CN103666559B - A kind of FCC gasoline ultra-deep desulfurization combined method - Google Patents
A kind of FCC gasoline ultra-deep desulfurization combined method Download PDFInfo
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Abstract
A kind of FCC gasoline ultra-deep desulfurization combined method, comprise step: (1) with full cut FCC gasoline and hydrogen for raw material, under proper condition in dialkene removal reactor with protective material 1,2 and selectivity dialkene removal catalyst exposure, remove the most of diolefine in full cut FCC gasoline raw material; (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 obtains of step (2) under proper handling condition with the catalyst exposure in selective hydrodesulfrization reactor; (4) light gasoline fraction obtained through step (2) and mixing with new hydrogen again after the heavy naphtha mixing of step (3) selective hydrodesulfrization, under proper condition with adsorbent contact in absorption ultra-deep desulfurization reactor, remove most of sulphur in gasoline, obtain sulphur content lower than 10ppmw super low-sulfur oil product.
Description
Technical field
The present invention relates to a kind of FCC gasoline ultra-deep desulfurization combined method, the particularly FCC gasoline ultra-deep desulfurization combined method of sulphur content 200-1000ppmw, sulphur in the FCC gasoline of sulphur content 200-1000ppmw can be taken off to below 10ppm by this combination process, and loss of octane number is lower than 1.5 units, 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 the precious metal in engine tail gas purification system " three-way catalyst " produce irreversible poisoning, be the significant contributor, corroding metal equipment etc. of Atmospheric Grains matter.For this reason, the U.S. has promulgated new Clean Air Act Amendment (CAAA) in early 1990s, work out stricter environmental legislation, stricter restriction has been carried out to the sulphur content in gasoline, and perform the super low-sulfur oil standard lower than 30ppmw in 2006.The developed country such as Japanese, Canadian, European has also worked out corresponding regulation, performs super low-sulfur oil (<10ppmw sulphur) standard in 2005.Estimate, Europe will perform the lower content of sulfur in gasoline standard of sulphur content after 2014.China's gasoline sulfur index request is also more and more higher, takes the lead in performing the capital V super low-sulfur oil standard of sulphur content lower than 10ppmw on June 1st, 2012 in Beijing.
Gasoline except being used as except power fuel in communications and transportation, because it is storing and high-energy-density in transportation, to be easy to get and the advantage such as safe, thus it is very likely used as the raw material of vehicle-mounted reformation hydrogen production in the engine system of new generation taking fuel cell as power.But, no matter be gasoline reforming hydrogen manufacturing part or fuel battery engines part, all must intimate without sulphur (lower than 0.1ppm) condition under carry out, because the noble metal catalyst (as platinum etc.) used in these parts is easy to by sulphur irreversible poisoning.Thus from the angle of the development & application of fuel cell, the intimate sweet gasoline of production is also a very urgent research topic.
Although traditional hydrogenating desulfurization (HDS) effectively can remove the sulfocompound (as mercaptan, thioether, thiophene and derivatives and thionaphthene and derivative etc. thereof) in gasoline, but along with the increase of the hydrogenating desulfurization degree of depth, be present in a large amount of alkene in gasoline and aromatic hydrocarbons also by hydrotreated lube base oil.This not only considerably increases hydrogen consumption, improves running cost, but also greatly reduces gasoline octane rating.In addition, in the later stage of reaction, the alkene generation addition reaction of dissolving in hydrogen sulfide in the product and oil product regenerates mercaptan, and the amount of mercaptan, often beyond 10ppmw, which greatly increases the difficulty of ultra-deep desulfurization.So, after selective hydrodesulfrization, also must could meet product mercaptans content index by caustic wash desulfuration alcohol technique.The environmental problem that caustic wash desulfuration alcohol technique must bring alkaline residue to discharge.US Patent No. 4131537 discloses a kind of gasoline selective hydrodesulfrization method, it be gasoline is cut into light, weigh two cuts, lighting end is by caustic wash desulfuration alcohol, and light, last running through desulfurization, by hydrogenating desulfurization, are finally mixed into sweet gasoline by last running.The method desulfurization depth is very limited, can not sulphur content be taken off to below 10ppmw higher than the sulphur in the full cut FCC gasoline of 300ppmw, a major reason is, hydrogenating desulfurization unavoidably causes dissolving hydrogen sulfide in the product and alkene and again to react generation mercaptan, and the amount of the mercaptan of generation is often beyond 10ppmw.And when the olefin(e) centent of last running is higher, the loss of octane number of sweet gasoline is comparatively large, more than 2 units.Chinese patent CN1158378C discloses a kind of method for making of low-sulphur oil.It mainly comprises: 1, removed by selec-tive hydrogenation method by the diolefine in sour gasoline; 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, light constituent hydrogenating desulfurization is carried out; 4, at least containing on the catalyzer of a kind of group VIII metal and/or at least one group vib metal, heavy constituent selective hydrodesulfrization; 5, each component mixing of desulfurization.Wherein hydrodesulfurization condition that is light, heavy constituent has following feature: temperature of reaction 160-420 ° of 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 of sulphur content lower than 10ppmw by this patent, when in heavy constituent during olefin(e) centent height, loss of octane number is comparatively large, more than 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 is taken off to below 10ppmw, post-refining must be carried out to the mercaptan generated.This must cause the increase of process cost.US Patent No. 5318690 discloses a kind of gasoline desulfating method, comprises and first gasoline rectifying is become 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 hydrotreated lube base oil when hydrogenating desulfurization, causes loss of octane number larger.In order to compensate the loss of octane value, this patent proposes on zeolite ZSM-5, make the alkane generation cracking of the saturated generation of some olefin generate some alkene, but this unavoidably causes, and dry gas increases, the reduction of liquid yield.In addition, these alkene easily react with the hydrogen sulfide dissolved and regenerate mercaptan.Thus also need supplementary hydro-sweetening, the production of sulphur content lower than the super low-sulfur oil of 10ppmw could be realized.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 also exist very large gap, and along with the continuous increase to crude oil demand amount, need from external import substantial oil, wherein major part is Middle East high-sulfur crude oil, so China more needs, exploitation is a kind of efficiently, the gasoline desulfur technology of low cost.Adsorption desulfurize is considered to one of very promising desulfurization technology of one.
