CN100560695C - The method of hydrodesulfurizationof of naphtha - Google Patents
The method of hydrodesulfurizationof of naphtha Download PDFInfo
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- CN100560695C CN100560695C CNB2005100042560A CN200510004256A CN100560695C CN 100560695 C CN100560695 C CN 100560695C CN B2005100042560 A CNB2005100042560 A CN B2005100042560A CN 200510004256 A CN200510004256 A CN 200510004256A CN 100560695 C CN100560695 C CN 100560695C
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Abstract
A kind of sulfur method of full range naphtha stream is disclosed, wherein in the catalytic distillation tower reactor full boiling range naphtha stream be separated into simultaneously gently, the light naphthar of heavy naphtha and thioetherification.Only handle heavy petroleum naphtha to remove organonitrogen catalyzer poison, hydrogenating desulfurization then.Lighter hydrocarbons and light naphthar logistics can be handled through last hydrogenating desulfurization in the refining reaction device.
Description
Technical background
Invention field
The present invention requires the right of priority of the U.S. Provisional Application 60/454,259 of application on March 13rd, 1.
The present invention relates to contain the hydrogenating desulfurization of the full boiling range naphtha stream of organic nitrogen compound.More particularly, the present invention relates to utilize hydrogenating desulfurization to handle of the improvement of fluid cracking petroleum naphtha with the method for removing organosulfur compound.More particularly, the present invention relates to catalytic distillation tower reaction, and the contacting of restriction organic nitrogen compound and hydrotreating catalyst.
Relevant information
Contain various organic chemistry components in the petroleum distillation logistics.Usually, logistics can determine that by them the boiling range of forming defines.The processing of logistics also influences composition.For example, come the product of catalytic cracking or thermocracking process to contain the olefin feed of high density and saturated (alkane) material and poly-unsaturated material (diolefine).In addition, these components can be any various isomer of described compound.
Mainly be subjected to the influence of crude petroleum sources when composition from the untreated naphtha of crude oil or virgin naphtha.Petroleum naphtha from the paraffinic crude source contains more saturated straight chain or ring compound.Usually, most " low-sulfur " (low-sulfur) crude oil and petroleum naphtha are paraffinic bases.Naphthenic base crude contains more unsaturated cyclic and polynuclear compound.The crude oil of higher sulfur content is cycloalkyl often.The processing of different virgin naphthas is slightly different, depends on their composition owing to crude petroleum sources.
Reformed naphtha or reformate do not need other processing usually, unless possible distillation or solvent extraction are used to remove valuable aromatic product.Reformed naphtha is not because pretreated harshness of technology and technology itself thereof have amounts of sulphur contaminants basically.
When pressure naphtha has high relatively octane value during from cat cracker, because wherein include alkene and aromatic compound.In some cases, this cut carry can in the refinery tank up to half gasoline and the octane value of obvious part is provided.
Usually form significantly part (≈ 1/3) of gasoline products jar at U.S.'s catalytic cracking petroleum naphtha gasoline boiling range material, it provides the sulphur of largest portion.Sulphur impurity will be removed, and meets environmental regulation by hydrofining with index or the assurance of satisfying product usually.
Removing the usual method of sulphur is by hydrogenating desulfurization (HDS), and its PetroChina Company Limited.'s distillate is by containing the solid particle catalyst of load hydrogenation metal on the alumina host.A large amount of in addition hydrogen are included in the charging.Following equation illustrates the unitary reaction of typical HDS:
(1)RSH+H
2→RH+H
2S
(2)RCl+H
2→RH+HCl
(3)2RN+4H
2→2RH+2NH
3
(4)ROOH+2H
2→RH+2H
2O
The typical operational condition of HDS is as follows:
Temperature, °F 600～780
Pressure, psig 600～3000
H
2Cycle rate, SCF/bbl 1500～3000
The fresh H that replenishes
2, SCF/bbl 700～1000
Organosulfur compound in refinery stream and hydrogen form H on catalyzer
2The reaction of S claims hydrogenating desulfurization usually.Hydrofining is to comprise alkene and aromatic hydrocarbons is saturated and organic nitrogen compound forms the more generalized term of the reaction of ammonia.But, comprising hydrogenating desulfurization, it claims hydrofining simply sometimes.After hydrofining is finished, product can by fractionation or simply flash distillation to discharge sulfhydrate and to collect the petroleum naphtha of desulfurization.
