CN103666559A

CN103666559A - Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline

Info

Publication number: CN103666559A
Application number: CN201210326170.XA
Authority: CN
Inventors: 李�灿; 蒋宗轩; 刘铁峰; 杨民
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2012-09-05
Filing date: 2012-09-05
Publication date: 2014-03-26
Anticipated expiration: 2032-09-05
Also published as: CN103666559B

Abstract

The invention relates to a super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline. The method comprises the steps of (1) with full fraction FCC gasoline and hydrogen as raw materials, enabling the raw materials to contact with protective agents 1 and 2 and a catalyst selectively removing alkadiene in a reactor removing alkadiene under proper conditions so as to remove most alkadiene in full fraction FCC gasoline raw material; (2) after the full fraction FCC gasoline with alkadiene removed in step (1) passes through a gas-liquid separator, dividing the liquid entering a fractionating tower into a light gasoline fraction and a heavy gasoline fraction; (3) enabling the heavy gasoline fraction obtained in step (2) to contact with the catalyst in a selective hydrogen desulfurization reactor under proper operation condition; (4) mixing the light gasoline fraction obtained in step (2) with the heavy gasoline fraction subjected to selective hydrogen desulfurization in step (3), then mixing with new hydrogen, and enabling the mixture to contact with an adsorbent in an adsorbing super deep desulfurization reactor under proper condition so as to remove most sulphur in the gasoline to obtain the ultra low sulphur gasoline product with content of sulphur less than 10ppmw.

Description

A kind of FCC gasoline ultra-deep desulfurization combined method

Technical field

The present invention relates to a kind of FCC gasoline ultra-deep desulfurization combined method, the FCC gasoline ultra-deep desulfurization combined method of sulphur content 200-1000ppmw particularly, by this combination process, the sulphur in the FCC gasoline of sulphur content 200-1000ppmw can be taken off to 10ppm, and loss of octane number is lower than 1.5Ge unit, liquid yield is greater than 99.8%.

Background technology

The SOx that organic sulfide in gasoline produces after engine combustion produces much harm to environment, mainly contains: acid rain, make precious metal " three-way catalyst " in engine tail gas purification system produce irreversible poisoning, be main contributions person, corroding metal equipment of Atmospheric Grains matter etc.For this reason, the U.S. has promulgated new Clean Air Act Amendment (CAAA) in early 1990s, work out stricter environmental legislation, the sulphur content in gasoline has been carried out to stricter restriction, and carried out the super low-sulfur oil standard lower than 30ppmw in 2006.The developed country such as Japanese, Canadian, European has also worked out corresponding rules, has carried out super low-sulfur oil (<10ppmw sulphur) standard in 2005.Estimate, the content of sulfur in gasoline standard that sulphur content is lower will be carried out in Europe after 2014.China's gasoline sulfur index request is also more and more higher, on June 1st, 2012, takes the lead in carrying out sulphur content lower than the capital V super low-sulfur oil standard of 10ppmw in Beijing.

Gasoline except being used as power fuel in communications and transportation, because of its store and transportation in high-energy-density, be easy to get and the advantage such as safe, thereby it is very likely used as the raw material of vehicle-mounted reformation hydrogen production in the engine system of new generation that fuel cell is power take.Yet, be no matter gasoline reforming hydrogen manufacturing part or fuel battery engines part, all must under being close to without sulphur (lower than 0.1ppm) condition, carry out, (as platinum etc.) is easy to by sulphur irreversible poisoning because the noble metal catalyst of using in these parts.Thereby from the angle of exploitation and the application of fuel cell, producing and being close to sweet gasoline is also a very urgent research topic.

Although traditional hydrogenating desulfurization (HDS) can remove the sulfocompound (as mercaptan, thioether, thiophene and derivatives and thionaphthene and derivative thereof etc.) in gasoline very effectively, but along with the increase of the hydrogenating desulfurization degree of depth, a large amount of alkene and the aromatic hydrocarbons that are present in gasoline are also saturated by hydrogenation.This has not only increased hydrogen consumption greatly, has improved running cost, but also greatly reduces gasoline octane rating.In addition, in the later stage of reaction, be dissolved in hydrogen sulfide in product and regenerate mercaptan with the alkene generation addition reaction in oil product, the amount of mercaptan is often over 10ppmw, and this has greatly increased the difficulty of ultra-deep desulfurization.So, after selecting hydrogenating desulfurization, also must could meet product mercaptans content index by caustic wash desulfuration alcohol technique.Caustic wash desulfuration alcohol technique must be brought the environmental problem of alkaline residue discharge.US Patent No. 4131537 discloses a kind of gasoline and has selected hydrodesulfurizationprocess process, it be by gasoline cut into light, weigh two cuts, lighting end is by caustic wash desulfuration alcohol, last running is by hydrogenating desulfurization, finally by through desulfurization gently, last running is mixed into sweet gasoline.The method desulfurization depth is very limited, sulphur content can not be taken off to 10ppmw higher than the sulphur in the full cut FCC gasoline of 300ppmw, a major reason is, hydrogenating desulfurization unavoidably causes being dissolved in hydrogen sulfide in product and the alkene generation mercaptan that again reacts, and the amount of the mercaptan of generation often surpasses 10ppmw.And when the olefin(e) centent of last running is higher, the loss of octane number of sweet gasoline is larger, surpass 2 units.Chinese patent CN1158378C discloses a kind of method for making of low-sulphur oil.It mainly comprises: 1, the diolefine in sour gasoline is removed by selection method of hydrotreating; 2, the sour gasoline of dialkene removal is divided into light constituent and heavy constituent, makes light constituent wherein contain alkene as much as possible; 3, on nickel-base catalyst, carry out light constituent hydrogenating desulfurization; 4, at least containing on the catalyzer of a kind of VIII family's metal and/or at least one group vib metal, heavy constituent is selected hydrogenating desulfurization; 5, each component of desulfurization is mixed.Wherein hydrodesulfurization condition light, heavy constituent has following feature: temperature of reaction 160-420 ° C, pressure 0.5-8MPa, liquid hourly space velocity 0.5-10h ^-1, hydrogen to oil volume ratio 100-600NL/L.Although can prepare sulphur content lower than the super low-sulfur oil of 10ppmw by this patent, when in heavy constituent, olefin(e) centent is high, loss of octane number is larger, surpasses 2 units.In addition, this sulfur method route is oversize, and energy consumption is larger.Moreover the hydrogenating desulfurization of heavy constituent also unavoidably causes mercaptan again to generate.Therefore, sulphur content be taken off to 10ppmw, must carry out post-refining to the mercaptan generating.This must cause the increase of process cost.US Patent No. 5318690 discloses a kind of gasoline desulfating method, comprises first gasoline rectifying is become to light, last running, lighting end mercaptan removal, heavy fractioning hydrogenation desulfurization.Because last running contains relatively a large amount of alkene, wherein a part of alkene hydrogenation when hydrogenating desulfurization is saturated, causes loss of octane number larger.In order to compensate the loss of octane value, the alkane generation cracking that this patent proposes to make part olefin saturated produce on zeolite ZSM-5 generates some alkene, but this unavoidably causes, dry gas increases, the reduction of liquid yield.In addition, these alkene easily react and regenerate mercaptan with the hydrogen sulfide dissolving.Thereby also need to supplement hydro-sweetening, could realize sulphur content lower than the production of the super low-sulfur oil of 10ppmw.This certainly will cause the increase greatly of process cost.

Based on above reason, develop new super low sulfur or intimate sweet gasoline production technology has become domestic and international research field with keen competition.For China, the developed countries such as quality of gasoline index and Europe, the United States also exist very large gap, and along with the continuous increase to crude oil demand amount, need to be from external import substantial oil, wherein major part is Middle East high-sulfur crude oil, thus China more need to develop a kind of efficiently, gasoline desulfur technology cheaply.Adsorption desulfurize is considered to one of a kind of very promising desulfurization technology.

