CN102757817B - Gasoline processing method - Google Patents
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Abstract
A gasoline processing method includes: subjecting raw materials of full distillates to a fractionating tower to be fractioned into three fractions, and removing mercaptan sulfur in a light fraction by means of alkali extraction to obtain a liquid product I which is a gasoline blending component; processing an intermediate fraction through a first hydrogenation unit to obtain a liquid product II which is a qualified aromatics extraction raw material; and processing a heavy fraction through a second hydrogenation unit to obtain a liquid product III which is a gasoline blending component. By the gasoline processing method, a qualified aromatic hydrocarbon product and a qualified gasoline product can be obtained simultaneously, sources of the aromatic hydrocarbon product are widened, and compared with raw materials, the obtained gasoline product has the advantages that the induction period is greatly prolonged, sulfur content is greatly reduced, and aromatic hydrocarbon content, especially benzene content is reduced.
Description
Technical field
The invention belongs to a kind of method of refining hydrocarbon ils in the presence of hydrogen, more particularly, is a kind of method of hydrotreating processing secondary processing of gasoline cut.
Background technology
Along with the development of petrochemical complex and textile industry, in the world the demand of aromatic hydrocarbon product is constantly increased, especially faster to the demand growth of benzene and dimethylbenzene.For a long time, the output of the aromatic hydrocarbon product of China can not satisfy the demands always.At present, the major part source of aromatic hydrocarbons is the gasoline of refinery catalytic reforming unit production and the pyrolysis gasoline of ethylene unit by-product, the method mainly solvent extraction of aromatics separation from these two kinds of gasoline.Therefore, how widening aromatics extraction raw material source is the problem needing to solve.
In addition, along with the increasingly stringent of environmental requirement, the composition of countries in the world to motor spirit proposes stricter restriction, comprises sulphur content and aromaticity content.China's quality of gasoline upgrading rapidly, is planned to require the national standard (GB17930-2006) come into effect from December 3rd 1,2009 that in state (III) normal benzene, sulphur content is less than 150 μ g/g.In the provincial standard that Beijing, Shanghai City and Guangzhou have been implemented, require that sulfur content in gasoline is less than 50 μ g/g.
Catalytic cracking take heavy distillate as raw material, obtains the important process of light ends oil, and its catalytically cracked gasoline is mainly used as gasoline blending component.Catalytic pyrolysis (DCC) technique be China grow up on the basis of traditional fluid catalytic cracking (FCC) Technology by the catalyst cracking technology of heavy raw oil producing more propylene.DCC gasoline aromaticity content is high, octane value is high, and diene content is higher simultaneously, and oxidation stability is poor.If directly as gasoline blending component, can be poor and affect gasoline performance due to its stability, in addition because its aromaticity content is high, must concoct with the gasoline fraction of other low arene content.And catalytically cracked gasoline is generally main blending component in gasoline pool in China, the blending ratio of reformed gasoline can be limited like this.In addition, DCC gasoline aromaticity content is high, can reach 70 heavy more than %, can using after the process of DCC gasoline hydrogenation as the raw material of production aromatic hydrocarbons.But conventional hydro can make aromatic hydrocarbons supersaturation, in aromatics extraction raw material, aromaticity content reduces, also make Aromatic raffinate reduce further as octane value during gasoline blending component simultaneously, therefore, how existing Technology Production Flow Chart is optimized, adopts rational technique to process DCC gasoline, reduce aromatic saturation rate, both produced qualified aromatics extraction raw material, and also can obtain part of gasoline blending component simultaneously, seem necessary.
According to existing Hydrofining Technology, DCC gasoline direct is tapped into capable desulfurization removing nitric simply and can there are problems: because in DCC gasoline, diene content is higher, easily at beds top polymerization coking, reactor pressure decrease is caused to rise, the long period smooth running of extreme influence device.In addition, carry out hydrofining can make aromatic hydrocarbons supersaturation to full cut DCC gasoline, reduce aromatic hydrocarbon product yield, loss of octane number increases.Therefore, while the qualified aromatics extraction raw material of production and super low-sulfur oil blending component, need aromatic saturation reaction to occur less as far as possible.