Main light or more lower boiling sulphur compound is a mercaptan, and the compound of heavier or higher is thiophene and other heterogeneous ring compounds.Separate by fractionation separately and can not remove mercaptan.But mercaptan is removed by the oxidising process that comprises neutralizing treatment usually in the past.In U.S. Pat 5,320, oxidation removal mercaptan is disclosed with aftercut and the hydrofining combination than last running in 742.Remove in the mercaptan in oxidation, mercaptan is converted into corresponding disulphide.
Remove the mercaptan than the petroleum naphtha of light fraction except handling, lighter fraction also is used for the unitary charging of catalytic reforming usually to increase octane value, if necessary.And lighter cut also can be through further separation to remove valuable C
5It can be used for preparing ether alkene (amylene).
More recent new technology can be carried out the processing and the fractionation of petroleum products simultaneously, and described product comprises the particularly petroleum naphtha of fluid catalytic cracking (FCC petroleum naphtha) of petroleum naphtha.See the US 5,510,568,5,597,476,5,779,883,5,807,477 and 6,083,378 that for example owns together.
Know, organic nitrogen compound suppresses hydrodesulfurization reaction, suppresses hydrogenation reaction to a certain extent.See, for example " Poisoning of Thiophene Hydrodesulfurization byNitrogen Compounds ", Vito LaVopa and Charles N.Satterfield is published in Journal of Catalysis, Volume 110 (1988), and pages 375～387.In addition, after deliberation the influence of water and ammonia to hydrotreating catalyst.See that " Influence of Water andAmmonia on Hydrotreating Catalysts and Activity for TetralinHydrogenation " is published in Catalysis Today Vol.29 (1996), pages 229～233.
An advantage of the invention is that the catalyzer that uses in the organic nitrogen compound that suppressed in the whole naphtha feed and the hydrotreatment contacts.Special advantage be the catalytic distillation reaction charging can be separated into be used for hydrotreatment than light fraction, and organic nitrogen compound concentrated enter in the charging that comprises the heavier part of lacking than whole charging, therefore the charging of more a spot of formation gasoline products has to contact with the organic nitrogen compound sorbent material.Feature of the present invention is that the protection Hydrobon catalyst does not contact with organic nitrogen compound with thioetherification catalyst.Advantage of these and other and feature are apparent from following description.
Summary of the invention
Briefly, present invention resides under the catalytic distillation condition and to handle full boiling range naphtha stream (boiling point is at C
5～about 420 scope) to remove organosulfur compound, wherein remove mercaptan by thioetherification, the boiling range that the while petroleum naphtha is separated into simultaneously as overhead product is C
5～160 lighting end and be 160～420 last running as the boiling range of bottom product.Thioetherification catalyst is positioned at the top of tower, and wherein the preferred diene of light naphtha fraction migration and mercaptan and alkene reacts to form heavier sulfide, and described sulfide drops in the bottom product that contains heavy naphtha fraction.The treating column bottom product preferably makes organic nitrogen compound pass through absorbing unit to remove organic nitrogen compound, and wherein most organic nitrogen compound is adsorbed from logistics.Remove unitary effluent from organic nitrogen compound and enter the second column reactor that contains Hydrobon catalyst with hydrogen then, wherein most organosulfur compound changes sulfide into.If necessary, side stream, after removing hydrogen sulfide and removing, can enter the refining reaction device to obtain the desulfurization of level of hope from the effluent of the bottom product of second column reactor and/or from the mid range petroleum naphtha of first distillation column reactor.
Removing organic nitrogen compound from the charging that enters hydrodesulphurisatioreactors reactors makes this method have the advantage of three aspects:
1, about 20～50% higher catalyst activities are possible,
2, for the desulfurization of any given level, the selectivity of system can be improved the conversion of light alkene, and
3, improve the work-ing life of catalyzer,
Distillation tower the term " distillation column reactor " that uses as the present invention is meant, it also contains catalyzer, reacts like this and distills and can carry out simultaneously in a tower.One preferred embodiment in, Preparation of Catalyst is a distillation structure, not only can be used as catalyzer and but also can be used as distillation structure.Term " catalytic distillation " is used to be described in the tower and reacts simultaneously and fractionation.For purpose of the present invention, no matter in tower, use structure how, any other the method that term " catalytic distillation " comprises reactive distillation and carries out simultaneously in tower internal reaction and distillation.
