CN103721668A - Gasoline ultra-deep desulfurization adsorbent and application thereof - Google Patents
Gasoline ultra-deep desulfurization adsorbent and application thereof Download PDFInfo
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Abstract
The invention relates to a FCC (fluid catalytic cracking) gasoline ultra-deep desulfurization adsorbent and a preparation method and application thereof. The adsorbent comprises a reduced VIII group transition metal, a reduced IB group transition metal, a IIB group transition metal oxide, a IVB group metal oxide, a VIB group metal oxide, a VIIB group metal oxide and a lanthanide-metal oxide which are capable of activating sulfur-containing molecules, and aluminum oxide as an adhesive. The adsorbent can absorb almost all sulfur-containing compounds in FCC gasoline to obtain ultra-low sulfur gasoline with the sulfur content of less 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 burning, can make vehicle exhaust conversion system catalyst poisoning, further affects effective conversion of NOx, CO, CH, and oxygen sulfur compound is discharged into meeting formation Acid Rain Pollution environment in atmosphere.Along with the pay attention to day by day of people to environmental protection, environmental regulation is also day by day strict, and the index of global 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 be implemented integrally state's III standard in 31 days l2 months in 2009.Beijing area was implemented integrally capital mark C(and has been equivalent to state's IV standard in 1 day January in 2008), content of sulfur in gasoline requires to drop to 50ppmw from 150ppmw, and state's IV standard also will be carried out in advance in Shanghai, Guangzhou aspect sulfur content.Beijing takes the lead in carrying out sulfur content lower than the so-called capital V content of sulfur in gasoline standard of 10ppmw on June 1st, 2012, and Zhe Jiudui China oil refining enterprise gasoline desulfur technology is had higher requirement.
Adsorption desulfurize method is a kind of in many gasoline desulfur technology, and it is object that this method be take the organosulfur compound that thiophene, benzothiophene etc. are difficult to remove, and gasoline is carried out to deep desulfuration.Adsorption desulfurize ratio juris is by fully the contacting of gasoline and adsorbent, by the sulfur compounds adsorption in gasoline on adsorbent, thereby reach the object that reduces content of sulfur in gasoline.Many adsorbents all have the ability that removes sulfur-bearing from gasoline, contain oxygen or nitrogenous polar organic compound, study at present more gasoline desulphurization sorbent and are mainly molecular screen base desulfuration adsorbent, metal oxide base desulfurizing adsorbent, absorbent charcoal based desulfuration adsorbent etc.
The method of sulfur-containing impurities in gasoline that removes in the world of report mainly contains following several at present.The first kind is hydrodesulfurization technology.Tradition HDS technology is when removing sulfide in petrol in a large number, also make the antiknock component in gasoline---olefins hydrogenation, cause the loss of octane number, therefore exploitation has compared with high desulfurization activity, octane number is affected to the focus that less hydrodesulfurization technology becomes current hydrodesulfurization technical research, mainly comprises selective hydrodesulfurization and hydrodesulfurization octane value recovering technology.
SCAN-fining technology, the technique of Shi You U.S. ExxonMobil exploitation, adopts the catalyst RT-225 developing jointly with Akzo, can directly process full cut catalytic gasoline without fractionation, and desulfurization degree is 92% ~ 95%, loss of octane number 1 ~ 1.5Ge unit.The full distillation gasoline selective hydrogenation desulfurization process of the another kind OCTGAIN technology of ExxonMobil exploitation is a kind of hydrodesulfurization-cracking that can make octane number be restored-isomerization combination process, is suitable for the deep desulfuration of higher and the most difficult desulfurization component in cracking gasoline.But owing to there is certain cracking reaction, yield of gasoline loses approximately 5 ~ l0 percentage point.