CN1990830A discloses a kind of hydrofinishing method for coker gasoline, the method first contacts with hydrogenation protecting agent at low temperatures, again at high temperature with Hydrobon catalyst contact reacts, in gasoline fraction after refining, olefin(e) centent is less than 1 volume %, sulphur content is less than 300 μ g/g, nitrogen content is less than 2 μ g/g, all can meet the feed needs of reformed pre-hydrogenated device and preparing ethylene by steam cracking device, adopt this technical process can the pressure drop of delayed response device to extend the Hydrogenation of Coker Gasoline device operational cycle, but coker gasoline after treatment sulphur nitrogen content is still higher, also need further process.
CN1035775C discloses a kind of method processing catalytic cracking gasoline, and the method has the presulfurization non-precious metal catalyst series connection of different activities and variable grain diameter by two, segmentation is contained in a reactor or is divided in two reactors.The maleic value of hydrogenated products is less than 1gI/100g, inductive phase is not more than 3 units more than 480min, loss of octane number.These hydrogenated products are as gasoline blending component.But the method itself does not relate to desulfurization, after the method process, in product, sulphur content reduces hardly, it can be used as gasoline blending component that vehicle gasoline and sulfur content in vehicle gasoline can be made higher, this current for motor spirit in sulphur content restriction increasingly stringent megatrend under be inappropriate.
Summary of the invention
The object of the invention is to provide a kind of gasoline processing and treating method on the basis of existing technology.
Method provided by the invention, comprising:
(1) full distillation gasoline raw material is fractionated into three strands of cuts through separation column, and obtaining lighting end (LCN) from separation column top is C
5and following component, gained lighting end removes mercaptan sulfur wherein through alkali density, obtains liquid product I; Gained liquid product I total sulfur content is less than 10 μ g/g, and octane value does not lose, and is gasoline blending component.
(2) in the middle part of separation column, C is obtained
6~ C
8middle cut (MCN), in gained, cut processes through the first hydrogenation unit, obtains liquid product II; Gained liquid product II is qualified aromatics extraction raw material
(3) obtaining last running (HCN) from fractionation column base is C
9and above component, gained last running processes through the second hydrogenation unit, obtains liquid product III, and it is little that gained liquid product III sulphur content is less than 10 μ g/g loss of octane number, is gasoline blending component.
The aromaticity content of described full distillation gasoline raw material is at least 30 heavy %.
Described full distillation gasoline raw material is selected from one or more in the by-product gasoline of catalytic cracking gasoline, reformed gasoline, the by-product gasoline of preparing ethylene by steam cracking, coker gasoline and methanol-to-olefins.
Described full distillation gasoline raw material is catalytic cracking gasoline (DCC gasoline), and its maleic value is at least 3.0gI/100g.The measuring method of maleic value is oils iodine number and unsaturated hydrocarbons content measurement method (iodine-alcohol dissolution method), i.e. petroleum chemical industry standard SH/T 0234-92.
The first described hydrogenation unit arranges two reaction zones, and wherein the first reaction zone temperature of reaction is 160 ~ 260 DEG C, volume space velocity is 3 ~ 10h
-1, load hydrogenation in the first reaction zone and take off diene catalyzer, with diene content in cut in reducing; Second reaction zone temperature of reaction is 270 ~ 380 DEG C, volume space velocity is 2 ~ 6h
-1, in second reaction zone, load Hydrobon catalyst.Second reaction zone effluent sulphur content, nitrogen content are all less than 1 below μ g/g, and bromine valency is less than 0.5gBr/100g, meet the requirement of aromatic extraction unit to charging.Described other reaction conditions of the first hydrogenation unit is: hydrogen dividing potential drop 3.0 ~ 6.0MPa, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3.
