CN103721668B - A kind of Gasoline ultra-deep desulfurization adsorbent and application thereof - Google Patents
A kind of Gasoline ultra-deep desulfurization adsorbent and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of FCC gasoline ultra-deep desulfurization absorbent and method for making and application.Desulfuration adsorbent used is by selected from having the activation reduction-state VIII transition metal of sulfur-containing molecules, reduction-state IB group 4 transition metal, Group IIB transition metal oxide, Group IVB metal-oxide, group vib metal-oxide, VIIB family metal oxide, lanthanide metal oxide and forming for adhesive with aluminium oxide.This adsorbent can adsorb the nearly all sulfur compound in FCC gasoline, obtains the sulfur content super low-sulfur oil lower than 5ppmw.
Description
Technical field
The present invention relates to a kind of FCC gasoline ultra-deep desulfurization absorbent and method for making and application.
Background technology
Sulfur-containing compound in gasoline can generate oxysulfide SOx after combustion, can make vehicle exhaust conversion system catalyst poisoning, affects effective conversion of NOx, CO, CH further, and oxygen sulfur compound is discharged in air and can form Acid Rain Pollution environment.Along with people's pay attention to day by day to environmental conservation, environmental regulation is also day by day strict, and the index of whole world content of sulfur in gasoline is just increasingly strict.Equally, China's motor petrol standard is also more and more higher to the requirement of sulfur content.According to national standard body's requirement, gasoline product quality will implement integrally state III standard in 31 days l2 months in 2009.Beijing area has been implemented integrally capital mark C(in 1 day January in 2008 and has been equivalent to state IV standard), content of sulfur in gasoline requires to drop to 50ppmw from 150ppmw, and Shanghai, Guangzhou also will carry out state IV standard in advance in sulfur content.Beijing in June 1 in 2012 rate per diem first carry out the sulfur content so-called capital V content of sulfur in gasoline standard lower than 10ppmw, oil refining enterprise of China gasoline desulfurization technology is just had higher requirement by this.
Absorption doctor treatment is the one in many gasoline desulfurization technology, and this method is difficult to the organosulfur compound of elimination for object with thiophene, benzothiophene etc., and gasoline is carried out deep desulfuration.Absorption desulfurization ratio juris is being fully contacted by gasoline and adsorbent, by the sulfur compounds adsorption in gasoline on the sorbent, thus reducing the purpose of content of sulfur in gasoline.Many adsorbents all have the ability removing sulfur-bearing, oxygen-containing or nitrogenous polar organic compound from gasoline, study more gasoline desulphurization sorbent at present and are mainly molecular screen base desulfuration adsorbent, metal-oxide base desulfurizing adsorbent, absorbent charcoal based desulfuration adsorbent etc..
In the gasoline of elimination in the world of report, the method for sulfur-containing impurities mainly has following several at present.The first kind is hydrodesulfurization technology.Tradition HDS technology is while a large amount of elimination sulfide in petrol, also the antiknock component olefins hydrogenation in gasoline is made, cause the loss of octane number, therefore exploitation has compared with high desulfurization activity, the focus that the less hydrodesulfurization technology of octane number impact becomes current hydrodesulfurization technical research, mainly includes selective hydrodesulfurization and hydrodesulfurization octane value recovering technology.
SCAN-fining technology, is the technique developed by U.S. ExxonMobil, adopts and the Akzo catalyst RT-225 developed jointly, can not be fractionated into directly processing full fraction catalytic gasoline, and desulfurization degree is 92% ~ 95%, 1 ~ 1.5 unit of loss of octane number.The another kind of full distillation gasoline selective hydrogenation desulfurization process OCTGAIN technology of ExxonMobil exploitation is a kind of hydrodesulfurization-cracking-isomerization Combined machining process that octane number can be made to be restored, and is suitable in cracking gasoline higher and is most difficult to the deep desulfuration of desulfurization component.But owing to there is certain cracking reaction, yield of gasoline loss about 5 ~ l0 percentage point.
The Prime-G that IFP (IFP) develops+Gasoline is separated into the light fraction of rich olefins and the heavy distillat of rich sulfur by technology by fractional distillation, heavy distillat catalyst without alkadienes is carried out selective hydrogenation, process conditions relax, hydrogenation of olefins activity is low, does not occur aromatic hydrocarbons saturated and cracking reaction, and liquid yield reaches 100%, desulfurization degree is more than 98%, loss of octane number is few, and hydrogen consumption is low, can meet the requirement that content of sulfur in gasoline is not more than 10ppmw.
