est choisi dans le groupe constitué par le platine, le palladium, le nickel.
- Procédé selon la revendication 2 dans le quel le catalyseur contient 1 % poids à 20% poids de nickel déposé sur un support inerte.
- Procédé selon la revendication 1 dans lequel le métal du Groupe VIII est le cobalt.
- Procédé selon l'une des revendications précédentes dans lequel ledit catalyseur comprend 1 % poids à 20% poids de métal du groupe VIB.
- Procédé selon l'un des revendications précédentes dans lequel le métal du groupe VIB est le molybdène ou le tungstène.
- Procédé selon l'une des revendications précédentes dans lequel ledit catalyseur opère sous une pression de 0,4 à 5 MPa, à une température de 50 à 300°C avec une vitesse spatiale horaire de la charge de 1 h-1 à 12 h-1.
- Procédé selon l'une des revendications précédentes dans lequel ladite hydrogénation est effectuée en présence d'une quantité d'hydrogène en faible excès par rapport à la valeur stoechiométrique nécessaire pour hydrogéner l'ensemble des diènes présents dans la charge initiale d'hydrocarbures.
- Procédé selon l'une des revendications précédentes dans lequel ladite fraction hydrocarbonée présente un point d'ébullition supérieur qui est inférieur à 100°C.
- Procédé selon la revendication 6 dans lequel ledit point d'ébullition est inférieur à 60°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0300693A FR2850113B1 (fr) | 2003-01-22 | 2003-01-22 | Procede d'obtention d'une charge utilisable dans une unite d'etherification |
FR0300693 | 2003-01-22 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1445299A1 true EP1445299A1 (fr) | 2004-08-11 |
EP1445299B1 EP1445299B1 (fr) | 2012-03-14 |
Family
ID=32605935
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04290069A Expired - Lifetime EP1445299B1 (fr) | 2003-01-22 | 2004-01-09 | Procédé d'obtention d'une charge utilisable dans une unité d'etherification |
Country Status (4)
Country | Link |
---|---|
US (1) | US7025872B2 (fr) |
EP (1) | EP1445299B1 (fr) |
ES (1) | ES2381785T3 (fr) |
FR (1) | FR2850113B1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2816094A1 (fr) | 2013-06-19 | 2014-12-24 | IFP Energies nouvelles | Procédé de production d'une essence à basse teneur en soufre et en mercaptans |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100389874C (zh) * | 2006-07-14 | 2008-05-28 | 谷育英 | 一种用于c5石油树脂中烯烃加氢反应催化剂及其制备方法和应用 |
US7553995B2 (en) * | 2007-09-11 | 2009-06-30 | Catalytic Distillation Technologies | Method of producing tertiary amyl ethyl ether |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5321163A (en) * | 1993-09-09 | 1994-06-14 | Chemical Research & Licensing Company | Multi-purpose catalytic distillation column and eterification process using same |
US5948942A (en) * | 1994-12-13 | 1999-09-07 | Intevep, S.A. | Bimetallic catalyst for the simultaneous selective hydrogenation of diolefins and nitriles and method of making same |
US6469223B2 (en) * | 2000-01-04 | 2002-10-22 | Fina Technology, Inc. | Selective hydrogenation of dienes |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4175033A (en) * | 1976-05-06 | 1979-11-20 | Uop Inc. | Hydroprocessing of hydrocarbons over nickel, moly, platinum catalyst |
US5968347A (en) * | 1994-11-25 | 1999-10-19 | Kvaerner Process Technology Limited | Multi-step hydrodesulfurization process |
US5712415A (en) * | 1994-12-13 | 1998-01-27 | Intevep, S.A. | Process for the simultaneous selective hydrogenation of diolefins and nitriles |
US6210561B1 (en) * | 1996-08-15 | 2001-04-03 | Exxon Chemical Patents Inc. | Steam cracking of hydrotreated and hydrogenated hydrocarbon feeds |
US6042719A (en) * | 1998-11-16 | 2000-03-28 | Mobil Oil Corporation | Deep desulfurization of FCC gasoline at low temperatures to maximize octane-barrel value |
US6123830A (en) * | 1998-12-30 | 2000-09-26 | Exxon Research And Engineering Co. | Integrated staged catalytic cracking and staged hydroprocessing process |
FR2807061B1 (fr) * | 2000-03-29 | 2002-05-31 | Inst Francais Du Petrole | Procede de desulfuration d'essence comprenant une desulfuration des fractions lourde et intermediaire issues d'un fractionnement en au moins trois coupes |
US20040178123A1 (en) * | 2003-03-13 | 2004-09-16 | Catalytic Distillation Technologies | Process for the hydrodesulfurization of naphtha |
-
2003
- 2003-01-22 FR FR0300693A patent/FR2850113B1/fr not_active Expired - Lifetime
-
2004
- 2004-01-09 EP EP04290069A patent/EP1445299B1/fr not_active Expired - Lifetime
- 2004-01-09 ES ES04290069T patent/ES2381785T3/es not_active Expired - Lifetime
- 2004-01-22 US US10/761,240 patent/US7025872B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5321163A (en) * | 1993-09-09 | 1994-06-14 | Chemical Research & Licensing Company | Multi-purpose catalytic distillation column and eterification process using same |
US5948942A (en) * | 1994-12-13 | 1999-09-07 | Intevep, S.A. | Bimetallic catalyst for the simultaneous selective hydrogenation of diolefins and nitriles and method of making same |
US6469223B2 (en) * | 2000-01-04 | 2002-10-22 | Fina Technology, Inc. | Selective hydrogenation of dienes |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2816094A1 (fr) | 2013-06-19 | 2014-12-24 | IFP Energies nouvelles | Procédé de production d'une essence à basse teneur en soufre et en mercaptans |
Also Published As
Publication number | Publication date |
---|---|
EP1445299B1 (fr) | 2012-03-14 |
FR2850113B1 (fr) | 2007-03-02 |
ES2381785T3 (es) | 2012-05-31 |
US7025872B2 (en) | 2006-04-11 |
US20040167363A1 (en) | 2004-08-26 |
FR2850113A1 (fr) | 2004-07-23 |
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