Adsorption desulfurize is because of advantages such as its operational condition are gentle, do not consume hydrogen or hydrogen-consuming volume is low, desulfurization depth is high, loss of octane number is little, process cost is relatively low, thereby gets more and more people's extensive concerning.US Patent No. P5730860 discloses a kind of gasoline and has selected desulfurizing method by adsorption, has developed a kind of IRVAD ^tMtechnique.Whole operating process does not consume hydrogen, there is no loss of octane number.Catalytic cracking (FCC) gasoline that it can be 1276ppm by sulphur content or coker gasoline desulfurization are to 120ppm.But the loading capacity of the desulfuration adsorbent using in this technological process is lower, thereby regeneration is frequent; Desulfurization depth is low, is difficult to sulphur content to take off to 10ppmw.This has greatly limited the industrial application of this technology in super low-sulfur oil is produced.

US Patent No. P6531053, USP6346190, USP6056871, USP6184176, USP6254766 etc. disclose a kind of gasoline reaction-desulfurizing method by adsorption, developed a kind of S-Zorb technique, the FCC gasoline desulfur that it can be 775ppm by sulphur content is to 10ppm, and loss of octane number Wei1-2Ge unit.But this process operation condition is harsh, still need in comparatively high temps and certain hydrogen dividing potential drop, (370 ~ 410 ° of C, pressure be 7.1 ~ 21.2kg/cm ²) under carry out, thereby process cost is high.In addition, the sorbent material absorption sulfur capacity using due to this patent is low, thereby adsorbent reactivation is frequent, in order to realize serialization, produces, and this patent has been used fluidized-bed process.In fluidized-bed process, because the collision of absorbent particles and reactor wall is serious, and lower containing the sorbent material intensity of zinc oxide, thereby sorbent material loss is serious, running cost is high; And when high (when olefin(e) centent is greater than 20w%), loss of octane number surpasses 2 units at sulphur and olefin(e) centent.

The people such as Yang (Ind.Eng.Chem.Res., 2003,42 (13): 3103.) investigated model thiophene and benzene at Cu ⁺/ Y and Ag ⁺absorption behavior on/Y sorbent material.Compare Cu with NaY ⁺/ Y and Ag ⁺/ Y all has larger loading capacity and adsorption selectivity to thiophene and benzene under lower pressure.Molecular Orbital Calculation shows, absorption mode is π complexing action, and action intensity is thiophene > benzene, Cu ⁺>Ag ⁺.According to author, such be take π complexing action and is applied to, in true gasoline desulfur, show certain sweetening effectiveness as basic sorbent material.Under normal temperature, normal pressure, use Cu ⁺/ Y is sorbent material, and the gasoline that is 335ppm to sulphur content carries out desulfurization, and every gram of sorbent material can produce the sweet gasoline of 14.7mL; When using gac to do protective layer, every gram of producible sweet gasoline of sorbent material is further brought up to 19.6mL.This absorption sulfur capacity that this sorbent material is described still can not meet the requirement of industrial application; On the other hand, because univalent copper ion is very unstable, disproportionation reaction easily occurs, generate more stable bivalent cupric ion and metallic copper, thereby this has also limited its industrial application greatly.

In sum, in existing document or patent, also there is the following weak point in gasoline ultra-deep desulfurization (sulphur content is lower than 10ppmw) technology: 1, select hydrodesulfurization route long, energy consumption is high, and loss of octane number is large, and process cost is high; 2, in selecting hydrogenating desulfurization, caustic wash desulfuration alcohol technique has also produced the environmental problems such as a large amount of alkaline residues; 3, the sorbent material of selecting adsorption desulfurize to use is lower to the adsorption selectivity of sulfide and loading capacity, is difficult to realize industrialization; 4, at fluidized-bed, face in H-H reaction-adsorption desulfurize, operational condition is harsh, and energy consumption is high, and sorbent material loss is serious, and process cost is high.Particularly, when olefin(e) centent is high, the loss of octane number causing surpasses 2 units; 5, at fluidized-bed, face in H-H reaction-adsorption desulfurize, sorbent material sulfur capacity is low, and adsorbent reactivation is frequent, and energy consumption is high, and process cost is high.

Summary of the invention

The object of this invention is to provide a kind of FCC gasoline ultra-deep desulfurization combined method, particularly sulphur content 200-1000ppmw, preferably 200-350ppmw, the preferably full cut FCC gasoline ultra-deep desulfurization combined method of 200-250ppmw.Can be by sulphur content 200-1000ppmw by this combined method, preferred 200-350ppmw, preferably the sulphur in the full cut FCC gasoline of 200-250ppmw takes off to 10ppm, and loss of octane number is lower than 1.5Ge unit, liquid yield is greater than 99.8%.

Combined method of the present invention is a kind of full cut FCC gasoline dialkene removal, dialkene removal material to be fractionated into light gasoline fraction and heavy naphtha, heavy naphtha through selecting hydrogenating desulfurization, through selecting the light gasoline fraction that the heavy naphtha of hydrogenating desulfurization obtains with fractionation again to mix the combined method of connecting by absorption ultra-deep desulfurization fixed-bed reactor.For guaranteeing desulfuration adsorbent long-time steady operation, sulfur method of the present invention is particularly suitable for the ultra-deep desulfurization of the full cut FCC gasoline of sulphur content 200-250ppmw.

In combined method of the present invention; dialkene removal fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, 1, the three layer of filling protective material 2 of second layer filling protective material; the 4th layer of filling dialkene removal catalyzer loads inert ceramic balls below dialkene removal catalyzer.Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and lower end is provided with product outlet.Wherein, protective material 1, protective material 2 and dialkene removal catalyzer adopt grading loading technology, and this grading loading technology comprises following several aspect, the granular size of (1), agent.Protective material 1 particle is maximum, protective material 2 takes second place, dialkene removal catalyzer minimum.(2), the hydrogenation activity of agent size.Protective material 1, protective material 2 and dialkene removal catalyzer all contain sulfide hydrogenation activity component.Its hydrogenation activity is sequentially dialkene removal catalyzer > protective material 2> protective material 1.(3), the bulk density size order of agent is dialkene removal catalyzer > protective material 2> protective material 1.(4), the pore volume size order of agent is protective material 1> protective material 2> dialkene removal catalyzer.

Protective material 1, protective material 2 contain at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K) conventionally, and these metal loads are to having on the carrier of specified pore structure.Wherein protective material 1 has following technical characterictic: in oxide compound and take catalyzer as benchmark, the content of VIII family metal is 0.5-1.5wt%, and the content of vib metal is 2-3wt%, and the content of IA family metal is 0.1-0.5wt%, and surplus is carrier.The pore volume of protective material 1 is 0.92-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 15% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 70% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 15% of total pore volume.Protective material 2 has following technical characterictic: in oxide compound and take catalyzer as benchmark, the content of VIII family metal is 1.8-3.5wt%, and the content of vib metal is 3.5-5.5wt%, and the content of IA family metal is 0.55-0.95wt%, and surplus is carrier.The pore volume of protective material 2 is 0.70-0.90mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 60% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 30% of total pore volume.

Dialkene removal catalyzer at least contains a kind of VIII family metal, a kind of+3 valency metals, a kind of IA family metal, a kind of IVB family metal, the SiO of a kind of IIB family metal, Liang ZhongⅥ B family's metal and equal amount ₂-Al ₂o ₃the mixed metal oxide forming, it is characterized in that, in oxide compound and take catalyzer as benchmark, in this catalyzer, contain 10-40 % by weight VIII family metal, 5-30 % by weight+3 valency metals, the IA family metal of 0.1-8 % by weight, the IIB family metal of the IVB family metal of 0.1-8 % by weight, 0.1-30 % by weight are, Liang ZhongⅥ B family's metal of 5-50 % by weight and the SiO of equal amount ₂-Al ₂o ₃; The specific surface area of this catalyzer is greater than 150m ²/ g, pore volume is greater than 0.4ml/g.