Adsorption desulfurize, 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, thus gets more and more people's extensive concerning.US Patent No. P5730860 discloses a kind of gasoline adsorption selection sulfur method, develops a kind of IRVAD
tMtechnique.Whole operating process does not consume hydrogen, does not have loss of octane number.Sulphur content can be that catalytic cracking (FCC) gasoline of 1276ppm or coker gasoline desulfurization are to below 120ppm by it.But the loading capacity of the desulfuration adsorbent used in this technological process is lower, thus regeneration is frequent; Desulfurization depth is low, is difficult to sulphur content to take off to below 10ppmw.This greatly limits 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, develop a kind of S-Zorb technique, it can be by sulphur content the FCC gasoline desulfurization of 775ppm to below 10ppm, and loss of octane number is 1-2 unit.But this process conditions is harsh, still need (370 ~ 410 ° of C, pressure be 7.1 ~ 21.2kg/cm in comparatively high temps and certain hydrogen dividing potential drop
2) under carry out, thus process cost is high.In addition, the adsorbent sulfur capacity used due to this patent is low, and thus adsorbent reactivation is frequent, and in order to realize continuous prodution, this patent employs fluidized-bed process.In fluidized-bed process, because absorbent particles and reactor wall collide seriously, and lower containing the sorbent material intensity of zinc oxide, and thus sorbent material loss is serious, and running cost is high; And when sulphur and olefin(e) centent height (when olefin(e) centent is greater than 20w%), loss of octane number is more than 2 units.
The people such as Yang (Ind.Eng.Chem.Res., 2003,42 (13): 3103.) have investigated model thiophene and benzene at Cu
+/ Y and Ag
+absorption behavior on/Y sorbent material.Compared with NaY, Cu
+/ Y and Ag
+/ Y all has larger loading capacity and adsorption selectivity to thiophene and benzene at lower pressures.Molecular Orbital Calculation shows, absorption mode is π complexing action, and action intensity is thiophene > benzene, Cu
+>Ag
+.According to author, such sorbent material based on π complexing action is applied in true gasoline desulfur, shows certain sweetening effectiveness.Under normal temperature, normal pressure, use Cu
+/ Y is sorbent material, and carry out desulfurization to the gasoline that sulphur content is 335ppm, 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 brings up to 19.6mL further.This illustrates that the absorption sulfur capacity of this sorbent material still can not meet the requirement of industrial application; On the other hand, because univalent copper ion is very unstable, easily disproportionation reaction occurs, generate more stable bivalent cupric ion and metallic copper, thus this also greatly limit its industrial application.
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, selective hydrodesulfrization operational path is long, and energy consumption is high, and loss of octane number is large, and process cost is high; 2, in selective hydrodesulfrization, caustic wash desulfuration alcohol technique also creates the environmental problems such as a large amount of alkaline residues; 3, adsorption selection desulfurization use sorbent material to the adsorption selectivity of sulfide and loading capacity lower, be 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 sorbent material loss is serious, and process cost is high.Particularly when olefin(e) centent height, the loss of octane number caused is more than 2 units; 5, face in H-H reaction-adsorption desulfurize at fluidized-bed, 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, the full cut FCC gasoline ultra-deep desulfurization combined method of preferred 200-350ppmw, best 200-250ppmw.Can by sulphur content 200-1000ppmw by this combined method, the sulphur in the full cut FCC gasoline of preferred 200-350ppmw, best 200-250ppmw takes off to below 10ppm, and loss of octane number is lower than 1.5 units, and liquid yield is greater than 99.8%.
Combined method of the present invention be a kind ofly full cut FCC gasoline dialkene removal, dialkene removal fractionate are become light gasoline fraction and heavy naphtha, heavy naphtha mixes the combined method of being undertaken connecting by adsorbing ultra-deep desulfurization fixed-bed reactor through selective hydrodesulfrization, the light gasoline fraction that obtains with fractionation again through the heavy naphtha of selective hydrodesulfrization.For ensureing 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; the dialkene removal fixed-bed reactor inert ceramic balls that topmost loaded particles is larger, second layer filling protective material 1, third layer filling protective material 2; 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 exit.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 is minimum.(2), the hydrogenation activity size of agent.Protective material 1, protective material 2 and dialkene removal catalyzer all contain sulfide hydrogenation active component.Its hydrogenation activity order is 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 are usually containing at least one group VIII metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA race metal (being preferably selected from K), and these metal loads are on the carrier with specified pore structure.Wherein protective material 1 has following technical characteristic: be benchmark with oxide basis and with catalyzer, and the content of group VIII metal is 0.5-1.5wt%, and the content of vib metal is the content of 2-3wt%, IA race 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 the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 15%, 20-100nm of total pore volume accounts for more than 70% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 15% of total pore volume.Protective material 2 has following technical characteristic: be benchmark with oxide basis and with catalyzer, and the content of group VIII metal is 1.8-3.5wt%, and the content of vib metal is the content of 3.5-5.5wt%, IA race 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 the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 20-100nm of total pore volume accounts for more than 60% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 30% of total pore volume.
