CN102899083A

CN102899083A - Ultra-deep combined desulphurization method for full-fraction FCC gasoline

Info

Publication number: CN102899083A
Application number: CN2012103398172A
Authority: CN
Inventors: 沈浩; 李�灿; 袁定雄; 罗万明; 刘宏伟; 王军峰; 李铖; 李达; 蒋宗轩; 刘铁峰; 杨民; 张�荣
Original assignee: Shaanxi Yanchang Petroleum Group Refining & Petrochemical Co; Dalian Institute of Chemical Physics of CAS
Current assignee: Shaanxi Yanchang Petroleum Group Refining & Petrochemical Co; Dalian Institute of Chemical Physics of CAS
Priority date: 2012-09-14
Filing date: 2012-09-14
Publication date: 2013-01-30
Anticipated expiration: 2032-09-14
Also published as: CN102899083B

Abstract

The invention relates to an ultra-deep combined desulphurization method for full-fraction FCC gasoline. The method comprises the following steps: (1) with full-fraction FCC gasoline and hydrogen as raw materials, successively contacting the raw materials with a protective agent 1, a protective agent 2 and a selective dialkene removing catalyst in a dialkene removing reactor under proper operation conditions to remove the most of dialkene in the full-fraction FCC gasoline raw material; (2) contacting the full-fraction FCC gasoline having undergone dialkene removal in step (1) with a catalyst in a selective hydrodesulfurization reactor under proper operation conditions so as to remove 40 to 60% of sulfur in the full-fraction FCC gasoline; and (3) subjecting the full-fraction FCC gasoline having undergone selective hydrodesulfurization in step (2) to separation in a gas-liquid separator and gas stripping to remove hydrogen sulfide dissolved in the full-fraction FCC gasoline, then mixing the full-fraction FCC gasoline with fresh hydrogen and contacting the full-fraction FCC gasoline with a catalyst in an adsorption ultra-deep desulphurization reactor under proper operation conditions so as to remove the most of sulfur in the gasoline, thereby obtaining a gasoline product with ultra low content of sulfur. The method has the advantages of low loss of an octane value, high liquid yield, high adsorptive selectivity of an adsorbent, great sulfur capacity and the like while carrying out ultra-deep desulphurization.

Description

A kind of full cut FCC gasoline ultra-deep desulfurization combined method

Technical field

The present invention relates to a kind of full cut FCC gasoline ultra-deep desulfurization combined method, particularly the full cut FCC gasoline dialkene removal of sulphur content 100-200ppmw with select hydrogenating desulfurization and absorption ultra-deep desulfurization combined method, sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw can be taken off to 10ppm by this combined method, and loss of octane number is lower than 1.5 units, and liquid yield is greater than 99.8%.

Background technology

The SO that organic sulfide in the gasoline produces behind engine combustion ₂Environment is produced many harm, mainly contains: acid rain, make precious metal " three-way catalyst " in the 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 the gasoline has been carried out stricter restriction, and carried out the super low-sulfur oil standard that is lower than 30ppmw in 2006.The developed country such as Japanese, Canadian, European also worked out corresponding rules, had carried out super low-sulfur oil (＜10ppmw sulphur) standard in 2005.Estimate that the content of sulfur in gasoline standard that sulphur content is lower than 1ppmw will be carried out later in 2014 in Europe.China's gasoline sulfur index request was also more and more higher, had taken the lead in carrying out the automobile-used super low-sulfur oil standard of capital V that sulphur content is lower than 10ppmw in Beijing on June 1st, 2012.

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

Although traditional hydrogenating desulfurization (HDS) can remove the sulfocompound (such as mercaptan, thioether, thiophene and derivatives and thionaphthene and derivative thereof etc.) in the 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 the gasoline are also saturated by hydrogenation.This has not only increased the hydrogen consumption greatly, has improved running cost, but also greatly reduces gasoline octane rating.In addition, behind hydrodesulfurization reaction, be dissolved in hydrogen sulfide in the gasoline and the alkene generation addition reaction in the gasoline and regenerate mercaptan, the amount of mercaptan is often greater than 10ppmw, and this has just increased the difficulty of gasoline ultra-deep desulfurization more.US Patent No. 4131537 discloses a kind of gasoline and has selected hydrodesulfurizationprocess process, it be with gasoline cut into light, weigh two cuts, lighting end is by caustic wash desulfuration alcohol, last running is by hydrogenating desulfurization, at last will through desulfurization gently, last running be mixed into sweet gasoline.The method desulfurization depth is very limited, sulphur in the full cut FCC gasoline can not be taken off to 10ppmw, a major reason is, hydrogenating desulfurization unavoidably causes being dissolved in hydrogen sulfide in the 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 was higher, the loss of octane number of sweet gasoline was larger, surpassed 2 units.Moreover, with full distillation gasoline cut into gently, last running need to expend a large amount of energy, process cost is higher.Chinese patent CN1158378C discloses a kind of method for making of low-sulphur oil.It mainly comprises: 1, the diolefine in the sour gasoline is removed by the selection method of hydrotreating; 2, the sour gasoline of dialkene removal is divided into light constituent and restructuring minute, makes light constituent wherein contain alkene as much as possible; 3, carry out the light constituent hydrogenating desulfurization at nickel-base catalyst; 4, on the catalyzer that contains at least a kind of VIII family's metal and/or at least a group vib metal, the hydrogenating desulfurization of restructuring component selections; 5, each component of desulfurization is mixed.Wherein light, the hydrodesulfurization condition of dividing of recombinating 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 the super low-sulfur oil that sulphur content is lower than 10ppmw by this patent, when restructuring minute middle olefin(e) centent was high, loss of octane number was larger, surpasses 2 units.In addition, this sulfur method route is oversize, and energy consumption is larger.Moreover the hydrogenating desulfurization that restructuring divides also unavoidably causes mercaptan again to generate.Therefore, sulphur content be taken off to 10ppmw, must carry out post-refining to the mercaptan that generates.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 gently, recombinates and divide, light constituent mercaptan removal, a restructuring minute hydrogenating desulfurization.Because restructuring divides and 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, this patent proposes to generate some alkene in the alkane generation cracking that zeolite ZSM-5 produces the part olefin saturated, and dry gas increases, the reduction of liquid yield but this unavoidably causes.In addition, these alkene react with the hydrogen sulfide that dissolves easily and regenerate mercaptan.Thereby also need to replenish hydro-sweetening, could realize that sulphur content is lower than the production of the super low-sulfur oil of 10ppmw.This certainly will cause the greatly increase 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 the 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.