Protective material 1, protective material 2 and dialkene removal catalyzer needed to carry out sulfidizing before carrying out dialkene removal reaction, made it be converted into the active phase of sulfide with hydrogenating function.Sulfuration can be carried out in dialkene removal reactor, also can carry out outward at dialkene removal reactor.These vulcanization process are that this research field is known.The conventional method of sulfuration in device for example: use containing 1-5wt%(and often adopt 2wt%) straight-run spirit of dithiocarbonic anhydride carries out prevulcanized as vulcanized oil to catalyzer (protective material 1, protective material 2 and dialkene removal catalyzer); concrete cure conditions is hydrogen dividing potential drop 1.6-4.0MPa; temperature 250-400 ° of C, liquid hourly space velocity 2.0-4.0h ^-1, hydrogen to oil volume ratio 100-500NL/L, curing time 30-70 hour.The outer conventional method of prevulcanized of device: organism or inorganics that the catalyst oxidation thing precursor dipping after roasting is contained to sulphur, the mole number of the sulphur conventionally containing in steeping fluid is 1.0-1.8 times of the theoretical value of all active metal complete cures in catalyzer.Load packs reactor into after having the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, before carrying out hydrogenation reaction, will in hydrogen, process 10-30 hour, and treatment temp is 200-360 ° of C, pressure 0.1-2.0MPa, and hydrogen gas space velocity is 360-1000NLH ₂/ L catalyzer hour.

Protective material 1, protective material 2 and dialkene removal catalyzer carry out hydrogenation dialkene removal reaction through vulcanizing laggard full cut FCC stock oil and hydrogen.Concrete reaction conditions is temperature of reaction 50-220 ° C, is preferably 60-210 ° of C; Hydrogen dividing potential drop 0.6-2.0MPa, is preferably 0.8-1.8; Hydrogen to oil volume ratio 10-150NL/L, is preferably 20-100NL/L; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1.In order to guarantee dialkene removal and to select hydrogenating desulfurization and the long-term stability operation of absorption ultra-deep desulfurization series combination technique, enter to select before hydrodesulphurisatioreactors reactors, diene content must take off to maleic value be 0.2g I ₂below/100g oil.Otherwise, easily polymerization reaction take place and the coking in the interchanger of desulphurization reactor front end of the diolefine of high-content, clogging heat exchanger tube road.

Protective material 1 protective material 2, dialkene removal catalyzer loading height ratio in dialkene removal reactor is generally 1-2:1-2:2-8.

The content of diolefine represents with maleic value, the measuring method of maleic value: adopt Maleic Anhydride Method to measure the maleic value in FCC gasoline.Concrete steps are as follows: (1), with the oil sample that analytical balance accurately weighs 10.00g, put into flask, add 20mL MALEIC ANHYDRIDE toluene solution (necessary standing over night after the preparation of MALEIC ANHYDRIDE toluene solution, after filtration, can use), add again 0.1mol/L toluene iodide solution 0.5mL, shake up.(2), then ground flask is filled on reflux condensing tube, in 110 ℃ ± 2 ℃ water-baths, reflux is 3 hours, then solution is cooled to room temperature, from prolong upper end, adds water 5mL, continue temperature rising reflux 15min, coolingly with 5mLMTBE, 20mL moisture, rinse for several times prolong respectively afterwards.(3), ground flask is pulled down from prolong, carefully solution in ground Erlenmeyer flask is transferred in separating funnel and (in process of the test, must be guaranteed the stopping property of separating funnel, with liquid-leakage preventing, affect result precision), first use 20mL MTBE, with 25mL water, divide respectively washing ground flask inwall three times again, washing lotion is poured in separating funnel.(4), vibration separating funnel 4～5 minutes, static layering, puts into ground Erlenmeyer flask by water layer, oil reservoir divides and adds respectively 25mL, 10mL, 10mL water vibration extracting for three times, and water layer is incorporated in ground Erlenmeyer flask.(5), in ground Erlenmeyer flask, drip 1～2 of phenolphthalein indicator, with NaOH standard titration solution, being titrated to solution, to be incarnadine be terminal, writes down the volume that consumes NaOH standard titration solution.(6), getting toluene 10.00g replaces sample to do blank test by aforesaid operations condition.(7), the parallel sample of doing, monitoring analysis result collimation.(8), result is calculated: (unit is g I to maleic value ₂/ 100g oil) be calculated as follows:

(M) (12.69)/W of maleic value=(B-A)

In formula:

A=sample consumes the volume of sodium hydroxide solution, and unit is milliliter (mL);

B=blank solution consumes the volume of sodium hydroxide solution, and unit is milliliter (mL)

The volumetric molar concentration of M=sodium hydroxide solution, unit is mol/L (mol/L);

W=sample mass (g)

Full cut FCC gasoline through dialkene removal is fractionated into light gasoline fraction and heavy naphtha again, and last running gasoline and recycle hydrogen mix, and enters to select in hydrogenating desulfurization fixed-bed reactor through interchanger heat exchange is laggard.In the top of reactor, fill out the inert ceramic balls that particle is larger, next Hydrobon catalyst, the larger inert ceramic balls of catalyzer lower end loaded particles are selected in filling.The selection Hydrobon catalyst that patent of the present invention is used contains at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K), at least one IIB family metal (being preferably selected from Mg), and these metal loads are to having on the carrier of specified pore structure.Described selection Hydrobon catalyst has following feature: in oxide compound and take catalyzer as benchmark, the content of VIII family metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA family metal is 0.5-4.5wt%, the content of IIA family metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 5-100nm accounts for the more than 85% of total pore volume, and the pore volume that is less than the hole of 5nm accounts for below 5% of total pore volume.Described selection Hydrobon catalyst needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of sulfide with hydrogenating desulfurization function.This selection Hydrobon catalyst at least can remove more than 70% sulphur, in other words can be by sulphur content lower than 1000ppmw, and preferred 350ppmw, preferably the sulphur in the last running gasoline of 250ppmw takes off to 100ppm.

Through selecting the last running gasoline of hydrogenating desulfurization, after gas-liquid separator separates, then by gas stripping column, the hydrogen sulfide being dissolved into is wherein down to below 1ppmw, so just obtained the last running gasoline of sulphur content lower than 100ppmw.Last running gasoline after this desulfurization adsorbs in ultra-deep desulfurization fixed-bed reactor with mixing to enter after interchanger heat exchange from light gasoline fraction out of separation column and new hydrogen.Absorption ultra-deep desulfurization fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, filled with adsorbent next, the larger inert ceramic balls of sorbent material lower end loaded particles.

In the previous work of the technical characterictic Yi Dalian Inst of Chemicophysics, Chinese Academy of Sciences of the sorbent material that patent of the present invention is used, be described in detail, such as CN101450302B describes a kind of C 4 olefin desulfurization absorbent and method for making and application in detail, this sorbent material also can the ultra-deep desulfurization combined method for the FCC gasoline of patent of the present invention among.By to be selected from reduction-state VIII family base metal, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound and the aluminum oxide of take with activation sulfur-containing molecules be main component, tamanori forms this desulfuration adsorbent.Wherein, VIII family base metal accounts for the 1-30% of total desulfuration adsorbent total mass, IB family metal accounts for the 1-40% of desulfuration adsorbent total mass, and IIB group 4 transition metal oxide compound (being selected from ZnO) accounts for the 10-70% of desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass.Sorbent material will be in hydrogen before carrying out adsorption desulfurize activation treatment 20-30 hour, activation temperature 250-400 ° of C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.Adsorption desulfurize operational condition is that hydrogen to oil volume ratio is 10-150NL/L, is preferably 20-100NL/L; Hydrogen dividing potential drop 0.6-2.0MPa, is preferably 0.8-1.8; Adsorption temp is 200-380 ° of C; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1.