The Prime-G of IFP (IFP) exploitation
+technology is separated into the light fraction of rich olefins and the heavy distillat of rich sulphur by fractionation by gasoline, the heavy distillat that does not contain alkadienes is carried out to selective hydrogenation with catalyst, process conditions relax, hydrogenation of olefins activity is low, and aromatic saturation and cracking reaction do not occur, and liquid yield reaches 100%, desulfurization degree is greater 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 research 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, had finally produced second generation ISAL technique.Adopt and the conventional essentially identical technological process of fixed bed hydrogenation process for refining, its catalyst has desulfurization, denitrogenation, olefins hydrogenation and alkane isomerization function, and can make the little molecule of cracking at catalyst surface generation molecular rearrangement reaction, thereby solved because olefin saturated causes octane number, significantly reduce the insurmountable difficult problem of this conventional hydrodesulfurization technology.It is reported, while 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 substantially constant, and alkene drops to 0.1% from 19.6%, alkane is increased 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.Adsorption desulfurize is to be adsorbent with oxide, molecular sieve, active carbon etc., by complexing, Van der Waals force or chemisorbed, remove the technology of the sulfur-containing compound in petrol and diesel oil, different according to adsorption mechanism, can be divided into physical absorption desulfurization, reaction adsorption desulfurize and selective absorption desulfurization three classes.
The IRVAD technology of being developed jointly by Black & Veatch Pritchard Inc. and AlcoalIndustrial Chemicals is typical physical adsorption techniques.Adopt multistage fluidized bed suction type, utilize the polarity of sulphur atom, select aluminum oxide-based selective solid absorbent low cost from hydro carbons to remove sulfur-bearing or other heteroatomic compounds, desulfurization degree can reach more than 90%.But this choice of technology absorption property is not high, and adsorption capacity is less, and the sulphur being removed still exists with the form of sulfur-containing compound, if need discharge also need further processing.
The S-Zorb technique of ConocoPhillips research and development is different from hydrotreatment, and it is optionally removed sulfide rather than transforms sulfide, can be low-sulphur oil by high-sulfur FCC gasoline conversion.S-Zorb technique is cited as a quantum jump of Clean Fuel Production technology, it is to face under the condition of hydrogen, adopt its unique patent adsorbent, sulphur atom in absorption sulfide, make it to be retained on adsorbent, the hydrocarbon structure part of sulfide is released back in process-stream, thus the sweetening process of realization.In this unique course of reaction, do not produce H
2s, thus H avoided
2s reacts generation mercaptan again with alkene.Process condition is: 343 ℃ ~ 413 ℃ of reaction temperatures, 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, sulfur content can be taken off to 5 ~ 10ppmw.
Dalian Inst of Chemicophysics, Chinese Academy of Sciences has developed a kind of C 4 olefin desulfurization absorbent (patent No. is CN101450302), this adsorbent also has good effect for FCC gasoline absorbing desulfurization, but also come with some shortcomings, for example: adsorbent specific area is on the low side, adsorbent Sulfur capacity is lower, and adsorption desulfurize temperature is higher, and energy consumption is high, operating cost is high, during regeneration because of problems such as the high easily sintering of temperature.
In addition, also has some other desulfurization process of gasoline.CDTech company has 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 FCC gasoline desulfur rate can be greater than 99.5%.BP company has developed the gasoline desulfur technology of thiophenic sulfur olefin alkylation (OATS), and thiophene-type sulfide is converted into higher, the easy component separated from gasoline fraction of boiling point, can make Sulfur Content in Catalytic Cracking Gasoline be reduced to below l0ppmw.But, this technology is actually a kind of sulphur transfer techniques, sulfur-containing compound is not substantially removed from hydrocarbon products.
Current domestic a series of desulfurization process of gasoline of also having developed.FCC gasoline Adsorption Desulfurization (the being LADS) technology of refining research institute of Luoyang Petrochemical engineering company exploitation, adopt supporting LADS-A desulfuration adsorbent and LADS-D regeneration 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) has developed catalytic gasoline hydroisomerizing desulfurating and reducing olefinic hydrocarbon technology (RIDOS) and RSDS (RSDS), RIDOS technology is by catalytically cracked gasoline segment processing, light component is through alkali extraction desulfurization alcohol, heavy constituent hydrodesulfurization, denitrogenation, fall alkene and octane value recovering, the gasoline products sulfur content of production will be reduced to 150ppmw from 500ppmw.
The OCT-M technique of Fushun Petrochemical Research Institute (FRIPP) exploitation is LCN and HCN by the fractionation of FCC gasoline, uses special-purpose FGH-20/FGH-11 dual catalyst system to HCN hydrodesulfurization, and then mixes with LCN and carry out removal of mercaptans processing.Commercial application shows, MIP gasoline is after the processing of OCT-M device is processed, and sulfur content is reduced to 24 ~ 53ppmw by 417 ~ 442ppmw.