The advantages such as adsorption desulfurize is gentle because of its operational condition, 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 get 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, does not have loss of octane number.It can be that catalytic cracking (FCC) gasoline of 1276ppm or coker gasoline desulfurization are to 120ppm with sulphur content.But the loading capacity of the desulfuration adsorbent that uses in this technological process is lower, thereby regeneration is frequent; Desulfurization depth is low, is difficult to sulphur content is taken 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, it can be with sulphur content the FCC gasoline desulfur of 775ppm to 10ppm, and loss of octane number is 1-2 unit.But this process operation condition is harsh, and still (370 ~ 410 ° of C, pressure are 7.1 ~ 21.2kg/cm to need with certain hydrogen dividing potential drop at comparatively high temps ²) under carry out, thereby process cost is high.In addition, because the sorbent material that this patent is used absorption sulfur capacity is low, thereby adsorbent reactivation is frequent, and in order to realize serialization production, this patent has been used fluidized-bed process.In fluidized-bed process, because the collision of absorbent particles and reactor wall is serious, and it is lower to contain the sorbent material intensity of zinc oxide, thereby the sorbent material loss is serious, the running cost height; And when sulphur and olefin(e) centent are high (when olefin(e) centent greater than 20w%), loss of octane number surpasses 2 units.

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 the/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 that absorption mode is the π complexing action, and action intensity is thiophene〉benzene, Cu ⁺Ag ⁺According to the author, such is applied in the true gasoline desulfur take the sorbent material of π complexing action as the basis, shows certain sweetening effectiveness.Under normal temperature, normal pressure, use Cu ⁺/ Y is sorbent material, is that the gasoline of 335ppm carries out desulfurization to sulphur content, and every gram sorbent material can produce the sweet gasoline of 14.7mL; When using gac to do protective layer, the producible sweet gasoline of every gram sorbent material is further brought up to 19.6mL.This illustrates that the absorption sulfur capacity of this sorbent material still can not satisfy the requirement of industrial application; On the other hand, because univalent copper ion is very unstable, disproportionation reaction occuring easily, 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 the 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 adsorption selectivity and the loading capacity of sulfide, is difficult to realize industrialization; 4, face in H-H reaction-adsorption desulfurize at fluidized-bed, operational condition is harsh, and energy consumption is high, and the sorbent material loss is serious, and process cost is high.Particularly when olefin(e) centent was high, the loss of octane number that causes surpassed 2 units; 5, face in H-H reaction-adsorption desulfurize at fluidized-bed, the 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 full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and absorption ultra-deep desulfurization combined method that the purpose of this invention is to provide a kind of full cut FCC gasoline ultra-deep desulfurization combined method, particularly sulphur content 100-200ppmw.Sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw can be taken off to 10ppm by this combined method, and loss of octane number is lower than 1.5 units, liquid yield is greater than 99.8%.

Technical scheme of the present invention is: a kind of full cut FCC gasoline ultra-deep desulfurization combined method, it is a kind of full cut FCC gasoline selective hydrogenation dialkene removal and selective hydrodesulfurization and selective adsorption ultra-deep desulfurization combined method, comprises the steps:

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

Step (2) through the full cut FCC gasoline of step (1) dialkene removal under the proper handling condition with select hydrodesulphurisatioreactors reactors in catalyzer contact, remove the sulphur more than 50% wherein;

Step (3) is selected hydrogenating desulfurization through step (2) full cut FCC gasoline mixes with new hydrogen after gas-liquid separator and air lift remove the hydrogen sulfide that is dissolved in wherein again, under suitable operational condition, contact with sorbent material in the absorption ultra-deep desulfurization reactor, remove the most of sulphur in the gasoline, namely obtain the super low-sulfur oil product;

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

Proper handling condition described in the step (2) refers to temperature of reaction 230-310 ° C; Hydrogen dividing potential drop 1.0-3.5MPa; Hydrogen to oil volume ratio 50-250NL/L; Liquid hourly space velocity 1.0-4.0h ^-1

Proper handling condition described in the step (3) refers to that hydrogen to oil volume ratio is 10-150NL/L; Hydrogen dividing potential drop 0.6-2.0MPa; Adsorption temp is 200-380 ° of C; Liquid hourly space velocity 1.0-4.0h ^-1