Compare with known technology, tool of the present invention has the following advantages:

(1) sorbent material is high to sulfur compounds adsorption selectivity and loading capacity;

(2) in facing hydrogen adsorption, alkene loss is little, and loss of octane number is less than 1.5Ge unit;

(3) dialkene removal protective material and catalyst activity are high, can at lower temperature, operate, long-term stability operation that can assurance device;

(4) adopt ADSORPTION IN A FIXED BED desulfurizer, sorbent material free of losses, liquid yield reaches more than 99.8%, has reduced process cost.

(5) in the situation that identical desulfurization depth, full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize series combination method, plant investment expense and process cost are lower than hydrogenating desulfurization and S-Zorb technique and select hydrodesulfurization more than 10%.

Accompanying drawing explanation

Fig. 1 is the simplification of flowsheet figure of combination process of the present invention.Hydrogen together enters after the first mixing tank 3 mixes and passes through First Heat Exchanger 4 heat exchange again through the second pipeline 2 through the first pipeline 1 and full cut FCC stock oil; through the hydrogen of heat exchange and full cut FCC stock oil mixture, through the 3rd pipeline 5, enter dialkene removal reactor 6, in dialkene removal reactor 6, be filled with successively from top to bottom in the first filler 7, protective material 1(Fig. 1 and be labeled as 8), be labeled as 9 in protective material 2(Fig. 1), dialkene removal catalyzer (being labeled as 10 in Fig. 1), the second filler 11.The material of dialkene removal enters the first gas-liquid separator 13 through the 4th pipeline 12, gas enters new hydrogen system through the 5th pipeline 14, liquid enters separation column 16 through the 6th pipeline 15, light gasoline fraction enters adsorption desulfurize reactor 41 through the 7th pipeline 18, heavy naphtha through the 8th pipeline 17 with the recycle hydrogen of the 9th pipeline 20 after the second mixing tank 19 mixes, again after the second interchanger 21 heat exchange, through the tenth pipeline 22, enter and select hydrodesulphurisatioreactors reactors 23 again, select to be filled with successively from top to bottom the 3rd filler 24 in hydrodesulphurisatioreactors reactors 23, catalyzer 25, the 4th filler 26, through selecting the material of hydrogenating desulfurization to enter the second gas-liquid separator 28 through the 11 pipeline 27, gas enters alkali tourie 30 absorbing hydrogen sulphides through the 12 pipeline 29, the hydrogen of depriving hydrogen sulphide enters the hydrogen recycle system through the 13 pipeline 31, from the second gas-liquid separator 28 liquid out, through the 14 pipeline 32, enter air lift tank 33 the hydrogen sulfide air lift being dissolved in liquid material is removed, the mixed gas of hydrogen and hydrogen sulfide enters recycle hydrogen system through the 15 pipeline 34, liquid material after air lift after the 16 pipeline 35 mixes in the 3rd mixing tank 36 with the light gasoline fraction of new hydrogen via the 17 pipeline 37 and the 7th pipeline 18 again through the 18 pipeline 38, after the 3rd interchanger 39 heat exchange, through the 19 pipeline 40, enter adsorption desulfurize reactor 41 again, in adsorption desulfurize reactor 41, one-time pad has the 5th filler 42 from top to bottom, sorbent material 43, the 6th filler 44, through the 20 pipeline 45, enter the 3rd gas-liquid separator 46 again, finally by the 21 pipeline 47, obtain sulphur content lower than 10ppmw, loss of octane number is lower than 1.5Ge unit, the super low-sulfur oil that liquid yield is greater than 99.8%.

Embodiment

In combined method of the present invention; dialkene removal fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, 1, the three layer of filling protective material 2 of second layer filling protective material; the 4th layer of filling dialkene removal catalyzer loads inert ceramic balls below dialkene removal catalyzer.Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and lower end is provided with product outlet.Wherein, protective material 1, protective material 2 and dialkene removal catalyzer adopt grading loading technology, and this grading loading technology comprises following several aspect, the granular size of (1), agent.Protective material 1 particle is maximum, protective material 2 takes second place, dialkene removal catalyzer minimum.(2), the hydrogenation activity of agent size.Protective material 1, protective material 2 and dialkene removal catalyzer all contain metallic sulfide hydrogenation activity component.Its hydrogenation activity is sequentially dialkene removal catalyzer > protective material 2> protective material 1.(3), the bulk density size order of agent is dialkene removal catalyzer > protective material 2> protective material 1.(4), the pore volume size order of agent is protective material 1> protective material 2> dialkene removal catalyzer.

Protective material 1, protective material 2 contain at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K) conventionally, and these metal loads are to carrier.Wherein protective material 1 has following technical characterictic: in oxide compound and take catalyst weight as benchmark, the content of VIII family metal is 0.5-1.5wt%, and the content of vib metal is 2-3wt%, and the content of IA family metal is 0.1-0.5wt%, and surplus is carrier.The pore volume of protective material 1 is 0.92-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 15% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 70% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 15% of total pore volume.Protective material 2 has following technical characterictic: in oxide compound and take catalyst weight as benchmark, the content of VIII family metal is 1.8-3.5wt%, and the content of vib metal is 3.5-5.5wt%, and the content of IA family metal is 0.55-0.95wt%, and surplus is carrier.The pore volume of protective material 2 is 0.70-0.90mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 60% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 30% of total pore volume.

Dialkene removal catalyzer at least contains a kind of VIII family metal, a kind of+3 valency metals, a kind of IA family metal, a kind of IVB family metal, a kind of IIB family metal, the SiO of Liang ZhongⅥ B family's metal and equal amount ₂-Al ₂o ₃the mixed metal oxide forming, it is characterized in that, in oxide compound and take catalyst weight as benchmark, in this catalyzer, contain 10-40 % by weight VIII family metal, 5-30 % by weight+3 valency metals, the IA family metal of 0.1-8 % by weight are, the Liang ZhongⅥ B family metal of the IIB family metal of the IVB family metal of 0.1-8 % by weight, 0.1-30 % by weight, 5-50 % by weight, the molar ratio of two kinds of group vib metals is 3:1-1:3,10-30 % by weight SiO ₂-Al ₂o ₃; SiO ₂-Al ₂o ₃middle SiO ₂account for the 90-99% of gross weight;

The specific surface area 150-300m of this catalyzer ²/ g, pore volume 0.4-0.8ml/g.

Protective material 1, protective material 2 and dialkene removal catalyzer needed to carry out sulfidizing before carrying out dialkene removal reaction, made it be converted into the active phase of metallic sulfide with hydrogenating function.Sulfuration can be carried out in dialkene removal reactor, also can carry out outward at dialkene removal reactor.These vulcanization process are that this research field is known.The conventional method of sulfuration in device for example: use containing 1-5wt%(and often adopt 2wt%) straight-run spirit of dithiocarbonic anhydride carries out prevulcanized as vulcanized oil to catalyzer (protective material 1, protective material 2 and dialkene removal catalyzer); concrete cure conditions is hydrogen dividing potential drop 1.6-4.0MPa; temperature 250-400 ° of C, liquid hourly space velocity 2.0-4.0h ^-1, hydrogen to oil volume ratio 100-500NL/L, curing time 30-70 hour.The outer conventional method of prevulcanized of device: organism or inorganics that the catalyst oxidation thing precursor dipping after roasting is contained to sulphur, the mole number of the sulphur conventionally containing in steeping fluid is 1.0-1.8 times of the theoretical value of all active metal complete cures in catalyzer.Load packs reactor into after having the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, before carrying out hydrogenation reaction, will in hydrogen, process 10-30 hour, and treatment temp is 200-360 ° of C, pressure 0.1-2.0MPa, and hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.