In sum, in existing document or patent or technique, also there is the following weak point in gasoline desulfur: 1, desulfurization depth is inadequate, is difficult to sulphur to take off to 5ppmw from 50 ~ 200ppmw; 2, adsorbent specific area is on the low side, and adsorbent Sulfur capacity is lower; 3, sweetening process energy consumption is large, and operating condition is comparatively harsh, and operating cost is high; 4, sweetening process is unfriendly to environment; 5, the loss of the regeneration Sulfur capacity of desulfurizing agent is larger; 6, during desulfurizer regeneration because of problems such as the high easily sintering of temperature.
Summary of the invention
The object of the present invention is to provide a kind of adsorbent for FCC gasoline ultra-deep desulfurization and its preparation method and application.
The present invention is also to provide a kind of FCC gasoline is carried out to the method that ultra-deep desulfurization can keep octane number not lose simultaneously.
The present invention is also to provide 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 characterized in that, adopt following method preparation:
1. by IIB group 4 transition metal salt, IVB family slaine, group vib slaine, VIIB family slaine, in the polar solvent (ethanol as moisture 50%) that lanthanide metal salt is containing proton with precipitating reagent (precipitating reagent consumption is that the pH value of solution is controlled between 6-9 after carrying out precipitation reaction), mix, in temperature, be under room temperature to 150 ° C, to carry out precipitation reaction (1-10 hour), precipitated product is filtered, washing, dry (dry 4-10 hour under 80-120 ° of C), under 300-500 ° of C, calcine 4-10 hour, obtain containing IIB group 4 transition metal oxide, IVB family metal oxide, group vib metal oxide, VIIB family metal oxide, the dry sample of the desulfuration adsorbent with nanoscale of lanthanide metal oxide.
②Jiang IB family slaine, VIII family base metal salt are dissolved in a small amount of water, on the dry sample of desulfuration adsorbent, flooding and supporting by 1. obtaining, impregnation product is dried to (dry 4-10 hour under 80-120 ° of C), calcining (4-10 hour) under 300-500 ° of C, obtains the dry sample of the oxide desulfuration adsorbent with nanoscale that contains IB family metal, VIII family base metal, IIB group 4 transition metal, IVB family metal, group vib metal, VIIB family metal, lanthanide series metal.
3. the dry sample of the desulfuration adsorbent with nanoscale by 2. obtaining and the dry glue of aluminium oxide binder are mixed, add Aci-Jel solvent (consumption is the 1-5% of the dry sample of desulfuration adsorbent and the dry glue weight of aluminium oxide binder) extruded moulding, after drying (dry 4-10 hour under 80-120 ° of C), roasting (4-10 hour), obtain with γ-Al
2o
3desulfuration adsorbent for carrier.
4. above-mentioned adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization.Before using adsorbent will reaction temperature for the atmosphere that contains hydrogen under 300-450 ° of C in reduction process 4-20 hour.
Wherein said gasoline ultra-deep desulfurization absorbent, is characterized in that described VIII family base metal is the combination by any one and/or they of iron, cobalt, nickel, preferably cobalt, nickel and/or its combination, preferably nickel; Described IB family base metal is the combination by any one and/or they of copper, silver, gold, preferably copper, silver and/or its combination, best copper.Described IIB family metal is zinc.Described IVB family metal is by titanium or zirconium, preferably zirconium.Described group vib metal is chromium, molybdenum, tungsten, preferably molybdenum.Described VIIB family metal is manganese.Described lanthanide series metal is the combination by any one and/or they of lanthanum, cerium, preferably lanthanum.Described precipitating reagent refers to solubility NaOH, potassium hydroxide, oxalic acid, urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, saleratus, sodium carbonate, potash and/or their combination, preferably oxalic acid, urea, ammonium carbonate and/or their combination, preferably oxalic acid or urea.The described solvent that contains proton refers to the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine and/or their combination, the mixed solvent of preferred water and ethanol.Described have nanoscale and refer to and be less than 100nm, is preferably less than 30nm; Described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination, preferably nitric acid; Described IB family base metal shared mass percent in adsorbent is 1-30%; Described VIII family base metal shared mass percent in adsorbent is 1-30%; Described IIB group 4 transition metal shared mass percent in adsorbent is 10-79%; Described IVB family base metal shared mass percent in adsorbent is 1-30%; Described group vib base metal shared mass percent in adsorbent is 1-20%; Described VIIB family base metal shared mass percent in adsorbent is 1-40%; Described lanthanide series metal shared mass percent in adsorbent is 1-40%; The mass percent of described aluminium oxide binder in adsorbent is 5-50%.
