CN102899083B - Ultra-deep combined desulphurization method for full-fraction FCC gasoline - Google Patents
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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
Technical field
The present invention relates to a kind of full cut FCC gasoline ultra-deep desulfurization combined method, particularly sulphur content 100-200ppmw full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorb ultra-deep desulfurization combined method, can the sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw be taken off to below 10ppm by this combined method, and loss of octane number is lower than 1.5 units, liquid yield is greater than 99.8%.
Background technology
The SO that organic sulfide in gasoline produces after engine combustion
2much harm is produced 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 content of sulfur in gasoline standard of sulphur content lower than 1ppmw after 2014.China's gasoline sulfur index request is also more and more higher, takes the lead in performing the capital V automobile-used 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 0.1ppmw) 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, after hydrodesulfurization reaction, dissolve hydrogen sulfide in the oil and regenerate mercaptan with the alkene generation addition reaction in gasoline, the amount of mercaptan is often greater than 10ppmw, and this just adds the difficulty of gasoline ultra-deep desulfurization more.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 the sulphur in full cut FCC gasoline be taken off to below 10ppmw, 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.Moreover cut into by full distillation gasoline gently, energy that last running needs at substantial, process cost is higher.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, heavy constituent, light constituent mercaptan removal, heavy constituent hydrogenating desulfurization.Because heavy constituent 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 full cut FCC gasoline dialkene removal and selective hydrodesulfrization of full cut FCC gasoline ultra-deep desulfurization combined method, particularly sulphur content 100-200ppmw and adsorb ultra-deep desulfurization combined method.Sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw can be taken off to below 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, and it be a kind of cut FCC gasoline removing alkadiene by selective hydrogenation entirely and selective hydrodesulfurization and selective adsorption ultra-deep desulfurization combined method, comprises the steps:
Step (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 FCC gasoline raw material;
Step (2) through the full cut FCC gasoline of step (1) dialkene removal under proper handling condition with the catalyst exposure in selective hydrodesulfrization reactor, remove the sulphur of more than 50% wherein;
Step (3) to remove after the hydrogen sulfide be dissolved in wherein through gas-liquid separator and air lift through the full cut FCC gasoline of step (2) selective hydrodesulfrization and mixes with new hydrogen, under appropriate operating conditions with the adsorbent contact in absorption ultra-deep desulfurization reactor, remove the most of sulphur in gasoline, namely obtain super low-sulfur oil product;
Wherein, the proper handling condition described in step (1) refers to temperature of reaction 50-220 ° of 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 (2) refers to temperature of reaction 230-310 ° of 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 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;
The most of diolefine removed in FCC gasoline raw material described in step (1) refer to the diene content in gasoline take off to maleic value be 0.2g I
2below/100g oil;
Described in step (2) remove wherein more than 50% sulphur refer to the sulphur in the FCC gasoline raw material of 100-200ppmw taken off to below 100ppmw;
Super low-sulfur oil described in step (3) refers to the gasoline products of sulphur content lower than 10ppmw;
Air lift described in step (4) removes the hydrogen sulfide be dissolved in wherein and refers to and take off the hydrogen sulfide be dissolved in FCC gasoline to below 1ppm.
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.
Protective material 1 described in step (1), the metal oxide of protective material 2 containing at least one group VIII metal, at least one vib metal, at least one IA race metal, these metal loads are on carrier; Described carrier is: aluminum oxide.
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.
Protective material 1 described in step (1) has following feature: 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; 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.
Described 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.
Selective hydrodesulfrization catalyzer described in step (2) 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 (2) 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.
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, made it be converted into have the sulfide active phase of hydrogenating function;
Selective hydrodesulfrization catalyzer described in step (2) needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into have the sulfide active phase of hydrogenating desulfurization function.
Sorbent material described in step (3) 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;
VIII base metal described in step (3) 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 is the 10-70% that ZnO accounts for desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass;
Sorbent material described in step (3) 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 360-1000NL H
2/ L catalyzer hour.
Technique of the present invention is a kind of by full cut FCC gasoline dialkene removal fixed-bed reactor and selective hydrodesulfrization and adsorb the combined method that ultra-deep desulfurization fixed-bed reactor carry out connecting.For ensureing 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 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.Described 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 catalyzer (protective material 1, protective material 2 and dialkene removal catalyzer) the oxide 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 360-1000NL H
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.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 0.2g I
2below/100g oil.Otherwise, easily polymerization reaction take place and the coking in the interchanger of desulphurization reactor front end of the diolefine of high-content, clogging heat exchanger tube road.
