CN1958740A - Hydrogenization method for deep desulfurization of gasoline, and lowering olefin - Google Patents
Hydrogenization method for deep desulfurization of gasoline, and lowering olefin Download PDFInfo
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Abstract
This invention discloses a method for deeply desulfurizing and hydrogenating gasoline. The method comprises: (1) performing selective hydrogenation and desulfurization on gasoline raw material in the first hydrogenation reactor, mixing the effluent with that of the second hydrogenation reactor, cooling and separating in a fractionation column to obtain different fractions; (2) introducing the light fraction into the product tank; (3) returning part of medium fraction to the first hydrogenation reactor; (4) introducing the rest medium fraction into the product tank; (5) introducing part of all heavy fraction into the second hydrogenation reactor, performing hydrogenation, desulfurization and octane number recovery reactions, and introducing residual heavy fraction into the product tank. The method can be used to treat high-sulfur and high-olefin catalytic cracking gasoline, and has a desulfurization rate above 90 wt. % and a gasoline yield above 95 wt. %. Although the olefin content is reduced by 15%, the octane number loss is very low. The method can supply high operation flexibility for producing clean gasoline.
Description
Technical field
The invention belongs in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, be a kind of deep desulfurization of gasoline, fall the method for hydrotreating of alkene.
Background technology
As everyone knows, atmospheric pollution brings serious environmental problem, and a large amount of engine emissions is to cause one of air-polluting major reason.In recent years, be the protection environment, countries in the world have proposed stricter restriction to the composition of motor spirit, to reduce emission of harmful substances.Wherein more harsh to the restriction of sulphur in the gasoline and olefin(e) centent.China's motor spirit standard also just progressively walks with world's pace: on July 1st, 2005, begin to carry out Europe II emission standard in the whole nation; To carry out Europe III emission standard in the whole nation in 2008; Beijing has taken the lead in coming into effect on July 1st, 2005 Europe III emission standard.Contrast China's motor spirit new standard and Europe III emission standard can find that the subject matter of China's quality of gasoline is sulphur content and olefin(e) centent height.The major cause of sulfur in gasoline and olefin(e) centent superelevation is because the ratio that catalytically cracked gasoline accounts in the gasoline pool is too high, is main blend component in the gasoline mediation pond at China's catalytically cracked gasoline, accounts for more than the 80 heavy %.And, along with the raw material of catalyzed cracking processing develops to the heaviness direction, cause sulphur content and olefin(e) centent in the catalytically cracked gasoline further to increase.Therefore reduce that sulphur and olefin(e) centent will become the main path that motor spirit cleans in the catalytically cracked gasoline.
The sulphur content that reduces catalytically cracked gasoline can adopt hydrotreating of FCC feedstock or two kinds of technical schemes of catalytic gasoline hydrogenation desulfurization usually.The hydrotreating of FCC feedstock device need all be operated under the exacting terms at temperature and pressure very much, and treatment capacity is big, and the hydrogen consumption is big, and this will improve the investment of device, and this technical scheme is limited to the olefin(e) centent effect that reduces catalytically cracked gasoline.Though traditional catalytic gasoline hydrogenation desulfurization technology can reduce sulphur content and olefin(e) centent significantly,, cause the gasoline products loss of octane number very big because it is saturated in a large number to have high-octane olefin component in the hydrogenation process.Olefin(e) centent height in special China catalytically cracked gasoline, generally more than 40 volume %, aromaticity content is low, be 15～25 volume %, so loss of octane number is bigger.
EP0940464 discloses a kind of processing method of catalytically cracked gasoline desulfurization.This method adopts the conventional fixed-bed reactor with two beds, with catalytically cracked gasoline cut into gently, in, weigh three kinds of different cuts.Last running is in the first bed hydrogenating desulfurization, and its resultant of reaction and middle runnings enter second bed and carry out hydrogenating desulfurization after mixes in the first bed exit.This method provides a kind of method that reduces sulphur content in the catalytically cracked gasoline, but hydrogenation process alkene saturation exponent is too high, and loss of octane number is excessive.