ISAL technique is that INTEVEP institute begins one's study in the early 1990s, and the mid-90, Uop Inc. cooperated to be engaged in exploitation and the industrialization of ISAL catalyst with INTEVEP, finally created second filial generation ISAL technique.Adopt the technological process essentially identical with conventional fixed bed hydrogenation process for refining, its catalyst has desulfurization, denitrogenation, olefins hydrogenation and alkane isomerization function, and the little molecule of cracking can be made at catalyst surface generation molecular rearrangement reaction, cause that owing to alkene is saturated octane number is greatly lowered this insurmountable difficult problem of conventional hydrodesulfurization technology thus solving.It is reported, when processing C7+FCC gasoline fraction, its C5+ liquid is received and is reached 99.7%, sulfur content drops to 10ppmw from 1450ppmw, anti-knock index loss 1.6, and Aromatic Hydrocarbon in Gasoline and naphthene content are basically unchanged, and alkene drops to 0.1% from 19.6%, alkane increases to 37.2% from 17.7%, and wherein isomery/positive structure ratio can bring up to 3.4 from 3.1, and this technique 1996-1997 implements industrialization.
Equations of The Second Kind sulfur method is process for adsorption desulfuration.Absorption desulfurization is use oxide, molecular sieve, activated carbon etc. is adsorbent, the technology of the sulfur-containing compound in petrol and diesel oil is removed by complexation, Van der Waals force or chemisorbed, different according to adsorption mechanism, physical absorption desulfurization, reaction absorption desulfurization and selective absorption desulfurization three class can be divided into.
The IRVAD technology developed jointly by Black&VeatchPritchardInc. and AlcoalIndustrialChemicals, is typical physical adsorption techniques.Adopting multistage fluidized bed suction type, utilize the polarity of sulphur atom, select aluminum oxide-based selective solid absorbent low cost elimination sulfur-bearing or other heteroatomic compounds from hydro carbons, desulfurization degree is up to more than 90%.But this choice of technology absorption property is not high, and adsorption capacity is less, and the sulfur being removed still exists with the form of sulfur-containing compound, also needs further process if need to discharge.
The S-Zorb technique of ConocoPhillips research and development is different from hydrotreatment, and it is optionally removed sulfide rather than converts sulfide, high-sulfur FCC gasoline can be converted into low-sulphur oil.S-Zorb technique is cited as a quantum jump of Clean Fuel Production technology, it is when facing hydrogen, adopt the patent adsorbent of its uniqueness, sulphur atom in absorption sulfide, so as to retain on the sorbent, the hydrocarbon moieties of sulfide is then discharged back in process-stream, thus realizing sweetening process.The course of reaction of this uniqueness does not produce H2S, thus avoiding H2S and alkene react generation mercaptan again.Process condition is: reaction temperature 343 DEG C ~ 413 DEG C, pressure 2.5 ~ 2.9MPa, weight (hourly) space velocity (WHSV) 4 ~ l0h-1.This technology loss of octane number is little, hydrogen consumption is low, can take off sulfur content to 5 ~ 10ppmw.
Dalian Inst of Chemicophysics, Chinese Academy of Sciences develops a kind of C 4 olefin desulfurization absorbent (patent No. is CN101450302), this adsorbent also has good effect for FCC gasoline absorption desulfurization, but the some shortcomings of there is also, such as: adsorbent specific surface area is on the low side, adsorbent Sulfur capacity is relatively low, and absorption desulfurization temperature is higher, and energy consumption is high, operating cost is high, because of problems such as the high easily sintering of temperature during regeneration.
In addition, also has some other desulfurization process of gasoline.CDTech company have developed CDHydro/CDHDS technique, hydrodesulfurization reaction and catalytic distillation technology can be combined in a tower and carry out, and adopts two-phase method catalytic distillation to make the FCC gasoline desulfurization degree can more than 99.5%.BP company develops the gasoline desulfurization technology of thiophenic sulfur olefin alkylation (OATS), thiophene-type sulfide is converted into boiling point component higher, that easily separate from gasoline fraction, Sulfur Content in Catalytic Cracking Gasoline can be made to be reduced to below l0ppmw.But, this technology is actually a kind of sulfur transfer techniques, is not substantially removed from hydrocarbon products by sulfur-containing compound.
Domestic at present also develop a series of desulfurization process of gasoline.FCC gasoline Adsorption Desulfurization (i.e. LADS) Technology of Luoyang Petrochemical engineering company refining institute exploitation, adopting supporting LADS-A desulfuration adsorbent and LADS-D to regenerate desorbing agent, technological process is simple, and operating condition relaxes, desulfuration efficiency is higher, but working ability is limited.
Research Institute of Petro-Chemical Engineering (RIPP) develops gasoline hydrogenation isomery desulfurating and reducing olefinic hydrocarbon technology (RIDOS) and RSDS (RSDS), RIDOS technology is by catalytically cracked gasoline segment processing, light component is through alkali density removal of mercaptans, heavy constituent hydrodesulfurization, denitrogenation, Olefin decrease and octane value recovering, the gasoline products sulfur content of production will be reduced to 150ppmw from 500ppmw.