Described hydrogenation takes off diene catalyzer and contains alumina supporter and load hydrogenation active metals component on this carrier, described hydrogenation active metals component is at least one metal component that is selected from VIII and the combination of at least one metal component being selected from VB race, with oxide basis and with described catalyzer for benchmark, the content of described group VIII metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-15 % by weight.
One or more in the metal component chosen from Fe of described VIII, cobalt, nickel, VB race metal component is selected from vanadium and/or niobium, with oxide basis and with described catalyzer for benchmark, the content of described group VIII metal component is the content of 0.5-8 % by weight, VB race metal component is 0.5-10 % by weight.
The metal component of described VIII is cobalt or nickel, and VB race metal component is vanadium, and with oxide basis and with described catalyzer for benchmark, described group VIII metal component concentration is the content of 0.5-3 % by weight, VB race metal component is 1-8 % by weight.
Described hydrogenation takes off diene catalyzer and has higher hydrogenation activity and selectivity to diolefine, can under the reaction conditions comparatively relaxed, diene hydrogenation in middle cut is removed, thus the problem of the too fast rise of subsequent reactor pressure drop can effectively avoiding the condensation of etidine hydrocarbon to cause, effectively extend the life cycle of Hydrobon catalyst in second reaction zone.
Described Hydrobon catalyst is supported non-precious metal catalyst, carrier is unformed aluminum oxide, active metal is the metal component being selected from group vib and/or group VIII, it consists of: with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 10 ~ 30 heavy %, and the content of nickel and/or cobalt is 0.01 ~ 5 heavy %, and surplus is aluminum oxide.
The second described hydrogenation unit arranges two reaction zones, and wherein the first reaction zone temperature of reaction is 160 ~ 260 DEG C, volume space velocity is 3 ~ 10h
-1, load hydrogenation protecting agent I, hydrogenation protecting agent II and hydrogenation protecting agent III in the first reaction zone successively, to reduce diene content in last running; Second reaction zone temperature of reaction is 240 ~ 340 DEG C, volume space velocity is 4 ~ 8h
-1, load catalyst for selectively hydrodesulfurizing in second reaction zone, selective hydrodesulfurization carried out to last running, namely only removes sulphur impurity possibly, unsaturated olefin, thus make the loss reduction of octane value.Described other reaction conditions of the second hydrogenation unit is: hydrogen dividing potential drop 1.0 ~ 2.5MPa, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3.
Described hydrogenation protecting agent I consists of, and with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 6 heavy %, and the content of nickel and/or cobalt is 0.2 ~ 3 heavy %, and surplus is aluminum oxide.
Described hydrogenation protecting agent II consists of, and with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 10 heavy %, and the content of nickel and/or cobalt is 0.5 ~ 3 heavy %, and surplus is aluminum oxide.
Described hydrogenation protecting agent III consists of, and with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 10 heavy %, and the content of nickel and/or cobalt is 2 ~ 6 heavy %, and surplus is aluminum oxide.
Three kinds of protective materials have same carrier and active metal, but active different, and shape is also different.By by three kinds of protective materials active and mate in shape, remove diene content in last running, avoid the raw material containing diolefine to enter high temperature main reactor, prolong operating period.
Described catalyst for selectively hydrodesulfurizing contains carrier, is selected from the hydrogenation active metals component of at least one group vib and at least one group VIII, be benchmark with oxide basis and with catalyzer, the content of group vib metal component is 1 ~ 20 % by weight, the content of group VIII metal component is 0.5 ~ 8 % by weight, the content of carrier is 72 ~ 98.5 % by weight, and wherein, described carrier is containing silica, take carrier as benchmark, described silica content is for being greater than 15 % by weight to 100 % by weight.Preferably described group vib metal component is molybdenum, and group VIII metal component is cobalt.
The pore volume of described carrier is 0.7 ~ 1ml/g, and specific surface area is 270 ~ 400m
2/ g.