Dialkene removal catalyzer at least contains a kind of VIII race's metal, a kind of+3 valency metals, a kind of IA race metal, a kind of IVB race metal, the SiO of a kind of IIB race metal, two kind of VI B race metal and equal amount
2-Al
2o
3the mixed metal oxide of composition, it is characterized in that, be benchmark with oxide basis and with catalyzer, the SiO of the IA race metal of the group VIII metal containing 10-40 % by weight in this catalyzer ,+3 valency metals of 5-30 % by weight, 0.1-8 % by weight, the IVB race metal of 0.1-8 % by weight, the IIB race metal of 0.1-30 % by weight, two kind of VI B race metal of 5-50 % by weight and 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 have the sulfide active phase of hydrogenating function.Sulfuration can be carried out in dialkene removal reactor, also can carry out outside dialkene removal reactor.These vulcanization process are known by this research field.The method that such as, in device sulfuration is conventional: use and often adopt 2wt% containing 1-5wt%() 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 method that ex situ presulfiding is conventional: the organism or the inorganics that the catalyst oxidation thing precursor dipping after roasting are contained sulphur, the mole number of the sulphur contained in usual steeping fluid is 1.0-1.8 times of the theoretical value of all active metal complete cures in catalyzer.Load loads reactor after having the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, will process 10-30 hour before carrying out hydrogenation reaction in hydrogen, 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 the laggard full cut FCC stock oil of sulfuration and hydrogen.Concrete reaction conditions is temperature of reaction 50-220 ° of 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 ensure that the long-term stability of dialkene removal and selective hydrodesulfrization and absorption ultra-deep desulfurization series combination technique is run, before entering selective hydrodesulfrization reactor, diene content must take off to maleic value be 0.2gI
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 the maleic value in Maleic Anhydride Method mensuration FCC gasoline.Concrete steps are as follows: (1), put into flask with the oil sample of analytical balance precise 10.00g, (MALEIC ANHYDRIDE toluene solution is necessary hold over night after preparing to add 20mL MALEIC ANHYDRIDE toluene solution, can use after filtration), add 0.1mol/L toluene iodide solution 0.5mL again, shake up.(2), then ground flask is filled on reflux condensing tube, in 110 DEG C ± 2 DEG C water-baths, reflux 3 hours, is then cooled to room temperature by solution, and add water from prolong upper end 5mL, continue temperature rising reflux 15min, after cooling, rinse prolong for several times with 5mLMTBE, 20mL moisture respectively.(3), ground flask is pulled down from prolong, carefully solution in ground Erlenmeyer flask is transferred in separating funnel and (stopping property of separating funnel in process of the test, must be ensured, with liquid-leakage preventing, affect result precision), first use 20mLMTBE, divide respectively with 25mL water and wash ground flask inwall for three times, 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 25mL, 10mL, 10mL water vibration extracting for three times respectively, and is incorporated in ground Erlenmeyer flask by water layer.(5), in ground Erlenmeyer flask, drip phenolphthalein indicator 1 ~ 2, with NaOH standard titration solution, to be titrated to solution be incarnadine is terminal, writes down the volume consuming NaOH standard titration solution.(6), getting toluene 10.00g replaces sample to do blank test by aforesaid operations condition.(7), parallelly sample is made, monitoring analysis result collimation.(8), result calculates: (unit is gI to maleic value
2/ 100g oil) be calculated as follows:
Maleic value=(B-A) (M) (12.69)/W
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, last running gasoline and recycle hydrogen mixing, through interchanger heat exchange laggard enter in selective hydrodesulfrization fixed-bed reactor.The larger inert ceramic balls of particle is filled out, next filling selective hydrodesulfrization catalyzer, the inert ceramic balls that catalyzer lower end loaded particles is larger in the top of reactor.The selective hydrodesulfrization catalyzer that patent of the present invention uses contains at least one group VIII metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA race metal (being preferably selected from K), at least one IIB race metal (being preferably selected from Mg), and these metal loads are on the carrier with specified pore structure.Described selective hydrodesulfrization catalyzer has following feature: be benchmark with oxide basis and with catalyzer, the content of group VIII metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA race metal is 0.5-4.5wt%, the content of IIA race metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 5-100nm of total pore volume accounts for more than 85% of total pore volume, and the pore volume being less than the hole of 5nm accounts for less than 5% of total pore volume.Described selective hydrodesulfrization catalyzer needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into have the sulfide active phase of hydrogenating desulfurization function.The sulphur of more than 70% at least can remove by this selective hydrodesulfrization catalyzer, in other words can by sulphur content lower than 1000ppmw, and the sulphur in the last running gasoline of preferred 350ppmw, best 250ppmw takes off to below 100ppm.
Through the last running gasoline of selective hydrodesulfrization, after gas-liquid separator separates, then by gas stripping column, the hydrogen sulfide be dissolved into wherein is down to below 1ppmw, so just obtains the last running gasoline of sulphur content lower than 100ppmw.Last running gasoline after this desulfurization mixes with from separation column light gasoline fraction out and new hydrogen to enter after interchanger heat exchange and adsorbs in ultra-deep desulfurization fixed-bed reactor.The absorption ultra-deep desulfurization fixed-bed reactor inert ceramic balls that topmost loaded particles is larger, following filled with adsorbent, the inert ceramic balls that sorbent material lower end loaded particles is larger.
The technical characteristic of the sorbent material that patent of the present invention uses is described in detail in the previous work of Dalian Inst of Chemicophysics, Chinese Academy of Sciences, such as CN101450302B describes a kind of C 4 olefin desulfurization absorbent and method for making and application in detail, and this sorbent material also may be used among the ultra-deep desulfurization combined method of the FCC gasoline of patent of the present invention.This desulfuration adsorbent has the activation reduction-state VIII base metal of sulfur-containing molecules, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound by being selected from and being that the tamanori of main component forms with aluminum oxide.Wherein, VIII base metal accounts for the 1-30% of total desulfuration adsorbent total mass, IB race 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 before carrying out adsorption desulfurize will in hydrogen activation treatment 20-30 hour, activation temperature 250-400 ° C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NLH
2/ L catalyzer hour.Adsorption desulfurize operational condition is 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.