FCC gasoline fractional distillation is LCN and HCN by the OCT-M technique that Fushun Petrochemical Research Institute (FRIPP) develops, and uses special FGH-20/FGH-11 dual catalyst system to HCN hydrodesulfurization, then mixes with LCN again and carries out removal of mercaptans process.Commercial application shows, MIP gasoline is after OCT-M device processed, and sulfur content is reduced to 24 ~ 53ppmw by 417 ~ 442ppmw.
In sum, in existing document or patent or technique, gasoline desulfurization there is also the following weak point: 1, desulfurization depth is inadequate, it is difficult to is taken off to below 5ppmw from 50 ~ 200ppmw by sulfur；2, adsorbent specific surface area is on the low side, and adsorbent Sulfur capacity is relatively low；3, sweetening process energy consumption is big, and operating condition is comparatively harsh, and operating cost is high；4, sweetening process is unfriendly to environment；5, the regeneration Sulfur capacity loss of desulfurizing agent is bigger；6, because of problems such as the high easily sintering of temperature during desulfurizer regeneration.
Summary of the invention
It is an object of the invention to provide a kind of adsorbent for FCC gasoline ultra-deep desulfurization and its preparation method and application.
The present invention also resides in the method that octane number can be kept not lose the while that offer is a kind of carrying out ultra-deep desulfurization to FCC gasoline.
The present invention also resides in and provides a kind of and adsorbent can be regenerated use and keep desulphurizing activated method.
The invention provides a kind of adsorbent for FCC gasoline ultra-deep desulfurization, it is characterised in that adopt following method to prepare:
1. by Group IIB transition metal salt, Group IVB slaine, group vib slaine, VIIB race slaine, lanthanide metal salt mixes in the polar solvent (ethanol such as moisture 50%) containing proton with precipitant (precipitant consumption is that the pH value of solution controls between 6-9 after carrying out precipitation), it is that room temperature carries out precipitation (1-10 hour) to 150 ° of C in temperature, precipitated product is filtered, washing, dry (under 80-120 ° of C dry 4-10 hour), calcine 4-10 hour under 300-500 ° of C, namely obtain containing Group IIB transition metal oxide, Group IVB metal-oxide, group vib metal-oxide, VIIB family metal oxide, the desulfuration adsorbent with nanoscale of lanthanide metal oxide dries sample.
2. IB race slaine, VIII base metal salt are dissolved in a small amount of water, supporting by 1. obtaining the dry sample of desulfuration adsorbent carries out dipping, impregnation product is dried (under 80-120 ° of C dry 4-10 hour), under 300-500 ° of C, calcine (4-10 hour), namely obtain the dry sample of the oxide desulfuration adsorbent with nanoscale containing IB race metal, VIII base metal, Group IIB transition metal, Group IVB metal, group vib metal, VIIB race metal, lanthanide series metal.
3. by by the dry sample of the desulfuration adsorbent with nanoscale 2. obtained and aluminium oxide adhesive dry glue mix homogeneously, add Aci-Jel solvent (consumption is the 1-5% that desulfuration adsorbent dries sample and aluminium oxide adhesive dry glue weight) extruded moulding, after drying (under 80-120 ° of C dry 4-10 hour), roasting (4-10 hour), obtain with γ-Al2O3Desulfuration adsorbent for carrier.
4. above-mentioned adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization.Use front adsorbent will reaction temperature be under 300-450 ° of C the atmosphere containing hydrogen in reduction treatment 4-20 hour.
Wherein said Gasoline ultra-deep desulfurization adsorbent, it is characterised in that described VIII base metal be by ferrum, cobalt, nickel the combination of any one and/or they, it is preferable that cobalt, nickel and/or its combination, it is desirable to nickel；Described IB race base metal be by copper, silver, gold the combination of any one and/or they, it is preferable that copper, silver and/or its combine, it is desirable to copper.Described Group IIB metal is zinc.Described Group IVB metal is by titanium or zirconium, it is preferable that zirconium.Described group vib metal is chromium, molybdenum, tungsten, it is preferable that molybdenum.Described VIIB race metal is manganese.Described lanthanide series metal is by the combination of lanthanum, any one and/or they of cerium, it is desirable to lanthanum.Described precipitant refers to soluble sodium hydroxide, potassium hydroxide, oxalic acid, carbamide, ammonia, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate and/or their combination, preferred oxalic acid, carbamide, ammonium carbonate and/or their combination, it is desirable to oxalic acid or carbamide.The described solvent containing proton refers to aqueous solution, ethanol, methanol, isopropanol, ethylene glycol, glycerol and/or their combination, it is preferable that the mixed solvent of water and ethanol.The described nanoscale that has is meant less than 100nm, it is preferable that less than 30nm；Described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination, it is preferable that nitric acid；Described IB race base metal mass percent shared by adsorbent is 1-30%,；Described VIII base metal mass percent shared by adsorbent is 1-30%；Described Group IIB transition metal mass percent shared by adsorbent is 10-79%；Described Group IVB base metal mass percent shared by adsorbent is 1-30%；Described group vib base metal mass percent shared by adsorbent is 1-20%；Described VIIB race base metal mass percent shared by adsorbent is 1-40%；Described lanthanide series metal mass percent shared by adsorbent is 1-40%；Described aluminium oxide adhesive mass percent in adsorbent is 5-50%.
