CN100351348C - Method for rectifying gasoline - Google Patents
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- CN100351348C CN100351348C CNB2004101028180A CN200410102818A CN100351348C CN 100351348 C CN100351348 C CN 100351348C CN B2004101028180 A CNB2004101028180 A CN B2004101028180A CN 200410102818 A CN200410102818 A CN 200410102818A CN 100351348 C CN100351348 C CN 100351348C
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Abstract
The present invention relates to a gasoline modifying method which comprises the following steps: a), under the technique condition of olefin isomerization, gasoline distillate oil contacts an olefin framework isomerization catalyst; b), under the technique condition of hydrodesulphurization, reaction effluences of the step a) contact a hydrodesulfurization catalyst, wherein the olefin framework isomerization catalyst is formed by combining a catalyst I and a catalyst II, the catalyst comprises a molecular sieve with deca-element ring pore canals, and the catalyst II comprises a molecular sieve with dodeca-element ring pore canals; taking the catalyst total amount as reference, in the combined catalyst, the content of the catalyst I is equal to 0 to 95 vol. %, and the content of the catalyst II is equal to 5-100 vol. %. The method used for modifying gasoline distillate oil causes the octane value loss of gasoline to be small.
Description
Technical field
The invention relates to a kind of gasoline modifying method.
Background technology
As everyone knows, the nuisance of a large amount of motor car engine dischargings is to cause one of air-polluting primary pollution source.And contained sulfide and alkene is the main precursor that produces noxious emission in the gasoline.
Catalytically cracked gasoline, particularly the sulfide in petrol that is obtained by heavy oil and residual oil catalytic cracking and the content height of alkene are the main sources of sulfur in gasoline and alkene.Therefore, solve sulfur in gasoline and alkene problem, mainly be will solve the desulfurization of catalytically cracked gasoline and fall alkene.
Under the hydrofining condition, sulphur and alkene in the gasoline fraction oil remove easily.But the olefin(e) centent in the catalytically cracked gasoline is obvious to the influence of gasoline octane rating.Olefin(e) centent is high more, and the alkene saturation exponent is also high more in the hydrodesulfurization process, and loss of octane number is also big more.For example, when the alkene in the catalytically cracked gasoline was reduced to 0 by 49.3 weight %, the RON of gasoline lost up to 23.5 units.Therefore, how reducing the gasoline octane rating loss in deep desulfuration and reduction olefin(e) centent is the difficult point of this technology.
Generally speaking, for the alkane and the olefin hydrocarbon molecules of structure proximate, the octane value of alkene is higher than alkane, and along with the increase of hydro carbons carbon number, this gap is more and more significant; The alkane of side chain is than straight-chain paraffin octane value height, and the side chain number is many more, and octane value is high more.Therefore, reduce the olefin(e) centent in the catalytically cracked gasoline and keep higher octane value, effective means is the skeletal isomerization reaction of carrying out alkene, make straight chain in the catalytically cracked gasoline or single branched-chain alkene transform into the isomer of higly branched chainization, could after further hydrogenation is saturated, make gasoline keep higher octane value like this.
CN 1264417A discloses the method for modifying of the sulfur-bearing alkene charging of a kind of boiling point in the gasoline boiling range, this charging contains and comprises the low octane rating normal paraffin, alkene and aromatic hydrocarbons, this method comprises: comprising that temperature is that the sulfur feed stock cut contacts with solid acid catalyst under 204-427 ℃ the gentle cracking conditions in first step, this catalyzer is made up of the ZSM-5 with α value acid activity between 20-800 basically, the alkene that is present in the charging with conversion becomes aromatic hydrocarbons and aromatic hydrocarbons side chain, with the low octane rating alkane in the cracked charge, alkene and formation intermediate product, the temperature that is raising, intermediate product contacts with Hydrobon catalyst under the combination condition of elevated pressure and hydrogeneous atmosphere, sulfocompound in the intermediate product is transformed into inorganic sulphide, and with the yield generation desulfurization product based on described charging cut at least 90 weight %, this desulfurization product contains in the gasoline boiling range and contains to the common liq cut that is less than 50 weight %C6-C10.