The accompanying drawing summary
Accompanying drawing is the schematic flow sheet of a preferred embodiment of the invention.
Detailed Description Of The Invention
To use the advantage of catalytic distillation pattern and nitrogen absorption be separated stream, is characterized as naphtha Organonitrogen compound is most of boiling range at heavy naphtha often. Basically there is not organic nitrogen chemical combination The light naphtha fraction of thing is not admitted to absorption, has therefore reduced the load to adsorption plant, this Installation and operating cost have been reduced. Nitrogen-containing compound in the full boiling range pressure naphtha can comprise Nitrile, carbazole, benzo carbazole, indoles, pyrimidine, quinoline, acridine and tetrahydroquinoline are characterized as Naturally occurring polar compound.
Pressure naphtha is the charging of optimal process of the present invention, because its tool light olefin likely With undesirable nitrogen and sulphur compound. Typical fluid cracking naphtha boiling range is C5～approximately 420 °F, contain typical mercaptan and lighter thiophene compound. Contain most of valuable alkene The low boiling range (C of the naphtha of hydrocarbon5～about 160 °F) therefore process without Hydrobon catalyst, But to not too serious degree, the mercaptan that wherein contains and two alkene reactions that wherein contain are to form Sulfide (thioetherification), described sulfide has higher boiling point, with heavier naphtha Shift out together. Typical reaction exists in accordance with regulations lower at the naphtha separator, in nickel or palladium catalysis Carry out in the agent, wherein light fraction is taken out as overhead, and heavy distillat is got as tower bottom product Go out. Advantageously, sulfide shifts out with tower bottom product, processes finally by hydrodesulfurization. Thioetherification
The catalyst that is fit to that is used for alkadienes and thiol reactant is at 7～14 order Al2O
3(oxygen Change aluminium) Pd of the 0.4wt% on the bead provides called after G-68C by Sud-Chemie. By The typical physics and chemistry performance of the catalyst that manufacturer provides is as follows:
Table I
Title G-68C
The form sphere
Nominal size 7 * 14 orders
Pd?wt％ 0.4(0.37～0.43)
The carrier high purity aluminium oxide
Another kind is used for the Ni that mercaptan-diolefine catalyst for reaction is the 58wt% on 8～14 order alumina globules, provides called after E-475-SR by Calcicat.The typical physics and the chemical property of the catalyzer that is provided by manufacturers are as follows:
Table II
Title E-475-SR
The form sphere
Nominal size 8 * 14 orders
Ni?wt％ 54
Alumina catalyst support
The speed of relative response device hydrogen will be enough keeping reaction, but keep below the speed that causes the tower overflow, described hydrogen speed is understood that " the hydrogen amount that can finish " as used in the present invention.Hydrogen is at least 1.0 to 1.0 with the ratio of diolefine and acetylene in the charging, is preferably 2.0 to 1.0.
Hydrogenating desulfurization
Utilize organosulfur compound and hydrogen evolution H in the refinery stream of catalyzer
2The reaction of S is called hydrogenating desulfurization.Hydrogenation is a generalized term, and it saturated and organic nitrogen compound reaction that comprises alkene and aromatic hydrocarbon forms ammonia.But, comprise hydrogenating desulfurization, simply be called hydrotreatment sometimes.
The catalyzer that is used for hydrodesulfurization reaction comprises VIII family metal for example cobalt, nickel, palladium, is used in combination separately or with other metals such as molybdenum or tungsten, is carried on the appropriate carriers such as aluminum oxide, silica-alumina, oxidation titania-zirconia.Usually metal provides as the metal oxide that is carried on extrudate or the bead, just because of this usually not as distillation structure.