Consisting of of preferred described catalyst for selectively hydrodesulfurizing: with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum is 5 ~ 13 heavy %, the content of cobalt is 1 ~ 5 heavy %, surplus is the carrier of silicon oxide-containing, and wherein the content of silicon oxide is 20 ~ 30 heavy %.
Advantage of the present invention is:
(1) improvement is optimized to the technological process of production, develop a kind of Technology that simultaneously can obtain aromatics extraction raw material and gasoline blending component, widen the source of aromatics extraction raw material, by method provided by the invention, can by high for maleic value content, the gasoline fraction that foreign matter content is high is changed, and the product sulphur content obtained, nitrogen content are all less than 1 below μ g/g, bromine valency is less than 0.5gBr/100g, meets the requirement of aromatic extraction unit to charging.
(2) gained gasoline blending component sulphur content is less than 10ppm, and gasoline products is compared with raw material, and its inductive phase improves greatly, and sulphur content significantly declines, aromaticity content, and especially benzene content declines.
(3) device can long period steady running, in the present invention, two hydrogenation unit arrange two reaction zones series connection, by removing diene in the first hydroconversion reaction zone, to delay second reaction zone Primary Catalysts bed top coking, assurance device can stablize long-term operation.
Accompanying drawing explanation
Fig. 1 is gasoline processing and treating method schematic flow sheet provided by the invention.
Fig. 2 is the first hydrogenation unit, the second hydrogenation unit schematic flow sheet.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.
As shown in Figure 1, gasoline processing and treating method flow process provided by the invention: from pipeline 1 gasoline stocks through interchanger 2 with from after the material-heat-exchanging of Fractionator Bottom, enter separation column 4 through pipeline 3.The light gasoline fraction obtained from fractionation tower top enters after water cooler 6 cooling through pipeline 5, surge tank 8 is entered through pipeline 7, the logistics flowed out bottom surge tank 8, wherein one stream passes via line 9 is back to fractionation tower top, another strand of stream passes via line 10 enters after alkali density desulfurization unit 11 carries out mercaptan removal process, goes out device through pipeline 12 as gasoline blending component.From separation column side line obtains, cut enters the first hydrogenation unit 14 through pipeline 13, takes off after diene, hydrogenating desulfurization, denitrogenation and olefin saturated through hydrogenation, liquid product II through pipeline 15 as aromatics extraction raw material.The heavy naphtha part obtained from fractionation column base enters after reboiler 17 heating through pipeline 16, Fractionator Bottom is returned through pipeline 18, a part enters second hydrogenation unit 20 through pipeline 19 with the charging from pipeline 1 after interchanger 2 heat exchange, take off after diene and selective hydrodesulfurization process through hydrogenation, liquid product III goes out device through pipeline 21 as gasoline blending component.
As shown in Figure 2, first hydrogenation unit, second hydrogenation unit flow process is described in detail as follows: from the raw material of pipeline 1 after pump 2 pressure-raising, mix with the hydrogen from pipeline 22, interchanger 4 is entered through pipeline 3, with from after the logistics heat exchange of pipeline 14, the first hydrogenator 6 is entered through pipeline 5, after removing diolefine wherein, interchanger 8 is entered through pipeline 7, the second reactor 12 is entered through pipeline 11 with from entering after process furnace 10 heats through pipeline 9 after the logistics heat exchange of pipeline 13, there is selective hydrodesulfurization in reactor 12 after, reaction product flows out through pipeline 13, with the logistics from pipeline 7 after interchanger 8 heat exchange, interchanger 4 is entered again through pipeline 14, with from after the logistics heat exchange of pipeline 3, high-pressure separator 16 is entered through pipeline 15, two bursts of logistics are divided in high-pressure separator 16, wherein one is hydrogen rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen simultaneously, ammonia and lighter hydrocarbons.Hydrogen rich stream enters circulating hydrogen compressor 20 through pipeline 19, and the gas part after compressor boosting uses as cold hydrogen through pipeline 21, and another part uses with raw material mixing Posterior circle through pipeline 22 after pipeline 23 mixes with the hydrogen make-up from pipeline 24.The isolated liquid phase stream of high-pressure separator enters follow-up stable system 18 through pipeline 17, and the discharge gas of gained is discharged through pipeline 24, and the lighter hydrocarbons of gained are discharged through pipeline 25, and the stream passes via line 26 of discharging bottom stable system 18 is extracted out, and it is final liquid-phase product.