CN 1339564A discloses a kind of method of carrying out upgrading by three sections reaction pair gasoline, this method comprises three sections reactions, gasoline at first carries out the diene selective hydrogenation reaction at first section, enters second section then and carries out olefin isomerization, enters the 3rd section at last and carries out hydrogenation reaction.Wherein, second section olefin isomerization, catalyzer is selected from Al
2O
3, halogen-containing Al
2O
3, SAPO-11, ZSM-12, ZSM-35, ZSM-22, MCM-22, MCM-41 one or more, reaction conditions is temperature of reaction 100-500 ℃, reaction pressure 0.1-4.0Mpa, gasoline weight space velocity 0.1-10h
-1, the mol ratio of carrier gas and liquid gasoline is 0.1-100.
Employing has the catalyzer of the molecular sieve of central hole structure, can eliminate the restriction of thermodynamic(al)equilibrium wholly or in part, and the reaction that makes linear chain olefin skeleton isomerism be converted into branched-chain alkene reaches very high transformation efficiency.Its shortcoming be isomerization product based on single branched-chain alkene, higly branched chain product content is low.And this single branched-chain alkene octane value after hydrogenation is saturated is still lower, and is little to the maintenance contribution of gasoline octane rating.
Summary of the invention
When the objective of the invention is to carry out olefin skeletal isomerization at the molecular sieve catalyst that existing method has a central hole structure in employing, the higly branched chain product yield is low, behind hydrogenation the big shortcoming of gasoline octane rating loss, a kind of new gasoline modifying method is provided.
Method provided by the invention may further comprise the steps: a) under the isomerisation of olefin processing condition, gasoline fraction oil is contacted with a kind of olefin skeletal isomerization catalyzer; B) under the hydrodesulfurization condition, with the reaction effluent of step a) with contact with a kind of Hydrobon catalyst, wherein said olefin skeletal isomerization catalyzer is combined by catalyst I and catalyst I I, catalyst I contains a kind of molecular sieve with ten-ring duct, catalyst I I contains a kind of zeolite molecular sieve with twelve-ring duct, with the catalyzer total amount is benchmark, the content of catalyst I is 0-95 volume % in the described combination catalyst, and the content of catalyst I I is 5-100 volume %.
Compare with existing method, when adopting method provided by the invention that gasoline fraction oil is carried out upgrading, the gasoline octane rating loss is little.
For example, adopting method provided by the invention is that the stock oil of 1680ppm, RON90.8, MON79.8, olefin(e) centent 31.5% carries out upgrading (diene catalyzer RGO-2 (RGO-2 and I+IIC volume ratio are 1: 5) is taken off in selective hydrogenation to a kind of sulphur content; Olefin isomerization catalyst is I+IIC combination (volume ratio of IIC and I is 2: 1); Catalyst for selectively hydrodesulfurizing RSDS-1 (RSDS-1 and I+IIC volume ratio are 1: 2)), the RON of its product is 88.6, MON is 79.3, sulphur content 90ppm, olefin(e) centent 24.8%, yield of gasoline 98.9%; And adopt that Comparative Examples method (olefin isomerization catalyst is I, catalyst for selectively hydrodesulfurizing RSDS-1), the RON of its product only are 85.4, MON only is 77.8, sulphur content 90ppm, olefin(e) centent 19.9%, yield of gasoline only are 95.2%.
Description of drawings
Fig. 1 is a kind of schematic flow sheet that the invention provides method.
Embodiment
According to the invention provides method, described molecular sieve with ten-ring pore structure is a mesoporous molecular sieve known in the field, for example, be selected among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and the SAPO-41 one or more, be preferably ZSM-5.
Described molecular sieve with twelve-ring duct can be selected from one or more among L zeolite, y-type zeolite, X type zeolite, β zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, the SAPO-5, be preferably among y-type zeolite, β zeolite, mordenite, the SAPO-5 one or more, more preferably the β zeolite.
Wherein, described molecular sieve with twelve-ring duct also contains non-framework silicon, is benchmark in oxide compound and with the molecular sieve total amount, and the content of described silicon is 1-20 weight %, is preferably 2-10 weight %.
