CN102407094A - Gasoline desulfurization adsorbent and preparation and application thereof - Google Patents
Gasoline desulfurization adsorbent and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a gasoline desulfurization adsorbent and preparation and application thereof. A preparation method of the gasoline desulfurization adsorbent comprises the following steps of: mixing a zinc salt, a VIII family non-precious metal salt, other salts and a precipitant in a proton-containing polar solvent, and undergoing a precipitation reaction at the temperature ranging from the room temperature to 15 DEG C to obtain a sulfur storing agent; and soaking a soluble salt containing a VIB and/or VIII family transition metal into a molecular sieve carrier containing gamma-Al2O3 to obtain an octane number restorative, wherein the gasoline desulfurization adsorbent comprises 5-50 percent by mass of molecular sieve, 5-80 percent by mass of zinc oxide, 1-30 percent by mass of VIB and/or VIII family non-precious metal and 5-50 percent of other bonding agents; the sulfur storing agent and the octane number restorative can be combined for using by mixing, soaking, performing deposition sedimentation and co-precipitating, and can be used separately; and the absorbent can be used for adsorbing almost all sulfides in gasoline to obtain ultra-low-sulfur even sulfur-free gasoline while the octane number is kept to be constant or be increased slightly.
Description
Technical field
The present invention relates to a kind of gasoline ultra-deep desulfurization absorbent and preparation and application.
Background technology
Black & Veatch Pritchard, the IRVAD of Inc.and Alco Industrial Chemicals (USP5730860) exploitation
TMTechnology has adopted a brand-new desulfurization thought.They will select the notion of absorption to be used for the gasoline ultra-deep desulfurization.The whole operation process does not consume hydrogen, does not have loss of octane number.It can be that catalysis (FCC) gasoline or the coker gasoline desulfurization of 1276ppm is to 120ppm with sulfur content.But the adsorption capacity of the desulfuration adsorbent that uses in this technical process is lower, thereby regeneration is frequent, has limited this technological commercial Application.
The S-Zorb technology of Conoco Phillips oil company exploitation (USP:6531053,6346190,6056871,6184176,6254766 etc.); It can with sulfur content be the FCC gasoline desulfur of 775ppm to 10ppm, and loss of octane number is a 1-2 unit.But this process operation condition is harsh, and still (370～410 ℃, pressure is 7.1～21.2kg/cm to need with certain hydrogen dividing potential drop at higher temperature
2) under carry out, the absorption sulfur capacity is lower than 0.1g sulphur/g adsorbent, the adsorbent loss is serious, running cost is higher, and when sulphur and olefin(e) centent were high, loss of octane number was above 1 unit.
People such as Yang (Ind.Eng.Chem.Res., 2003,42 (13): 3103.) investigated model thiophene and benzene at Cu
+/ Y and Ag
+Absorption behavior on the/Y adsorbent.Compare Cu with NaY
+/ Y and Ag
+/ Y all has bigger adsorption capacity and adsorptive selectivity to thiophene and benzene under lower pressure.Molecular Orbital Calculation shows that absorption mode is the π complexing, and action intensity is thiophene＞benzene, Cu
+＞Ag
+According to the author, such adsorbent that is the basis with the π complexing is applied in the true gasoline desulfur, shows certain desulfurized effect.Under normal temperature, normal pressure, use Cu
+/ Y is an adsorbent, is that the gasoline of 335ppm carries out desulfurization to sulfur content, and every gram adsorbent can produce the sweet gasoline of 14.7mL; When using active carbon to do overcoat, the producible sweet gasoline of every gram adsorbent is further brought up to 19.6mL.The absorption sulfur capacity of this this adsorbent of explanation still can not satisfy industrial application requirements; On the other hand, because univalent copper ion is very unstable, disproportionated reaction taking place easily, generates more stable bivalent cupric ion and metallic copper, thus this also big limitations its commercial Application.