US6495030 discloses a kind of processing method of catalytically cracked gasoline desulfurization.This method has two catalytic distillation reactors at least, and first catalytic distillation reactor loads thioetherification catalyst at rectifying section, and second catalytic distillation reactor loads Hydrobon catalyst at rectifying section.The catalytically cracked gasoline raw material is fractionated into earlier lighting end and heavier cut in the first catalytic distillation reactor, when thioetherification catalyst is passed through in lighting end, contained mercaptan sulfur is transformed the sulfide of attaching most importance to, and with going out to enter the second catalytic distillation reactor than last running from tower bottom flow.Logistics is fractionated into middle runnings and last running in the second catalytic distillation reactor, middle runnings is carried out hydrogenating desulfurization by rectifying section, last running goes out to enter from tower bottom flow carries out desulfurization the 3rd catalytic distillation tower or the hydrodesulphurisatioreactors reactors, after will handling at last light, in, last running mixes and obtains full cut product.This method only provides a kind of method that reduces sulphur content in the catalytically cracked gasoline, do not consider that hydrogenation process alkene is saturated after, the problem of loss of octane number.And the flow process complexity, operation inconvenience.
This method of US5290427 provides a kind of processing method that improves the catalytically cracked gasoline quality.This method is cut into a plurality of cuts with catalytically cracked gasoline, according to the cut boiling range from high to low, enters first hydrogenator successively from top to bottom and carries out hydrogenating desulfurization, and its reaction effluent enters second hydrogenator and carries out octane value recovering reaction then.Anti-be whole gasoline fractions owing to enter two, octane value recovering catalyst is an acidic catalyst of ZSM-5 Zeolite support, therefore have side reaction such as cracking and exist, so the present invention exists yield of gasoline low, the problem that the hydrogen consumption is big.
At western developed country catalytically cracked gasolines such as USA and Europe proportion in whole gasoline pool is about 30 heavy %, and olefin(e) centent is low, is generally about 25 volume %, and aromaticity content is 25～35 volume %.Therefore, the catalytic gasoline hydrogenation treatment technology of external exploitation only has result preferably to handling the lower raw material of olefin(e) centent, is used to handle the catalytically cracked gasoline of domestic high olefin content, and loss of octane number is bigger.
Summary of the invention
The objective of the invention is the method for hydrotreating that a kind of deep desulfurization of gasoline is provided on the basis of existing technology, falls alkene.
Method provided by the invention comprises: gasoline stocks with enter first hydrotreating reactor after hydrogen mixes, contact with hydrotreating catalyst, carry out the selective hydrodesulfurization reaction.The reaction effluent of first hydrotreating reactor cools off, separates with after the reaction effluent of second hydrotreating reactor mixes, and isolated hydrogen-rich gas recycles, and isolated liquid phase stream enters separation column.The liquid phase stream that enters separation column is cut into light gasoline fraction, middle gasoline fraction and heavy naphtha; Light gasoline fraction is extracted out and is entered the product jar; Optional middle gasoline fraction returns with gasoline stocks and is mixed into first hydrotreating reactor, and remaining middle gasoline fraction is extracted out and entered the product jar; All or part of second hydrotreating reactor that enters of heavy naphtha carries out the reaction of hydrogenating desulfurization and octane value recovering, and remaining heavy naphtha enters the product jar.Enter and obtain gasoline products after the light gasoline fraction in the product jar, middle gasoline fraction and heavy naphtha mix.
The present invention can handle the catalytically cracked gasoline of high-sulfur high olefin, and desulfurization degree reaches more than the 90 heavy %, and yield of gasoline is up to more than the 95 heavy %, although olefin(e) centent descends about 15 percentage points, loss of octane number is little.The present invention can be refinery's production clean gasoline more flexibility of operation is provided.
Description of drawings
Accompanying drawing is deep desulfurization of gasoline provided by the invention, fall the method for hydrotreating schematic flow sheet of alkene.
Embodiment
The used gasoline stocks of the present invention is catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline wherein any or several mixing oils.The working ability of China's catalytic cracking accounts for the large percentage of secondary processing, and catalytically cracked gasoline is the main source of commercial gasoline, and other gasoline component is few, the mediation ability.Various blend components from gasoline pool, sulphur in the catalytically cracked gasoline and alkene are sulphur and alkene main sources in the gasoline pool; Especially along with processing import high-sulfur crude oil amount constantly rises, and the raw material of catalyzed cracking processing is to the continuous development of heaviness direction, and sulphur content, olefin(e) centent will continue to maintain higher level in the catalytically cracked gasoline.Therefore reducing sulphur and olefin(e) centent in the catalytically cracked gasoline will become the main path of sulphur and olefin(e) centent in the control motor spirit.