Described full cut FCC gasoline refers to the catalytic gasoline of whole fraction of total sulfur content 100-200ppmw, and full cut FCC gasoline refers to that boiling range is the FCC gasoline of 20-220 ° of C cut;

Most of diolefine in the described FCC of the removing gasoline stocks of step (1) refer to the diene content in the gasoline take off to maleic value be 0.2g I ₂Below/100g the oil;

The described sulphur more than 50% that removes wherein of step (2) refers to the sulphur in the FCC gasoline stocks of 100-200ppmw is taken off to 100ppmw;

The described super low-sulfur oil of step (3) refers to that sulphur content is lower than the gasoline products of 10ppmw;

The described air lift of step (4) removes the hydrogen sulfide that is dissolved in wherein and refers to that the hydrogen sulfide that will be dissolved in the FCC gasoline takes off to 1ppm.

Protective material 1 described in the step (1), protective material 2 and the filling of removing alkadiene by selective hydrogenation catalyzer in the dialkene removal reactor sequentially are: 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 the lower end is provided with the product outlet;

The described protective material 1 of step (1), protective material 2 and dialkene removal catalyzer adopt the 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, the dialkene removal catalyzer is 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 sequentially is the dialkene removal catalyzer〉protective material 2〉protective material 1; (3), the bulk density size order of agent is the dialkene removal catalyzer〉protective material 2〉protective material 1; (4), the pore volume size order of agent is protective material 1〉protective material 2〉the dialkene removal catalyzer.

The described protective material 1 of step (1), protective material 2 contain the metal oxide of at least a VIII family metal, at least a vib metal, at least a IA family metal, and these metal loads are to carrier; Described carrier is: aluminum oxide.

The described dialkene removal catalyzer of step (1) contains a kind of VIII family metal at least, and is 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, two kinds of VI B family's metals and equal amount ₂-Al ₂O ₃The mixed metal oxide that forms.

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 its mesoporous accounts for more than 15% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 20-100nm accounts for more than 70% of total pore volume, accounts for below 15% of total pore volume less than the pore volume in the hole of 20nm;

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 its mesoporous accounts for more than 10% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 20-100nm accounts for more than 60% of total pore volume, accounts for below 30% of total pore volume less than the pore volume in the hole of 20nm;

The described dialkene removal catalyzer of step (1) has following feature: in oxide compound and take catalyst weight as benchmark, contain in this catalyzer the 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 IVB family metal of 0.1-8 % by weight, the IIB family metal of 0.1-30 % by weight, 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 ₃SiO 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.

Described 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.

The described selection Hydrobon catalyst of step (2) contains at least a VIII family metal, at least a vib metal, at least a IA family metal, at least a IIB family metal, 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 its mesoporous accounts for more than 10% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 5-100nm accounts for more than 85% of total pore volume, accounts for below 5% of total pore volume less than the pore volume in the hole of 5nm.

The described protective material 1 of step (1), protective material 2 and dialkene removal catalyzer need to carry out sulfidizing before the dialkene removal reaction carrying out, and make it be converted into the active phase of the sulfide with hydrogenating function;

The described selection Hydrobon catalyst of step (2) needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of the sulfide with hydrogenating desulfurization function.

The described sorbent material of step (3) 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 tamanori aluminum oxide with activation sulfur-containing molecules;

The described VIII of step (3) 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, IIB group 4 transition metal oxide compound is the 10-70% that ZnO accounts for the desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass;

The described sorbent material of step (3) will be in hydrogen before carrying out adsorption desulfurize activation treatment 20-30 hour, activation temperature 250-400 ° of C, and pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.

Technique of the present invention is a kind of with full cut FCC gasoline dialkene removal fixed-bed reactor and the combined method of selecting hydrogenating desulfurization and absorption ultra-deep desulfurization fixed-bed reactor to connect.For guaranteeing the desulfuration adsorbent long-time steady operation, sulfur removal technology of the present invention is particularly suitable for the full cut FCC gasoline of sulphur content 100-200ppmw.