Catalyzer comprises from V, VIB, VIII family metal component or its mixture in the periodic table of elements.Use Distallation systm can reduce inactivation, and can provide than fixed bed hydrogenation unit longer working time in the prior art.VIII family metal can increase total average activity.Contain group vib metal such as molybdenum and VIII family metal for example the catalyzer of cobalt or nickel be preferred.Suitable Hydrobon catalyst comprises Co-Mo, Ni-Mo and Ni-W catalyzer.Metal usually be carried on matrix for example the oxide compound on aluminum oxide, the silica-alumina etc. exist.Be sulfide in use or before by contacting metallic reducing with the logistics that contains sulfide.But catalyzer is alkene and the polyene hydrocarbon hydrogenation in the light pressure naphtha of catalysis also, so that the isomery of some monoolefines reduces to lesser extent.The hydrogenation particularly monoolefin hydrogenation in the lighter fraction is undesirable.
The performance of the Hydrobon catalyst that the Table III explanation is common.
Table III
Manufacture criterion catalyst co.
Title C-448
Form cloverleaf pattern (Tri-lobe) extrudate
Nominal size 1.2mm diameter
Metal wt%
Co 2～5％
Mo 5～20％
Alumina catalyst support
The common diameter of the catalyzer of extrudate form is 1/8,1/16 or 1/32 inch, and L/D is 1.5～10.The ball that catalyzer also has same diameter.They can directly be loaded in the straight-through fixed-bed reactor of standard, and it comprises carrier and reactant distribution structures.But they form too fine and close material with common form, must be prepared as the form of catalytic distillation structure so.Catalytic distillation structure can be as catalyzer and as mass transfer media.Catalyzer must be able to be fit to be carried on Ta Nei and have certain interval with as catalytic distillation structure.In a preferred implementation, the catalyzer that contains in the braided wires web frame is disclosed in US 5,266, in 546, is hereby incorporated by.More preferably catalyzer is contained in a plurality of wire mesh tube, and described pipe is in each end sealing and cross for example scum dredger silk screen placement of screen fabric sheet.Described is rolled up then with pipe is that bale is to be loaded in the distillation column reactor.This embodiment is described in US5, in 431,890, is hereby incorporated by.Other catalytic distillation structures that are used for the object of the invention are described in US 4,731, in 229,5,073,236,5,431,890 and 5,730,843, are hereby incorporated by.
The condition of the hydrodesulfurizationof of naphtha that is fit in distillation column reactor is very different with condition in the trickle-bed reactor of standard, particularly stagnation pressure and hydrogen dividing potential drop.Representative condition in the reactive distillation zone in the hydrodesulfurizationof of naphtha distillation column reactor is:
450～700 of temperature
Total pressure 75～300psig
H
2Dividing potential drop 6～75psi
The LHSV of petroleum naphtha about 1～5
H
2Speed 10～1000SCFB
The operation of distillation column reactor causes liquid not only being arranged in the distillation reaction district but also steam being arranged.The steam of considerable part is an a hydrogen and part is the hydrocarbon gas from petroleum fractions.In fact separating only is the consideration of next.
Do not limit the scope of the invention, advise mechanism that technology of the present invention effectively carries out for considering a part of part steam in the reactive system, thereby its double team in condensed fluid there is enough hydrogen to contact the hydrogenation that causes them with the hydrogen in the presence of catalyzer that needing to obtain and sulphur compound tight.Particularly, sulfur species concentrates and alkene and H in liquid
2S concentrates in steam, can make the transformation efficiency height of sulfide like this and the transformation efficiency of alkene species is low.
The result of operating procedure can use lower hydrogen dividing potential drop (therefore lower stagnation pressure) in distillation column reactor.
As in any distillation, in distillation column reactor, there is thermograde.At the temperature of the lower end of the tower that contains the higher material temperature height than the tower upper end.More lower boiling cut contains the easier sulfide of removing, and can provide better choice through the processing of the lesser temps of top of tower, and promptly the hydrocarbon pyrolysis still less or desired olefin(e) compound is saturated.The part of the higher Temperature Treatment higher through the lower end of distillation column reactor can cracking sulphur-containing cyclic compound and made sulphur hydrogenation.