IB family base metal shared preferred 2.5-20% of mass percent in adsorbent;
VIII family base metal shared preferred 2.5-20% of mass percent in adsorbent;
IIB group 4 transition metal shared preferred 15-60% of mass percent in adsorbent;
IVB family base metal shared preferred 2.5-20% of mass percent in adsorbent;
Group vib base metal shared preferred 1-15% of mass percent in adsorbent;
VIIB family base metal shared preferred 2-30% of mass percent in adsorbent;
Lanthanide series metal shared preferred 2.5-30% of mass percent in adsorbent;
The preferred 10-45% of the mass percent of aluminium oxide binder in adsorbent.
IB family base metal shared best 2.5-10% of mass percent in adsorbent;
VIII family base metal shared best 5-15% of mass percent in adsorbent;
IIB group 4 transition metal shared best 30-50% of mass percent in adsorbent;
IVB family base metal shared best 2.5-15% of mass percent in adsorbent;
Group vib base metal shared best 1-10% of mass percent in adsorbent;
VIIB family base metal shared best 2-20% of mass percent in adsorbent;
Lanthanide series metal shared best 2.5-20% of mass percent in adsorbent;
The best 15-40% of the mass percent of aluminium oxide binder in adsorbent.
The method of above-mentioned absorbent preparation FCC super low-sulfur oil for the present invention, adopts fixed-bed operation, and adsorption operations condition is as follows: adsorption temp 200-400 ℃, and hydrogen partial pressure 0.02-2MPa, hydrogen and gasoline volume ratio are 2000:1-5:1, liquid volume air speed 1-20h
-1.
The present invention's above-mentioned adsorbent used can be regenerated after losing activity after using, and regeneration condition is as follows: regeneration temperature 30-650 ℃, and regenerating system pressure 0.1-1MPa, gas flow rate is 0.2-10Lh
-1, regeneration gas is the mist of air, oxygen and nitrogen, oxygen content 1%-21%, preferably 1.5-15%, preferably 2.5-10%.
Compare with known technology, the present invention has the following advantages:
1, adsorbent is high to the adsorptive selectivity of sulfide and adsorption capacity;
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, adopt fixed-bed operation, adsorbent free of losses, operating cost is low;
5, the adsorbent use of can regenerating, and activity keeping is constant.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the desulfuration adsorbent A of nanoscale.The particle size that can see desulfuration adsorbent A is about 8nm.
The specific embodiment
The invention provides a kind of adsorbent for FCC gasoline ultra-deep desulfurization, it is characterized in that, adopt following method preparation: 1. by IIB group 4 transition metal salt, IVB family slaine, group vib slaine, VIIB family slaine, lanthanide metal salt mixes in containing the polar solvent of proton with precipitating reagent, in temperature, be to carry out precipitation reaction under room temperature to 150 ° C, precipitated product is filtered, washing, dry, under 300-500 ° of C, calcine, obtain containing IIB group 4 transition metal oxide, IVB family metal oxide, group vib metal oxide, VIIB family metal oxide, the dry sample of the desulfuration adsorbent with nanoscale of lanthanide metal oxide.②Jiang IB family slaine, VIII family base metal salt are dissolved in a small amount of water, on the dry sample of desulfuration adsorbent, flooding and supporting by 1. obtaining, impregnation product is dried, under 300-500 ° of C, calcine, obtain the dry sample of the oxide desulfuration adsorbent with nanoscale that contains IB family metal, VIII family base metal, IIB group 4 transition metal, IVB family metal, group vib metal, VIIB family metal, lanthanide series metal.3. the dry sample of the desulfuration adsorbent with nanoscale by 2. obtaining and the dry glue of aluminium oxide binder are mixed, add Aci-Jel solvent extruded moulding, after drying, roasting, obtain with γ-Al
2o
3desulfuration adsorbent for carrier.4. above-mentioned adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization.Before using adsorbent will reaction temperature for the atmosphere that contains hydrogen under 300-450 ° of C in reduction process 4-20 hour.