In combination process of the present invention; the dialkene removal fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, 1, the three layer of filling of second layer filling protective material protective material 2; the 4th layer of filling dialkene removal catalyzer, filling inert ceramic balls below the dialkene removal catalyzer.Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and the lower end is provided with the product outlet.Described protective material 1, protective material 2 and dialkene removal catalyzer need to carry out sulfidizing before the dialkene removal reaction carrying out, and make it be converted into the active phase of the sulfide with hydrogenating function.Sulfuration can be carried out in the dialkene removal reactor, also can carry out outside the dialkene removal reactor.These vulcanization process are that this research field is known.Sulfuration method commonly used in the device for example: use to contain 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 prevulcanized of device method commonly used: the catalyzer after the roasting (protective material 1, protective material 2 and dialkene removal catalyzer) oxide precursor is flooded organism or the inorganics that contains sulphur, and the mole number of the sulphur that usually contains in the steeping fluid is 1.0-1.8 times of the theoretical value of all reactive metal complete cures in the catalyzer.Load has the reactor of packing into after the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, will process in hydrogen 10-30 hour before carrying out hydrogenation reaction, 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 the hydrogenation dialkene removal reaction through vulcanizing laggard full cut FCC stock oil and hydrogen.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, before advancing to select hydrodesulphurisatioreactors reactors, diene content must take off to maleic value be 0.2g I ₂Below/100g the 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 the 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 the maleic value in the Maleic Anhydride Method mensuration FCC gasoline.Concrete steps are as follows: (1), put into flask with the oil sample of the accurate weighing 10.00g of analytical balance, add 20mL MALEIC ANHYDRIDE toluene solution (necessary hold over night after the preparation of MALEIC ANHYDRIDE toluene solution, can use after the filtration), add again 0.1mol/L toluene iodide solution 0.5mL, shake up.(2), then the ground flask is filled on the reflux condensing tube, reflux is 3 hours in 110 ℃ ± 2 ℃ water-baths, then solution is cooled to room temperature, adds water 5mL from the prolong upper end, continue temperature rising reflux 15min, wash for several times prolong with 5mLMTBE, 20mL moisture respectively after the cooling.(3), the ground flask is pulled down from prolong, carefully solution in the ground Erlenmeyer flask is transferred in the separating funnel and (must be guaranteed the stopping property of separating funnel in the process of the test, with liquid-leakage preventing, affect result precision), use first 20mL MTBE, divide respectively washing ground flask inwall three times with 25mL water again, washing lotion is poured in the separating funnel.(4), vibration separating funnel 4～5 minutes, static layering is put into the ground Erlenmeyer flask with water layer, oil reservoir divides and adds respectively 25mL, 10mL, 10mL water vibration extracting for three times, and water layer is incorporated in the ground Erlenmeyer flask.(5), in the ground Erlenmeyer flask, drip 1～2 of phenolphthalein indicator, being titrated to solution with the NaOH standard titration solution, to be incarnadine be terminal point, writes down the volume of consumption NaOH standard titration solution.(6), getting toluene 10.00g replaces sample to do blank test by the aforesaid operations condition.(7), the parallel sample of doing, monitoring analysis is collimation as a result.(8), the result calculates: (unit is g I to maleic value ₂/ 100g oil) be calculated as follows:

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

In the formula:

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

The 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 and unreacted hydrogen through dialkene removal mix with recycle hydrogen, enter to select in the hydrogenating desulfurization fixed-bed reactor through the interchanger heat exchange is laggard again.Fill out the larger inert ceramic balls of particle in the top of reactor, next Hydrobon catalyst, the larger inert ceramic balls of catalyzer lower end loaded particles are selected in filling.Described selection Hydrobon catalyst needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of the sulfide with hydrogenating desulfurization function.This selection Hydrobon catalyst can remove the sulphur more than 50% at least, the sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw can be taken off to 100ppm in other words.

Through selecting the FCC gasoline of hydrogenating desulfurization, after gas-liquid separator separates, the hydrogen sulfide that will be dissolved into wherein by gas stripping column again is down to below the 1ppmw, has so just obtained the full cut FCC gasoline that sulphur content is lower than 100ppmw.Full cut FCC gasoline after this desulfurization mixes with new hydrogen to enter after the interchanger heat exchange again and adsorbs in the ultra-deep desulfurization fixed-bed reactor.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.The technical characterictic of the employed sorbent material of patent of the present invention is described in detail in the previous work of Dalian Inst of Chemicophysics, Chinese Academy of Sciences, describe a kind of C 4 olefin desulfurization absorbent and method for making and application in detail such as CN101450302B, this sorbent material also can be used among the ultra-deep desulfurization combined method of full cut FCC gasoline of patent of the present invention.This desulfuration adsorbent forms by being selected from reduction-state VIII family base metal (such as cobalt and/or nickel), reduction-state IB group 4 transition metal (such as copper and/or silver), IIB group 4 transition metal oxide compound and tamanori aluminum oxide with activation sulfur-containing molecules.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, and pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NL H ₂/ L catalyzer hour.The 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, the present invention has following advantage:

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

(2) in facing hydrogen adsorption, the alkene loss is little, and loss of octane number is less than 1 unit;

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

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

(5) in the situation of 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%.

The invention will be further described below in conjunction with specific embodiment, but not as limitation of the present invention.The part that is not described in detail in the present embodiment is to adopt prior art, and industry standard or known approaches.

Description of drawings

Fig. 1 is the simplification of flowsheet figure of combination process of the present invention.

Among the figure: 1, the first pipeline; 2, the second pipeline; 3, the first mixing tank; 4, First Heat Exchanger; 5, the 3rd pipeline; 6, dialkene removal reactor; 7, the first filler; 8, protective material 1; 9, protective material 2; 10, dialkene removal catalyzer; 11, the second filler; 12, the 4th pipeline; 13, the second mixing tank; 14, the 5th pipeline; 15, the second interchanger; 16, the 6th pipeline 17, selection hydrodesulphurisatioreactors reactors; 18, the 3rd filler; 19, dialkene removal catalyzer; 20, the 4th filler; 21, the 7th pipeline; 22, gas-liquid separator; 23, the 8th pipeline; 24, alkali tourie; 25, the 9th pipeline; 26, the tenth pipeline; 27, air lift tank; 28, the 11 pipeline; 29, the 12 pipeline; 30, the 3rd mixing tank; 31, the 13 pipeline; 32, the 14 pipeline; 33, the 3rd interchanger; 34, the 15 pipeline; 35, adsorption desulfurize reactor; 36, the 5th filler; 37, sorbent material; 38, the 6th filler; 39, the 16 pipeline; 40, gas-liquid separator; 41, the 17 pipeline.