Described non-framework silicon is contacted with the solution of silicon-containing compound by described molecular sieve and the method for roasting is introduced.For example, with described molecular sieve silicon-containing compound solution impregnation and roasting, maturing temperature is 350-650 ℃, is preferably 450-550 ℃, roasting time 1-24 hour, is preferably 2-8 hour.
Described silicon-containing compound is selected from the various organosilicons that are commonly used for the modification of molecular sieve silicon, in the inorganic silicon compound one or more.For example; can be selected from the phenmethyl siloxanes; the styroyl siloxanes; the hydrocinnamyl siloxanes; hexamethyldisiloxane; the decamethyl trisiloxanes; the phenylbenzene tetramethyl disiloxane; tetraethyl orthosilicate; trimethylchlorosilane; CMDMCS chloromethyl dimethyl chlorosilane; the N-trimethyl-silyl-imidazole; adjacent; between-two (trimethyl silyl) ethylidine imidazoles; the N-methyl-just-the trimethyl silyl ethanamide; instead-butyl dimetylsilyl imidazoles; N-trimethyl silyl ethanamide; methyltrimethoxy silane; vinyltriethoxysilane; ethyl trimethoxy silane; propyl trimethoxy silicane; (3; 3; the 3-trifluoro propyl) Trimethoxy silane; (3-(2-amino-ethyl) aminopropyl) Trimethoxy silane; the cyano ethyl Trimethoxy silane; TSL 8330; phenyl trimethoxy silene; (3-chloropropyl) Trimethoxy silane; (3-thiohydroxy propyl group) Trimethoxy silane; (3-glycidyl propyl group) Trimethoxy silane; vinyl three (B-methoxy ethoxy) silane; (r-methacryloyl propyl group) Trimethoxy silane; (4-aminopropyl) Trimethoxy silane; (r-(B-aminoethylamino) propyl group l) Trimethoxy silane; (r-glycidyl propyl group) Trimethoxy silane; (B-(3, the 4-epoxycyclohexyl) ethyl) Trimethoxy silane; (r-thiohydroxy ethyl) Trimethoxy silane; (r-chloropropyl) Trimethoxy silane; methyl silicate; tetraethoxy; SiCl4; in the silicon sol one or more.In the preferred methyl silicate, tetraethoxy, SiCl4 wherein one or more.In oxide compound and with the molecular sieve total amount is benchmark, and the introducing amount of described silicon is 1-20%, be preferably 2-10%.
To the grain size of described molecular sieve with twelve-ring duct without limits, but for the catalyzer of optimum performance, preferably the crystal grain of this molecular sieve is less than 300 nanometers, and further preferred crystal grain is the 50-200 nanometer.
Described crystal grain can be by any one existing method preparation less than the molecular sieve of 300 nanometers.For example, crystal grain can adopt the synthetic method preparation of the applicant's disclosed beta zeolite in small crystal grain in CN 1108213A, CN 1108214A, CN 1100004C less than the β zeolite of 300 nanometers.Details about these synthetic methods discloses in above-mentioned patent (application) in detail, does not give unnecessary details herein.
According to method provided by the invention, described catalyst I and catalyst I I also contain at least a metal component that is selected from group VIII respectively, preferred nickel wherein.In oxide compound and with the catalyzer total amount is benchmark, and the content of group VIII metal is preferably 0.1-10 weight %, more is preferably 0.1-5 weight %.The method of introducing the group VIII metal component is an ordinary method, as adopting ion-exchange, dipping, mixing method such as pinch.
According to method provided by the invention, can also contain heat-resistant inorganic oxide among described catalyst I and the catalyst I I, described heat-resistant inorganic oxide plays binding agent, support of the catalyst in catalyzer, it can improve the intensity of catalyzer, and can improve and reconcile the physico-chemical property of catalyzer, as improving the pore structure of catalyzer.Described heat-resistant inorganic oxide is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in the optional self-alumina of described heat-resistingization thing, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more, preferred aluminum oxide.With the catalyzer total amount is benchmark, and the content of described heat-resistant inorganic oxide is that 10-90 weight % is preferably and is 30-70 weight %.