Wherein said gasoline ultra-deep desulfurization absorbent, is characterized in that described VIII family base metal is the combination by any one and/or they of iron, cobalt, nickel, preferably cobalt, nickel and/or its combination, preferably nickel; Described IB family base metal is the combination by any one and/or they of copper, silver, gold, preferably copper, silver and/or its combination, best copper.Described IIB family metal is zinc.Described IVB family metal is by titanium or zirconium, preferably zirconium.Described group vib metal is chromium, molybdenum, tungsten, preferably molybdenum.Described VIIB family metal is manganese.Described lanthanide series metal is the combination by any one and/or they of lanthanum, cerium, preferably lanthanum.Described precipitating reagent refers to solubility NaOH, potassium hydroxide, oxalic acid, urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, saleratus, sodium carbonate, potash and/or their combination, preferably oxalic acid, urea, ammonium carbonate and/or their combination, preferably oxalic acid or urea.The described solvent that contains proton refers to the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine and/or their combination, the mixed solvent of preferred water and ethanol.Described have nanoscale and refer to and be less than 100nm, is preferably less than 30nm; Described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination, preferably nitric acid; Described IB family base metal shared mass percent in adsorbent is 1-30%; Described VIII family base metal shared mass percent in adsorbent is 1-30%; Described IIB group 4 transition metal shared mass percent in adsorbent is 10-79%; Described IVB family base metal shared mass percent in adsorbent is 1-30%; Described group vib base metal shared mass percent in adsorbent is 1-20%; Described VIIB family base metal shared mass percent in adsorbent is 1-40%; Described lanthanide series metal shared mass percent in adsorbent is 1-40%; The mass percent of described aluminium oxide binder in adsorbent is 5-50%.
The method of above-mentioned absorbent preparation FCC super low-sulfur oil for the present invention, adopts fixed-bed operation, and adsorption operations condition is as follows: adsorption temp 200-400 ℃, and hydrogen partial pressure 0.02-2MPa, hydrogen and gasoline volume ratio are 2000:1-5:1, liquid volume air speed 1-20h
-1.
The present invention's above-mentioned adsorbent used can be regenerated after losing activity after using, and regeneration condition is as follows: regeneration temperature 30-650 ℃, and regenerating system pressure 0.1-1MPa, gas flow rate is 0.2-10Lh
-1, regeneration gas is the mist of air, oxygen and nitrogen, oxygen content 1%-21%, preferably 1.5-15%, preferably 2.5-10%.
Fig. 1 is the transmission electron microscope picture of the desulfuration adsorbent A of nanoscale.The particle size that can see desulfuration adsorbent A is about 8nm.
In order to further illustrate the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Being prepared as follows of desulfuration adsorbent in the present invention:
(1), take 21.20g zinc acetate, 2.60g zirconium nitrate, 3.20g ammonium heptamolybdate, 2.80g manganese acetate and 1.27g lanthanum nitrate and be dissolved in 1000ml distilled water, add at 95 ℃, 30.10g urea and fully stir and within 24 hours, make precipitating reagent complete hydrolysis (pH detection paper is emitted without ammonia), after filtration, deionized water washing, obtain wet cake, drier in 120 ° of C, obtain dry sample, to be dried sample in Muffle furnace in 400 ° of C roastings, obtain adsorbent roasting sample; (2), take 1.85 nickel nitrates and 0.82g copper nitrate is dissolved in 7.5ml deionized water, at 7.22g, by (1), obtained flooding and supporting on desulfuration adsorbent roasting sample, impregnation product is dried, under 300-500 ° of C, calcine; (3) above-mentioned oxide carrier is fully mixed with 2.00g alumina dry glue, adding concentration of nitric acid is 2% the abundant kneading of aqueous solution 5ml, makes body of paste, with banded extruder, be extruded into cloverleaf pattern again, 120 ° of C dried overnight, 450 ° of C roasting 4h, obtain adsorbent A.
Embodiment 2
With embodiment 1, difference from Example 1 is, the amount that just takes nickel nitrate is 1.20 grams, obtains adsorbent B.
Embodiment 3
With embodiment 1, difference from Example 1 is, the amount that just takes nickel nitrate is 2.40 grams, obtains adsorbent C.
Embodiment 4
With embodiment 1, difference from Example 1 is, the amount that just takes nickel nitrate is 3.0 grams, obtains adsorbent D.
Embodiment 5
With embodiment 1, difference from Example 1 is, does not just add nickel nitrate, then the amount that takes cobalt nitrate is 1.860 grams, obtains adsorbent E.