Should believe that distillation column reaction of the present invention at first is favourable, because distill when reacting, initial reaction product and other stream components are removed as quickly as possible from reaction zone, reduce the possibility that side reaction takes place.Secondly because all components can seethe with excitement, by under system pressure by the boiling point may command temperature of reaction of mixture.Reaction heat only makes it seethe with excitement more, but does not increase under the temperature of setting pressure.As a result, a large amount of control to speed of response and products distribution can realize by regulation system pressure.The advantage that another this reaction can obtain from distillation column reaction is the washing effect that internal reflux offers catalyzer, has reduced the accumulation and the coking of polymkeric substance thus.At last, upwards mobile hydrogen can be used as steam stripping agent, helps to remove the H that produces in the distillation column reaction district
2S.
Absorbing unit can be have that a bed adsorbs and other one carry out the double-fixed bed of desorption.Absorbing unit also can be to have the fluidized-bed of drawing continuously and carrying out adsorbent reactivation.Sorbent material is characterised in that to adsorbing the solid particulate matter of organic nitrogen compound.The example of spendable sorbent material comprises aluminum oxide, acid kaolin, Fuller's earth, gac, aqueous alumina, silica gel and ion exchange resin.Sorbent material can for example hydrogen or nitrogen be regenerated with hot gas.
With reference to the accompanying drawings, it has illustrated the block diagram of one embodiment of the present invention.Petroleum naphtha enters the first catalytic distillation reactor 10 by flowline 101, and described reactor contains two 12 and 14 the thioetherification catalyst that is positioned at the upper end, or is lower than the rectifying section of bed.Hydrogen enters so that catalyzer remains hydride state by flowline 101A if necessary.Mercaptan in catalyst bed in the petroleum naphtha and diolefine react to form sulfide.It is C that the while petroleum naphtha is separated into boiling range
5～about 160 more lower boiling cut takes out from flowline 103 as overhead product.The bottom product that contains the most of mercaptan that shift out contains the sulphur content of minimizing.Part overhead product is condensed and returns distillation column reactor as reflux (not signal).Containing the mid range cut that is mainly thiophene is drawn by flowline 104 between bed 12 and 14 as the sulphur component.
Lighter component is removed from the petroleum naphtha of distillation column reactor 10 stripping stages, and described distillation column reactor contains for example sieve-tray tower, bubble cap or the structured packing of distillation structure 16 of standard.Therefore gentlier be moved out of with overhead product by steam stripped component.Contain the sulfide of bottom product, higher of organic nitrogen compound and thiophene compound and be moved out of by flowline 102 and enter in the absorbing unit 20, wherein organic nitrogen compound is removed.Be added into second column reactor 30 from the effluent of absorbing unit 20 in flowline 105, described distillation column reactor contains two 32 and 34 Hydrobon catalyst.Hydrogen is positioned at a place, bottom by flowline 105A and enters.Organosulfur compound in the effluent and H-H reaction are to produce hydrogen sulfide.Simultaneously to be separated into boiling range be about 160～350 °F than low boiler cut to effluent, and described cut comprises gasiform hydrogen sulfide and any light hydrocarbon polymer and since catalyzer this can cause the hydrocracking slightly of charging.More lower boiling cut is moved out of by flowline 106 as overhead product, and bottom product is moved out of by flowline 107.The part of overhead product is condensed and returns distillation column reactor as reflux (not signal).Bottom product and overhead product combination in flowline 108, and send into separation vessel 40, the distillation tower of standard for example, wherein hydrogen sulfide is moved out of by flowline 109.Liquid from separation vessel 40 is moved out of by flowline 110, combine with the mid range cut in flowline 104, add in the refining reaction device 50, described refining reaction device contains Hydrobon catalyst bed 52, wherein sulphur content reduces to the level of hope, for example＜and 50wppm.Be added in the refining reaction device by flowline 111A as needs hydrogen.At last, be removed by flowline 112 from the effluent of refining reaction device 50 and send into second separation vessel, wherein the hydrogen sulfide that produces in the refining reaction device is moved out of by flowline 113, the petroleum naphtha of desulfurization is moved out of by flowline 114, combines in flowline 115 with from the overhead product in thioetherification reaction device 10 flowline 103.