Protective material 1, protective material 2 and dialkene removal catalyzer carry out hydrogenation dialkene removal reaction through vulcanizing laggard full cut FCC stock oil and hydrogen.Concrete reaction conditions is temperature of reaction 50-220 ° C, is preferably 60-210 ° of C; Hydrogen dividing potential drop 0.6-2.0MPa, is preferably 0.8-1.8; Hydrogen to oil volume ratio 10-150NL/L, is preferably 20-100NL/L; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1.In order to guarantee dialkene removal and to select hydrogenating desulfurization and the long-term stability operation of absorption ultra-deep desulfurization series combination method, enter to select before hydrodesulphurisatioreactors reactors, diene content must take off to maleic value be 0.2g I ₂below/100g oil.Otherwise, easily polymerization reaction take place and the coking in the interchanger of desulphurization reactor front end of the diolefine of high-content, clogging heat exchanger tube road.

(M) (12.69)/W of maleic value=(B-A)

In formula:

W=sample mass (g)

Full cut FCC gasoline through dialkene removal is fractionated into light gasoline fraction and heavy naphtha (light gasoline fraction refers to that boiling point is lower than 100 ° of C cuts, and heavy naphtha refers to that boiling point is higher than 100 ° of C cuts) again.Last running gasoline and recycle hydrogen mix, and enter to select in hydrogenating desulfurization fixed-bed reactor through interchanger heat exchange is laggard.In the top of reactor, fill out the inert ceramic balls that particle is larger, next Hydrobon catalyst, the larger inert ceramic balls of catalyzer lower end loaded particles are selected in filling.The selection Hydrobon catalyst that patent of the present invention is used contains at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K), at least one IIB family metal (being preferably selected from Mg), and these metal loads are to having on the carrier of specified pore structure.Described selection Hydrobon catalyst has following feature: in oxide compound and take catalyzer as benchmark, the content of VIII family metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA family metal is 0.5-4.5wt%, the content of IIA family metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 5-100nm accounts for the more than 85% of total pore volume, and the pore volume that is less than the hole of 5nm accounts for below 5% of total pore volume.Described selection Hydrobon catalyst needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of sulfide with hydrogenating desulfurization function.This selection Hydrobon catalyst at least can remove more than 70% sulphur, in other words can be by sulphur content lower than 1000ppmw, and preferred 350ppmw, preferably the sulphur in the last running gasoline of 250ppmw takes off to 100ppm.

Through selecting the last running gasoline of hydrogenating desulfurization, after gas-liquid separator separates, then by gas stripping column, the hydrogen sulfide being dissolved into is wherein down to below 1ppmw, so just obtained the last running gasoline of sulphur content lower than 100ppmw.Last running gasoline after this desulfurization adsorbs in ultra-deep desulfurization fixed-bed reactor with mixing to enter after interchanger heat exchange from light gasoline fraction out of separation column and new hydrogen.Absorption ultra-deep desulfurization fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, filled with adsorbent next, the larger inert ceramic balls of sorbent material lower end loaded particles.In the previous work of the technical characterictic Yi Dalian Inst of Chemicophysics, Chinese Academy of Sciences of the sorbent material that patent of the present invention is used, be described in detail, such as CN101450302B describes a kind of C 4 olefin desulfurization absorbent and method for making and application in detail, this sorbent material also can the ultra-deep desulfurization combined method for the FCC gasoline of patent of the present invention among.By to be selected from reduction-state VIII family base metal, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound and the aluminum oxide of take with activation sulfur-containing molecules be main component, tamanori forms this desulfuration adsorbent.Wherein, VIII family base metal accounts for the 1-30% of total desulfuration adsorbent total mass, IB family metal accounts for the 1-40% of desulfuration adsorbent total mass, and IIB group 4 transition metal oxide compound (being selected from ZnO) accounts for the 10-70% of desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass.Sorbent material will be in hydrogen before carrying out adsorption desulfurize activation treatment 20-30 hour, activation temperature 250-400 ° of C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.Adsorption desulfurize operational condition is that hydrogen to oil volume ratio is 10-150NL/L, is preferably 20-100NL/L; Hydrogen dividing potential drop 0.6-2.0MPa, is preferably 0.8-1.8; Adsorption temp is 200-380 ° of C; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1.

Fig. 1 is the simplification of flowsheet figure of combination process of the present invention.Hydrogen together enters after the first mixing tank 3 mixes and passes through First Heat Exchanger 4 heat exchange again through the second pipeline 2 through the first pipeline 1 and full cut FCC stock oil; through the hydrogen of heat exchange and full cut FCC stock oil mixture, through the 3rd pipeline 5, enter dialkene removal reactor 6, in dialkene removal reactor 6, be filled with successively from top to bottom in the first filler 7, protective material 1(Fig. 1 and be labeled as 8), be labeled as 9 in protective material 2(Fig. 1), dialkene removal catalyzer (being labeled as 10 in Fig. 1), the second filler 11.The material of dialkene removal enters the first gas-liquid separator 13 through the 4th pipeline 12, gas enters new hydrogen system through the 5th pipeline 14, liquid enters separation column 16 through the 6th pipeline 15, light gasoline fraction enters adsorption desulfurize reactor 41 through the 7th pipeline 18, heavy naphtha through the 8th pipeline 17 with the recycle hydrogen of the 9th pipeline 20 after the second mixing tank 19 mixes, again after the second interchanger 21 heat exchange, through the tenth pipeline 22, enter and select hydrodesulphurisatioreactors reactors 23 again, select to be filled with successively from top to bottom the 3rd filler 24 in hydrodesulphurisatioreactors reactors 23, catalyzer 25, the 4th filler 26, through selecting the heavy naphtha of hydrogenating desulfurization to enter the second gas-liquid separator 28 through the 11 pipeline 27, gas enters alkali tourie 30 absorbing hydrogen sulphides through the 12 pipeline 29, the hydrogen of depriving hydrogen sulphide enters the hydrogen recycle system through the 13 pipeline 31, from the second gas-liquid separator 28 heavy naphtha out, through the 14 pipeline 32, enter air lift tank 33 the hydrogen sulfide air lift being dissolved in liquid material is removed, the mixed gas of hydrogen and hydrogen sulfide enters recycle hydrogen system through the 15 pipeline 34, heavy naphtha after air lift after the 16 pipeline 35 mixes in the 3rd mixing tank 36 with the light gasoline fraction of new hydrogen via the 17 pipeline 37 and the 7th pipeline 18 again through the 18 pipeline 38, after the 3rd interchanger 39 heat exchange, through the 19 pipeline 40, enter adsorption desulfurize reactor 41 again, in adsorption desulfurize reactor 41, one-time pad has the 5th filler 42 from top to bottom, sorbent material 43, the 6th filler 44, through the 20 pipeline 45, enter the 3rd gas-liquid separator 46 again, finally by the 21 pipeline 47, obtain sulphur content lower than 10ppmw, loss of octane number is lower than 1.5Ge unit, the super low-sulfur oil that liquid yield is greater than 99.8%.

Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and lower end is provided with product outlet; Hydrodesulphurisatioreactors reactors and adsorption desulfurize reactor upper end are provided with feed(raw material)inlet, and lower end is provided with product outlet;

Protective material 1, protective material 2 adopt equi-volume impregnating preparation, and concrete steps are as follows:

1, the preparation of protective material 1: with 100 grams of alumina supporters of 116 milliliters of dippings of the solution containing 0.44 gram, potassium hydroxide; after 120 degree oven dry, 450 degree roastings; dipping is containing 85 milliliters of the common dipping solutions of 5.95 grams and 3.72 grams ammonium molybdates of nickelous nitrate again; through 120 degree oven dry, 450 degree roastings, obtain protective material 1, it consists of 1.43wt%NiO-2.86wt%-0.30wt%/Al ₂o ₃.The preparation method of the protective material 1 using in the following example 1-embodiment 8 is identical, and just each component concentration is different.