The following examples to method provided by the invention, will be further described, but not thereby limiting the invention.
The hydrogenation that in embodiment, the first hydrogenation unit uses takes off diene catalyzer: carrier is aluminum oxide, and active metal consists of: vanadium oxide 4.5 % by weight, the heavy % of nickel oxide 1.3.
In embodiment, the trade names of the Hydrobon catalyst that the first hydrogenation unit uses are RS-1, for China Petrochemical Corp.'s catalyzer Chang Ling branch office produces.
With the gross weight of catalyzer for benchmark, and with oxide basis, the hydrogenation protecting agent A that in embodiment, the second hydrogenation unit is used consists of: nickel 0.5%, molybdenum 2.5%; Hydrogenation protecting agent B consists of: nickel 1.0%, molybdenum 5.5%; Hydrogenation protecting agent C consists of: nickel 2.5%, molybdenum 5.0%.Wherein the shape of hydrogenation protecting agent A and hydrogenation protecting agent B is Raschig ring, and the shape of hydrogenation protecting agent C is trifolium.
In embodiment, the second hydrogenation unit catalyst for selectively hydrodesulfurizing used preparation method is as follows:
Take silicon-dioxide (Qingdao Haiyang chemical industry special silica-gel company limited product, specific surface area 387m
2/ g, pore volume 0.99ml/g) bead 100g, this silicon oxide pellets is called carrier.The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier.First, take ammonium molybdate 18.1 grams, take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 18.0 grams, with 16 % by weight NH
3aqueous dissolution become 120 ml solns, with this solution impregnation 100 grams of carriers 4 hours, in 120 DEG C of dryings 4 hours, 420 DEG C of roastings 4 hours; Obtain catalyzer D.With oxide basis, in D, cobalt contents is 3.6%, molybdenum content is 12.0%.
Comparative example 1
With a kind of catalytic cracking gasoline for raw material I, character is as shown in table 1.Contacted with hydrofining agent RS-1 with hydrogen by stock oil I, carry out hydrofining reaction at 300 DEG C, reaction effluent enters stabilizer tower, by obtaining final liquid-phase product at the bottom of stabilizer tower after cooling, separation.Hydrogenation process conditions and product property as shown in table 2.
As can be seen from Table 2, hydrogenated products sulphur content < 1 μ g/g, nitrogen content < 1 μ g/g, bromine valency < 0.5gBr/100g, aromatics quality content 65.0%, aromatic saturation rate is 12.2%, and wherein the saturation exponent of benzene is 12.5%, the saturation exponent of toluene is 12.2%, and the saturation exponent of dimethylbenzene is 10.7%.
Embodiment 1
Raw materials used identical with comparative example, character is as shown in table 1.Stock oil I is cut into lighting end (C by first full cut
5and following), middle cut (C
6~ C
8) and last running (C
9and above cut), lighting end ratio is 6 heavy %, carry out alkali density mercaptan removal, process fore/aft properties in table 3, as can be seen from Table 3, after alkali density, lighting end sulphur content is less than 10 μ g/g, alkali density process lighting end composition is constant, and octane value does not lose, and can be used as premium blending component.