In sum, in existing literature or patent, also there is the following weak point in the research of absorption ultra-deep desulfurization: 1, adsorbent is lower to the adsorptive selectivity and the adsorption capacity of sulfide; 2, in facing H-H reaction absorption, the saturated loss of octane number that causes of alkene and aromatic hydrocarbons surpasses 1 unit; 3, operating condition is harsh, and the hydrogen consumption is high, and energy consumption is high, and operating cost is high.
Summary of the invention
The object of the present invention is to provide a kind of adsorbent and preparation and application that is used for the gasoline ultra-deep desulfurization.This adsorbent carries out ultra-deep desulfurization to gasoline can guarantee that the octane number loss is less than 1 unit even increase slightly simultaneously.
A kind of adsorbent that is used for the gasoline ultra-deep desulfurization of the present invention; It is characterized in that; Adopt the preparation of following method: 1., zinc salt, VIII family base metal salt and its salt are mixed in containing the polar solvent of proton with precipitating reagent;, temperature carries out precipitation reaction under being room temperature to 150 ℃; To precipitated product filter, wash, dry, roasting, what promptly obtain containing VIII group 4 transition metal oxide be the adsorbent that mainly stores up the sulphur component and contain other binder component with zinc oxide with what have nanoscale; 2., acidic molecular sieve and alumina dry glue are mixed, add Aci-Jel solvent extruded moulding, after drying, roasting, obtain containing γ-Al
2O
3Molecular sieve carrier; To contain the soluble-salt of VIB and/or VIII group 4 transition metal, be impregnated into the above-mentioned γ of containing-Al
2O
3Molecular sieve carrier on, after dry, roasting, obtain containing the octane value recovering agent of VIB and/or VIII group 4 transition metal oxide; Also can with 1., methods such as component in 2. pinches through mixing, dipping, deposition sedimentation, co-precipitation are combined into one and use.3., above-mentioned adsorbent can be used in the middle of the gasoline ultra-deep desulfurization.Before using 1., 2. two kinds of reagent will be 200-550 ℃ of reduction down in reaction temperature all.During use, storage sulfur absorbent and octane value recovering agent can mix use, also can separately use.
Wherein said VIII family base metal is the combination by any one and/or they of iron, cobalt, nickel, preferred cobalt, nickel and/or its combination, preferably nickel; Said precipitating reagent is meant solubility NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, saleratus, sodium carbonate, potash and/or their combination; Preferred urea, ammonium carbonate, sodium carbonate and/or their combination, preferably urea; The said solvent that contains proton is meant the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine and/or their combination, the mixed solvent of preferred water and ethylene glycol; Described have nanoscale and be meant less than 100nm, preferably less than 50nm; Described molecular sieve is meant ZSM-5, Y, USY, SAPO-11, ZSM-22, β and/or their mixture, preferred SAPO-11, ZSM-22, β, preferably β; Described Aci-Jel solvent is meant nitric acid, phosphoric acid, acetate and/or their combination, preferred nitric acid; Described group vib metal is meant chromium, molybdenum, tungsten and/or their combination, preferred molybdenum, tungsten and/or their combination, preferably molybdenum; Described zinc oxide shared mass percent in adsorbent is 5-80%, preferred 10-75%, preferably 20-60%; Described molecular sieve shared mass percent in adsorbent is 5-50%, preferred 10-45%; Described VIII family's base metal shared mass percent in adsorbent is 1-30%, preferred 2.5-20%; Described other salt is meant aluminum nitrate, sodium metasilicate, Boratex, magnesium nitrate; Described other binder is aluminium oxide, silica, boron oxide, magnesia and/or their combination; The mass percent of described other binder in adsorbent is 5-50%.