Compared with known technology, tool of the present invention has the following advantages:
(1) sorbent material to sulfur compounds adsorption selectivity and loading capacity high;
(2) facing in hydrogen adsorption, olefin loss is little, and loss of octane number is less than 1.5 units;
(3) dialkene removal protective material and catalyst activity high, can operate at a lower temperature, can assurance device long-term stability run;
(4) adopt ADSORPTION IN A FIXED BED desulfurizer, sorbent material free of losses, liquid yield reaches more than 99.8%, reduces process cost.
(5) when identical desulfurization depth, full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize series combination method, plant investment expense and process cost are lower than hydrogenating desulfurization and S-Zorb technique and selective hydrodesulfrization technique 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 mixing again through First Heat Exchanger 4 heat exchange through the second pipeline 2 through the first pipeline 1 and full cut FCC stock oil; 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 dialkene removal reactor 6 in 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 recycle hydrogen of the 8th pipeline 17 and the 9th pipeline 20 after the second mixing tank 19 mixes, again after the second interchanger 21 heat exchange, selective hydrodesulfrization reactor 23 is entered again through the tenth pipeline 22, the 3rd filler 24 is filled with from top to bottom successively in selective hydrodesulfrization reactor 23, catalyzer 25, 4th filler 26, material through selective hydrodesulfrization enters the second gas-liquid separator 28 through the 11 pipeline 27, gas enters Alkali absorption tank 30 absorbing hydrogen sulphide through the 12 pipeline 29, the hydrogen of depriving hydrogen sulphide enters the hydrogen recycle system through the 13 pipeline 31, the hydrogen sulfide air lift removing will be dissolved in liquid material air lift tank 33 is entered through the 14 pipeline 32 from the second gas-liquid separator 28 liquid out, the mixed gas of hydrogen and hydrogen sulfide enters recycle hydrogen system through the 15 pipeline 34, liquid material after air lift through the 16 pipeline 35 after mixing in the 3rd mixing tank 36 via the new hydrogen of the 17 pipeline 37 and the light gasoline fraction of the 7th pipeline 18 again through the 18 pipeline 38, adsorption desulfurize reactor 41 is entered through the 19 pipeline 40 again after the 3rd interchanger 39 heat exchange, in adsorption desulfurize reactor 41, one-time pad has the 5th filler 42 from top to bottom, sorbent material 43, 6th filler 44, the 3rd gas-liquid separator 46 is entered again through the 20 pipeline 45, sulphur content is obtained lower than 10ppmw finally by the 21 pipeline 47, loss of octane number is lower than 1.5 units, the super low-sulfur oil that liquid yield is greater than 99.8%.
Embodiment
In combined method of the present invention; the dialkene removal fixed-bed reactor inert ceramic balls that topmost loaded particles is larger, second layer filling protective material 1, third layer filling protective material 2; 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 exit.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 is minimum.(2), the hydrogenation activity size of agent.Protective material 1, protective material 2 and dialkene removal catalyzer all contain metallic sulfide hydrogenation active component.Its hydrogenation activity order is 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 are usually containing at least one group VIII metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA race metal (being preferably selected from K), and these metal loads are on carrier.Wherein protective material 1 has following technical characteristic: be benchmark with oxide basis and with catalyst weight, and the content of group VIII metal is 0.5-1.5wt%, and the content of vib metal is the content of 2-3wt%, IA race 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 the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 15%, 20-100nm of total pore volume accounts for more than 70% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 15% of total pore volume.Protective material 2 has following technical characteristic: be benchmark with oxide basis and with catalyst weight, and the content of group VIII metal is 1.8-3.5wt%, and the content of vib metal is the content of 3.5-5.5wt%, IA race 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 the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 20-100nm of total pore volume accounts for more than 60% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 30% of total pore volume.
Dialkene removal catalyzer at least contains a kind of VIII race's metal, a kind of+3 valency metals, a kind of IA race metal, a kind of IVB race metal, a kind of IIB race metal, the SiO of two kind of VI B race metal and equal amount
2-Al
2o
3the mixed metal oxide of composition, it is characterized in that, be benchmark with oxide basis and with catalyst weight, group VIII metal ,+3 valency metals of 5-30 % by weight, the IA race metal of 0.1-8 % by weight, the IVB race metal of 0.1-8 % by weight, the IIB race metal of 0.1-30 % by weight, two kind of VI B race metal of 5-50 % by weight containing 10-40 % by weight in this catalyzer, 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 have the active phase of the metallic sulfide of hydrogenating function.Sulfuration can be carried out in dialkene removal reactor, also can carry out outside dialkene removal reactor.These vulcanization process are known by this research field.The method that such as, in device sulfuration is conventional: use and often adopt 2wt% containing 1-5wt%() 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 method that ex situ presulfiding is conventional: the organism or the inorganics that the catalyst oxidation thing precursor dipping after roasting are contained sulphur, the mole number of the sulphur contained in usual steeping fluid is 1.0-1.8 times of the theoretical value of all active metal complete cures in catalyzer.Load loads reactor after having the catalyzer drying of sulfurous organic compound or sulfur-bearing inorganics, will process 10-30 hour before carrying out hydrogenation reaction in hydrogen, 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 the laggard full cut FCC stock oil of sulfuration and hydrogen.Concrete reaction conditions is temperature of reaction 50-220 ° of 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 ensure that the long-term stability of dialkene removal and selective hydrodesulfrization and absorption ultra-deep desulfurization series combination method is run, before entering selective hydrodesulfrization reactor, diene content must take off to maleic value be 0.2gI