The preferred 2.5-20% of mass percent that IB race base metal is shared in adsorbent；
The preferred 2.5-20% of mass percent that VIII base metal is shared in adsorbent；
The preferred 15-60% of mass percent that Group IIB transition metal is shared in adsorbent；
The preferred 2.5-20% of mass percent that Group IVB base metal is shared in adsorbent；
The preferred 1-15% of mass percent that group vib base metal is shared in adsorbent；
The preferred 2-30% of mass percent that VIIB race base metal is shared in adsorbent；
The preferred 2.5-30% of mass percent that lanthanide series metal is shared in adsorbent；
The preferred 10-45% of aluminium oxide adhesive mass percent in adsorbent.
The best 2.5-10% of mass percent that IB race base metal is shared in adsorbent；
The best 5-15% of mass percent that VIII base metal is shared in adsorbent；
The best 30-50% of mass percent that Group IIB transition metal is shared in adsorbent；
The best 2.5-15% of mass percent that Group IVB base metal is shared in adsorbent；
The best 1-10% of mass percent that group vib base metal is shared in adsorbent；
The best 2-20% of mass percent that VIIB race base metal is shared in adsorbent；
The best 2.5-20% of mass percent that lanthanide series metal is shared in adsorbent；
The best 15-40% of aluminium oxide adhesive mass percent in adsorbent.
The present invention method of above-mentioned absorbent preparation FCC super low-sulfur oil, adopts fixed-bed operation, and adsorption operations condition is as follows: adsorption temp 200-400 DEG C, hydrogen partial pressure 0.02-2MPa, and hydrogen and gasoline-volume ratio is for 2000:1-5:1, liquid volume air speed 1-20h-1。
Above-mentioned adsorbent used by the present invention can regenerate after losing activity after using, and regeneration condition is as follows: regeneration temperature 30-650 DEG C, regenerating system pressure 0.1-1MPa, and gas flow rate is 0.2-10L h-1, regeneration gas is the mixing gas of air, oxygen and nitrogen, oxygen content 1%-21%, it is preferable that 1.5-15%, it is desirable to 2.5-10%.
Compared with known technology, the invention have the advantages that
1, adsorbent is high to adsorptive selectivity and the adsorption capacity of sulfide；
2, in facing H-H reaction absorption, alkene does not lose；
3, catalyst preparation process is simple, and raw material is easy to get, and production cost is low, non-environmental-pollution；
4, adopting fixed-bed operation, adsorbent free of losses, operating cost is low；
5, adsorbent can regenerate use, and activity remains unchanged.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the desulfuration adsorbent A of nanoscale.It can be seen that the particle size of desulfuration adsorbent A is about 8nm.
Detailed description of the invention
The invention provides a kind of adsorbent for FCC gasoline ultra-deep desulfurization, it is characterized in that, following method is adopted to prepare: 1. by Group IIB transition metal salt, Group IVB slaine, group vib slaine, VIIB race slaine, lanthanide metal salt mixes in the polar solvent containing proton with precipitant, it is that room temperature carries out precipitation to 150 ° of C in temperature, precipitated product is filtered, washing, dry, calcine under 300-500 ° of C, namely obtain containing Group IIB transition metal oxide, Group IVB metal-oxide, group vib metal-oxide, VIIB family metal oxide, the desulfuration adsorbent with nanoscale of lanthanide metal oxide dries sample.2. IB race slaine, VIII base metal salt are dissolved in a small amount of water, supporting by 1. obtaining the dry sample of desulfuration adsorbent carries out dipping, impregnation product is dried, calcine under 300-500 ° of C, namely obtain the dry sample of the oxide desulfuration adsorbent with nanoscale containing IB race metal, VIII base metal, Group IIB transition metal, Group IVB metal, group vib metal, VIIB race metal, lanthanide series metal.3. by by the dry sample of the desulfuration adsorbent with nanoscale 2. obtained and aluminium oxide adhesive dry glue mix homogeneously, add Aci-Jel solvent extruded moulding, after drying, roasting, obtain with γ-Al2O3Desulfuration adsorbent for carrier.4. above-mentioned adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization.Use front adsorbent will reaction temperature be under 300-450 ° of C the atmosphere containing hydrogen in reduction treatment 4-20 hour.