The present invention prepares the method for super low-sulfur oil with above-mentioned adsorbent, adopts fixed-bed operation, and the adsorption operations condition is following: adsorption temp 250-400 ℃, hydrogen partial pressure 0.02-2MPa, hydrogen to oil volume ratio are 10-1000, volume space velocity 1-20h
-1
Compare with known technology, the present invention has the following advantages:
1, adsorbent is high to the adsorptive selectivity and the adsorption capacity of sulfide;
2, in facing H-H reaction absorption, loss of octane number is less than a unit;
3, catalyst preparation process is simple, and raw material is easy to get, and production cost is low;
4, adopt fixed-bed operation, the adsorbent free of losses, operating cost is low.
The specific embodiment
Comparative Examples (with reference to USP6531053)
The following desulfuration adsorbent of producing: 20.02g diatomite and 25.03g zinc oxide mixture ground 15 minutes in mortar after; The solution that will contain 6.38g aluminium oxide, 22.5g deionized water and 316g glacial acetic acid adds in the said mixture, continues to grind after 30 minutes, on banded extruder, is extruded into the bar that diameter is 2mm; After drying under the room temperature; Drying is 10 hours under 120 ℃, 500 ℃ of following roastings 4 hours, processes adsorbing agent carrier.Then gained adsorbing agent carrier (500g) is flooded with the 673.8g Nickelous nitrate hexahydrate that is dissolved in the 20g deionized water.With above-mentioned dipping be pulled in 120 ℃ dry 12 hours down, 500 ℃ of following roastings 4 hours.
Embodiment 1
The preparation of desulfuration adsorbent among the present invention.
As an illustrative examples, be prepared as follows storage sulphur agent: take by weighing 3.20g six water nickel nitrates, 3.20g six water aluminum nitrates and 7.35g zinc nitrate hexahydrate and be dissolved in 200ml distilled water, add 8.10g urea and fully stir down for 90 ℃ and made the precipitating reagent complete hydrolysis in 24 hours; Through filtering; The deionized water washing obtains wet cake, gets green solid through vacuum drying again; In 500 ℃ of following roastings 4 hours, sample number into spectrum was A.
Embodiment 2
The preparation of octane value recovering agent among the present invention.
As an illustrative examples, be prepared as follows the octane value recovering agent: take by weighing 32.5g H β, the 17.5g boehmite is even with their ground and mixed, add 1mL 63% dense HNO
3With 37mL distilled water, grind to form the suitable muffin body of appropriateness.On banded extruder, be extruded into the bar that diameter is 2mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of following roastings 4 hours, processes catalyst carrier.Take by weighing 0.8227 gram ammonium molybdate adding 4mL distilled water and make it dissolving, the distilled water that 3mL is contained 0.5mL 85% phosphoric acid joins in the above-mentioned ammonium molybdate solution.10 gram catalyst carriers are joined in the middle of the above-mentioned mixed solution, floods after 24 hours, 120 ℃ dry 12 hours down, follow in 500 ℃ of following roastings 4 hours, sample number into spectrum is B.
Embodiment 3
The present invention contains the preparation of the mixed adsorbent of storage sulphur agent and octane value recovering agent.
The wet cake that obtains among the embodiment 1 and 2g H β, 1g boehmite are mixed, put into baking oven, add 3% aqueous solution of nitric acid 3ml again and mix and pinch the back extruded moulding in 60 ℃ of dried 1 hour; In 120 ℃ of oven dry, after 500 ℃ of roastings, obtain the roasting sample behind the airing; Same procedure load molybdenum and the phosphorus of pressing embodiment 2 again promptly obtain catalyst C on above-mentioned roasting sample.
Embodiment 4
With embodiment 2, the molecular sieve that only is to use is the HY molecular sieve, and sample number into spectrum is D.
Embodiment 5
With embodiment 2, the molecular sieve that just uses among the embodiment 5 is the HZSM-5 molecular sieve, and sample number into spectrum is E.
Embodiment 6
With embodiment 2, the molecular sieve that just uses among the embodiment 7 is the SAPO-11 molecular sieve, and sample number into spectrum is F.