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 the maleic value in Maleic Anhydride Method mensuration FCC gasoline.Concrete steps are as follows: (1), put into flask with the oil sample of analytical balance precise 10.00g, (MALEIC ANHYDRIDE toluene solution is necessary hold over night after preparing to add 20mL MALEIC ANHYDRIDE toluene solution, can use after filtration), add 0.1mol/L toluene iodide solution 0.5mL again, shake up.(2), then ground flask is filled on reflux condensing tube, in 110 DEG C ± 2 DEG C water-baths, reflux 3 hours, is then cooled to room temperature by solution, and add water from prolong upper end 5mL, continue temperature rising reflux 15min, after cooling, rinse prolong for several times with 5mLMTBE, 20mL moisture respectively.(3), ground flask is pulled down from prolong, carefully solution in ground Erlenmeyer flask is transferred in separating funnel and (stopping property of separating funnel in process of the test, must be ensured, with liquid-leakage preventing, affect result precision), first use 20mLMTBE, divide respectively with 25mL water and wash ground flask inwall for three times, 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 25mL, 10mL, 10mL water vibration extracting for three times respectively, and is incorporated in ground Erlenmeyer flask by water layer.(5), in ground Erlenmeyer flask, drip phenolphthalein indicator 1 ~ 2, with NaOH standard titration solution, to be titrated to solution be incarnadine is terminal, writes down the volume consuming NaOH standard titration solution.(6), getting toluene 10.00g replaces sample to do blank test by aforesaid operations condition.(7), parallelly sample is made, monitoring analysis result collimation.(8), result calculates: (unit is gI to maleic value
2/ 100g oil) be calculated as follows:
Maleic value=(B-A) (M) (12.69)/W
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 (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 mixing, through interchanger heat exchange laggard enter in selective hydrodesulfrization fixed-bed reactor.The larger inert ceramic balls of particle is filled out, next filling selective hydrodesulfrization catalyzer, the inert ceramic balls that catalyzer lower end loaded particles is larger in the top of reactor.The selective hydrodesulfrization catalyzer that patent of the present invention uses contains at least one group VIII metal (being preferably selected from nickel, cobalt), at least one vib metal (being preferably selected from molybdenum, tungsten), at least one IA race metal (being preferably selected from K), at least one IIB race metal (being preferably selected from Mg), and these metal loads are on the carrier with specified pore structure.Described selective hydrodesulfrization catalyzer has following feature: be benchmark with oxide basis and with catalyzer, the content of group VIII metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA race metal is 0.5-4.5wt%, the content of IIA race metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 5-100nm of total pore volume accounts for more than 85% of total pore volume, and the pore volume being less than the hole of 5nm accounts for less than 5% of total pore volume.Described selective hydrodesulfrization catalyzer needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into have the sulfide active phase of hydrogenating desulfurization function.The sulphur of more than 70% at least can remove by this selective hydrodesulfrization catalyzer, in other words can by sulphur content lower than 1000ppmw, and the sulphur in the last running gasoline of preferred 350ppmw, best 250ppmw takes off to below 100ppm.
Through the last running gasoline of selective hydrodesulfrization, after gas-liquid separator separates, then by gas stripping column, the hydrogen sulfide be dissolved into wherein is down to below 1ppmw, so just obtains the last running gasoline of sulphur content lower than 100ppmw.Last running gasoline after this desulfurization mixes with from separation column light gasoline fraction out and new hydrogen to enter after interchanger heat exchange and adsorbs in ultra-deep desulfurization fixed-bed reactor.The absorption ultra-deep desulfurization fixed-bed reactor inert ceramic balls that topmost loaded particles is larger, following filled with adsorbent, the inert ceramic balls that sorbent material lower end loaded particles is larger.The technical characteristic of the sorbent material that patent of the present invention uses is described in detail in the previous work of Dalian Inst of Chemicophysics, Chinese Academy of Sciences, such as CN101450302B describes a kind of C 4 olefin desulfurization absorbent and method for making and application in detail, and this sorbent material also may be used among the ultra-deep desulfurization combined method of the FCC gasoline of patent of the present invention.This desulfuration adsorbent has the activation reduction-state VIII base metal of sulfur-containing molecules, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound by being selected from and being that the tamanori of main component forms with aluminum oxide.Wherein, VIII base metal accounts for the 1-30% of total desulfuration adsorbent total mass, IB race 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 before carrying out adsorption desulfurize will in hydrogen activation treatment 20-30 hour, activation temperature 250-400 ° C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NLH
2/ L catalyzer hour.Adsorption desulfurize operational condition is 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 mixing again through First Heat Exchanger 4 heat exchange through the second pipeline 2 through the first pipeline 1 and full cut FCC stock oil; 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 dialkene removal reactor 6 in 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 recycle hydrogen of the 8th pipeline 17 and the 9th pipeline 20 after the second mixing tank 19 mixes, again after the second interchanger 21 heat exchange, selective hydrodesulfrization reactor 23 is entered again through the tenth pipeline 22, the 3rd filler 24 is filled with from top to bottom successively in selective hydrodesulfrization reactor 23, catalyzer 25, 4th filler 26, heavy naphtha through selective hydrodesulfrization enters the second gas-liquid separator 28 through the 11 pipeline 27, gas enters Alkali absorption tank 30 absorbing hydrogen sulphide through the 12 pipeline 29, the hydrogen of depriving hydrogen sulphide enters the hydrogen recycle system through the 13 pipeline 31, the hydrogen sulfide air lift removing will be dissolved in liquid material air lift tank 33 is entered through the 14 pipeline 32 from the second gas-liquid separator 28 heavy naphtha out, the mixed gas of hydrogen and hydrogen sulfide enters recycle hydrogen system through the 15 pipeline 34, heavy naphtha after air lift through the 16 pipeline 35 after mixing in the 3rd mixing tank 36 via the new hydrogen of the 17 pipeline 37 and the light gasoline fraction of the 7th pipeline 18 again through the 18 pipeline 38, adsorption desulfurize reactor 41 is entered through the 19 pipeline 40 again after the 3rd interchanger 39 heat exchange, in adsorption desulfurize reactor 41, one-time pad has the 5th filler 42 from top to bottom, sorbent material 43, 6th filler 44, the 3rd gas-liquid separator 46 is entered again through the 20 pipeline 45, sulphur content is obtained lower than 10ppmw finally by the 21 pipeline 47, loss of octane number is lower than 1.5 units, 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 exit; Hydrodesulphurisatioreactors reactors and adsorption desulfurize reactor upper end are provided with feed(raw material)inlet, and lower end is provided with product exit;
Protective material 1, protective material 2 adopt equi-volume impregnating to prepare, and concrete steps are as follows:
1, the preparation of protective material 1: with the solution 116 milliliters dipping 100 grams of alumina supporters containing 0.44 gram, potassium hydroxide; after 120 degree of oven dry, 450 degree of roastings; dipping is containing the common dipping solution 85 milliliters of nickelous nitrate 5.95 grams and 3.72 grams ammonium molybdates again; namely obtain protective material 1 through 120 degree of oven dry, 450 degree of roastings, it consists of 1.43wt%NiO-2.86wt%-0.30wt%/Al
2o
3.The preparation method of the protective material 1 used in the following example 1-embodiment 8 is identical, and just each component concentration is different.