Embodiment

In combined method of the present invention; the dialkene removal fixed-bed reactor are the larger inert ceramic balls of loaded particles topmost, 1, the three layer of filling of second layer filling protective material protective material 2; the 4th layer of filling dialkene removal catalyzer, filling inert ceramic balls below the dialkene removal catalyzer.Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and the lower end is provided with the product outlet.Wherein, protective material 1, protective material 2 and dialkene removal catalyzer adopt the 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, the dialkene removal catalyzer is 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 sequentially is the dialkene removal catalyzer〉protective material 2〉protective material 1.(3), the bulk density size order of agent is the dialkene removal catalyzer〉protective material 2〉protective material 1.(4), the pore volume size order of agent is protective material 1〉protective material 2〉the dialkene removal catalyzer.

Protective material 1, protective material 2 contain the metal oxide of at least a VIII family's metal (preferably being selected from nickel, cobalt), at least a vib metal (preferably being selected from molybdenum, tungsten) and at least a IA family's metal (preferably being selected from K) usually, and these metal loads are to carrier; Described carrier is: aluminum oxide; 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 its mesoporous accounts for more than 15% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 20-100nm accounts for more than 70% of total pore volume, accounts for below 15% of total pore volume less than the pore volume in the hole of 20nm.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 its mesoporous accounts for more than 10% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 20-100nm accounts for more than 60% of total pore volume, accounts for below 30% of total pore volume less than the pore volume in the hole of 20nm.

The dialkene removal catalyzer contains a kind of VIII family metal at least, and is 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 two kinds of VI B family's metals and equal amount ₂-Al ₂O ₃The mixed metal oxide that forms, it is characterized in that, in oxide compound and take catalyst weight as benchmark, contain in this catalyzer the 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 IVB family metal of 0.1-8 % by weight, the IIB family metal of 0.1-30 % by weight, two kinds of VI B family metals 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 ₃SiO ₂-Al ₂O ₃Middle SiO ₂Account for the 90-99% of gross weight;

Protective material 1, protective material 2 and dialkene removal catalyzer need to carry out sulfidizing before the dialkene removal reaction carrying out, and make it be converted into the active phase of the metallic sulfide with hydrogenating function.Sulfuration can be carried out in the dialkene removal reactor, also can carry out outside the dialkene removal reactor.These vulcanization process are that this research field is known.Sulfuration method commonly used in the device for example: use to contain 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 prevulcanized of device method commonly used: the catalyst oxidation thing precursor after the roasting is flooded organism or the inorganics that contains sulphur, and the mole number of the sulphur that usually contains in the steeping fluid is 1.0-1.8 times of the theoretical value of all reactive metal complete cures in the catalyzer.Load has the reactor of packing into after the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, will process in hydrogen 10-30 hour before carrying out hydrogenation reaction, 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 the 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 ^-1In order to guarantee dialkene removal and to select hydrogenating desulfurization and the long-term stability operation of absorption ultra-deep desulfurization series combination method, before advancing to select hydrodesulphurisatioreactors reactors, diene content must take off to maleic value be 0.2g I ₂Below/100g the 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.

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

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

In the formula:

W=sample mass (g)

Full cut FCC gasoline and unreacted hydrogen through dialkene removal mix with recycle hydrogen, enter to select in the hydrogenating desulfurization fixed-bed reactor through the interchanger heat exchange is laggard again.Fill out the larger inert ceramic balls of particle in the top of reactor, next Hydrobon catalyst, the larger inert ceramic balls of catalyzer lower end loaded particles are selected in filling.The employed selection Hydrobon catalyst of patent of the present invention contains at least a VIII family's metal (preferably being selected from nickel, cobalt), at least a vib metal (preferably being selected from molybdenum, tungsten), at least a IA family's metal (preferably being selected from K), at least a IIB family's metal (preferably being selected from Mg), and these metal loads are to carrier.Described selection Hydrobon catalyst 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 its mesoporous accounts for more than 10% of total pore volume greater than the pore volume in the hole of 100nm, and the pore volume in the hole of 5-100nm accounts for more than 85% of total pore volume, accounts for below 5% of total pore volume less than the pore volume in the hole of 5nm.Described selection Hydrobon catalyst needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into the active phase of the sulfide with hydrogenating desulfurization function.This selection Hydrobon catalyst can remove the sulphur more than 50% at least, the sulphur in the FCC gasoline of sulphur content 100-200ppmw can be taken off to 100ppm in other words.