Embodiment 7
With embodiment 2, the molecular sieve that just uses among the embodiment 7 is the ZSM-22 molecular sieve, and sample number into spectrum is G.
Embodiment 8
With embodiment 2, the molecular sieve that just uses among the embodiment 8 is the USY molecular sieve, and sample number into spectrum is H.
Embodiment 9
With embodiment 2, just use ammonium metatungstate to replace ammonium molybdate among the embodiment 9, sample number into spectrum is I.
Embodiment 10
With embodiment 3, the molecular sieve that just uses among the embodiment 10 is the HY molecular sieve, and sample number into spectrum is J.
Embodiment 11
With embodiment 3, just the molecular sieve that uses of embodiment 11 is the USY molecular sieve, and sample number into spectrum is K.
Embodiment 12
With embodiment 3, the molecular sieve that uses among the embodiment 12 is the HZSM-5 molecular sieve, and sample number into spectrum is L.
Embodiment 13
With embodiment 3, the molecular sieve that uses among the embodiment 13 is the ZSM-22 molecular sieve, and sample number into spectrum is M.
Embodiment 14
With embodiment 3, the molecular sieve that uses among the embodiment 14 is the SAPO-11 molecular sieve, and sample number into spectrum is N.
Embodiment 15
Desulfurized effect when investigating independent use desulfuration adsorbent with different FCC gasoline stocks is reflected in the fixed bed reactors and carries out.Adsorption conditions is: desulfuration adsorbent quality 1g, reaction temperature is at 370 ℃, Hydrogen Vapor Pressure 1.0Mpa, hydrogen flow rate 30mL/min, volume space velocity 6h
-1What adopt for the test of sulfur content in the sample is RPA-100 type micro-coulometric titration appearance; The octane number of gasoline (RON) analysis is being equipped with capillary column (PONA; 50m * 0.2mm, id * 0.5 μ m) carries out on gas chromatograph (Agilent 6890) and the flame ionic detector (FID).Performance evaluation result lists in the table 1.Can find out from table 1, though the Comparative Examples adsorbent can cause a large amount of losses of octane number simultaneously at 370 ℃ of organic sulfur compounds in down can the effective elimination gasoline stocks.The desulfuration adsorbent of this patent protection, the nearly all sulfide in can effective elimination gasoline, with the Comparative Examples adsorbent relatively, adsorbent A of the present invention is keeping octane number more to have superiority aspect not losing.
The situation of change of table 1, different gasoline stocks its octane number and sulfur content after desulfuration adsorbent is handled
Embodiment 16
Be lower than in absorption temperature under 300 ℃ the situation, the desulfurized effect when investigating independent use desulfuration adsorbent with different FCC gasoline stocks is reflected in the fixed bed reactors and carries out.Reaction condition is: desulfuration adsorbent quality 1g, reaction temperature is at 270 ℃, Hydrogen Vapor Pressure 1.0Mpa, hydrogen flow rate 30mL/min, volume space velocity 6h
-1What adopt for the test of sulfur content in the sample is RPA-100 type micro-coulometric titration appearance; The octane number of gasoline (RON) analysis is being equipped with capillary column (PONA; 50m * 0.2mm, id * 0.5 μ m) carries out on gas chromatograph (Agilent 6890) and the flame ionic detector (FID).Performance evaluation result lists in the table 2.Can find out that from table 2 the Comparative Examples adsorbent is under 270 ℃, though can keep less its desulphurizing ability loss of octane number loss bigger, promptly sulfur capacity is low.The desulfuration adsorbent of this patent protection; Still have desulphurizing activated preferably at a lower temperature; Nearly all sulfide in can effective elimination gasoline can obtain the super low-sulfur oil product, meanwhile; The sulfur capacity of adsorbent is much higher than the Comparative Examples adsorbent, and the octane number loss is also less relatively.