Middle cut ratio is 68 heavy %, itself and hydrogen enter the first reactor (is anti-) in the first hydrogenation unit and take off diene catalyst exposure with hydrogenation, diolefine is removed at 180 DEG C, its reaction effluent contacts with hydrofining agent RS-1 at the second reactor (two is anti-), hydrofining reaction is carried out at 280 DEG C, reaction effluent enters stabilizer tower, by obtaining final liquid-phase product at the bottom of stabilizer tower after cooling, separation.Hydrogenation process conditions and product property as shown in table 4.As can be seen from Table 4, cut product sulphur content < 1 μ g/g in hydrogenation, nitrogen content < 1 μ g/g, bromine valency < 0.5gBr/100g, aromatics quality content drops to 72.5% from 77.2, and aromatic saturation rate is only 6.1%, wherein the saturation exponent of benzene is 5.1%, the saturation exponent of toluene is 6.0%, and the saturation exponent of dimethylbenzene is 6.3%, can be used as good aromatics extraction raw material.
Last running ratio is 26 heavy %; it enters the first reactor (is anti-) with hydrogen in the second hydrogenation unit and contacts with hydrogenation protecting agent A, B, C successively; diolefine is removed at 180 DEG C; its reaction effluent contacts with catalyst for selectively hydrodesulfurizing D at the second reactor (two is anti-); selective hydrodesulfurization reaction is carried out at 280 DEG C; reaction effluent enters stabilizer tower, by obtaining final liquid-phase product at the bottom of stabilizer tower after cooling, separation.With the integer catalyzer of the first reactor for benchmark, described hydrogenation protecting agent A, hydrogenation protecting agent B and hydrogenation protecting agent C admission space percentage ratio are respectively 18 volume %, 36 volume % and 46 volume %.Hydrogenation process conditions and product property as shown in table 5.As can be seen from Table 5, hydrogenation last running product sulphur content < 10 μ g/g, loss of octane number 0.2 unit, can be used as high octane value gasoline blending component, and not containing benzene.
Embodiment 2
With a kind of catalytic cracking gasoline for raw material II, character is as shown in table 1.Stock oil II is cut into lighting end (C by first full cut
5and following), middle cut (C
6~ C
8) and last running (C
9and above cut), lighting end ratio is 5 heavy %, carry out alkali density mercaptan removal, process fore/aft properties in table 3, as can be seen from Table 3, after alkali density, lighting end sulphur content is less than 10 μ g/g, alkali density process lighting end composition is constant, and octane value does not lose, and can be used as premium blending component.
Middle cut ratio is 70 heavy %, itself and hydrogen enter the first reactor (is anti-) in the first hydrogenation unit and take off diene catalyst exposure with hydrogenation, diolefine is removed at 180 DEG C, its reaction effluent contacts with hydrofining agent RS-1 at the second reactor (two is anti-), hydrofining reaction is carried out at 280 DEG C, reaction effluent enters stabilizer tower, by obtaining final liquid-phase product at the bottom of stabilizer tower after cooling, separation.Hydrogenation process conditions and product property as shown in table 4.As can be seen from Table 4, cut product sulphur content < 1 μ g/g in hydrogenation, nitrogen content < 1 μ g/g, bromine valency < 0.5gBr/100g, aromatics quality content drops to 74.0% from 78.8, and aromatic saturation rate is only 6.1%, wherein the saturation exponent of benzene is 4.8%, the saturation exponent of toluene is 6.2%, and the saturation exponent of dimethylbenzene is 6.3%, can be used as good aromatics extraction raw material.
Last running ratio is 25 heavy %; it enters the first reactor (is anti-) with hydrogen in the second hydrogenation unit and contacts with hydrogenation protecting agent A, B, C successively; diolefine is removed at 180 DEG C; its reaction effluent contacts with catalyst for selectively hydrodesulfurizing D at the second reactor (two is anti-); selective hydrodesulfurization reaction is carried out at 280 DEG C; reaction effluent enters stabilizer tower, by obtaining final liquid-phase product at the bottom of stabilizer tower after cooling, separation.With the integer catalyzer of the first reactor for benchmark, described hydrogenation protecting agent A, hydrogenation protecting agent B and hydrogenation protecting agent C admission space percentage ratio are respectively 18 volume %, 36 volume % and 46 volume %.Hydrogenation process conditions and product property as shown in table 5.As can be seen from Table 5, hydrogenated products sulphur content < 10 μ g/g, loss of octane number 0.3 unit, can be used as high octane value gasoline blending component, and not containing benzene.