2, the preparation of protective material 2: with the solution 100 milliliters dipping 100 grams of alumina supporters containing 0.92 gram, potassium hydroxide; after 120 degree of oven dry, 450 degree of roastings; dipping is containing the common dipping solution 70 milliliters of nickelous nitrate 11.90 grams and 7.44 grams ammonium molybdates again; namely obtain protective material 2 through 120 degree of oven dry, 450 degree of roastings, it consists of 2.73wt%NiO-5.48wt%-0.60wt%/Al
2o
3.The preparation method of the protective material 2 used 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. a certain amount of nickelous nitrate, zinc nitrate and aluminum nitrate is taken respectively, wherein Ni
2+0.1mol, Zn
2+0.1mol, Al
3+they are dissolved in 200ml water and form the aqueous solution, slowly drip K wherein by 0.05mol
+concentration is KOH and the K of 0.2mol/L
2cO
3(the K of KOH and 0.05mol/L of 0.1mol/L
2cO
3) mixing solutions, regulate pH=12, and be heated to temperature of reaction 80 DEG C, generate green mixed reaction solution, back flow reaction 25 hours under 80 DEG C of temperature of reaction; The green precipitate be obtained by reacting is filtered; This catalyst precursor is added in 200ml water, is configured to slurry precursor;
B. a certain amount of ammonium molybdate and ammonium metawolframate is taken respectively, wherein Mo
6+0.01mol, W
6+they are dissolved in 350ml water by 0.01mol, form solution, and this solution is heated to temperature of reaction, constantly stir, and form colourless transparent solution; Measure the homemade slurry precursor of part subsequently, wherein containing Ni
2+0.03mol, Zn
2+0.03mol, Al
3+0.015mol is heated to temperature of reaction 80 DEG C; These slurries are added at leisure in above-mentioned colourless transparent solution, form green reaction liquid, 80 DEG C of temperature of reaction, back flow reaction 5 hours; Filtered by the yellow-green precipitate be obtained by reacting, and dry 12 hours at 120 DEG C, 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 the bar shaped of φ 2.0 trifolium through banded extruder, and through 120 ° of C dryings 12 hours, 420 ° of C roastings defined 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 96% of gross weight).The preparation method of the dialkene removal catalyzer used in the following example 1-embodiment 8 is identical, and just each component concentration is different.
Selective hydrodesulfrization catalyzer adopts equi-volume impregnating preparation, and concrete preparation method is as follows:
With the mixing solutions 100 milliliters dipping 100 grams of alumina supporters containing 0.94 gram, saltpetre and magnesium nitrate 25.92 grams, after 120 degree of oven dry, 450 degree of roastings, dipping is containing the common dipping solution 70 milliliters of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 9.20 grams and 10.34 grams ammonium molybdates again, namely obtain selective hydrogenation catalyst through 120 degree of oven dry, 450 degree of roastings, 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 used in the following example 1-embodiment 8 is identical.
The preparation method of sorbent material: by Dalian Inst of Chemicophysics, Chinese Academy of Sciences Chinese invention patent CN101450302B embodiment 1 described by method preparation.Concrete steps are as follows: (1) takes 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 and joins in the distilled water of 200 milliliters, add abundant stirring under 90 degree, 8.10 grams of urea and within 24 hours, make precipitation agent complete hydrolysis, after filtration, deionized water wash, obtain wet cake, dry in 120 degree again, obtain dry sample; (2) fully mixed with 1 gram of alumina dry glue by above-mentioned dry sample, add the aqueous solution 5 milliliters of abundant kneadings that concentration of nitric acid is 2%, make body of paste, then be extruded into cloverleaf pattern with banded extruder, 120 degree of dried overnight, 450 degree of 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 the sorbent material used 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 invention scope that each accessory claim defines.
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 raw material used.