According to method provided by the invention, the preparation method of described catalyst I and catalyst I I comprises described molecular sieve is contained or do not contain heat-resistant inorganic oxide and/or its precursor moulding, roasting, introduces the group VIII metal component afterwards.Wherein, the precursor of described heat-resistant inorganic oxide refers to can form after the roasting compound of described heat-resistant inorganic oxide, typically refers to oxyhydroxide, hydrous oxide, contains the gel of its oxide compound, oxyhydroxide and in the colloidal sol one or more.For example, the precursor of aluminum oxide can be selected from one or more in various hydrated aluminum oxides, the aluminium colloidal sol.Described moulding adopts ordinary method to carry out, as methods such as compressing tablet, spin, extrusions.When extrusion moulding, can add an amount of extrusion aid and/or tackiness agent, extrusion moulding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.The temperature of described roasting is 450-650 ℃, and roasting time is 1-10 hour.
According to method provided by the invention, the combination of described olefin skeletal isomerization catalyst I and catalyst I I, it can be mixing with customary way machinery in catalyst I and the catalyst I I employing prior art, also can be that described catalyst I and catalyst I I layering are filled in same reactor or fill in series connection use in two or more reactors respectively, the combination of preferred catalyst I and catalyst I I contacts the stock oil that enters reactor successively with catalyst I I with catalyst I.
With the catalyzer total amount is benchmark, and the content of catalyst I is 0-95 volume % in the described combination catalyst, is preferably 10-90 volume %, and the content of catalyst I I is 5-100 volume %, is preferably 10-90 volume %.
According to the invention provides method, the catalyzer that is used for hydrodesulfurisationstep step is conventional Hydrobon catalyst, and this catalyzer contains heat-resistant inorganic oxide carrier to be formed with the VI family and/or the VIII family metal that load on this carrier.VI family metal is molybdenum or tungsten normally, and VIII family metal is nickel or cobalt normally.Be typically mixture as Ni-W, Ni-Mo or Co-Mo.In oxide compound and with the catalyzer is benchmark, and described catalyzer preferably contains the VI family metal of 0.5-35 weight %, is preferably 5-30 weight %, and the VIII family metal of 0.1-10 weight % is preferably 1-8 weight %.
According to the invention provides method, described olefin skeletal isomerization processes condition comprises that temperature of reaction is 200-400 ℃, to elect temperature of reaction as be 250-350 ℃, and the hydrogen dividing potential drop is that 1-4 MPa, excellent hydrogen dividing potential drop are the 1.2-3.2 MPa, and liquid hourly space velocity is 0.5-6 hour
-1, be preferably 1-4 hour
-1, hydrogen to oil volume ratio is 100-800, be preferably 200-400; Described hydrofining technology condition comprises that temperature of reaction is 200-400 ℃, to elect temperature of reaction as be 250-350 ℃, and the hydrogen dividing potential drop is that 1-4 MPa, excellent hydrogen dividing potential drop are the 1.2-3.2 MPa, and liquid hourly space velocity is 0.5-6 hour
-1, be preferably 1-4 hour
-1, hydrogen to oil volume ratio is 100-800, be preferably 200-400.
For gasoline fraction oil, particularly come from and more or less all contain a certain amount of diolefine in the catalytically cracked gasoline distillate, and the existence of diolefine stable unfavorable to catalyzer.According to method provided by the invention, stock oil can at first contact with the removing alkadiene by selective hydrogenation catalyzer, so that it is sloughed with before the skeletal isomerization catalyzer contacts.The catalyzer that removing alkadiene by selective hydrogenation adopted is preferably the Hydrobon catalyst that contains alkaline components, in oxide compound and with the catalyzer is benchmark, this catalyzer contains cobalt and/or the nickel of 0.5-8 amount amount %, molybdenum and/or the tungsten of 2-25 weight %, 0.5-8 the basic metal of weight % and the carrier of equal amount, described carrier is preferably aluminum oxide, and described basic metal is preferably potassium.This Preparation of catalysts method is well known in the art, for example, under the condition that is enough to molybdenum and/or tungsten, cobalt and/or nickel and basic metal is deposited on the described alumina supporter, with the described carrier of solution impregnation that contains molybdenum and/or tungsten, nickel, alkali-metal compound.Wherein, molybdenum and/or tungsten, cobalt and/or nickel and basic metal can also can be incorporated in the alumina supporter respectively simultaneously.