2, the preparation of protective material 2: with 100 grams of alumina supporters of 100 milliliters of dippings of the solution containing 0.92 gram, potassium hydroxide; after 120 degree oven dry, 450 degree roastings; dipping is containing 70 milliliters of the common dipping solutions of 11.90 grams and 7.44 grams ammonium molybdates of nickelous nitrate again; through 120 degree oven dry, 450 degree roastings, obtain protective material 2, it consists of 2.73wt%NiO-5.48wt%-0.60wt%/Al ₂o ₃.The preparation method of the protective material 2 using in the following example 1-embodiment 8 is identical, and just each component concentration is different.

The preparation method of dialkene removal catalyzer is as follows:

A. take respectively a certain amount of nickelous nitrate, zinc nitrate and aluminum nitrate, wherein Ni ²⁺0.1mol, Zn ²⁺0.1mol, Al ³⁺0.05mol, is dissolved in them in 200ml water and forms the aqueous solution, slowly drips wherein K ⁺concentration is KOH and the K of 0.2mol/L ₂cO ₃(KOH of 0.1mol/L and the K of 0.05mol/L ₂cO ₃) mixing solutions, regulate pH=12, and be heated to 80 ℃ of temperature of reaction, generate green mixed reaction solution, under 80 ℃ of temperature of reaction, back flow reaction is 25 hours; The green precipitate that reaction is obtained filters; This catalyst precursor is added in 200ml water, be configured to slurry precursor;

B. take respectively a certain amount of ammonium molybdate and ammonium metawolframate, wherein Mo ⁶⁺0.01mol, W ⁶⁺0.01mol, is dissolved in them in 350ml water, forms solution, and this solution is heated to temperature of reaction, constantly stirs, and forms colourless transparent solution; Measure subsequently the homemade slurry precursor of part, wherein containing Ni ²⁺0.03mol, Zn ²⁺0.03mol, Al ³⁺0.015mol is heated to 80 ℃ of temperature of reaction; These slurries are added in above-mentioned colourless transparent solution at leisure, form green reaction liquid, 80 ℃ of temperature of reaction, back flow reaction 5 hours; The yellow-green precipitate that reaction is obtained filters, and dries 12 hours at 120 ℃, and 420 ° of C roastings obtain NiZnAlKMoW particulate state brownish black catalyst precursor for 4 hours.

C. NiZnAlKMoW catalyst precursor is pulverized, be sieved into 160 object powders, add the SiO containing Ti ₂-Al ₂o ₃the abundant kneading of binding agent of mixture, is extruded into φ 2.0 trifolium bar shapeds through banded extruder, through 120 ° of C, is dried 12 hours, and 420 ° of C roastings have formed the catalyst n iZnAlKTiMoW/SiO with highly disperse active species for 4 hours ₂-Al ₂o ₃.Through X-light fluorescence (XRF) ultimate analysis, this catalyzer consist of 16.9%NiO, 18.4%ZnO, 10.9%MoO ₃, 17.5%WO ₃, 5.8%Al ₂o ₃, 2.7%TiO ₂, 2.8%K ₂o, 25.0%SiO ₂-Al ₂o ₃(SiO ₂-Al ₂o ₃middle SiO ₂account for gross weight 96%).The preparation method of the dialkene removal catalyzer using in the following example 1-embodiment 8 is identical, and just each component concentration is different.

Select Hydrobon catalyst to adopt equi-volume impregnating preparation, concrete preparation method is as follows:

With the 100 grams of alumina supporters of 100 milliliters of dippings of mixing solutions that contain 25.92 grams of 0.94 gram, saltpetre and magnesium nitrates, after 120 degree oven dry, 450 degree roastings, dipping is containing 70 milliliters of the common dipping solutions of 9.20 grams and 10.34 grams ammonium molybdates of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES again, through 120 degree oven dry, 450 degree roastings, obtain selective hydrogenation catalyst, it consists of 2.0wt%CoO-7.1wt%MoO ₃-1.5wt%K ₂o-3.5wt%MgO/Al ₂o ₃.The preparation method of the protective material 1 using in the following example 1-embodiment 8 is identical.

The preparation method of sorbent material: by the described method preparation of the Chinese invention patent CN101450302B embodiment 1 of Dalian Inst of Chemicophysics, Chinese Academy of Sciences.Concrete steps are as follows: (1) takes in the distilled water that 1.60 grams of nickelous nitrates, 3.20 grams of cupric nitrates, 0.51 gram of aluminum oxide and 7.35 grams of zinc nitrates join 200 milliliters, add the lower fully stirring of 8.10 grams of urea, 90 degree within 24 hours, to make precipitation agent complete hydrolysis, deionized water wash after filtration,, obtain wet cake, dry in 120 degree again, obtain dry sample; (2) above-mentioned dry sample is fully mixed with 1 gram of alumina dry glue, adding concentration of nitric acid is 5 milliliters of abundant kneadings of the aqueous solution of 2%, makes body of paste, then is extruded into cloverleaf pattern with banded extruder, and in 120 degree dried overnight, 450 degree roastings 4 hours, obtain sorbent material.This sorbent material consist of 8.6wt%NiO-18.1wt%CuO-41.9wt%ZnO-18.1wt%Al ₂o ₃, the preparation method of the sorbent material using in the following example 1-embodiment 8 is identical, and just each component concentration is different.

Embodiment

In order to further illustrate the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.

Protective material 1 protective material 2, dialkene removal catalyzer loading height in dialkene removal reactor is 1-2:1-2:2-8 than can adopt loading height ratio for 1:1:4().

Table 1 represents the character of the present invention's full cut FCC gasoline stocks used.

The full cut FCC gasoline property of table 1

The character of table 2 light gasoline fraction

The character of table 3 heavy naphtha

Embodiment 1

The full cut FCC gasoline of character as described in Table 1 mixes with hydrogen by entering dialkene removal reactor after interchanger heat exchange, is filled with protective material 1(1.2%NiO-2.4%MoO in dialkene removal reactor ₃-0.28%K ₂o/Al ₂o ₃) 2.5mL, protective material 2(2.8%NiO-5.2%MoO ₃-0.8%K ₂o/Al ₂o ₃) 2.5mL, dialkene removal catalyzer (16.2%NiO-18.2%ZnO-10.4%MoO ₃-13.5%WO ₃-5.2%Al ₂o ₃-2.4%TiO ₂-3.2%K ₂o/30.9%SiO ₂-Al ₂o ₃) 10mL, at oil product and hydrogen, entering before dialkene removal reactor, protective material and dialkene removal catalyzer will carry out prevulcanized in device.Cure conditions is to use the straight-run spirit containing 2wt% dithiocarbonic anhydride to carry out prevulcanized to catalyzer, and concrete cure conditions is hydrogen dividing potential drop 1.6MPa, 290 ° of C of temperature, liquid hourly space velocity 2.0h ^-1, hydrogen to oil volume ratio 300, curing time 9 hours.Vulcanize laggard raw material and hydrogen and carried out hydrogenation dialkene removal reaction.Dialkene removal reaction conditions is 80 ° of C of temperature of reaction, hydrogen dividing potential drop 1.4MPa, hydrogen to oil volume ratio 50NL/L, night hourly space velocity 2.0h ^-1.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Full cut FCC gasoline after dialkene removal is divided into light gasoline fraction (character is in Table 2) and heavy naphtha (character is in Table 3) through separation column, heavy naphtha and hydrogen enter to select hydrodesulphurisatioreactors reactors, the catalyzer (2.0wt%CoO-7.1wt%MoO in this reactor through interchanger heat exchange is laggard after mixing with the recycle hydrogen of metering again ₃-1.5wt%K ₂o-3.5wt%MgO/Al ₂o ₃) prevulcanized of 10mL, prevulcanized condition is to use the straight-run spirit containing 2wt% dithiocarbonic anhydride to carry out prevulcanized to selection Hydrobon catalyst, concrete cure conditions is hydrogen dividing potential drop 1.6MPa, 290 ° of C of temperature, liquid hourly space velocity 2.0h ^-1, hydrogen to oil volume ratio 300, curing time 9 hours.Vulcanize laggard raw material and hydrogen and selected hydrodesulfurization reaction.Hydrodesulfurization reaction condition is 280 ° of C of temperature of reaction, hydrogen dividing potential drop 2.0MPa, hydrogen to oil volume ratio 200NL/L, night hourly space velocity 2.0h ^-1.React sampling analysis after 500 hours, find that sulphur content drops to 86.0ppmw from 689ppmw, octane value is 89.0, and loss of octane number is only 0.4.Through selecting the heavy naphtha of hydrogenating desulfurization and enter adsorption desulfurize reactor after light gasoline fraction out of separation column fractionation and new hydrogen mixing by interchanger heat exchange.Sorbent material (13%NiO-3%CuO-65%ZnO-19%Al in this adsorption desulfurize reactor ₂o ₃, 10mL) preactivated, activation condition is: 400 ° of C of activation temperature, and pressure 0.1MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L sorbent material hour, soak time 25 hours.Adsorption desulfurize operational condition is: 300 ° of C of adsorption temp, hydrogen dividing potential drop 1.0MPa, hydrogen to oil volume ratio 25NL/L, night hourly space velocity 2.0h ^-1.React sampling analysis after 500 hours, find, total sulfur content has been down to 7.6ppmw, and octane value is down to 89.2 from 90.6 of stock oil, and loss of octane number is 1.4Ge unit only; Olefin(e) centent is down to 23.6% from 27.8% of stock oil, has only declined 4.2%, liquid yield 99.9%.Result of the present invention shows, adopt dialkene removal provided by the invention and select hydrogenating desulfurization and adsorption desulfurize combination process, not only the sulphur in the full cut FCC raw material of sulphur content 268.6ppmw can be taken off to 10ppmw, and loss of octane number is less than 1.5Ge unit, liquid yield is greater than 99.8%.