Catalytically cracked gasoline can be divided into normal paraffin (n-P), isoparaffin (i-P), naphthenic hydrocarbon (N), alkene (O) and five components of aromatic hydrocarbons (A) from forming, and wherein the octane value of normal paraffin is low, and the long more octane value of carbochain is low more.The octane value of isoparaffin is higher, and the collateralization degree is high more, it is high more to arrange compact more octane value.Alkene, aromatic hydrocarbons are high-octane number components, with the octane value of aromatic hydrocarbons for the highest.China's catalytically cracked gasoline presents the feature of high olefin, low arene content, and about 40～50 volume %, aromaticity content is less than 20 volume % usually for olefin(e) centent.Alkene becomes the important component in China catalytically cracked gasoline gasoline octane rating source, thereby the variation of olefin(e) centent is very big to the influence of catalytically cracked gasoline octane value.Alkene distributes in the catalytically cracked gasoline increases along with the boiling point lowering of cut; And sulphur mainly concentrates in the heavy naphtha, and based on thiophene-type sulfide, mercaptan sulfur mainly concentrates in the light gasoline fraction.
Method provided by the invention is so concrete enforcement:
Gasoline stocks with enter first hydrotreating reactor after hydrogen mixes, contact with hydrotreating catalyst, at hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, volume space velocity 0.5～4.0h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3Reaction conditions under carry out selective hydrodesulfurization reaction.
Hydrotreating catalyst in first hydrotreating reactor is group vib and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.Preferred hydrotreating catalyst contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, and the content of described molybdenum and/or tungsten is 3～20 heavy %, and the content of nickel and/or cobalt is 0.3～2 heavy %, and the auxiliary agent Mg content is 1～7 heavy %, and described zeolite content is 5～60 heavy %.The selectivity of preferred hydrotreating catalyst hydrogenating desulfurization is very high, has avoided promptly that alkene has been removed mercaptan and other sulfide that easily removes in the gasoline stocks again by saturated in a large number in the gasoline stocks.
The reaction effluent of first hydrotreating reactor is with after the reaction effluent of second hydrotreating reactor mixes, cool off, separate through interchanger, high-pressure separator and light pressure separator successively, isolated hydrogen-rich gas recycles as recycle hydrogen, and isolated liquid phase stream enters separation column.
The regularity of distribution according to sulphur and alkene in the liquid phase stream that enters separation column is cut into different cuts, then different fractions is carried out different processing.The liquid phase stream that enters separation column locates to be cut into light gasoline fraction, middle gasoline fraction and heavy naphtha at 60～80 ℃ and 100 ℃～140 ℃ respectively.Olefin(e) centent height in the light gasoline fraction, sulphur content are lower, so directly extract the product jar out.Middle gasoline fraction requires directly to extract out to enter the product jar as the product blend component according to the product sulphur content; Also can be all or part of with enter first hydrotreating reactor after gasoline stocks mixes, carry out further hydrogenating desulfurization, rest parts is as the product blend component.Olefin(e) centent is low in the heavy naphtha, sulphur content is high, heavy naphtha all or part of (heavy naphtha of the heavy % in 100 heavy %～50) enters second hydrotreating reactor, under the effect of hydrogen and hydrogenation catalyst, at hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, volume space velocity 0.5～4.0h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3Reaction conditions carry out hydrogenating desulfurization, fall the reaction of alkene and octane value recovering; Remaining heavy naphtha enters the product jar, and obtains gasoline products after the light gasoline fraction that enters the product jar, middle gasoline fraction mix.
The hydrogenation catalyst that loads in second hydrotreating reactor is the independent filling of the combination loading or the catalyst for hydro-upgrading of Hydrobon catalyst and octane value recovering catalyst.
Hydrobon catalyst is group vib and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.Octane value recovering catalyst is a kind of catalyzer by zeolite and the carrier loaded non-noble metal components of aluminum oxide composite molding, metal component is molybdenum and/or the tungsten that is selected from group VIII cobalt and/or nickel, group vib, and described zeolite is one or more the mixture that is selected among faujusite, Beta zeolite, ZSM-5 zeolite and the SAPO-11.