Embodiment 6
With embodiment 1, difference from Example 1 is, does not just add lanthanum nitrate, then the amount that takes cerous nitrate is 1.27 grams, obtains adsorbent F.
Embodiment 7
With embodiment 1, difference from Example 1 is, the amount that just takes lanthanum nitrate is 1.60 grams, obtains adsorbent G.
Embodiment 8
With embodiment 1, difference from Example 1 is, the amount that just takes zinc acetate is 27.20 grams, obtains adsorbent H.
Embodiment 9
With embodiment 1, difference from Example 1 is, the amount that just takes zinc acetate is 15.10 grams, obtains adsorbent I.
Embodiment 10
With embodiment 1, difference from Example 1 is, the amount that just takes zirconium nitrate is 1.30 grams, obtains adsorbent J.
Embodiment 11
With embodiment 1, difference from Example 1 is, the amount that just takes manganese acetate is 1.40 grams, obtains adsorbent K.
Embodiment 12
With embodiment 1, difference from Example 1 is, the amount that just takes manganese acetate is 4.30 grams, obtains adsorbent L.
Embodiment 13
With embodiment 1, difference from Example 1 is, just when extrusion, adding the amount of alumina dry glue is 1.00 grams, obtains adsorbent M.
Embodiment 14
With embodiment 1, difference from Example 1 is, just when extrusion, adding the amount of alumina dry glue is 3.00 grams, obtains adsorbent N.
Embodiment 15
With embodiment 1, difference from Example 1 is, just changes precipitating reagent into the 1000ml aqueous solution containing 32.10 grams, carbonic hydroammonium, obtains adsorbent O.
Embodiment 16
With embodiment 15, be with embodiment 15 differences, just change precipitating reagent into the 1000ml aqueous solution containing 15.10 grams, NaOH, obtain adsorbent P.
Embodiment 17
With embodiment 15, be with embodiment 15 differences, just change precipitating reagent into the 1000ml aqueous solution containing 15.10 grams, sodium carbonate, obtain adsorbent Q.
Embodiment 18
With embodiment 1, difference from Example 1 is, just changes precipitating reagent into oxalic acid 32.10g, obtains adsorbent S.
Embodiment 19
With embodiment 1, difference from Example 1 is, just changes nitric acid peptizing agent into aqueous solution 5ml containing acetic acid 5%, obtains adsorbent R.
Embodiment 20
With embodiment 1, difference from Example 1 is, just changes 1000ml distilled water into ethanol water that 1200ml volume ratio is 1:2, obtains adsorbent T.
Embodiment 21
The gasoline that the sulfur content of take is 150ppmw is investigated the desulfurized effect of adsorbent as raw material, is adsorbed in fixed bed reactors and carries out.Adsorption conditions is: desulfuration adsorbent quality 1.00g, and adsorption temp is 280 ℃, Hydrogen Vapor Pressure 0.1MPa, 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 pressure, hydrogen treat 4 hours.In sample, sulfur content adopts Antek 9000VLLS Sulfur Analysis instrument to measure, and detects and is limited to 0.1ppm(V/V).Gasoline content analysis is carried out being equipped with on the gas chromatograph (Agilent 6890) of capillary column (PONA, 50m * 0.2mm, id * 0.5 μ m) and flame ionic detector (FID).Absorption result is listed in table 2.
Embodiment 22
With embodiment 21, be with embodiment 21 differences, just the volume ratio of hydrogen and gasoline is 90:1, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 23
With embodiment 21, be with embodiment 21 differences, just the volume ratio of hydrogen and gasoline is 300:1, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 24
With embodiment 21, be with embodiment 21 differences, just the volume ratio of hydrogen and gasoline is 600:1, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 25
With embodiment 21, be with embodiment 21 differences, just 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, be with embodiment 21 differences, just 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, be with embodiment 21 differences, just 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, be with embodiment 21 differences, just Hydrogen Vapor Pressure is 0.5MPa, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 29
With embodiment 21, be with embodiment 21 differences, just Hydrogen Vapor Pressure is 1.0MPa, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 30
With embodiment 21, be with embodiment 21 differences, just Hydrogen Vapor Pressure is 1.5MPa, only investigates the absorption property of adsorbent A, absorption result is listed in table 2.