Embodiment 2

The protective material using, dialkene removal catalyzer, select Hydrobon catalyst and sorbent material with embodiment 1, just dialkene removal processing condition become 100 ° of C of temperature of reaction, hydrogen dividing potential drop 1.4MPa, hydrogen to oil volume ratio 80NL/L, night hourly space velocity 3.0h ^-1.React sampling analysis after 500 hours, find that maleic value is from 1.1gI _2/100g oil drops to below 0.1.Select hydrodesulfurization condition to become 280 ° of C of temperature of reaction, hydrogen dividing potential drop 1.2MPa, hydrogen to oil volume ratio 100NL/L, night hourly space velocity 2.5h ^-1.Process for adsorption desulfuration condition becomes 300 ° of C of adsorption temp, hydrogen dividing potential drop 1.4MPa, hydrogen to oil volume ratio 50NL/L, night hourly space velocity 3.0h ^-1.React sampling analysis after 500 hours, find, total sulfur content is down to 7.6ppmw from the 268.6ppmw of raw material, and octane value is down to 89.3 from 90.6 of stock oil, loss of octane number is 1.3Ge unit only, olefin(e) centent is down to 23.8% from 27.8% of stock oil, has only declined 4.0%, liquid yield 99.9%.

Embodiment 3

Except the protective material in embodiment 11 is changed into

0.58%NiO-1.4%MoO ₃-0.29%K ₂o/Al ₂o ₃change into protective material 2

1.20%NiO-2.60%MoO ₃-0.7%K ₂o/Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.4ppmw from the 268.6ppmw of raw material, and octane value is down to 89.2 from 90.6 of stock oil, and loss of octane number is 1.4Ge unit only, and olefin(e) centent is down to 23.5% from 27.8% of stock oil, has only declined 4.3%, liquid yield 99.9%.

Embodiment 4

Except changing the dialkene removal catalyzer in embodiment into 32.3%NiO-15.2%ZnO-5.8%MoO ₃-10.5%WO ₃-10.3%Al ₂o ₃-2.2%TiO ₂-3.0%K ₂o-20.7%SiO ₂-Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 6.8ppmw from the 268.6ppmw of raw material, and octane value is down to 89.3 from 90.6 of stock oil, and loss of octane number is 1.3Ge unit only, and olefin(e) centent is down to 23.6% from 27.8% of stock oil, has only declined 4.3%, liquid yield 99.9%.

Embodiment 5

Except changing the sorbent material in the adsorption desulfurize reactor in embodiment 1 into 8%NiO-6%CuO-66%ZnO-20%Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.8ppmw from the 268.6ppmw of raw material, and octane value is down to 89.5 from 90.6 of stock oil, and loss of octane number is 1.1Ge unit only, and olefin(e) centent is down to 23.9% from 27.8% of stock oil, has only declined 3.9%, liquid yield 99.9%.

Embodiment 6

Except changing the sorbent material in the adsorption desulfurize reactor in embodiment 1 into 12.5%NiO-2.5%CuO-65%ZnO-20%Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.8ppmw from the 268.6ppmw of raw material, and octane value is down to 89.3 from 90.6 of stock oil, and loss of octane number is 1.3Ge unit only, and olefin(e) centent is down to 23.6% from 27.8% of stock oil, has only declined 4.2%, liquid yield 99.9%.

Embodiment 7

Except changing the sorbent material in the adsorption desulfurize reactor in embodiment 1 into 7.5%NiO-2.5%CuO-65%ZnO-25%Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 9.3ppmw from the 268.6ppmw of raw material, and octane value is down to 89.7 from 90.6 of stock oil, and loss of octane number is 0.9Ge unit only, and olefin(e) centent is down to 24.1% from 27.8% of stock oil, has only declined 3.7%, liquid yield 99.9%.

Embodiment 8

Except changing the sorbent material in the adsorption desulfurize reactor in embodiment 1 into 25%NiO-2.5%CuO-52.5%ZnO-20%Al ₂o ₃outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.1gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 4.3ppmw from the 268.6ppmw of raw material, and octane value is down to 89.2 from 90.6 of stock oil, and loss of octane number is 1.4Ge unit only, and olefin(e) centent is down to 23.4% from 27.8% of stock oil, has only declined 4.4%, liquid yield 99.9%.

Combined method of the present invention not only has operational condition and relaxes, saved and selected the mercaptan removal step in hydrodesulfurization, hydrogen-consuming volume is low, process cost is low, and when carrying out ultra-deep desulfurization (sulphur content is lower than 10ppmw), loss of octane number low (being less than 1.5Ge unit), liquid yield high (being greater than 99.8%), the advantages such as sorbent material adsorption selectivity is high, current capacity large (surpassing 15%).

Claims

1. a FCC gasoline ultra-deep desulfurization combined method, comprises the steps:

(1) take full cut FCC gasoline and hydrogen is raw material, under proper handling condition, in dialkene removal reactor, contacts successively with protective material 1, protective material 2 and selectivity dialkene removal catalyzer, removes the most of diolefine in full cut FCC gasoline stocks;

(2) through the full cut FCC gasoline of step (1) dialkene removal after gas-liquid separator, liquid enters separation column and is divided into light gasoline fraction and heavy naphtha;

(3) heavy naphtha that step (2) obtains contacts with selecting the catalyzer in hydrodesulphurisatioreactors reactors under proper handling condition, and sulphur is wherein taken off to 100ppmw;

(4) light gasoline fraction obtaining through step (2) and mixing with hydrogen again after step (3) selects the heavy naphtha of hydrogenating desulfurization to mix; under proper handling condition, contact with the sorbent material in absorption ultra-deep desulfurization reactor; remove the most of sulphur in gasoline, obtain sulphur content lower than 10ppmw super low-sulfur oil product;

Wherein, the proper handling condition described in step (1) refers to temperature of reaction 50-220 ° C, is preferably 60-210 ° of C; Hydrogen dividing potential drop 1.0-3.5MPa, is preferably 1.5-3.0; Hydrogen to oil volume ratio 50-250NL/L, is preferably 80-200NL/L; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1;

Proper handling condition described in step (3) refers to temperature of reaction 230-310 ° C, is preferably 240-300 ° of C; Hydrogen dividing potential drop 1.0-3.5MPa, is preferably 1.5-3.0; Hydrogen to oil volume ratio 50-250NL/L, is preferably 80-200NL/L; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1;

Proper handling condition described in step (4) refers to that hydrogen to oil volume ratio is 10-150NL/L, is preferably 20-100NL/L; Hydrogen dividing potential drop 0.6-2.0MPa, is preferably 0.8-1.8; Adsorption temp is 200-380 ° of C; Liquid hourly space velocity 1.0-4.0h ^-1, be preferably 1.5-3.5h ^-1.