The situation of change of table 2, different gasoline stocks its octane number and sulfur content after desulfuration adsorbent is handled
Embodiment 17
Investigate the performance of desulfuration adsorbent and octane value recovering catalyst with different FCC gasoline stocks, be reflected in the fixed bed reactors and carry out.Reaction condition is: desulfuration adsorbent quality 1g, and octane value recovering catalyst quality 1g, reaction temperature is at 270 ℃, Hydrogen Vapor Pressure 1.0Mpa, hydrogen flow rate 30mL/min, volume space velocity 6h
-1What adopt for the test of sulfur content in the sample is RPA-100 type micro-coulometric titration appearance; The octane number of gasoline (RON) analysis is being equipped with capillary column (PONA; 50m * 0.2mm, id * 0.5 μ m) carries out on gas chromatograph (Agilent 6890) and the flame ionic detector (FID).Performance evaluation result lists in the table 3.Can find out from table 3; Gasoline stocks is contacted with octane value recovering catalyst with the desulfuration adsorbent of this patent protection successively; Nearly all sulfide in can effective elimination gasoline can obtain the super low-sulfur oil product that sulfur content is lower than 10ppm, can guarantee that the octane number loss is less than a unit simultaneously; And sulfur capacity can reach near 0.3g sulphur/g adsorbent, demonstrates huge industrial application value.
The situation of change of table 3, different gasoline stocks its octane number and sulfur content after desulfuration adsorbent and octane value recovering catalyst are handled
Claims (10)
1. the preparation method of a gasoline desulphurization sorbent is characterized in that:
(1) zinc salt, VIII family base metal salt, other salt and precipitating reagent are mixed in containing the polar solvent of proton;, temperature carries out precipitation reaction under being room temperature to 150 ℃; To precipitated product filter, wash, dry, roasting, what promptly obtain containing VIII group 4 transition metal oxide is main component and the storage sulphur agent that contains other binder with zinc oxide with what have nanoscale;
Said other salt is meant aluminum nitrate, sodium metasilicate, Boratex or magnesium nitrate;
Other binder is aluminium oxide, silica, boron oxide, magnesia and/or their combination;
(2) acidic molecular sieve and alumina dry glue are mixed, add Aci-Jel solvent extruded moulding, after drying, roasting, obtain containing γ-Al
2O
3Molecular sieve carrier; To contain the soluble-salt of VIB and/or VIII group 4 transition metal, be impregnated into the above-mentioned γ of containing-Al
2O
3Molecular sieve carrier on, after dry, roasting, obtain containing the octane value recovering agent of VIB and/or VIII group 4 transition metal oxide;
(3) or with the component in (1), (2) pinch through mixing, dipping, deposition sedimentation, coprecipitation method be combined into one and use;
Described molecular sieve shared mass percent in adsorbent is 5-50%;
Described zinc oxide shared mass percent in adsorbent is 5-80%;
Described VIB and/or VIII family base metal shared mass percent in adsorbent is 1-30%;
The mass percent of described other binder in adsorbent is 5-50%.
2. the preparation method of gasoline desulphurization sorbent according to claim 1 is characterized in that: said VIII family base metal is the combination by any one and/or they of iron, cobalt, nickel.
3. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: said precipitating reagent is solubility NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, urea, ammoniacal liquor, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, saleratus, sodium carbonate, potash and/or their combination.
4. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: the said solvent that contains proton is the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine and/or their combination.
5. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: described molecular sieve is ZSM-5, Y, USY, SAPO-11, ZSM-22, β and/or their mixture.
6. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: described Aci-Jel solvent is nitric acid, phosphoric acid, acetate and/or their combination.
7. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: described group vib metal is chromium, molybdenum, tungsten and/or their combination.
8. the preparation method of gasoline desulphurization sorbent according to claim 1, it is characterized in that: described group vib metal is meant chromium, molybdenum, tungsten and/or their combination.
9. a gasoline desulphurization sorbent is characterized in that: the gasoline desulphurization sorbent of preparation method's preparation of gasoline desulphurization sorbent according to claim 1.