Protective material 1 protective material 2, dialkene removal catalyzer loading height ratio in dialkene removal reactor is generally 1-2:1-2:2-8.
The content of diolefine represents with maleic value, the measuring method of maleic value: adopt 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 20mL MTBE, 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 g I 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)
Mix with recycle hydrogen through the full cut FCC gasoline of dialkene removal and unreacted hydrogen, then 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.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 50% at least can remove by this selective hydrodesulfrization catalyzer, the sulphur in the full cut FCC gasoline of sulphur content 100-200ppmw can be taken off to below 100ppm in other words.
Through the FCC 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 full cut FCC gasoline of sulphur content lower than 100ppmw.Full cut FCC gasoline after this desulfurization mixes with new hydrogen to enter after interchanger heat exchange again 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 full cut FCC gasoline of patent of the present invention.This desulfuration adsorbent has the activation reduction-state VIII base metal (as cobalt and/or nickel) of sulfur-containing molecules, reduction-state IB group 4 transition metal (as copper and/or silver), IIB group 4 transition metal oxide compound and tamanori aluminum oxide form by being selected from.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 360-1000NL H
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 unit;
(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%.
Below in conjunction with specific embodiment, the invention will be further described, but not as limitation of the present invention.The part do not described in detail in the present embodiment adopts prior art, and industry standard or known approaches.
Accompanying drawing explanation
Fig. 1 is the simplification of flowsheet figure of combination process of the present invention.
In 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, selective hydrodesulfrization reactor; 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 absorption tank; 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 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 metal oxide 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) and at least one IA race metal (being preferably selected from K), these metal loads are on carrier; Described carrier is: aluminum oxide; 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 360-1000NL H
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 0.2g I
2below/100g oil.Otherwise, easily polymerization reaction take place and the coking in the interchanger of desulphurization reactor front end of the diolefine of high-content, clogging heat exchanger tube road.
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 20mL MTBE, 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)
Mix with recycle hydrogen through the full cut FCC gasoline of dialkene removal and unreacted hydrogen, then 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 carrier.Described selective hydrodesulfrization catalyzer 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.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 50% at least can remove by this selective hydrodesulfrization catalyzer, the sulphur in the FCC gasoline of sulphur content 100-200ppmw can be taken off to below 100ppm in other words.
Through the FCC gasoline of selective hydrodesulfrization, after gas-liquid separator separates, then by air lift, the hydrogen sulfide be dissolved into wherein is down to below 1ppmw, so just obtains the full cut FCC gasoline of sulphur content lower than 100ppmw.Full cut FCC gasoline after this desulfurization mixes with new hydrogen to enter after interchanger heat exchange again 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 this research group, 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 full cut FCC gasoline of patent of the present invention.This desulfuration adsorbent by be selected from have activation sulfur-containing molecules reduction-state VIII base metal, reduction-state IB group 4 transition metal, IIB group 4 transition metal oxide compound and be that tamanori 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 combined method 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 after the second mixing tank 13 mixes with the recycle hydrogen from the 5th pipeline 14 through the 4th pipeline 12, again after the second interchanger 15 heat exchange, selective hydrodesulfrization reactor 17 is entered again through the 6th pipeline 16, the 3rd filler 18, catalyzer 19, the 4th filler 20 is filled with from top to bottom successively in selective hydrodesulfrization reactor 17, material through selective hydrodesulfrization enters gas-liquid separator 22 through the 7th pipeline 21, gas enters Alkali absorption tank 24 absorbing hydrogen sulphide through the 8th pipeline 23, and hydrogen enters the hydrogen recycle system through the 9th pipeline 25, the hydrogen sulfide air lift removing that will be dissolved in liquid material air lift tank 27 is entered through the tenth pipeline 26 from gas-liquid separator 22 liquid out, the mixed gas of hydrogen and hydrogen sulfide enters recycle hydrogen system through the 11 pipeline 28, liquid material after air lift after the 12 pipeline 29 mixes in the 3rd mixing tank 30 with the new hydrogen via the 13 pipeline 31 again through the 14 pipeline 32, adsorption desulfurize reactor 35 is entered through the 15 pipeline 34 again after the 3rd interchanger 33 heat exchange, in adsorption desulfurize reactor 35, one-time pad has the 5th filler 36 from top to bottom, sorbent material 37, 6th filler 38, gas-liquid separator 40 is entered again through the 16 pipeline 39, sulphur content is obtained lower than 10ppmw finally by the 17 pipeline 41, 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%MoO
3-0.60wt%K
2o/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. take 0.1mol nickelous nitrate, 0.1mol zinc nitrate and 0.05mol respectively, they are dissolved in 200ml water and form the aqueous solution, slowly drip K wherein
+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 the mixed metal oxide particulate state brownish black catalyst precursor of containing metal Ni, Zn, Al, K, Mo and W for 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 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.