Table 1
| Material name | I | II |
| Density (20 DEG C), g/cm 3 | 0.8250 | 0.8320 |
| Sulphur, μ g/g | 100 | 300 |
| Nitrogen, μ g/g | 55 | 72 |
| Bromine valency, gBr/100g | 40 | 28 |
| Hydro carbons quality forms, % | ||
| Alkane | 7.5 | 11.0 |
| Alkene | 18.0 | 13.0 |
| Aromatic hydrocarbons | 74.5 | 76.0 |
| Benzene | 4.0 | 4.2 |
| Toluene | 20.5 | 21.0 |
| Dimethylbenzene | 28.0 | 28.2 |
| Maleic value, gI/100g | 3.5 | 3.0 |
| Boiling range (ASTM D-86), DEG C | 40～185 | 42～190 |
Table 2
| Hydrogen dividing potential drop, MPa | 3.2 |
| Temperature of reaction, DEG C one anti- | - |
| Two is anti- | 300 |
| Hydrogen-oil ratio, Nm 3/m 3 | 500 |
| LHSV，h -1One is anti- | - |
| Two is anti- | 2.0 |
| Product property | |
| Density (20 DEG C), g/cm3 | 0.8130 |
| Sulphur content, μ g/g | ＜1 |
| Nitrogen content, μ g/g | ＜1 |
| Bromine valency, gBr/100g | ＜0.5 |
| Hydro carbons quality forms, % | |
| Alkane | 35.0 |
| Aromatic hydrocarbons | 65.0 |
| Benzene | 3.5 |
| Toluene | 18.0 |
| Dimethylbenzene | 25.0 |
| Boiling range (ASTM D-86), DEG C | 42～185 |
Table 3
Table 4
Table 5
Claims (12)
1. a gasoline processing and treating method, comprising:
(1) full distillation gasoline raw material is fractionated into three strands of cuts through separation column, and obtaining lighting end LCN from separation column top is C
5and following component, gained lighting end removes mercaptan sulfur wherein through alkali density, obtains liquid product I, and gained liquid product I is gasoline blending component;
(2) in the middle part of separation column, C is obtained
6~ C
8middle cut MCN, in gained, cut processes through the first hydrogenation unit, obtains liquid product II, and gained liquid product II is qualified aromatics extraction raw material; The first described hydrogenation unit arranges two reaction zones, and wherein the first reaction zone temperature of reaction is 160 ~ 260 DEG C, volume space velocity is 3 ~ 10h
-1, load hydrogenation in the first reaction zone and take off diene catalyzer; Second reaction zone temperature of reaction is 270 ~ 380 DEG C, volume space velocity is 2 ~ 6h
-1, load Hydrobon catalyst in second reaction zone, described other reaction conditions of the first hydrogenation unit is: hydrogen dividing potential drop 3.0 ~ 6.0MPa, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
(3) obtaining last running HCN from fractionation column base is C
9and above component, gained last running processes through the second hydrogenation unit, obtains liquid product III, and the liquid product III of gained is gasoline blending component; The second described hydrogenation unit arranges two reaction zones, and wherein the first reaction zone temperature of reaction is 160 ~ 260 DEG C, volume space velocity is 3 ~ 10h
-1, in the first reaction zone, load hydrogenation protecting agent I, hydrogenation protecting agent II and hydrogenation protecting agent III successively; Second reaction zone temperature of reaction is 240 ~ 340 DEG C, volume space velocity is 4 ~ 8h
-1, load catalyst for selectively hydrodesulfurizing in second reaction zone, described other reaction conditions of the second hydrogenation unit is: hydrogen dividing potential drop 1.0 ~ 2.5MPa, hydrogen to oil volume ratio 200 ~ 1000Nm
3/ m
3;
The aromaticity content of described full distillation gasoline raw material is at least 30 heavy %.