Claims (11)
1, a kind of method of handling naphtha stream comprises the steps:
(a) hydrogen and the naphtha stream that contains alkene, diolefine, mercaptan, thiophene, thiophene compound and organic nitrogen compound are added in first distillation column reactor:
(b) simultaneously in described first distillation column reactor:
(i) in the distillation reaction district in the presence of thioetherification catalyst, make diolefine and thiol reactant with produce sulfide and
(ii) petroleum naphtha is separated at least two kinds of cuts, contain reduce sulphur content first than low boiler cut, and contain the first higher cut of sulfide, thiophene, thiophene compound and organic nitrogen compound,
(c) shift out as overhead product from first distillation column reactor first than low boiler cut;
(d) shift out the first higher cut from first distillation column reactor as first bottom product;
(e) handle first bottom product to remove organic nitrogen compound, produce effluent with minimizing organic nitrogen compound content; With
(f) hydrogen and effluent are joined in the hydrodesulphurisatioreactors reactors that contains Hydrobon catalyst, wherein a part of sulfide, thiophene, thiophene compound and H-H reaction form hydrogen sulfide.
2, method as claimed in claim 1, the processing of wherein said step (e) comprise first bottom product are joined in the nitrogen absorbing unit.
3, method as claimed in claim 1, wherein said hydrodesulphurisatioreactors reactors comprises the second column reactor, effluent by be separated into simultaneously contain hydrogen sulfide second than the low boiler cut and the second higher cut, further comprise the steps:
(g) from the second column reactor, remove as second overhead product second than low boiler cut;
(h) from the second column reactor, remove the second higher cut as second bottom product;
(i) make described second overhead product and described second bottom product in conjunction with and join in the hydrogen sulfide separation vessel, wherein hydrogen sulfide is as separating in the gas from liquid effluent;
(j) join in the refining reaction device that contains Hydrobon catalyst with hydrogen with from the liquid efflunent of hydrogen sulfide separation vessel, wherein other sulfide, thiophene, thiophene compound and H-H reaction are to form hydrogen sulfide and to reduce the effluent of sulphur; With
(k) hydrogen sulfide is separated with the effluent that reduces sulphur.
4, method as claimed in claim 3, wherein said first distillation column reactor contains the thioetherification catalyst of two berths in described distillation reaction district, the mid range cut that contains thiophene shifts out between described bed, and combine with described liquid efflunent from the hydrogen sulfide separation vessel, join in the described refining reaction device.
5, method as claimed in claim 2, wherein said absorbing unit comprise the described solid particulate matter that can select to adsorb organic nitrogen compound.
6, method as claimed in claim 5, wherein said solid particulate matter can select to adsorb organic nitrogen compound, comprises aluminum oxide, acid kaolin, Fuller's earth, gac, zeolite, hydrated aluminum oxide, silica gel, ion exchange resin or its mixture.
7, a kind of method of handling naphtha stream comprises the steps:
(a) hydrogen and the naphtha stream that contains alkene, diolefine, mercaptan, thiophene, thiophene compound and organic nitrogen compound are joined first distillation column reactor that contains two thioetherification catalyst:
(b) simultaneously in described first distillation column reactor:
(i) in the distillation reaction district in the presence of thioetherification catalyst, make diolefine and thiol reactant with produce sulfide and
(ii) petroleum naphtha is separated at least three kinds of cuts, contain reduce sulphur content first than low boiler cut, and contain the first higher cut of sulfide, thiophene compound and organic nitrogen compound and contain the mid range cut of thiophene;
(c) shift out as first overhead product from first distillation column reactor first than low boiler cut;
(d) shift out the first higher cut from first distillation column reactor as first bottom product;
(e) shift out the mid range cut that contains thiophene that the conduct between described two is sideed stream,
(f) first bottom product is joined in the nitrogen absorbing unit, wherein organic nitrogen compound is removed from described first bottom product, produces to have first effluent that reduces nitrogen compound content;
(g) hydrogen and first effluent are joined contain second of Hydrobon catalyst and add in the distillation column reactor;
(h) simultaneously in described second column reactor:
(i) make sulfide and thiophene compound and H-H reaction with produce hydrogen sulfide and
(ii) first effluent is separated into contain hydrogen sulfide second than the low boiler cut and the second higher cut;
(i) shift out as second overhead product from the second column reactor second than low boiler cut;
(j) shift out the second higher cut from the second column reactor as bottom product;
(k) make described second overhead product and described second bottom product in conjunction with and join in the hydrogen sulfide separation vessel, wherein hydrogen sulfide is as separating in the gas from liquid effluent;
(l) join in the refining reaction device that contains Hydrobon catalyst with hydrogen with from the liquid efflunent and described the sideing stream of hydrogen sulfide separation vessel, wherein other sulfide, thiophene, thiophene compound and H-H reaction are to form hydrogen sulfide and to reduce the effluent of sulphur; With
(m) hydrogen sulfide is separated with the effluent that reduces sulphur; And
(n) effluent of described minimizing sulphur is combined with described first overhead product.