Catalyst for hydro-upgrading is group vib and/or the group VIII non-precious metal catalyst that loads on the Zeolite support, catalyzer contains the zeolite of one or more modifications, one or more group vib and/or group VIII base metal and alumina host, and described zeolite is one or more the mixture in HY zeolite, Beta zeolite and the ZSM-5 zeolite.
Advantage of the present invention: the present invention has adaptability preferably for higher these characteristics of domestic catalytic cracking gasoline olefine content, can be refinery's production clean gasoline more flexibility of operation is provided, can effectively solve domestic catalytically cracked gasoline sulphur and olefin(e) centent problem, and can reduce amplitude according to product requirement flexible desulfurization depth and alkene.
The present invention has certain flexibility of operation, regulates by flexible and changeable operation to reach different quality product requirements.As quality index according to stock oil character such as olefin(e) centent, sulphur content, boiling range scope etc. and product, but the reaction severity of flexible reactor, also can adjust separation column outlet material ratio, or the ratio of distillation gasoline and/or last running gasoline Returning reactor in regulating.
The present invention can handle the catalytically cracked gasoline of high-sulfur high olefin, and desulfurization degree reaches more than the 90 heavy %, and yield of gasoline is up to more than the 95 heavy %, although olefin(e) centent descends about 15 percentage points, loss of octane number is little.The present invention can satisfy the needs that the refinery produces clean gasoline.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is deep desulfurization of gasoline provided by the invention, fall the method for hydrotreating synoptic diagram of alkene.
Deep desulfurization of gasoline provided by the invention, the method for hydrotreating technical process of falling alkene are described in detail as follows: the gasoline stocks from pipeline 1 is extracted out by pipeline 3 after feedstock pump 2 boosts, after hydrogen stream from pipeline 13 mixes, enter first hydrotreating reactor 4.By contacting, under appropriate reaction conditions, carry out the selective hydrodesulfurization reaction at this with hydrotreating catalyst.With after reaction effluent from second hydrotreating reactor 7 of pipeline 8 mixes, enter high-pressure separator 9 through the reaction effluent of first hydrotreating reactor 4 that pipeline 5 is extracted out, carry out gas-liquid separation by flash distillation.The hydrogen rich stream at high-pressure separator 9 tops enters circulating hydrogen compressor 11 by pipeline 10, after circulating hydrogen compressor 11 superchargings, with be divided into two-way after new hydrogen from pipeline 12 mixes, one the tunnel mixes with gasoline stocks from pipeline 3 through pipeline 13, and mix with heavy naphtha from pipeline 27 through pipeline 14 on another road.The liquid phase stream of high-pressure separator 9 bottoms enters light pressure separator 16 through pipeline 15, carries out further gas-liquid separation at this, and isolated gas is extracted out through pipeline 17; The liquid of light pressure separator bottom enters separation column 19 through pipeline 18.The liquid phase stream that enters separation column 19 is after fractionation, and the light hydrocarbon gas of fractionation cat head is extracted out by pipeline 20, and the light gasoline fraction that cuts into, middle gasoline fraction and heavy naphtha are extracted out through pipeline 21,23,26 successively.Light gasoline fraction enters product jar 22 through pipeline 21.In gasoline fraction after pipeline 23 is extracted out, be divided into two-way, the one tunnel enters product jar 22 through pipeline 24; Mix with gasoline stocks from pipeline 1 through pipeline 25 on another road.Heavy naphtha is divided into two-way after pipeline 26 is extracted out, the one tunnel enters product jar 22 through pipeline 28; Another road through pipeline 27 with after hydrogen stream from pipeline 14 mixes, heat up through process furnace 6, entering second hydrotreating reactor 7 then contacts with hydrogenation catalyst, carry out hydrogenating desulfurization, fall alkene and octane value recovering reaction, the reaction effluent of second hydrotreating reactor 7 is extracted out through pipeline 8, and mixes with reaction effluent from first hydrotreating reactor 4 of pipeline 5.Entering becomes gasoline products after the light gasoline fraction of product jar 22, middle gasoline fraction and heavy naphtha mix, and by pipeline 29 withdrawing devices.
The following examples will give further instruction to present method, but therefore not limit present method.The trade names of employed hydrotreating catalyst C are CH-18 in the Comparative Examples, the trade names of the hydrotreating catalyst D that uses among the embodiment are RSDS-1, the trade names of Hydrobon catalyst C are CH-18, the trade names of octane value recovering catalyst E are RIDOS-1, and these catalyzer are produced by Sinopec catalyzer branch office Chang Ling catalyst plant.