Described removing alkadiene by selective hydrogenation catalyzer can use the protection bed series connection as the olefin skeletal isomerization catalyzer.For example, fill in skeletal isomerization beds on as protective layer it or fill in respectively to connect in two or more reactors and use.
Described removing alkadiene by selective hydrogenation processing condition and olefin skeletal isomerization processes condition can be identical also can be different, its scope comprises that temperature of reaction is 200-400 ℃, to elect temperature of reaction as be 250-350 ℃, the hydrogen dividing potential drop is that 1-4 MPa, excellent hydrogen dividing potential drop are the 1.2-3.2 MPa, and liquid hourly space velocity is 0.5-6 hour
-1, be preferably 1-4 hour
-1, hydrogen to oil volume ratio is 100-800, be preferably 200-400.
According to method provided by the invention, an embodiment preferred can realize by flow process shown in Figure 1.
To introduce olefin isomerization district 1 from the stock oil of pipeline 4 with from the hydrogen of pipeline 5, contact with a kind of olefin skeletal isomerization catalyzer (containing or do not contain the removing alkadiene by selective hydrogenation catalyzer), its reaction effluent is introduced hydrodesulfurizationreaction reaction zone 2 through pipeline 6, contact with a kind of Hydrobon catalyst, its reaction effluent is introduced separator 3 through pipeline 7 and is separated, the hydrogen rich stream that obtains is drawn through pipeline 8, liquefied gas through pipeline 9 draw, low sulfur, low olefin gasoline draws through pipeline 10.
Method provided by the invention is suitable for the upgrading of gasoline fraction oil, and, octane value low with the production sulphur content keeps good gasoline fraction oil.Part or all of part or all that described gasoline fraction oil can be catalytically cracked gasoline, part or all of coker gasoline, other gasoline fraction that contains a certain amount of alkene.
The following examples will the invention will be further described.
Employed removing alkadiene by selective hydrogenation catalyzer, olefin skeletal isomerization catalyzer and Hydrobon catalyst and preparation method thereof are as follows in the embodiment of the invention:
1. removing alkadiene by selective hydrogenation catalyzer
Used removing alkadiene by selective hydrogenation catalyzer is a commercial catalyst among the embodiment, and its trade names are RGO-2 (Sinopec company limited Chang Ling oil-refining chemical head factory catalyst plant product).
2. olefin skeletal isomerization catalyzer
The olefin skeletal isomerization catalyst I
According to the 3 preparation catalyzer of the example among the CN 1448484A, wherein, high-Si zeolite containing rare-earth five-membered ring structure is Z1, and the silicon oxide of Z1 and alumina molar ratio are 82.2.Get 20 gram Z1 zeolites and a certain amount of hydrated aluminum oxides (German Condea company product, butt is 74 weight %) mix, on the twin screw banded extruder, be extruded into the trilobal bar of 1.1 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 550 ℃ of roastings 2 hours, get 20 grams with flooding under the 15 milliliters of room temperatures of the aqueous solution that contain nickelous nitrate 0.8 gram, after drying, the roasting, make the olefin skeletal isomerization catalyst I.With the catalyzer total amount is benchmark, and the content of high-Si zeolite containing rare-earth five-membered ring structure is 44.6 weight %, and the content of aluminum oxide is 54.4 weight %, and in oxide compound, the content of nickel is 1.0 weight %.