Wherein said Gasoline ultra-deep desulfurization adsorbent, it is characterised in that described VIII base metal be by ferrum, cobalt, nickel the combination of any one and/or they, it is preferable that cobalt, nickel and/or its combination, it is desirable to nickel；Described IB race base metal be by copper, silver, gold the combination of any one and/or they, it is preferable that copper, silver and/or its combine, it is desirable to copper.Described Group IIB metal is zinc.Described Group IVB metal is by titanium or zirconium, it is preferable that zirconium.Described group vib metal is chromium, molybdenum, tungsten, it is preferable that molybdenum.Described VIIB race metal is manganese.Described lanthanide series metal is by the combination of lanthanum, any one and/or they of cerium, it is desirable to lanthanum.Described precipitant refers to soluble sodium hydroxide, potassium hydroxide, oxalic acid, carbamide, ammonia, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate and/or their combination, preferred oxalic acid, carbamide, ammonium carbonate and/or their combination, it is desirable to oxalic acid or carbamide.The described solvent containing proton refers to aqueous solution, ethanol, methanol, isopropanol, ethylene glycol, glycerol and/or their combination, it is preferable that the mixed solvent of water and ethanol.The described nanoscale that has is meant less than 100nm, it is preferable that less than 30nm；Described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination, it is preferable that nitric acid；Described IB race base metal mass percent shared by adsorbent is 1-30%,；Described VIII base metal mass percent shared by adsorbent is 1-30%；Described Group IIB transition metal mass percent shared by adsorbent is 10-79%；Described Group IVB base metal mass percent shared by adsorbent is 1-30%；Described group vib base metal mass percent shared by adsorbent is 1-20%；Described VIIB race base metal mass percent shared by adsorbent is 1-40%；Described lanthanide series metal mass percent shared by adsorbent is 1-40%；Described aluminium oxide adhesive mass percent in adsorbent is 5-50%.
The present invention method of above-mentioned absorbent preparation FCC super low-sulfur oil, adopts fixed-bed operation, and adsorption operations condition is as follows: adsorption temp 200-400 DEG C, hydrogen partial pressure 0.02-2MPa, and hydrogen and gasoline-volume ratio is for 2000:1-5:1, liquid volume air speed 1-20h-1。
Above-mentioned adsorbent used by the present invention can regenerate after losing activity after using, and regeneration condition is as follows: regeneration temperature 30-650 DEG C, regenerating system pressure 0.1-1MPa, and gas flow rate is 0.2-10L h-1, regeneration gas is the mixing gas of air, oxygen and nitrogen, oxygen content 1%-21%, it is preferable that 1.5-15%, it is desirable to 2.5-10%.
Fig. 1 is the transmission electron microscope picture of the desulfuration adsorbent A of nanoscale.It can be seen that the particle size of desulfuration adsorbent A is about 8nm.
In order to further illustrate the present invention, enumerate following example, but it is not limiting as the invention scope that each accessory claim is defined.
Embodiment 1
In the present invention desulfuration adsorbent prepare as follows:
(1), weigh 21.20g zinc acetate, 2.60g zirconium nitrate, 3.20g ammonium heptamolybdate, 2.80g manganese acetate and 1.27g Lanthanum (III) nitrate and be dissolved in 1000ml distilled water, add to be sufficiently stirred for 24 hours at 95 DEG C of 30.10g carbamide and make precipitant complete hydrolysis (pH detection paper is released without ammonia), through filtering, deionized water wash, obtain wet cake, dry then at 120 ° of C, obtain dry sample, by dry sample in Muffle furnace in 400 ° of C roastings, obtain adsorbent roasting sample；(2), weigh 1.85 nickel nitrates and 0.82g copper nitrate is dissolved in 7.5ml deionized water, obtained that desulfuration adsorbent roasting sample carries out dipping at 7.22g by (1) and support, impregnation product is dried, calcine under 300-500 ° of C；(3) above-mentioned oxide carrier and 2.00g alumina dry glue are sufficiently mixed, add the abundant kneading of aqueous solution 5ml that concentration of nitric acid is 2%, make body of paste, then be extruded into cloverleaf pattern with banded extruder, be dried overnight at 120 ° of C, 450 ° of C roasting 4h, obtain adsorbent A.