Embodiment 31
With embodiment 21, just only investigate the absorption property of adsorbent A, by adsorption desulfurize time lengthening, until adsorbent A loses activity, by the adsorbent A of inactivation, be placed in tube furnace and regenerate, regeneration condition is as follows: 500 ℃ of regeneration temperatures, and regenerating system pressure normal pressure, gas flow rate is 5Lh
-1, regeneration gas is the gaseous mixture of oxygen and nitrogen, oxygen content 10%, and the recovery time is 120 hours, adsorbent A-1 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent A-1 is active, and the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 32
With embodiment 31, just by adsorption desulfurize time lengthening, until adsorbent A-1 loses activity, to be regenerated in adsorbent A-1 of inactivation, regeneration condition is with embodiment 31, adsorbent A-2 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent A-2 is active, and the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 33
With embodiment 32, just by adsorption desulfurize time lengthening, until adsorbent A-2 lose activity, to be regenerated in adsorbent A-2 of inactivation, regeneration condition is with embodiment 31, adsorbent A-3 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent A-3 is active, and the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 34
With embodiment 33, just by adsorption desulfurize time lengthening, until adsorbent A-3 lose activity, to be regenerated in adsorbent A-3 of inactivation, regeneration condition is with embodiment 31, adsorbent A-4 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent A-4 is active, and the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Embodiment 35
With embodiment 34, just by adsorption desulfurize time lengthening, until adsorbent A-4 lose activity, to be regenerated in adsorbent A-4 of inactivation, regeneration condition is with embodiment 31, adsorbent A-5 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent A-5 is active, and the implementation condition of investigation is with embodiment 21, and absorption result is listed in table 2.
Comparative example 1
Press the method Kaolinite Preparation of Catalyst that Chinese invention patent CN101450302 embodiment 1 is identical, the catalyst making represents with U.Absorption result is listed in table 2.
Comparative example 2
With comparative example 1, just by adsorption desulfurize time lengthening, until adsorbent U loses activity, the adsorbent U of inactivation to be regenerated, regeneration condition is with embodiment 31, the adsorbent U-1 after being regenerated.The gasoline absorbing desulfurization of investigating adsorbent U-1 is active, and the implementation condition of investigation is same
Embodiment 21, and absorption result is listed in table 2.
Table 1, four kinds of adsorbent A, A-1, U and U-1 specific area, pore volume and sulfur capacity contrasts
Table 2, gasoline stocks its alkene and sulfur content after desulfuration adsorbent is processed
As can be seen from the table, adopt the desulfuration adsorbent of patent of the present invention, can effectively remove the sulfide in gasoline, can obtain super-low sulfur (lower than 5ppmw) gasoline stocks, guarantee that olefin(e) centent does not lose simultaneously.With comparative example comparison, under identical adsorption operations condition, the desulfurization depth of adsorbent of the present invention is higher, and sulfur capacity is larger.Secondly, the patent desulfuration adsorbent of the present invention of inactivation, adopts after the renovation process regeneration of patent of the present invention, and desulfurization performance can effectively keep.
Claims (11)
1. a gasoline ultra-deep desulfurization absorbent, adopts following method preparation:
1. IIB group 4 transition metal salt, IVB family slaine, group vib slaine, VIIB family slaine, lanthanide metal salt are mixed in containing the polar solvent of proton with precipitating reagent, in temperature, be to carry out precipitation reaction under room temperature to 150 ° C, precipitated product is filtered, washs, is dried, under 300-500 ° of C, calcine, obtain the dry sample of the desulfuration adsorbent with nanoscale that contains IIB group 4 transition metal oxide, IVB family metal oxide, group vib metal oxide, VIIB family metal oxide, lanthanide metal oxide;
②Jiang IB family slaine, VIII family base metal salt are dissolved in the water, on the dry sample of desulfuration adsorbent, flooding and supporting by 1. obtaining, impregnation product is dried, under 300-500 ° of C, calcine, obtain the dry sample of the oxide desulfuration adsorbent with nanoscale that contains IB family metal, VIII family base metal, IIB group 4 transition metal, IVB family metal, group vib metal, VIIB family metal, lanthanide series metal;
3. will mix by 2. obtaining the dry sample of desulfuration adsorbent and the dry glue of aluminium oxide binder, add Aci-Jel solvent extruded moulding, after drying, roasting, obtain with γ-Al
2o
3desulfuration adsorbent for carrier.
2. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that: described IB family metal is the combination by any one and/or they of copper, silver, gold preferably copper, silver or copper and silver-colored combination, best copper;
Described VIII family base metal is any one and/or the two kinds of above combinations in them by iron, cobalt, nickel, preferably cobalt, nickel or cobalt and nickel combination, best nickel.
3. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that:
Described IIB family metal is zinc;
Described IVB family metal is by titanium or zirconium, preferably zirconium;
Described group vib metal is chromium, molybdenum, tungsten, preferably molybdenum;
Described VIIB family metal is manganese;
Described lanthanide series metal is the combination of two kinds of any one and/or they in lanthanum, cerium, preferably lanthanum.
4. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that:
Described precipitating reagent refers to solubility NaOH, potassium hydroxide, oxalic acid, urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, saleratus, sodium carbonate, potash and/or their combination, preferably oxalic acid, urea, ammonium carbonate and/or their combination, preferably oxalic acid or urea;
The consumption of precipitating reagent is that the pH value of solution is 6-9 after carrying out precipitation reaction.
5. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that: described in contain proton solvent refer to the combination of two kinds of any one and/or they in the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, the mixed solvent of preferred water and ethanol (the volume mixture ratio of water and ethanol is 5:95-95:5).
6. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that: described have nanoscale and refer to and be less than 100nm, is preferably less than 30nm, is preferably less than 20nm.
7. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that described Aci-Jel solvent refers to nitric acid, phosphoric acid, acetic acid and/or their combination, preferably nitric acid;
Will be by extruded moulding again after 2. obtaining the dry sample of desulfuration adsorbent and the dry glue of aluminium oxide binder, Aci-Jel solvent and mixing by weight 65:25:5, at the dry 4-10 hour of 80-120 ° of C, 300-600 ° of C roasting 4-10 hour, obtains with γ-Al
2o
3desulfuration adsorbent for carrier.
8. according to gasoline ultra-deep desulfurization absorbent claimed in claim 1, it is characterized in that:
In oxide,
Described IB family base metal shared mass percent in adsorbent is 1-30%;
Described VIII family base metal shared mass percent in adsorbent is 1-30%;
Described IIB group 4 transition metal shared mass percent in adsorbent is 10-79%;
Described IVB family base metal shared mass percent in adsorbent is 1-30%;
Described group vib base metal shared mass percent in adsorbent is 1-20%;
Described VIIB family base metal shared mass percent in adsorbent is 1-40%;
Described lanthanide series metal shared mass percent in adsorbent is 1-40%;
The mass percent of described aluminium oxide binder in adsorbent is 5-50%.
9. the application of an adsorbent claimed in claim 1, it is characterized in that: among the ultra-deep desulfurization for gasoline, adopt fixed-bed operation, adsorption operations condition is as follows: adsorption temp 200-400 ° C, hydrogen partial pressure 0.02-2MPa, hydrogen and gasoline volume ratio are 2000:1-5:1, liquid volume air speed 1-20h
-1.
10. according to application claimed in claim 9, it is characterized in that: after adsorbent absorption is saturated, can regenerate, adopt in fixed-bed operation or tube furnace and regenerate, regeneration condition is as follows: regeneration temperature 30-650 ℃, regenerating system pressure 0.1-1MPa, gas flow rate is 0.2L-10Lh
-1;
The regeneration gas that uses be air or oxygen and nitrogen mist, oxygen volume content 1%-21% in mist, preferably 1.5-15%, preferably 2.5-10%.
11. according to application claimed in claim 9, it is characterized in that: above-mentioned adsorbent can be used in the middle of FCC gasoline ultra-deep desulfurization; Before using, adsorbent will reduce under for 300-450 ° of C in reaction temperature, and reducing atmosphere is the mist of hydrogen or hydrogen and nitrogen.
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| CN105854896A (en) * | 2016-05-11 | 2016-08-17 | 北京化工大学 | Mn-Fe-Al composite metal oxide and application of Mn-Fe-Al composite metal oxide to catalyzing hydrolysis reaction on celluloses |
| CN108070416A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of liquefied petroleum gas process for adsorption desulfuration |
| CN108295801A (en) * | 2018-01-22 | 2018-07-20 | 燕山大学 | A kind of loading type Pd bimetallic adsorbent of deep desulfuration and preparation method thereof |
| CN109847730A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of regeneration method of desulfuration adsorbent |
| 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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| 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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