Through selecting the FCC gasoline of hydrogenating desulfurization, after gas-liquid separator separates, the hydrogen sulfide that will be dissolved into wherein by air lift again is down to below the 1ppmw, has so just obtained the full cut FCC gasoline that sulphur content is lower than 100ppmw.Full cut FCC gasoline after this desulfurization mixes with new hydrogen to enter after the interchanger heat exchange again and adsorbs in the ultra-deep desulfurization fixed-bed reactor.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.The technical characterictic of the employed sorbent material of patent of the present invention is described in detail in the previous work of this research group, describe a kind of C 4 olefin desulfurization absorbent and method for making and application in detail such as CN101450302B, this sorbent material also can be used among the ultra-deep desulfurization combined method of full cut FCC gasoline of patent of the present invention.This desulfuration adsorbent is by being selected from reduction-state VIII family base metal, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound with activation sulfur-containing molecules and forming take aluminum oxide as tamanori.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, and pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NLH ₂/ L catalyzer hour.The 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 combined method of the present invention.Hydrogen passes through First Heat Exchanger 4 heat exchange through the first pipeline 1 and full cut FCC stock oil again after the second pipeline 2 together enters 3 mixing of the first mixing tank; enter dialkene removal reactor 6 through the hydrogen of heat exchange and full cut FCC stock oil mixture through the 3rd pipeline 5, be filled with successively from top to bottom in the dialkene removal reactor 6 among the first filler 7, protective material 1(Fig. 1 and be labeled as 8), be labeled as 9 among protective material 2(Fig. 1), dialkene removal catalyzer (being labeled as 10 among Fig. 1), the second filler 11.The material of dialkene removal is after the 4th pipeline 12 enters the second mixing tank 13 and recycle hydrogen from the 5th pipeline 14 mixes, again after 15 heat exchange of the second interchanger, enter through the 6th pipeline 16 again and select hydrodesulphurisatioreactors reactors 17, select to be filled with successively from top to bottom the 3rd filler 18, catalyzer 19, the 4th filler 20 in the hydrodesulphurisatioreactors reactors 17, material through selecting hydrogenating desulfurization enters gas-liquid separator 22 through the 7th pipeline 21, gas enters alkali tourie 24 absorbing hydrogen sulphides through the 8th pipeline 23, and hydrogen enters the hydrogen recycle system through the 9th pipeline 25; Entering the hydrogen sulfide air lift that will be dissolved in the air lift tank 27 in the liquid material from gas-liquid separator 22 liquid out through the tenth pipeline 26 removes, the mixed gas of hydrogen and hydrogen sulfide enters the recycle hydrogen system through the 11 pipeline 28, through the liquid material after the air lift through the 12 pipeline 29 with after new hydrogen via the 13 pipeline 31 mixes in the 3rd mixing tank 30 again through the 14 pipeline 32, after 33 heat exchange of the 3rd interchanger, enter adsorption desulfurize reactor 35 through the 15 pipeline 34 again, in the adsorption desulfurize reactor 35 from top to bottom one-time pad the 5th filler 36 is arranged, sorbent material 37, the 6th filler 38, enter gas-liquid separator 40 through the 16 pipeline 39 again, obtain sulphur content finally by the 17 pipeline 41 and be lower than 10ppmw, loss of octane number is lower than 1.5 units, and liquid yield is greater than 99.8% super low-sulfur oil.Dialkene removal reactor upper end is provided with the feed(raw material)inlet of gasoline and hydrogen, and the lower end is provided with the product outlet; Hydrodesulphurisatioreactors reactors and adsorption desulfurize reactor upper end are provided with the feed(raw material)inlet, and the lower end is provided with the product outlet;

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

1, the preparation of protective material 1: with 116 milliliters of dippings of the solution that contains potassium hydroxide 0.44 gram, 100 gram alumina supporters; after 120 degree oven dry, 450 degree roastings; flood again the total immersions that contain nickelous nitrate 5.95 grams and 3.72 gram ammonium molybdates and steep 85 milliliters of solution; through 120 degree oven dry, the 450 degree roastings agent 1 that namely is protected, it consists of 1.43wt%NiO-2.86wt%-0.30wt%/Al ₂O ₃The preparation method of employed protective material 1 is identical among the following example 1-embodiment 8, and just each component concentration is different.

2, the preparation of protective material 2: with 100 milliliters of dippings of the solution that contains potassium hydroxide 0.92 gram, 100 gram alumina supporters; after 120 degree oven dry, 450 degree roastings; flood again the total immersions that contain nickelous nitrate 11.90 grams and 7.44 gram ammonium molybdates and steep 70 milliliters of solution; through 120 degree oven dry, the 450 degree roastings agent 2 that namely is protected, it consists of 2.73wt%NiO-5.48wt%MoO ₃-0.60wt%K ₂O/Al ₂O ₃The preparation method of employed protective material 2 is identical among the following example 1-embodiment 8, and just each component concentration is different.

The preparation method of dialkene removal catalyzer is as follows:

A. take by weighing respectively 0.1mol nickelous nitrate, 0.1mol zinc nitrate and 0.05mol, they are dissolved in the 200ml water form the aqueous solution, to wherein slowly dripping 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, back flow reaction is 25 hours under 80 ℃ of temperature of reaction; The green precipitate that reaction is obtained filters; This catalyst precursor is added in the 200ml water, be configured to slurry precursor;

B. take by weighing respectively a certain amount of ammonium molybdate and ammonium metawolframate, wherein Mo ⁶⁺0.01mol, W ⁶⁺0.01mol, they are dissolved in the 350ml water, form solution, and this solution is heated to temperature of reaction, constantly stir, form colourless transparent solution; Measure subsequently the homemade slurry precursor of part, wherein contain Ni ²⁺0.03mol, Zn ²⁺0.03mol, Al ³⁺0.015mol be heated to 80 ℃ of temperature of reaction; These slurries are added in the 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 120 ℃ of oven dry 12 hours, 420 ° of C roastings obtained the mixed metal oxide particulate state brownish black catalyst precursor of containing metal Ni, Zn, Al, K, Mo and W in 4 hours.