The full cut FCC gasoline character of table 1
The character of table 2 light gasoline fraction
The character of table 3 heavy naphtha
Embodiment 1
After interchanger heat exchange, enter dialkene removal reactor after the full cut FCC gasoline of character as described in Table 1 mixes with hydrogen, in dialkene removal reactor, be filled with protective material 1(1.2%NiO-2.4%MoO
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, before oil product and hydrogen enter dialkene removal reactor, protective material and dialkene removal catalyzer will carry out in-situ presulfurization.Cure conditions uses 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, temperature 290 ° of C, liquid hourly space velocity 2.0h
-1, hydrogen to oil volume ratio 300, curing time 9 hours.Sulfuration completes laggard raw material and hydrogen carries out hydrogenation dialkene removal reaction.Dialkene removal reaction conditions is temperature of reaction 80 ° of C, 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 less than 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, enter to select hydrodesulphurisatioreactors reactors through interchanger heat exchange is laggard again after heavy naphtha and hydrogen mix with the recycle hydrogen of metering, the catalyzer (2.0wt%CoO-7.1wt%MoO in this reactor
3-1.5wt%K
2o-3.5wt%MgO/Al
2o
3) 10mL prevulcanized, prevulcanized condition uses the straight-run spirit containing 2wt% dithiocarbonic anhydride to carry out prevulcanized to selective hydrodesulfrization catalyzer, and concrete cure conditions is hydrogen dividing potential drop 1.6MPa, temperature 290 ° of C, liquid hourly space velocity 2.0h
-1, hydrogen to oil volume ratio 300, curing time 9 hours.Sulfuration completes laggard raw material and hydrogen carries out selective hydrodesulfrization reaction.Hydrodesulfurization reaction condition is temperature of reaction 280 ° of C, 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 the heavy naphtha of selective hydrodesulfrization with enter adsorption desulfurize reactor after separation column fractionation light gasoline fraction out and new hydrogen mixing after 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: activation temperature 400 ° of C, pressure 0.1MPa, hydrogen gas space velocity is 360-1000NLH
2/ L sorbent material hour, soak time 25 hours.Adsorption desulfurize operational condition is: adsorption temp 300 ° of C, 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 is down to 7.6ppmw, and octane value is down to 89.2 from 90.6 of stock oil, and loss of octane number is 1.4 units only; Olefin(e) centent is down to 23.6% from 27.8% of stock oil, only have dropped 4.2%, liquid yield 99.9%.Result of the present invention shows, adopt dialkene removal provided by the invention and selective hydrodesulfrization and adsorption desulfurize combination process, not only can the sulphur in the full cut FCC raw material of sulphur content 268.6ppmw be taken off to below 10ppmw, and loss of octane number is less than 1.5 units, liquid yield is greater than 99.8%.
Embodiment 2
The protective material used, dialkene removal catalyzer, selective hydrodesulfrization catalyzer and sorbent material are with embodiment 1, and just dialkene removal processing condition become temperature of reaction 100 ° of C, 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 less than 0.1.Selective hydrodesulfrization processing condition become temperature of reaction 280 ° of C, 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 adsorption temp 300 ° of C, 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 1.3 units only, olefin(e) centent is down to 23.8% from 27.8% of stock oil, only have dropped 4.0%, liquid yield 99.9%.
Embodiment 3
Except the protective material 1 in embodiment 1 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 less than 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 1.4 units only, and olefin(e) centent is down to 23.5% from 27.8% of stock oil, only have dropped 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 less than 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 1.3 units only, and olefin(e) centent is down to 23.6% from 27.8% of stock oil, only have dropped 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 less than 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 1.1 units only, and olefin(e) centent is down to 23.9% from 27.8% of stock oil, only have dropped 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 less than 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 1.3 units only, and olefin(e) centent is down to 23.6% from 27.8% of stock oil, only have dropped 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 less than 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 0.9 unit only, and olefin(e) centent is down to 24.1% from 27.8% of stock oil, only have dropped 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 less than 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 1.4 units only, and olefin(e) centent is down to 23.4% from 27.8% of stock oil, only have dropped 4.4%, liquid yield 99.9%.
Combined method of the present invention not only has operational condition and relaxes, eliminate the mercaptan removal step in selective hydrodesulfrization technique, hydrogen-consuming volume is low, process cost is low, and while carrying out ultra-deep desulfurization (sulphur content is lower than 10ppmw), loss of octane number low (being less than 1.5 units), liquid yield high (being greater than 99.8%), the advantages such as adsorbent selectivity is high, current capacity large (more than 15%).
Claims (9)
1. a FCC gasoline ultra-deep desulfurization combined method, comprises the steps:
(1) with full cut FCC gasoline and hydrogen for raw material, under proper handling condition in dialkene removal reactor successively with protective material 1, protective material 2 and selectivity dialkene removal catalyst exposure, remove the most of diolefine in full cut FCC gasoline raw material;
(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 obtains of step (2) under proper handling condition with the catalyst exposure in selective hydrodesulfrization reactor, sulphur is wherein taken off to below 100ppmw;
(4) light gasoline fraction obtained through step (2) and mixing with hydrogen again after the heavy naphtha mixing of step (3) selective hydrodesulfrization, with the adsorbent contact in absorption ultra-deep desulfurization reactor under proper handling condition, remove the most of sulphur in gasoline, namely 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 DEG 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 step (3) refers to temperature of reaction 230-310 DEG 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 step (4) 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 DEG C; Liquid hourly space velocity 1.0-4.0h
-1;
Protective material 1 described in step (1), protective material 2 are containing at least one group VIII metal, at least one vib metal, at least one IA race metal, and these metal loads are on carrier;
Dialkene removal catalyzer described in step (1) at least contains a kind of VIII race's metal, a kind of+3 valency metals, a kind of IA race metal, a kind of IVB race metal, the SiO of a kind of IIB race metal, two kind of VI B race metal and equal amount
2-Al
2o
3the mixed metal oxide of composition.
2. according to combined method according to claim 1, it is characterized in that: described full cut FCC gasoline refers to that the catalytic gasoline of whole fraction of total sulfur content 200-1000ppmw, full cut FCC gasoline refer to that boiling range is the FCC gasoline of 20-220 DEG C of cut;
The most of diolefine removed in full cut FCC gasoline raw material described in step (1) refer to the diene content in gasoline take off to maleic value be 0.2gI
2below/100g oil;
Light gasoline fraction described in step (2) refers to that boiling point is lower than 100 DEG C of cuts, and heavy naphtha refers to that boiling point equals and/or higher than 100 DEG C of cuts.