Catalyst for hydro-upgrading F is the prepared in laboratory catalyzer, and the preparation method is as follows:
1. pseudo-boehmite (Shandong Aluminum Plant's production) and ZSM-5 zeolite (Catalyst Factory, Nankai Univ production) are mixed, add water after mix pinch, extrusion, make three leaf stripe shapes.Extrudate was descended dry 4 hours at 130 ℃,, make the alumina supporter that contains the ZSM-5 zeolite again in 600 ℃ of following roastings 4 hours.
2. will contain in the aqueous solution that immerses the Xiao Suangu (Beijing Chemical Plant) for preparing and ammonium molybdate (Beijing Chemical Plant) in the alumina supporter of ZSM-5 zeolite, flood 4 hours, 120 ℃ of dryings 4 hours, obtain catalyzer F in 4 hours then 550 ℃ of following roastings.
The composition of obtained catalyzer F: in oxide compound and with the total catalyst weight is benchmark, cobalt 2.7 heavy %, molybdenum 10.3 heavy %, ZSM-5 zeolite 55 heavy %, aluminum oxide 32 heavy %.
Comparative Examples
With a kind of catalytically cracked gasoline is stock oil A, and its stock oil character is as shown in table 1.This gasoline stocks and hydrogen and hydrotreating catalyst C carry out the promptly conventional hydrofining of single hop, and its reaction conditions and gasoline products character are as shown in table 2.As can be seen from Table 2, the sulphur content of gasoline products is 260ppm, and desulfurization degree only is 8.5 heavy %.
Embodiment 1
With a kind of catalytically cracked gasoline is stock oil A, and its stock oil character is as shown in table 1.Stock oil A contacts with hydrotreating catalyst D in first hydrotreating reactor and carries out the selective hydrodesulfurization reaction, its reaction effluent is with after the effluent of second hydrotreating reactor mixes, enter separation column through cooling, separation, be cut into light gasoline fraction (boiling range C
5～75 ℃), middle gasoline fraction (75 ℃～110 ℃ of boiling ranges) and heavy naphtha (110 ℃～195 ℃ of boiling ranges).The heavy naphtha of 60 heavy % enters second hydrotreating reactor, contacts with octane value recovering catalyst E with Hydrobon catalyst C successively, carries out the reaction of hydrogenating desulfurization and octane value recovering.The heavy naphtha of light gasoline fraction, middle gasoline fraction and 40 heavy % directly enters the product jar to be mixed, and extracts gasoline products out by the product jar.Concrete reaction conditions and product property are as shown in table 3, and the sulphur content of product is 27ppm as can be seen from Table 3, and desulfurization degree is 90.5 heavy %, and olefin(e) centent is 31.7 volume %, and anti-knock index only loses 1.5, and product yield is up to 95.12 heavy %.
Embodiment 2
With a kind of catalytically cracked gasoline is stock oil B, and its stock oil character is as shown in table 1.Stock oil B contacts with hydrotreating catalyst D in first hydrotreating reactor and carries out the selective hydrodesulfurization reaction, its reaction effluent is with after the effluent of second hydrotreating reactor mixes, enter separation column through cooling, separation, be cut into light gasoline fraction (boiling range C
5～70 ℃), middle gasoline fraction (70 ℃～105 ℃ of boiling ranges) and heavy naphtha (105 ℃～180 ℃ of boiling ranges).The heavy naphtha of 70 heavy % enters second hydrotreating reactor, contacts with octane value recovering catalyst E with Hydrobon catalyst C successively, carries out the reaction of hydrogenating desulfurization and octane value recovering.The heavy naphtha of light gasoline fraction, middle gasoline fraction and 30 heavy % directly enters the product jar to be mixed, and extracts gasoline products out by the product jar.Concrete reaction conditions and product property are as shown in table 3, and the sulphur content of product is 135ppm as can be seen from Table 3, and desulfurization degree is 90.4 heavy %, and olefin(e) centent is 29.0 volume %, and anti-knock index only loses 1.0, and product yield is up to 95.08 heavy %.