C. the mixed metal oxide particulate state brownish black catalyst precursor of containing metal Ni, Zn, Al, K, Mo and W is pulverized, be sieved into 160 purpose powders, add the SiO that contains Ti ₂-Al ₂O ₃The abundant kneading of the binding agent of mixture is extruded into φ 2.0 trifolium bar shapeds through banded extruder, and through dry 12 hours of 120 ° of C, 420 ° of C roastings formed the catalyst n iZnAlKTiMoW/SiO with highly disperse active species in 4 hours ₂-Al ₂O ₃Through 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 employed dialkene removal catalyzer is identical among the following example 1-embodiment 8, and just each component concentration is different.

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

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

The preparation method of sorbent material: by the Chinese invention patent CN101450302B embodiment 1 described method preparation of Dalian Inst of Chemicophysics, Chinese Academy of Sciences.Concrete steps are as follows: (1) takes by weighing 1.60 gram nickelous nitrates, 3.20 gram cupric nitrates, 0.51 gram aluminum oxide and 7.35 gram zinc nitrates and joins in 200 milliliters the distilled water, add under 8.10 gram urea, 90 degree and fully stir 24 hours so that the precipitation agent complete hydrolysis, after filtration, deionized water wash, obtain wet cake, dry in 120 degree again, obtain dry sample; (2) above-mentioned dry sample is fully mixed with 1 gram alumina dry glue, the adding concentration of nitric acid is 5 milliliters of abundant kneadings of the aqueous solution of 2%, makes body of paste, is extruded into cloverleaf pattern with banded extruder again, and in 120 degree dried overnight, 450 degree roastings 4 hours namely 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 employed sorbent material is identical among the following example 1-embodiment 8, and just each component concentration is different.

Embodiment

In order to further specify 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 the dialkene removal reactor is 1-2:1-2:2-8 than can adopt the loading height ratio for 1:1:4().

The character of the used full cut FCC gasoline stocks of table 1 expression the present invention.

Table 1, full cut FCC gasoline property

Embodiment 1(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

The full cut FCC gasoline of character as described in Table 1 mixes with hydrogen by entering the dialkene removal reactor after the interchanger heat exchange, is filled with protective material 1(1.2%NiO-2.4%MoO in the dialkene removal reactor (1 centimetre of internal diameter) 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 ₃2.5mL, 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 ₃10mL, before oil product and hydrogen entered the dialkene removal reactor, protective material and dialkene removal catalyzer will carry out prevulcanized in the device.Cure conditions is to use the straight-run spirit that contains 2wt% dithiocarbonic anhydride that catalyzer is carried out prevulcanized, 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.Laggard raw material is finished in sulfuration and hydrogen carries out the hydrogenation dialkene removal reaction.The 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 ^-1React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Through the gasoline behind the dialkene removal and hydrogen with enter to select hydrodesulphurisatioreactors reactors (1 centimetre of internal diameter), the catalyzer in this reactor through the interchanger heat exchange is laggard again after the recycle hydrogen of metering mixes

(2.0wt%CoO-7.1wt%MoO ₃-1.5wt%K ₂O-3.5wt%MgO/Al ₂O ₃) prevulcanized of 10mL, the prevulcanized condition is to use the straight-run spirit that contains 2wt% dithiocarbonic anhydride to selecting Hydrobon catalyst to carry out prevulcanized, 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.Laggard raw material is finished in sulfuration and hydrogen is selected hydrodesulfurization reaction.The hydrodesulfurization reaction condition is 260 ° of C of temperature of reaction, hydrogen dividing potential drop 1.4MPa, hydrogen to oil volume ratio 150NL/L, night hourly space velocity 2.0h ^-1React sampling analysis after 500 hours, find that sulphur content drops to 76.0ppmw from 165.6ppmw, octane value is 89.0, and loss of octane number only is 0.6.After mixing by the interchanger heat exchange, FCC gasoline through selecting hydrogenating desulfurization and new hydrogen enters the adsorption desulfurize reactor.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.The 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 ^-1React sampling analysis after 500 hours, find, total sulfur content is down to 7.6ppmw from the 76.0ppmw of raw material, and octane value is from selecting 89.0 of hydrogenation stock oil out to be down to 88.2, loss of octane number is 0.8 unit only, 0.6 octane value together with selecting the hydrogenating desulfurization loss loses 1.4 octane value units, altogether less than 1.5 octane value units; Olefin(e) centent is down to 22.3% from 26.5% of stock oil, has only descended 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 combined method, not only the sulphur in the full cut FCC raw material of sulphur content 100-200ppmw can be taken off to 10ppmw, and loss of octane number is less than 1.5 units, and liquid yield is greater than 99.8%.

Embodiment 2(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

The protective material that uses, dialkene removal catalyzer, selection Hydrobon catalyst and sorbent material are with embodiment 1; difference from Example 1 is that just the 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 ^-1React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Select the 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 ^-1The 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 ^-1React sampling analysis after 500 hours, find, total sulfur content is down to 7.8ppmw from the 165.6ppmw of raw material, and octane value is down to 88.3 from 89.6 of stock oil, loss of octane number is 1.3 units only, olefin(e) centent is down to 22.5% from 26.5% of stock oil, has only descended 4.0%, liquid yield 99.9%.

Embodiment 3(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except changing the protective material 1 among the embodiment 1 into 0.58%NiO-1.4%MoO ₃-0.29%K ₂O/Al ₂O ₃Change 1.20%NiO-2.60%MoO into protective material 2 ₃-0.7%K ₂O/Al ₂O ₃Outward, other conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.8ppmw from the 165.6ppmw of raw material, and octane value is down to 88.2 from 89.6 of stock oil, and loss of octane number is 1.4 units only, and olefin(e) centent is down to 22.2% from 26.5% of stock oil, has only descended 4.3%, liquid yield 99.9%.