Embodiment 2
With embodiment 1, difference from Example 1 is in that, the amount simply weighing nickel nitrate is 1.20 grams, obtains adsorbent B.
Embodiment 3
With embodiment 1, difference from Example 1 is in that, the amount simply weighing nickel nitrate is 2.40 grams, obtains adsorbent C.
Embodiment 4
With embodiment 1, difference from Example 1 is in that, the amount simply weighing nickel nitrate is 3.0 grams, obtains adsorbent D.
Embodiment 5
With embodiment 1, difference from Example 1 is in that, is simply not added with nickel nitrate, then the amount weighing cobalt nitrate is 1.860 grams, obtains adsorbent E.
Embodiment 6
With embodiment 1, difference from Example 1 is in that, is simply not added with Lanthanum (III) nitrate, then the amount weighing cerous nitrate is 1.27 grams, obtains adsorbent F.
Embodiment 7
With embodiment 1, difference from Example 1 is in that, the amount simply weighing Lanthanum (III) nitrate is 1.60 grams, obtains adsorbent G.
Embodiment 8
With embodiment 1, difference from Example 1 is in that, the amount simply weighing zinc acetate is 27.20 grams, obtains adsorbent H.
Embodiment 9
With embodiment 1, difference from Example 1 is in that, the amount simply weighing zinc acetate is 15.10 grams, obtains adsorbent I.
Embodiment 10
With embodiment 1, difference from Example 1 is in that, the amount simply weighing zirconium nitrate is 1.30 grams, obtains adsorbent J.
Embodiment 11
With embodiment 1, difference from Example 1 is in that, the amount simply weighing manganese acetate is 1.40 grams, obtains adsorbent K.
Embodiment 12
With embodiment 1, difference from Example 1 is in that, the amount simply weighing manganese acetate is 4.30 grams, obtains adsorbent L.
Embodiment 13
With embodiment 1, difference from Example 1 is in that, the amount simply adding alumina dry glue when extrusion is 1.00 grams, obtains adsorbent M.
Embodiment 14
With embodiment 1, difference from Example 1 is in that, the amount simply adding alumina dry glue when extrusion is 3.00 grams, obtains adsorbent N.
Embodiment 15
With embodiment 1, difference from Example 1 is in that, precipitant simply changes into the 1000ml aqueous solution containing ammonium hydrogen carbonate 32.10 grams, obtains adsorbent O.
Embodiment 16
With embodiment 15, it is different in that with embodiment 15, simply precipitant is changed into the 1000ml aqueous solution containing sodium hydroxide 15.10 grams, obtains adsorbent P.
Embodiment 17
With embodiment 15, it is different in that with embodiment 15, simply precipitant is changed into the 1000ml aqueous solution of containing sodium carbonate 15.10 grams, obtains adsorbent Q.
Embodiment 18
With embodiment 1, difference from Example 1 is in that, simply changes precipitant into oxalic acid 32.10g, obtains adsorbent S.
Embodiment 19
With embodiment 1, difference from Example 1 is in that, nitric acid peptizer simply changes into the aqueous solution 5ml containing acetic acid 5%, obtains adsorbent R.
Embodiment 20
With embodiment 1, difference from Example 1 is in that, simply changes 1000ml distilled water into ethanol water that 1200ml volume ratio is 1:2, obtains adsorbent T.
Embodiment 21
Investigate the desulfurized effect of adsorbent for raw material with the gasoline that sulfur content is 150ppmw, be adsorbed in fixed bed reactors and carry out.Adsorption conditions is: desulfuration adsorbent quality 1.00g, and adsorption temp is 280 DEG C, Hydrogen Vapor Pressure 0.1MPa, and the volume ratio of hydrogen and gasoline is 30:1, hydrogen flow rate 450mL/h, gasoline stocks volume space velocity 3h-1.Before absorption, adsorbent is first under 400 ° of C, normal pressures, hydrogen treat 4 hours.In sample, sulfur content adopts Antek9000VLLS sulphur content analyzer to measure, and detection is limited to 0.1ppm(V/V).Gasoline content is analyzed and is being carried out equipped with on the gas chromatograph (Agilent6890) of capillary column (PONA, 50m × 0.2mm, id × 0.5 μm) and flame ionic detector (FID).Absorption result is listed in table 2.