2. according to combined method claimed in claim 1; it is characterized in that: described full cut FCC gasoline refers to the catalytic gasoline of whole fraction of total sulfur content 200-1000ppmw; the catalytic gasoline of whole fraction of preferred sulphur content 200-350ppmw; the catalytic gasoline of whole fraction of best sulphur content 200-250ppmw, full cut FCC gasoline refers to that boiling range is the FCC gasoline of 20-220 ° of C cut;

Step (1) is described remove most of diolefine in full cut FCC gasoline stocks refer to diene content in gasoline take off to maleic value be 0.2g I ₂below/100g oil;

The described light gasoline fraction of step (2) refers to that boiling point is lower than 100 ° of C cuts, and heavy naphtha refers to that boiling point equals and/or higher than 100 ° of C cuts.

3. according to combined method claimed in claim 1, it is characterized in that the protective material 1 described in step (1), protective material 2 and the filling of removing alkadiene by selective hydrogenation catalyzer in dialkene removal reactor sequentially: be protective material 1, protective material 2, dialkene removal catalyzer from top to bottom successively, dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and lower end is provided with product outlet;

Described protective material 1, protective material 2 and the dialkene removal catalyzer of step (1) adopts grading loading technology, this grading loading technology comprises following several aspect, the granular size of (1), agent: protective material 1 particle is maximum, protective material 2 takes second place, dialkene removal catalyzer minimum; (2), the hydrogenation activity of agent size: protective material 1, protective material 2 and dialkene removal catalyzer all contain sulfide hydrogenation activity component; Its hydrogenation activity is sequentially dialkene removal catalyzer > protective material 2> protective material 1; (3), the bulk density size order of agent is dialkene removal catalyzer > protective material 2> protective material 1; (4), the pore volume size order of agent is protective material 1> protective material 2> dialkene removal catalyzer.

4. in accordance with the method for claim 1, it is characterized in that: described protective material 1, the protective material 2 of step (1) contains at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K), and these metal loads are to carrier;

The described dialkene removal catalyzer of step (1) at least contains a kind of VIII family metal, a kind of+3 valency metals, a kind of IA family metal, a kind of IVB family metal, the SiO of a kind of IIB family metal, Liang ZhongⅥ B family's metal and equal amount ₂-Al ₂o ₃the mixed metal oxide forming.

5. according to the method described in claim 1 or 4, it is characterized in that:

The described protective material 1 of step (1) has following feature: in oxide compound and take catalyst weight as benchmark, the content of VIII family metal is 0.5-1.5wt%, and the content of vib metal is 2-3wt%, and the content of IA family metal is 0.1-0.5wt%, and surplus is carrier; Pore volume is 0.92-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 15% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 70% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 15% of total pore volume;

The described protective material 2 of step (1) has following feature: in oxide compound and take catalyst weight as benchmark, the content of VIII family metal is 1.8-3.5wt%, the content of vib metal is 3.5-5.5wt%, and the content of IA family metal is 0.55-0.95wt%, and surplus is carrier; Pore volume is 0.70-0.90mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 20-100nm accounts for the more than 60% of total pore volume, and the pore volume that is less than the hole of 20nm accounts for below 30% of total pore volume;

The described dialkene removal catalyzer of step (1) has following feature: in oxide compound and take catalyst weight as benchmark, in this catalyzer, contain 10-40 % by weight VIII family metal, 5-30 % by weight+3 valency metals, the IA family metal of 0.1-8 % by weight, the IIB family metal of the IVB family metal of 0.1-8 % by weight, 0.1-30 % by weight are, the VI B family metal of 5-50 % by weight, the molar ratio of two kinds of group vib metals is 3:1-1:3,10-30 % by weight SiO ₂-Al ₂o ₃; SiO ₂-Al ₂o ₃middle SiO ₂account for the 90-99% of gross weight; The specific surface area 150-300m of this catalyzer ²/ g, pore volume 0.4-0.8ml/g.

6. it is characterized in that in accordance with the method for claim 5: wherein said VIII family metal is selected from Ni or Co; + 3 valency metals are selected from Cr or Al; IA family metal is selected from Na or K, and IVB family metal is selected from Ti or Zr, and IIB family metal is selected from Zn, and VI B family metal is selected from Mo and W.

7. according to the method described in claim 1,4,5 or 6, it is characterized in that: described protective material 1, protective material 2 and the dialkene removal catalyzer of step (1) needed to carry out sulfidizing before carrying out dialkene removal reaction, make it be converted into the active phase of sulfide with hydrogenating function;

Catalyzer in selection hydrodesulphurisatioreactors reactors described in step (3) needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of sulfide with hydrogenating desulfurization function;

The prevulcanized treatment condition of the catalyzer in the described selection hydrodesulphurisatioreactors reactors of protective material 1, protective material 2 and the dialkene removal catalyzer that step (1) is described and step (3) are: use containing 1-5wt%(and often adopt 2wt%) straight-run spirit of dithiocarbonic anhydride carries out prevulcanized as vulcanized oil to catalyzer (protective material 1, protective material 2 and dialkene removal catalyzer, select the catalyzer in hydrodesulphurisatioreactors reactors); concrete cure conditions is hydrogen dividing potential drop 1.6-4.0MPa; temperature 250-400 ° of C, liquid hourly space velocity 2.0-4.0h ^-1, hydrogen to oil volume ratio 100-500NL/L, curing time 30-70 hour.

8. it is characterized in that in accordance with the method for claim 1:

The described selection Hydrobon catalyst of step (2) contains at least one VIII family metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA family metal (being preferably selected from K), at least one IIB family metal (being preferably selected from Mg), and these metal loads are to carrier;

The described selection Hydrobon catalyst of step (2) has following feature: in oxide compound and take catalyst weight as benchmark, the content of VIII family metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA family metal is 0.5-4.5wt%, the content of IIA family metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that its mesoporous is greater than the hole of 100nm accounts for the more than 10% of total pore volume, and the pore volume in the hole of 5-100nm accounts for the more than 85% of total pore volume, and the pore volume that is less than the hole of 5nm accounts for below 5% of total pore volume;

The described sorbent material of step (4) forms by being selected from reduction-state VIII family base metal, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound and the tamanori aluminum oxide with activation sulfur-containing molecules;

The described VIII family base metal of step (4) accounts for the 1-30% of total desulfuration adsorbent total mass, IB family metal accounts for the 1-40% of desulfuration adsorbent total mass, IIB group 4 transition metal oxide compound accounts for the 10-70% of desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass.

9. it is characterized in that in accordance with the method for claim 8:

In selection Hydrobon catalyst described in step (2), VIII family metal is preferably selected from nickel and/or cobalt, and vib metal is preferably selected from molybdenum and/or tungsten, and IA family metal is selected from K, and IIB family metal is selected from Mg;

The described sorbent material of step (4) is selected from nickel and/or cobalt by being selected from the reduction-state VIII family base metal with activation sulfur-containing molecules, and reduction-state IB group 4 transition metal is selected from copper and/or silver, and IIB group 4 transition metal oxide compound is selected from ZnO.

10. in accordance with the method for claim 1, it is characterized in that: the described sorbent material of step (4) will be in hydrogen before carrying out adsorption desulfurize activation treatment 20-30 hour, activation temperature 250-400 ° of C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.