Embodiment 3
With a kind of catalytically cracked gasoline is stock oil C, and its stock oil character is as shown in table 1.Stock oil A contacts with hydrotreating catalyst D in first hydrotreating reactor and carries out the selective hydrodesulfurization reaction, its reaction effluent is with after the effluent of second hydrotreating reactor mixes, enter separation column through cooling, separation, be cut into light gasoline fraction (boiling range C
5～70 ℃), middle gasoline fraction (70 ℃～110 ℃ of boiling ranges) and heavy naphtha (110 ℃～190 ℃ of boiling ranges).The heavy naphtha of 70 heavy % enters second hydrotreating reactor, and F contacts with catalyst for hydro-upgrading, carries out the reaction of hydrogenating desulfurization and octane value recovering.The heavy naphtha of light gasoline fraction, middle gasoline fraction and 30 heavy % directly enters the product jar to be mixed, and extracts gasoline products out by the product jar.Concrete reaction conditions and product property are as shown in table 3, and the sulphur content of product is 127ppm as can be seen from Table 3, and desulfurization degree is that 90.2 heavy % olefin(e) centents are 27.7 volume %, and anti-knock index only loses 1.2, and product yield is up to 95.30 heavy %.
Table 1
| Material name | A | B | C |
| Density (20 ℃), g/cm 3 | 0.7220 | 0.7100 | 0.7150 |
| Sulphur, ppm | 284 | 1400 | 1300 |
| Olefin(e) centent, volume % | 47.1 | 43.4 | 40.0 |
| Boiling range (ASTM D-86), ℃ | |||
| Initial boiling point | 36 | 36 | 40 |
| 10％ | 53 | 44 | 48 |
| 50％ | 94 | 80 | 96 |
| Do | 195 | 180 | 190 |
| Anti-knock index | 85.0 | 85.5 | 84.5 |
Table 2
| Comparative Examples | |
| Stock oil | A |
| Catalyzer | C |
| Reaction conditions | |
| Temperature of reaction, ℃ | 200 |
| The hydrogen dividing potential drop, MPa | 3.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 |
| Volume space velocity, h -1 | 4.0 |
| Product property | |
| Density (20 ℃), g/cm 3 | 0.7200 |
| S，ppm | 260 |
| Olefin(e) centent, volume % | 30.8 |
| Anti-knock index | 80.7 |
| Desulfurization degree, heavy % | 8.5 |
| The anti-knock index loss | 4.3 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Stock oil | A | B | C |
| Reaction conditions | |||
| First hydrotreating reactor | |||
| Catalyzer | D | D | D |
| Temperature of reaction, ℃ | 270 | 280 | 280 |
| The hydrogen dividing potential drop, MPa | 3.2 | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 | 500 | 500 |
| Volume space velocity, h -1 | 4.0 | 4.0 | 4.0 |
| Second hydrotreating reactor | |||
| Catalyzer | C+E | C+E | F |
| Temperature of reaction, ℃ | 370 | 380 | 380 |
| The hydrogen dividing potential drop, MPa | 3.2 | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 | 500 | 500 |
| Volume space velocity, h -1 | 0.8 | 0.8 | 0.8 |
| Product property | |||
| Density (20 ℃), g/cm 3 | 0.7157 | 0.7100 | 0.7100 |
| S，ppm | 27 | 135 | 127 |
| Olefin(e) centent, volume % | 31.7 | 29.0 | 27.7 |
| Anti-knock index | 83.5 | 84.5 | 83.3 |
| Desulfurization degree, heavy % | 90.5 | 90.4 | 90.2 |
| The anti-knock index loss | 1.5 | 1.0 | 1.2 |
| Product yield, heavy % | 95.12 | 95.08 | 95.30 |
Claims (10)
1, a kind of deep desulfurization of gasoline, the method for hydrotreating of alkene falls, comprise the following steps:
(1) gasoline stocks with enter first hydrotreating reactor after hydrogen mixes, contact with hydrotreating catalyst, carry out the selective hydrodesulfurization reaction;
The reaction effluent of (2) first hydrotreating reactors cools off, separates with after the reaction effluent of second hydrotreating reactor mixes, and isolated hydrogen-rich gas recycles, and isolated liquid phase stream enters separation column;
(3) liquid phase stream that enters separation column is cut into light gasoline fraction, middle gasoline fraction and heavy naphtha; Light gasoline fraction is extracted out and is entered the product jar; Optional middle gasoline fraction returns with gasoline stocks and is mixed into first hydrotreating reactor, and remaining middle gasoline fraction is extracted out and entered the product jar; All or part of second hydrotreating reactor that enters of heavy naphtha carries out the reaction of hydrogenating desulfurization and octane value recovering, and remaining heavy naphtha enters the product jar;
(4) enter and obtain gasoline products after the light gasoline fraction in the product jar, middle gasoline fraction and heavy naphtha mix.