10. the application of a gasoline desulphurization sorbent according to claim 9; It is characterized in that: the desulfuration adsorbent that is used for gasoline; Adopt fixed-bed operation, the adsorption operations condition is following: adsorption temp 250-400 ℃, and hydrogen partial pressure 0.02-2MPa; Hydrogen to oil volume ratio is 10-1000, volume space velocity 1-20h
-1
Storage sulphur agent before using, restorative are 200-550 ℃ of reduction down in reaction temperature, and during use, storage sulphur agent and octane value recovering agent can mix use, also can separately use.
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Cited By (10)
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|---|---|---|---|---|
| CN102899083A (en) * | 2012-09-14 | 2013-01-30 | 陕西延长石油（集团）有限责任公司炼化公司 | Ultra-deep combined desulphurization method for full-fraction FCC gasoline |
| CN103623773A (en) * | 2013-12-03 | 2014-03-12 | 中国石油大学(华东) | Preparation and application method for catalyst for gasoline fine desulphurization |
| CN103666559A (en) * | 2012-09-05 | 2014-03-26 | 中国科学院大连化学物理研究所 | Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline |
| CN103721668A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulfurization adsorbent and application thereof |
| CN104549131A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Adsorption desulfurization additive, as well as preparation method and desulfurization system thereof |
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| CN105665031A (en) * | 2016-03-24 | 2016-06-15 | 山东成泰化工有限公司 | Preparation method of novel desulfurization catalyst |
| CN105944552A (en) * | 2016-05-12 | 2016-09-21 | 西安热工研究院有限公司 | Preparation method of barium ion doped calcium-based desulfurizer |
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| CN103666559B (en) * | 2012-09-05 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of FCC gasoline ultra-deep desulfurization combined method |
| CN103666559A (en) * | 2012-09-05 | 2014-03-26 | 中国科学院大连化学物理研究所 | Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline |
| CN102899083B (en) * | 2012-09-14 | 2015-06-17 | 陕西延长石油（集团）有限责任公司炼化公司 | Ultra-deep combined desulphurization method for full-fraction FCC gasoline |
| CN102899083A (en) * | 2012-09-14 | 2013-01-30 | 陕西延长石油（集团）有限责任公司炼化公司 | Ultra-deep combined desulphurization method for full-fraction FCC gasoline |
| CN103721668B (en) * | 2012-10-10 | 2016-07-13 | 中国科学院大连化学物理研究所 | A kind of Gasoline ultra-deep desulfurization adsorbent and application thereof |
| CN103721668A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulfurization adsorbent and application thereof |
| CN104549131A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Adsorption desulfurization additive, as well as preparation method and desulfurization system thereof |
| CN103623773B (en) * | 2013-12-03 | 2016-05-25 | 中国石油大学(华东) | A kind of preparation and application method for gasahol desulphurization catalyst |
| CN103623773A (en) * | 2013-12-03 | 2014-03-12 | 中国石油大学(华东) | Preparation and application method for catalyst for gasoline fine desulphurization |
| CN104707565A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulphurization and olefin reduction adsorbent, and preparation method and application thereof |
| CN106925337A (en) * | 2015-12-29 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of hydrodesulfurizationmodification modification catalyst and preparation method |
| CN106925337B (en) * | 2015-12-29 | 2019-12-10 | 中国石油天然气股份有限公司 | Hydrodesulfurization modification catalyst and preparation method thereof |
| CN105665031A (en) * | 2016-03-24 | 2016-06-15 | 山东成泰化工有限公司 | Preparation method of novel desulfurization catalyst |
| CN105944552A (en) * | 2016-05-12 | 2016-09-21 | 西安热工研究院有限公司 | Preparation method of barium ion doped calcium-based desulfurizer |
| CN105944552B (en) * | 2016-05-12 | 2018-06-19 | 西安热工研究院有限公司 | A kind of preparation method of barium ions doping calcium-based desulfurizing agent |
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