Olefin skeletal isomerization catalyst I Ia
Get 20 gram β zeolite (Chang Ling refinery products, the mol ratio of silicon oxide and aluminum oxide is 36, crystal grain is the 230-280 nanometer) with 63 gram hydrated aluminum oxides (German Condea company products, butt is 74 weight %) mix, on the twin screw banded extruder, be extruded into the trilobal bar of 1.1 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 550 ℃ of roastings 2 hours, get 20 grams with flooding 10 hours under the 200 milliliters of room temperatures of the aqueous solution that contain nickelous nitrate 10 grams, in 90-95 ℃ of water-bath, added heat exchange 4 hours afterwards, filter and dried 4 hours in 120 ℃, 550 ℃ of roastings 2 hours obtain catalyst I Ia.Molecular sieve content is 29.6 weight % among the catalyst I Ia, and the content of nickel oxide is 1.5 weight %, and alumina host is 68.9 weight %
Olefin skeletal isomerization catalyst I Ib
Get 21 gram β zeolites (the same), 550 ℃ of roastings 3 hours, after in air, being cooled to room temperature, getting 20 grams flooded 10 hours for 100 milliliters with the cyclohexane solution that contains 5.9 gram tetraethoxys, filter and under 60 ℃ of temperature dry 2 hours, 550 ℃ of following roastings 2 hours, obtain the β zeolite C1 of silicon modification afterwards.In oxide compound and with the molecular sieve total amount is benchmark, and calculating the amount of introducing silicon among the C1 is 7.6 weight %.
Get 20 gram C1 and 63 and restrain hydrated aluminum oxides (German Condea company product, butt is 74 weight %) mix, on the twin screw banded extruder, be extruded into the trilobal bar of 1.1 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 550 ℃ of roastings 2 hours, get 20 and restrain, in 90-95 ℃ of water-bath, added heat exchange 4 hours afterwards, filter and dried 4 hours in 120 ℃ with flooding 10 hours under the 200 milliliters of room temperatures of the aqueous solution that contain nickelous nitrate 10 grams, 550 ℃ of roastings 2 hours obtain catalyst I Ib.Molecular sieve content is 29.6 weight % among the catalyst I Ib, and the content of nickel oxide is 1.5 weight %, and alumina host is 68.9 weight %.
Olefin skeletal isomerization catalyst I Ic
Prepare the β zeolite according to 2 methods of the example among the CN 1108231A.Its crystal grain is the 70-80 nanometer.
Get 40 grams with 800 milliliters of dippings of the aqueous solution that contains nickelous nitrate 120 gram 10 hours, in 90-95 ℃ of water-bath, added heat exchange 4 hours afterwards, filter and, 550 ℃ of roastings 2 hours in 120 ℃ of oven dry 12 hours; After reducing to room temperature, get 20 grams with 100 milliliters of the cyclohexane solutions dipping that contains 3.7 gram tetraethoxys 10 hours, filter and under 60 ℃ of temperature dry 2 hours,, obtain nickeliferous silicon modified beta zeolite C2 afterwards 550 ℃ of following roastings 2 hours.In oxide compound and with the molecular sieve total amount is benchmark, and calculating the content of introducing silicon among the C2 is 5.3 weight %.
Get 20 gram C2 and mix, on the twin screw banded extruder, be extruded into the trilobal bar of 1.1 millimeters of φ with 63 gram hydrated aluminum oxides (Shandong Aluminum Plant's product, butt are 68 weight %), wet bar through 120 ℃ of dryings after 4 hours in 550 ℃ of roastings 2 hours, obtain catalyst I Ic.Molecular sieve content is 29.6 weight % among the catalyst I Ic, and the content of nickel oxide is 0.4 weight %, and alumina host is 70.0 weight %.
3. catalyst for selectively hydrodesulfurizing
Used Hydrobon catalyst is a commercial catalyst among the embodiment, and its trade names are RSDS-1 (Sinopec company limited Chang Ling oil-refining chemical head factory catalyst plant product).
According to Fig. 1 technical process gasoline fraction oil is carried out upgrading, stock oil character sees Table 1.Catalyzer wherein is: olefin isomerization catalyst IIA, catalyst for selectively hydrodesulfurizing RSDS-1.Operational condition sees Table 2, generates oil nature and sees Table 3.
According to Fig. 1 technical process gasoline fraction oil is carried out upgrading, stock oil character sees Table 1.Catalyzer wherein is: olefin isomerization catalyst I+IIB, the volume ratio of catalyst I IB and catalyst I is 1: 3, catalyst for selectively hydrodesulfurizing RSDS-1.Operational condition sees Table 2, generates oil nature and sees Table 3.