Embodiment 22
With embodiment 21, being different in that with embodiment 21, simply hydrogen is 90:1 with the volume ratio of gasoline, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 23
With embodiment 21, being different in that with embodiment 21, simply hydrogen is 300:1 with the volume ratio of gasoline, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 24
With embodiment 21, being different in that with embodiment 21, simply hydrogen is 600:1 with the volume ratio of gasoline, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 25
With embodiment 21, being different in that with embodiment 21, simply gasoline stocks volume space velocity is 1h-1, only investigate the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 26
With embodiment 21, being different in that with embodiment 21, simply gasoline stocks volume space velocity is 6h-1, only investigate the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 27
With embodiment 21, being different in that with embodiment 21, simply gasoline stocks volume space velocity is 9h-1, only investigate the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 28
With embodiment 21, being different in that with embodiment 21, simply Hydrogen Vapor Pressure is 0.5MPa, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 29
With embodiment 21, being different in that with embodiment 21, simply Hydrogen Vapor Pressure is 1.0MPa, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 30
With embodiment 21, being different in that with embodiment 21, simply Hydrogen Vapor Pressure is 1.5MPa, only investigates the absorption property of adsorbent A, and absorption result is listed in table 2.
Embodiment 31
With embodiment 21, simply only investigate the absorption property of adsorbent A, absorption desulfurization time is extended, until adsorbent A loses activity, by the adsorbent A of inactivation, it is placed in tube furnace and regenerates, regeneration condition is as follows: regeneration temperature 500 DEG C, regenerating system pressure normal pressure, and gas flow rate is 5L h-1, regeneration gas is the gaseous mixture of oxygen and nitrogen, oxygen content 10%, and the recovery time is 120 hours, the adsorbent A-1 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent A-1, the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 32
With embodiment 31, simply being extended by absorption desulfurization time, until adsorbent A-1 loses activity, the adsorbent A-1 of inactivation regenerated, regeneration condition is with embodiment 31, the adsorbent A-2 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent A-2, the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 33
With embodiment 32, simply being extended by absorption desulfurization time, until adsorbent A-2 loses activity, the adsorbent A-2 of inactivation regenerated, regeneration condition is with embodiment 31, the adsorbent A-3 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent A-3, the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 34
With embodiment 33, simply being extended by absorption desulfurization time, until adsorbent A-3 loses activity, the adsorbent A-3 of inactivation regenerated, regeneration condition is with embodiment 31, the adsorbent A-4 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent A-4, the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 35
With embodiment 34, simply being extended by absorption desulfurization time, until adsorbent A-4 loses activity, the adsorbent A-4 of inactivation regenerated, regeneration condition is with embodiment 31, the adsorbent A-5 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent A-5, the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Comparative example 1
Preparing catalyst by the method that Chinese invention patent CN101450302 embodiment 1 is identical, prepared catalyst U represents.Absorption result is listed in table 2.
Comparative example 2
With comparative example 1, simply being extended by absorption desulfurization time, until adsorbent U loses activity, regenerated by the adsorbent U of inactivation, regeneration condition is with embodiment 31, the adsorbent U-1 after being regenerated.Investigating the gasoline absorbing desulfurization activity of adsorbent U-1, the implementation condition of investigation is same
Embodiment 21, absorption result is listed in table 2.
Table 1, four kind of adsorbent A, A-1, U and U-1 specific surface area, pore volume and sulfur capacity contrast
Table 2, gasoline stocks be its alkene and sulfur content after desulfuration adsorbent processes
As can be seen from the table, the desulfuration adsorbent of patent of the present invention is adopted, it is possible to the effectively sulfide in elimination gasoline, it is possible to obtain super-low sulfur (lower than 5ppmw) gasoline stocks, ensure that olefin(e) centent does not lose simultaneously.Comparing with comparative example, when identical adsorption operations, the desulfurization depth of adsorbent of the present invention is higher, and sulfur capacity is bigger.Secondly, the patent desulfuration adsorbent of the present invention of inactivation, after adopting the renovation process regeneration of patent of the present invention, desulfurization performance can effectively keep.
Claims (10)
1. a Gasoline ultra-deep desulfurization adsorbent, adopts following method to prepare:
1. Group IIB transition metal zinc salt, Group IVB slaine, group vib slaine, VIIB race manganese metal salt, lanthanide metal salt are mixed in the polar solvent containing proton with precipitant, temperature be room temperature to 150 DEG C at carry out precipitation, precipitated product is filtered, washs, dries, calcine at 300-500 DEG C, namely obtain the dry sample of the desulfuration adsorbent with nanoscale containing Group IIB transition metal zinc oxide, Group IVB metal-oxide, group vib metal-oxide, VIIB race manganese metal oxide, lanthanide metal oxide；
2. IB race slaine, VIII base metal salt are dissolved in the water, supporting by 1. obtaining the dry sample of desulfuration adsorbent carries out dipping, impregnation product is dried, calcine at 300-500 DEG C, namely obtain the dry sample of the oxide desulfuration adsorbent with nanoscale containing IB race metal, VIII base metal, Group IIB transition metal zinc, Group IVB metal, group vib metal, VIIB race manganese metal, lanthanide series metal；
3. by 2. obtaining the dry sample of desulfuration adsorbent and aluminium oxide adhesive dry glue mix homogeneously, Aci-Jel solvent extruded moulding will be added, after drying, roasting, obtains with γ-Al2O3Desulfuration adsorbent for carrier；
In oxide,
Described IB race metal mass percent shared by adsorbent is 1-30%；
Described VIII base metal mass percent shared by adsorbent is 1-30%；
Described Group IIB transition metal zinc mass percent shared by adsorbent is 10-79%；
Described Group IVB metal mass percent shared by adsorbent is 1-30%；
Described group vib metal mass percent shared by adsorbent is 1-20%；
Described VIIB race manganese metal mass percent shared by adsorbent is 1-40%；
Described lanthanide series metal mass percent shared by adsorbent is 1-40%；
Described aluminium oxide adhesive mass percent in adsorbent is 5-50%.
2. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that: described IB race metal be by copper, silver, gold the combination of any one and/or they；
Described VIII base metal be by ferrum, cobalt, nickel any one and/or the combination of more than two kinds in them.
3. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that:
Described Group IVB metal is titanium or zirconium；
Described group vib metal is chromium, molybdenum, tungsten；
Described lanthanide series metal is by any one in lanthanum, cerium and/or their combinations of two kinds.
4. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that:
Described precipitant refers to soluble sodium hydroxide, potassium hydroxide, oxalic acid, carbamide, ammonia, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate and/or their combination；
The consumption of precipitant is that the pH value of solution is 6-9 after carrying out precipitation.
5. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that: the described solvent containing proton refers to the combination of any one and/or they two kinds in aqueous solution, ethanol, methanol, isopropanol, ethylene glycol, glycerol.
6. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that: the described nanoscale that has is meant less than 100nm.
7. the Gasoline ultra-deep desulfurization adsorbent described in claim 1, it is characterised in that: described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination；
Will by 2. obtaining the dry sample of desulfuration adsorbent and aluminium oxide adhesive dry glue, Aci-Jel solvent by weight extruded moulding again after 65:25:5 mix homogeneously, dry 4-10 hour at 80-120 DEG C, 300-600 DEG C of roasting 4-10 hour, obtain with γ-Al2O3Desulfuration adsorbent for carrier.
8. the application of the adsorbent described in a claim 1, it is characterized in that: among the ultra-deep desulfurization of gasoline, adopt fixed-bed operation, adsorption operations condition is as follows: adsorption temp 200-400 DEG C, hydrogen partial pressure 0.02-2MPa, hydrogen and gasoline-volume are than for 2000:1-5:1, liquid volume air speed 1-20h-1。
9. the application described in claim 8, it is characterized in that: regenerate after adsorbent is saturated, adopting regeneration in fixed-bed operation or tube furnace, regeneration condition is as follows: regeneration temperature 30-650 DEG C, regenerating system pressure 0.1-1MPa, gas flow rate is 0.2L-10L h-1；
Used regeneration gas is the mixing gas of air or oxygen and nitrogen, oxygen volume content 1%-21% in mixing gas.
10. the application described in claim 8, it is characterised in that: described adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization；Using front adsorbent to reduce at reaction temperature is 300-450 DEG C, reducing atmosphere is the mixing gas of hydrogen or hydrogen and nitrogen.
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| CN108070416B (en) * | 2016-11-11 | 2020-08-11 | 中国石油化工股份有限公司抚顺石油化工研究院 | Adsorption desulfurization process for liquefied petroleum gas |
| CN109847730B (en) * | 2017-11-30 | 2021-12-24 | 中国科学院大连化学物理研究所 | Regeneration method of desulfurization adsorbent |
| CN108295801B (en) * | 2018-01-22 | 2020-07-28 | 燕山大学 | Deep desulfurization supported Pd-based bimetallic adsorbent and preparation method thereof |
| CN112195037A (en) * | 2020-09-07 | 2021-01-08 | 中国建材国际工程集团有限公司 | Zero-emission closed operation device for normal-pressure oil tank |
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| US3450629A (en) * | 1966-12-27 | 1969-06-17 | Pan American Petroleum Corp | Reclamation of adsorptive material used in desulfurization of hydrocarbons |
| CN1511629A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院大连化学物理研究所 | Molecular sieve adsorbent for deep sulfide removing and preparation and use |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
| 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 |
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| US3450629A (en) * | 1966-12-27 | 1969-06-17 | Pan American Petroleum Corp | Reclamation of adsorptive material used in desulfurization of hydrocarbons |
| CN1511629A (en) * | 2002-12-30 | 2004-07-14 | 中国科学院大连化学物理研究所 | Molecular sieve adsorbent for deep sulfide removing and preparation and use |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
| 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 |
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