2, in accordance with the method for claim 1, it is characterized in that described gasoline stocks is catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline wherein any or several mixing oils.
3, in accordance with the method for claim 1, it is characterized in that the described liquid phase stream that enters separation column locates to be cut into light gasoline fraction, middle gasoline fraction and heavy naphtha at 60～80 ℃ and 100 ℃～140 ℃ respectively.
4, in accordance with the method for claim 1, the reaction conditions that it is characterized in that described first hydrotreating reactor and second hydrotreating reactor is: hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, volume space velocity 0.5～4.0h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3
5, in accordance with the method for claim 1, it is characterized in that the hydrotreating catalyst in described first hydrotreating reactor is group vib and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.
6,, it is characterized in that described hydrotreating catalyst contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite according to claim 1 or 5 described methods; In oxide compound and with the total catalyst weight is benchmark, and the content of described molybdenum and/or tungsten is 3～20 heavy %, and the content of nickel and/or cobalt is 0.3～2 heavy %, and the auxiliary agent Mg content is 1～7 heavy %, and described zeolite content is 5～60 heavy %.
7, in accordance with the method for claim 1, it is characterized in that in described second hydrotreating reactor it being the independent filling of combination loading or catalyst for hydro-upgrading of Hydrobon catalyst and octane value recovering catalyst.
8, in accordance with the method for claim 7, it is characterized in that described Hydrobon catalyst is group vib and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.
9, in accordance with the method for claim 7, it is characterized in that described octane value recovering catalyst is a kind of catalyzer by zeolite and the carrier loaded non-noble metal components of aluminum oxide composite molding, metal component is molybdenum and/or the tungsten that is selected from group VIII cobalt and/or nickel, group vib, and described zeolite is one or more the mixture that is selected among faujusite, Beta zeolite, ZSM-5 zeolite and the SAPO-11.
10, in accordance with the method for claim 7, it is characterized in that described catalyst for hydro-upgrading is group vib and/or the group VIII non-precious metal catalyst that loads on the Zeolite support, catalyzer contains the zeolite of one or more modifications, one or more group vib and/or group VIII base metal and alumina host, and described zeolite is one or more the mixture in HY zeolite, Beta zeolite and the ZSM-5 zeolite.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101591567B (en) * | 2008-05-29 | 2012-05-30 | 中国石油化工股份有限公司 | Method for lowering olefine content in gasoline in secondary processing |
| CN101440305B (en) * | 2007-11-22 | 2012-11-07 | 中国石油大学(北京) | Hydro-upgrading method for FCC gasoline |
| CN103074104A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Gasoline hydro-desulfurization method |
| CN103131467A (en) * | 2011-12-01 | 2013-06-05 | 北京海顺德钛催化剂有限公司 | Selective hydrodesulfurization process method of poor-quality gasoline and device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5346609A (en) * | 1991-08-15 | 1994-09-13 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| CN1208436C (en) * | 2002-06-27 | 2005-06-29 | 中国石油化工股份有限公司 | Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline |
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2005
- 2005-10-31 CN CNB2005101144947A patent/CN100448955C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440305B (en) * | 2007-11-22 | 2012-11-07 | 中国石油大学(北京) | Hydro-upgrading method for FCC gasoline |
| CN101591567B (en) * | 2008-05-29 | 2012-05-30 | 中国石油化工股份有限公司 | Method for lowering olefine content in gasoline in secondary processing |
| CN103074104A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Gasoline hydro-desulfurization method |
| CN103074104B (en) * | 2011-10-26 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of gasoline hydrodesulfurizationmethod method |
| CN103131467A (en) * | 2011-12-01 | 2013-06-05 | 北京海顺德钛催化剂有限公司 | Selective hydrodesulfurization process method of poor-quality gasoline and device |
| CN103131467B (en) * | 2011-12-01 | 2015-11-25 | 北京海顺德钛催化剂有限公司 | A kind of processing method of selectively hydrogenating and desulfurizing inferior gasoline and device |
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| Publication number | Publication date |
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| CN100448955C (en) | 2009-01-07 |
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