According to Fig. 1 technical process gasoline fraction oil is carried out upgrading, stock oil character sees Table 1.Catalyzer filling from top to bottom is protective material RGO-2, olefin isomerization catalyst I, olefin isomerization catalyst IIC, catalyst for selectively hydrodesulfurizing RSDS-1 in proper order.Wherein the volume ratio of olefin isomerization catalyst IIC and catalyst I is 2: 1, and catalyst for selectively hydrodesulfurizing RSDS-1 is 1: 2 with (I+IIC) volume ratio, and RGO-2 is 1: 5 with (I+IIC) volume ratio.Operational condition sees Table 2, generates oil nature and sees Table 3.
Comparative Examples 1
According to Fig. 1 technical process gasoline fraction oil is carried out upgrading, stock oil character sees Table 1.Catalyzer wherein is: olefin isomerization catalyst I, catalyst for selectively hydrodesulfurizing RSDS-1.Operational condition sees Table 4, generates oil nature and sees Table 5.
Table 1
| Title | Stock oil |
| Sulphur, ppm alkene, v% RON MON anti-knock index boiling range ASTM D-86, ℃ initial boiling point 50% final boiling point | 1680 31.5 90.8 79.8 85.3 92 135 190 |
Table 2
| | | | Comparative Examples 1 | |
| The hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 | 1.6 |
| Temperature of reaction, ℃ | ||||
| Selectivity is taken off diene | - | - | 240 | - |
| Olefin skeletal isomerization | 280 | 275 | 275 | 280 |
| Hydrogenating desulfurization | 290 | 290 | 290 | 290 |
| Liquid hourly space velocity, h -1 | ||||
| Selectivity is taken off diene | - | - | 10.0 | - |
| Olefin skeletal isomerization | 2.0 | 2.0 | 2.0 | 2.0 |
| Hydrogenating desulfurization | 4.0 | 4.0 | 4.0 | 4.0 |
| The inlet hydrogen-oil ratio, Nm 3/m 3 | 300 | 300 | 300 | 300 |
| Product property | ||||
| Sulphur content, ppm | ～90 | |||
| Olefin(e) centent, v% | 21.2 | 22.6 | 24.8 | 19.9 |
| RON | 86.3 | 86.4 | 88.6 | 85.4 |
| MON | 78.8 | 79.1 | 79.3 | 77.8 |
| Anti-knock index | 82.6 | 82.8 | 84.0 | 81.6 |
| Yield of gasoline, % | 96.0 | 96.6 | 98.9 | 95.2 |
The result who provides as table 2, when employing the invention provides method gasoline fraction oil is carried out upgrading, under the desulfurization degree condition suitable with the Comparative Examples method, its effect all is better than Comparative Examples, when particularly carrying out upgrading according to embodiment 3, give birth to olefiant RON and improve 3.2 units, yield improves 3.7 percentage points.
Claims (19)
1, a kind of gasoline modifying method may further comprise the steps: a) under the isomerisation of olefin processing condition, gasoline fraction oil is contacted with the olefin skeletal isomerization catalyzer; B) under the hydrodesulfurization condition, the reaction effluent of step a) is contacted with Hydrobon catalyst, wherein said olefin skeletal isomerization catalyzer is combined by catalyst I and catalyst I I, catalyst I contains a kind of molecular sieve with ten-ring duct, catalyst I I contains a kind of molecular sieve with twelve-ring duct, with the catalyzer total amount is benchmark, and the content of catalyst I is 0-95 volume % in the described catalyst combination, and the content of catalyst I I is 5-100 volume %.
2, method according to claim 1 is characterized in that, the combination of described catalyst I and catalyst I I contacts the stock oil that enters reactor successively with catalyst I I with catalyst I.
3, method according to claim 1 is characterized in that, is benchmark with the catalyzer total amount, and the content of described catalyst I is 10-90 volume %, and the content of catalyst I I is 10-90 volume %.
4, method according to claim 1, it is characterized in that described molecular screening with twelve-ring duct one or more in L zeolite, y-type zeolite, X type zeolite, β zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, SAPO-5.
5, method according to claim 4 is characterized in that, described molecular screening with twelve-ring duct one or more in y-type zeolite, β zeolite, mordenite, SAPO-5.
6, method according to claim 5 is characterized in that, described molecular sieve is the β zeolite.