3. according to combined method according to claim 1, it is characterized in that the protective material 1 described in step (1), protective material 2 and the removing alkadiene by selective hydrogenation catalyzer filling order in dialkene removal reactor is: 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 exit;
Protective material 1 described in step (1), protective material 2 and dialkene removal catalyzer adopt 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 is minimum; (2), the hydrogenation activity size of agent: protective material 1, protective material 2 and dialkene removal catalyzer all contain sulfide hydrogenation active component; Its hydrogenation activity order is 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:
Protective material 1 described in step (1) has following feature: be benchmark with oxide basis and with catalyst weight, the content of group VIII metal is 0.5-1.5wt%, the content of vib metal is the content of 2-3wt%, IA race metal is 0.1-0.5wt%, and surplus is carrier; Pore volume is 0.92-1.2mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 15%, 20-100nm of total pore volume accounts for more than 70% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 15% of total pore volume;
Protective material 2 described in step (1) has following feature: be benchmark with oxide basis and with catalyst weight, the content of group VIII metal is 1.8-3.5wt%, the content of vib metal is the content of 3.5-5.5wt%, IA race metal is 0.55-0.95wt%, and surplus is carrier; Pore volume is 0.70-0.90mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 20-100nm of total pore volume accounts for more than 60% of total pore volume, and the pore volume being less than the hole of 20nm accounts for less than 30% of total pore volume;
Dialkene removal catalyzer described in step (1) has following feature: be benchmark with oxide basis and with catalyst weight, group VIII metal ,+3 valency metals of 5-30 % by weight, the IA race metal of 0.1-8 % by weight, the IVB race metal of 0.1-8 % by weight, the IIB race metal of 0.1-30 % by weight, the VI B race metal of 5-50 % by weight containing 10-40 % by weight in this catalyzer, 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.
5. in accordance with the method for claim 4, it is characterized in that: wherein said group VIII metal is selected from Ni or Co; + 3 valency metals are selected from Cr or Al; IA race metal is selected from Na or K, and IVB race metal is selected from Ti or Zr, and IIB race metal is selected from Zn, and VI B race metal is selected from Mo and W.
6. according to the method described in claim 1 or 5, it is characterized in that: the protective material 1 described in step (1), protective material 2 and dialkene removal catalyzer needed to carry out sulfidizing before carrying out dialkene removal reaction, make it be converted into have the sulfide active phase of hydrogenating function;
Catalyzer in selective hydrodesulfrization reactor described in step (3) needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into have the sulfide active phase of hydrogenating desulfurization function;
The prevulcanized treatment condition of the catalyzer in the protective material 1 described in step (1), protective material 2 and dialkene removal catalyzer and the selective hydrodesulfrization reactor described in step (3) are: use the straight-run spirit containing 1-5wt% dithiocarbonic anhydride to carry out prevulcanized as vulcanized oil to catalyzer; concrete cure conditions is hydrogen dividing potential drop 1.6-4.0MPa; temperature 250-400 DEG C, liquid hourly space velocity 2.0-4.0h
-1, hydrogen to oil volume ratio 100-500NL/L, curing time 30-70 hour.
7. in accordance with the method for claim 1, it is characterized in that:
Selective hydrodesulfrization catalyzer described in step (3) contains at least one group VIII metal, at least one vib metal, at least one IA race metal, at least one IIB race metal, and these metal loads are on carrier;
Selective hydrodesulfrization catalyzer described in step (3) has following feature: be benchmark with oxide basis and with catalyst weight, the content of group VIII metal is 0.5-5.0wt%, the content of vib metal is 5-20wt%, the content of IA race metal is 0.5-4.5wt%, the content of IIA race metal is 0.5-6.5wt%, and surplus is carrier; Pore volume is 0.5-1.2mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100nm accounts for the hole of more than 10%, 5-100nm of total pore volume accounts for more than 85% of total pore volume, and the pore volume being less than the hole of 5nm accounts for less than 5% of total pore volume;
Sorbent material described in step (4) has the activation reduction-state VIII base metal of sulfur-containing molecules, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound and tamanori aluminum oxide form by being selected from;
Described VIII base metal accounts for the 1-30% of total desulfuration adsorbent total mass, IB race 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.
8. in accordance with the method for claim 7, it is characterized in that:
In selective hydrodesulfrization catalyzer described in step (3), group VIII metal is preferably selected from nickel and/or cobalt, and vib metal is preferably selected from molybdenum and/or tungsten, and IA race metal is selected from K, and IIB race metal is selected from Mg;
The described reduction-state VIII base metal with activation sulfur-containing molecules is selected from nickel and/or cobalt, 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.
9. in accordance with the method for claim 1, it is characterized in that: the sorbent material described in step (4) before carrying out adsorption desulfurize will in hydrogen activation treatment 20-30 hour, activation temperature 250-400 DEG C, pressure 0.1-2.0MPa, hydrogen gas space velocity is 360-1000NLH
2/ L catalyzer hour.
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| CN106520201A (en) * | 2016-12-07 | 2017-03-22 | 陕西延长石油（集团）有限责任公司 | Dialkene removal/hydrodesulfurization/hydrogenated adsorptive desulfurization combined treatment technology and dialkene removal/hydrodesulfurization/hydrogenated adsorptive desulfurization combined treatment equipment for full-range FCC gasoline |
| CN107488465B (en) | 2017-04-27 | 2019-04-30 | 中国石油大学(北京) | A kind of high-efficient treatment method and system of inferior patrol |
| CN116060039A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Selective sweetening catalyst and sweetening method |
| CN116064151A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Method for desulfurizing hydrocarbon oil |
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| CN102407094A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Gasoline desulfurization adsorbent and preparation and application thereof |
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
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| CN101724456A (en) * | 2008-10-23 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for producing aromatics extraction raw material |
| CN102407094A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Gasoline desulfurization adsorbent and preparation and application thereof |
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
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