Table 1, full cut FCC gasoline character
Embodiment 1(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
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 (internal diameter 1 centimetre), 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
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 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 1.2gI
2/ 100g oil drops to less than 0.1.Enter to select hydrodesulphurisatioreactors reactors (internal diameter 1 centimetre), the catalyzer in this reactor through interchanger heat exchange is laggard again after gasoline after dialkene removal and hydrogen mix with the recycle hydrogen of metering
(2.0wt%CoO-7.1wt%MoO
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 260 ° of C, hydrogen dividing potential drop 1.4MPa, hydrogen to oil volume ratio 150NL/L, night hourly space velocity 2.0h
-1.React 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 is only 0.6.After interchanger heat exchange, adsorption desulfurize reactor is entered after the FCC gasoline and the mixing of new hydrogen of selective hydrodesulfrization.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 360-1000NL H
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 from the 76.0ppmw of raw material, and octane value is down to 88.2 from 89.0 of selec-tive hydrogenation stock oil out, loss of octane number is 0.8 unit only, together with 0.6 octane value of selective hydrodesulfrization loss, lose 1.4 octane value units altogether, be less than 1.5 octane value units; Olefin(e) centent is down to 22.3% from 26.5% 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 combined method, not only can the sulphur in the full cut FCC raw material of sulphur content 100-200ppmw 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(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
The protective material used, dialkene removal catalyzer, selective hydrodesulfrization catalyzer and sorbent material are with embodiment 1; difference from Example 1 is, 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 1.2gI
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 7.8ppmw 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, only have dropped 4.0%, liquid yield 99.9%.
Embodiment 3(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
Except changing the protective material 1 in embodiment 1 into 0.58%NiO-1.4%MoO
3-0.29%K
2o/Al
2o
31.20%NiO-2.60%MoO is changed into protective material 2
3-0.7%K
2o/Al
2o
3outward, other condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI
2/ 100g oil drops to less than 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, only have dropped 4.3%, liquid yield 99.9%.
Embodiment 4(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
Except the dialkene removal catalyzer in 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 condition is identical.React sampling analysis after 500 hours, find that maleic value is from 1.2gI
2/ 100g oil drops to less than 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, only have dropped 4.3%, liquid yield 99.9%.
Embodiment 5(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
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 1.2gI
2/ 100g oil drops to less than 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, only have dropped 3.9%, liquid yield 99.9%.
Embodiment 6(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
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 1.2gI
2/ 100g oil drops to less than 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, only have dropped 4.2%, liquid yield 99.9%.
Embodiment 7(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
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 1.2gI
2/ 100g oil drops to less than 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, only have dropped 3.7%, liquid yield 99.9%.
Embodiment 8(is according to the present invention): full cut FCC gasoline dialkene removal and selective hydrodesulfrization and adsorption desulfurize combined method
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 1.2gI
2/ 100g oil drops to less than 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, 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%).
The part that the present embodiment does not describe in detail and english abbreviation belong to the common practise of the industry, can search on the net, do not describe one by one here.
Claims (9)
1. a full cut FCC gasoline ultra-deep desulfurization combined method, it is a kind of full cut FCC gasoline removing alkadiene by selective hydrogenation and selective hydrodesulfurization and selective adsorption ultra-deep desulfurization combined method, comprises the steps:
Step (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 FCC gasoline raw material;
Step (2) through the full cut FCC gasoline of step (1) dialkene removal under proper handling condition with the catalyst exposure in selective hydrodesulfrization reactor, the mass percent removed wherein is the sulphur of more than 50%;
Step (3) to remove after the hydrogen sulfide be dissolved in wherein through gas-liquid separator and air lift through the full cut FCC gasoline of step (2) selective hydrodesulfrization and mixes with new hydrogen, under appropriate operating conditions with the adsorbent contact in absorption ultra-deep desulfurization reactor, remove the most of sulphur in gasoline, namely obtain 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 1.0-3.5 MPa; Hydrogen to oil volume ratio 50-250NL/L; Liquid hourly space velocity 1.0-4.0 h
-1; 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 0.5-1.5 wt%, the content of vib metal is the content of 2-3 wt%, IA race metal is 0.1-0.5 wt%, and surplus is carrier; Pore volume is 0.92-1.2 mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100 nm accounts for the hole of more than 15%, 20-100 nm of total pore volume accounts for more than 70% of total pore volume, and the pore volume being less than the hole of 20 nm 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 1.8-3.5 wt%, the content of vib metal is the content of 3.5-5.5 wt%, IA race metal is 0.55-0.95 wt%, and surplus is carrier; Pore volume is 0.70-0.90 mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100 nm accounts for the hole of more than 10%, 20-100 nm of total pore volume accounts for more than 60% of total pore volume, and the pore volume being less than the hole of 20 nm 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 150-300 m of this catalyzer
2/ g, pore volume 0.4-0.8ml/g;
Proper handling condition described in step (2) refers to temperature of reaction 230-310 DEG C; Hydrogen dividing potential drop 1.0-3.5 MPa; Hydrogen to oil volume ratio 50-250NL/L; Liquid hourly space velocity 1.0-4.0 h
-1;
Proper handling condition described in step (3) refers to that hydrogen to oil volume ratio is 10-150NL/L; Hydrogen dividing potential drop 0.6-2.0 MPa; Adsorption temp is 200-380 DEG C; Liquid hourly space velocity 1.0-4.0 h
-1.
2. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that: described full cut FCC gasoline refers to that the catalytic gasoline of whole fraction of total sulfur content 100-200 ppmw, 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 FCC gasoline raw material described in step (1) refer to the diene content in gasoline take off to maleic value be 0.2 g I
2below/100g oil;
Described in step (2) remove wherein more than 50% sulphur refer to the sulphur in the FCC gasoline raw material of 100-200 ppmw taken off to 100 below ppmw;
Super low-sulfur oil described in step (3) refers to the gasoline products of sulphur content lower than 10 ppmw;
Air lift described in step (3) removes the hydrogen sulfide be dissolved in wherein and refers to and take off the hydrogen sulfide be dissolved in FCC gasoline to 1 below ppm.
3. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, 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. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that: the protective material 1 described in step (1), the metal oxide of protective material 2 containing at least one group VIII metal, at least one vib metal and at least one IA race metal, these metal loads are on carrier; Described carrier is: aluminum oxide;
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.
5., according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that: described 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 one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that: the selective hydrodesulfrization catalyzer described in step (2) 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 (2) 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 5-20 wt%, the content of IA race metal is 0.5-4.5 wt%, the content of IIA race metal is 0.5-6.5 wt%, and surplus is carrier; Pore volume is 0.5-1.2 mL/g, and the pore volume that the pore volume that its mesoporous is greater than the hole of 100 nm accounts for the hole of more than 10%, 5-100 nm of total pore volume accounts for more than 85% of total pore volume, and the pore volume being less than the hole of 5 nm accounts for less than 5% of total pore volume.
7. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, 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;
Selective hydrodesulfrization catalyzer described in step (2) needed to carry out sulfidizing before carrying out hydrodesulfurization reaction, made it be converted into have the sulfide active phase of hydrogenating desulfurization function.
8. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that: the sorbent material described in step (3) 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;
VIII base metal described in step (3) 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 is the 10-70% that ZnO accounts for desulfuration adsorbent total mass, and tamanori accounts for the 10-50% of desulfuration adsorbent total mass.
9. according to one according to claim 1 full cut FCC gasoline ultra-deep desulfurization combined method, it is characterized in that sorbent material described in step (3) before carrying out adsorption desulfurize will in hydrogen activation treatment 20-30 hour, activation temperature 250-400 DEG C, pressure 0.1-2.0 MPa, hydrogen gas space velocity is 360-1000 NL H
2/ L catalyzer hour.
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| US10144883B2 (en) | 2013-11-14 | 2018-12-04 | Uop Llc | Apparatuses and methods for desulfurization of naphtha |
| CN104711018A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | FCC gasoline ultra-deep desulphurization combination method |
| CN103789038B (en) * | 2014-02-28 | 2015-09-30 | 南京大学连云港高新技术研究院 | A kind of full cut high-sulfur inferior patrol produces the method for high-clean gasoline |
| CN105505591A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Method for hydrotreating of biomass pyrolysis oil |
| CN104312626B (en) * | 2014-11-05 | 2016-06-29 | 实友化工（扬州）有限公司 | A kind of mechanical industry is used as the hydrofinishing process of the liquefied coal coil of fuel |
| CN106590738A (en) * | 2016-12-07 | 2017-04-26 | 陕西延长石油（集团）有限责任公司 | Full-fraction FCC (fluid catalytic cracking) gasoline alkadiene removal/super deep desulfurization composite treatment method and device |
| CN109575992B (en) * | 2017-09-29 | 2021-01-08 | 中国石油化工股份有限公司 | Clean production method of low-sulfur gasoline |
| CN111389454B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油（集团）有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
| CN114433114B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst |
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