According to each described method in the claim 1,3,4 or 5, it is characterized in that 7, described molecular sieve with twelve-ring duct contains non-framework silicon, is benchmark in oxide compound and with the molecular sieve, and the content of described silicon is 1-20 weight %.
8, method according to claim 7 is characterized in that, the content of described silicon is 2-10 weight %.
According to each described method in the claim 1,3,4 or 5, it is characterized in that 9, the crystal grain of described molecular sieve with twelve-ring duct is less than 300 nanometers.
10, method according to claim 9 is characterized in that, described crystal grain is the 50-200 nanometer.
11, method according to claim 1 is characterized in that, also contains a kind of group VIII metal component in the described olefin skeletal isomerization catalyzer, is benchmark in oxide compound and with the catalyzer total amount, and its content is 0.1-10 weight %.
12, method according to claim 11 is characterized in that, described group VIII metal component is a nickel, is benchmark in oxide compound and with the catalyzer total amount, and its content is 0.1-5 weight %.
13, method according to claim 1 is characterized in that, also contains heat-resistant inorganic oxide in the described olefin skeletal isomerization catalyzer, is benchmark with the catalyzer total amount, and the content of described heat-resistant inorganic oxide is 10-90 weight %.
14, method according to claim 13 is characterized in that, described heat-resistant inorganic oxide is an aluminum oxide, and its content is 20-80 weight %.
15, method according to claim 1 is characterized in that, described gasoline fraction oil with take off the diene catalyzer with selective hydrogenation earlier before the olefin skeletal isomerization catalyzer contacts and contact.
16, method according to claim 15, it is characterized in that, described selective hydrogenation is taken off the diene catalyzer and is contained a kind of alumina supporter and the cobalt and/or nickel, molybdenum and/or tungsten and the basic metal that load on this carrier, in oxide compound and with the catalyzer is benchmark, the content of cobalt and/or nickel is 0.5-8 weight %, the content of molybdenum and/or tungsten is 2-25 weight %, and alkali-metal content is the carrier of 0.5-8 weight % and equal amount.
17, method according to claim 1 is characterized in that, the reaction conditions of described isomerisation of olefin comprises: temperature is 200-400 ℃, and the hydrogen dividing potential drop is the 1-4 MPa, and liquid hourly space velocity is 0.5-6 hour
-1, hydrogen to oil volume ratio is 100-800; The reaction conditions of described hydrogenating desulfurization comprises: temperature is 200-400 ℃, and the hydrogen dividing potential drop is the 1-4 MPa, and liquid hourly space velocity is 0.5-6 hour
-1, hydrogen to oil volume ratio is 100-800.
18, method according to claim 17 is characterized in that, the reaction conditions of described isomerisation of olefin comprises: temperature is 250-350 ℃, and the hydrogen dividing potential drop is the 1.2-3.2 MPa, and liquid hourly space velocity is 1-4 hour
-1, hydrogen to oil volume ratio is 200-600; The reaction conditions of described hydrogenating desulfurization comprises: temperature is 250-350 ℃, and the hydrogen dividing potential drop is the 1.2-3.2 MPa, and liquid hourly space velocity is 1-4 hour
-1, hydrogen to oil volume ratio is 200-600.
19, method according to claim 1 is characterized in that, described gasoline fraction oil is catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or its mixture.
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| CNB2004101028180A CN100351348C (en) | 2004-12-28 | 2004-12-28 | Method for rectifying gasoline |
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| CNB2004101028180A CN100351348C (en) | 2004-12-28 | 2004-12-28 | Method for rectifying gasoline |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057635A (en) * | 1990-02-08 | 1991-10-15 | Uop | Process for isomerizing olefins in gasoline streams |
| CN1316485A (en) * | 2000-04-05 | 2001-10-10 | 中国科学院大连化学物理研究所 | Process for modifying gasoline by isomerizing hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057635A (en) * | 1990-02-08 | 1991-10-15 | Uop | Process for isomerizing olefins in gasoline streams |
| CN1316485A (en) * | 2000-04-05 | 2001-10-10 | 中国科学院大连化学物理研究所 | Process for modifying gasoline by isomerizing hydrogenation |
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