2. in accordance with the method for claim 1, it is characterized in that, described full distillation gasoline raw material is selected from one or more in the by-product gasoline of catalytic cracking gasoline, reformed gasoline, the by-product gasoline of preparing ethylene by steam cracking, coker gasoline and methanol-to-olefins.
3. in accordance with the method for claim 1, it is characterized in that, described full distillation gasoline raw material is catalytic cracking gasoline, and its maleic value is at least 3.0gI/100g.
4. in accordance with the method for claim 1, it is characterized in that, described hydrogenation takes off diene catalyzer and contains alumina supporter and load hydrogenation active metals component on this carrier, described hydrogenation active metals component is at least one metal component that is selected from VIII and the combination of at least one metal component being selected from VB race, with oxide basis and with described catalyzer for benchmark, the content of described group VIII metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-15 % by weight.
5. in accordance with the method for claim 4, it is characterized in that, one or more in the metal component chosen from Fe of described VIII, cobalt, nickel, VB race metal component is selected from vanadium and/or niobium, with oxide basis and with described catalyzer for benchmark, the content of described group VIII metal component is the content of 0.5-8 % by weight, VB race metal component is 0.5-10 % by weight.
6. in accordance with the method for claim 5, it is characterized in that, the metal component of described VIII is cobalt or nickel, VB race metal component is vanadium, with oxide basis and with described catalyzer for benchmark, described group VIII metal component concentration is the content of 0.5-3 % by weight, VB race metal component is 1-8 % by weight.
7. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst is supported non-precious metal catalyst, carrier is unformed aluminum oxide, and active metal is the metal component being selected from group vib and/or group VIII, and it consists of: with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 10 ~ 30 heavy %, and the content of nickel and/or cobalt is 0.01 ~ 5 heavy %, and surplus is aluminum oxide.
8. in accordance with the method for claim 1, it is characterized in that, described hydrogenation protecting agent I consists of; with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 6 heavy %; the content of nickel and/or cobalt is 0.2 ~ 3 heavy %, and surplus is aluminum oxide.
Described hydrogenation protecting agent II consists of, and with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 10 heavy %, and the content of nickel and/or cobalt is 0.5 ~ 3 heavy %, and surplus is aluminum oxide.
Described hydrogenation protecting agent III consists of, and with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum and/or tungsten is 2 ~ 10 heavy %, and the content of nickel and/or cobalt is 2 ~ 6 heavy %, and surplus is aluminum oxide.
9. in accordance with the method for claim 1, it is characterized in that, described catalyst for selectively hydrodesulfurizing contains carrier, is selected from the hydrogenation active metals component of at least one group vib and at least one group VIII, be benchmark with oxide basis and with catalyzer, the content of group vib metal component is 1 ~ 20 % by weight, the content of group VIII metal component is 0.5 ~ 8 % by weight, the content of carrier is 72 ~ 98.5 % by weight, wherein, described carrier is containing silica, take carrier as benchmark, described silica content is for being greater than 15 % by weight to 100 % by weight.
10. in accordance with the method for claim 9, it is characterized in that, described group vib metal component is molybdenum, and group VIII metal component is cobalt.
11. in accordance with the method for claim 9, it is characterized in that, the pore volume of described carrier is 0.7 ~ 1ml/g, and specific surface area is 270 ~ 400m
2/ g.
12. in accordance with the method for claim 9, it is characterized in that, consisting of of described catalyst for selectively hydrodesulfurizing: with the gross weight of catalyzer for benchmark, and with oxide basis, the content of molybdenum is 5 ~ 13 heavy %, the content of cobalt is 1 ~ 5 heavy %, and surplus is the carrier of silicon oxide-containing, and wherein the content of silicon oxide is 20 ~ 30 heavy %.
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| CN101306371A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
| CN101724456A (en) * | 2008-10-23 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for producing aromatics extraction raw material |
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| CN101306371A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
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