Embodiment 4(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except the dialkene removal catalyzer among the embodiment is changed 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 conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 6.8ppmw from the 165.6ppmw of raw material, and octane value is down to 88.3 from 89.6 of stock oil, and loss of octane number is 1.3 units only, and olefin(e) centent is down to 22.2% from 26.5% of stock oil, has only descended 4.3%, liquid yield 99.9%.

Embodiment 5(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except changing the sorbent material in the adsorption desulfurize reactor among the embodiment 1 into 8%NiO-6%CuO-66%ZnO-20%Al ₂O ₃Outward, other conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.8ppmw from the 165.6ppmw of raw material, and octane value is down to 88.5 from 89.6 of stock oil, and loss of octane number is 1.1 units only, and olefin(e) centent is down to 22.6% from 26.5% of stock oil, has only descended 3.9%, liquid yield 99.9%.

Embodiment 6(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except changing the sorbent material in the adsorption desulfurize reactor among the embodiment 1 into 12.5%NiO-2.5%CuO-65%ZnO-20%Al ₂O ₃Outward, other conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 8.8ppmw from the 165.6ppmw of raw material, and octane value is down to 88.3 from 89.6 of stock oil, and loss of octane number is 1.3 units only, and olefin(e) centent is down to 22.3% from 26.5% of stock oil, has only descended 4.2%, liquid yield 99.9%.

Embodiment 7(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except changing the sorbent material in the adsorption desulfurize reactor among the embodiment 1 into 7.5%NiO-2.5%CuO-65%ZnO-25%Al ₂O ₃Outward, other conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 9.3ppmw from the 165.6ppmw of raw material, and octane value is down to 88.7 from 89.6 of stock oil, and loss of octane number is 0.9 unit only, and olefin(e) centent is down to 22.8% from 26.5% of stock oil, has only descended 3.7%, liquid yield 99.9%.

Embodiment 8(is according to the present invention): full cut FCC gasoline dialkene removal and selection hydrogenating desulfurization and adsorption desulfurize combined method

Except changing the sorbent material in the adsorption desulfurize reactor among the embodiment 1 into 25%NiO-2.5%CuO-52.5%ZnO-20%Al ₂O ₃Outward, other conditionally complete is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI ₂/ 100g oil drops to below 0.1.Total sulfur content is down to 4.3ppmw from the 165.6ppmw of raw material, and octane value is down to 88.2 from 89.6 of stock oil, and loss of octane number is 1.4 units only, and olefin(e) centent is down to 22.1% from 26.5% of stock oil, has only descended 4.4%, liquid yield 99.9%.

Combined method of the present invention not only has operational condition and relaxes, saved the mercaptan removal step of selecting in the 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 (less than 1.5 units), liquid yield high (greater than 99.8%), the advantages such as the sorbent material adsorption selectivity is high, current capacity large (surpassing 15%).

The part that present embodiment is not described in detail and english abbreviation belong to the common practise of the industry, can search on the net, here not one by one narration.

Claims

1. full cut FCC gasoline ultra-deep desulfurization combined method, it is a kind of full cut FCC gasoline selective hydrogenation dialkene removal and selective hydrodesulfurization and selective adsorption ultra-deep desulfurization combined method, comprises the steps:

2. according to a kind of full cut FCC gasoline ultra-deep desulfurization 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 100-200ppmw, and full cut FCC gasoline refers to that boiling range is the FCC gasoline of 20-220 ° of C cut;

3. according to a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 1, it is characterized in that: the protective material 1 described in the step (1), protective material 2 and the filling of removing alkadiene by selective hydrogenation catalyzer in the dialkene removal reactor sequentially are: 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 the lower end is provided with the product outlet;

4. according to a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 1, it is characterized in that: the described protective material 1 of step (1), protective material 2 contain the metal oxide of at least a VIII family metal, at least a vib metal and at least a IA family metal, and these metal loads are to carrier; Described carrier is: aluminum oxide;

5. according to claim 1 or 4 described a kind of full cut FCC gasoline ultra-deep desulfurization combined methods, it is characterized in that:

6. according to a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 5, it is characterized in that: described 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 a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 1, it is characterized in that: the described selection Hydrobon catalyst of step (2) contains at least a VIII family metal, at least a vib metal, at least a IA family metal, at least a IIB family metal, and these metal loads are to carrier;

8. according to claim 1,5,6 or 7 described a kind of full cut FCC gasoline ultra-deep desulfurization combined methods, it is characterized in that: the described protective material 1 of step (1), protective material 2 and dialkene removal catalyzer need to carry out sulfidizing before the dialkene removal reaction carrying out, and make it be converted into the active phase of the sulfide with hydrogenating function;

9. according to a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 1, it is characterized in that: the described sorbent material of step (3) 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 tamanori aluminum oxide with activation sulfur-containing molecules;

The described VIII of step (3) 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, IIB group 4 transition metal oxide compound is the 10-70% that ZnO accounts for the desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass.

10. according to a kind of full cut FCC gasoline ultra-deep desulfurization combined method claimed in claim 1, it is characterized in that the described sorbent material of step (3) 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.