8, a kind of method of handling naphtha stream comprises the steps:
(a) hydrogen and the naphtha stream that contains alkene, diolefine, mercaptan, thiophene, thiophene compound and organic nitrogen compound are added first distillation column reactor:
(b) simultaneously in described first distillation column reactor:
(i) in the distillation reaction district in the presence of thioetherification catalyst, make diolefine and thiol reactant with produce sulfide and
(ii) petroleum naphtha is separated at least two kinds of cuts, contain reduce sulphur content first than low boiler cut, and contain the first higher cut of sulfide, thiophene, thiophene compound and organic nitrogen compound;
(c) shift out as overhead product from first distillation column reactor first than low boiler cut;
(d) shift out the first higher cut from first distillation column reactor as bottom product; With
(e) hydrogen and bottom product are joined in the hydrodesulphurisatioreactors reactors that contains Hydrobon catalyst, wherein a part of sulfide, thiophene, thiophene compound and H-H reaction form hydrogen sulfide;
Before wherein improvement is included in and joins bottom product in the hydrodesulphurisatioreactors reactors, described bottom product is joined in the organic nitrogen compound processing unit, and wherein organic nitrogen compound is removed from described bottom product with generation and contains the effluent that reduces nitrogen compound content.
9, method as claimed in claim 8, wherein said organic nitrogen compound processing unit comprises the nitrogen absorbing unit.
10, method as claimed in claim 9, wherein said absorbing unit comprises the solid particulate matter that can select to adsorb organic nitrogen compound.
11, as the method for claim 10, wherein said solid particulate matter can select to adsorb organic nitrogen compound, comprises aluminum oxide, acid kaolin, Fuller's earth, gac, zeolite, hydrated aluminum oxide, silica gel, ion exchange resin or its mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/790,909 US20040178123A1 (en) | 2003-03-13 | 2004-03-02 | Process for the hydrodesulfurization of naphtha |
| US10/790,909 | 2004-03-02 |
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| CN1664075A CN1664075A (en) | 2005-09-07 |
| CN100560695C true CN100560695C (en) | 2009-11-18 |
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| CN104479738B (en) * | 2014-12-16 | 2016-03-09 | 西安石油大学 | A kind of Deep Desulfurization of FCC Gasoline combination process |
| US9683183B2 (en) | 2015-02-04 | 2017-06-20 | China University of Petroleum—Beijing | Method for deep desulfurization of gasoline |
| WO2016123860A1 (en) * | 2015-02-04 | 2016-08-11 | 中国石油大学(北京) | Gasoline deep desulfurization method |
| CN106318459A (en) * | 2015-07-01 | 2017-01-11 | 中国石化扬子石油化工有限公司 | Optimized utilization method for light naphtha |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597476A (en) * | 1995-08-28 | 1997-01-28 | Chemical Research & Licensing Company | Gasoline desulfurization process |
| CN1277988A (en) * | 1999-06-02 | 2000-12-27 | 赫多特普索化工设备公司 | Modifying and hydrogenation processing for diesel union method |
-
2004
- 2004-12-22 BR BRPI0405793-7A patent/BRPI0405793B1/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597476A (en) * | 1995-08-28 | 1997-01-28 | Chemical Research & Licensing Company | Gasoline desulfurization process |
| CN1277988A (en) * | 1999-06-02 | 2000-12-27 | 赫多特普索化工设备公司 | Modifying and hydrogenation processing for diesel union method |
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| CN1664075A (en) | 2005-09-07 |
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