CN102407094B - 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-Al2O3to 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 ﹠amp; Veatch Pritchard, the IRVAD of Inc.and Alco Industrial Chemicals (USP5730860) exploitation
TMTechnique has adopted a brand-new desulfurization thought.They will select the concept of absorption to be used for the gasoline ultra-deep desulfurization.Whole operating process does not consume hydrogen, does not have loss of octane number.It can be that catalysis (FCC) gasoline of 1276ppm or coker gasoline desulfurization are 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 the commercial Application of this technology.
The S-Zorb technique of Conoco Phillips oil company exploitation (USP:6531053,6346190,6056871,6184176,6254766 etc.), it can be with sulfur content the FCC gasoline desulfur of 775ppm to 10ppm, and loss of octane number is 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 surpassed 1 unit.
The 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 larger adsorption capacity and adsorptive selectivity to thiophene and benzene under lower pressure.Molecular Orbital Calculation shows, absorption mode is the π complexing, and action intensity is thiophene＞benzene, Cu
+＞Ag
+According to the author, such is applied in the true gasoline desulfur take the adsorbent of π complexing as the basis, shows certain desulfurized effect.Under normal temperature, normal pressure, use Cu
+/ Y is 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.This illustrates that the absorption sulfur capacity of this adsorbent still can not satisfy the requirement of commercial Application; On the other hand, because univalent copper ion is very unstable, disproportionated reaction occuring easily, generate more stable bivalent cupric ion and metallic copper, thereby this has also limited its commercial Application greatly.
In sum, in existing document or patent, also there is the following weak point in the research of absorption ultra-deep desulfurization: 1, adsorbent is lower to adsorptive selectivity and the adsorption capacity of sulfide; 2, in facing H-H reaction absorption, the loss of octane number that alkene and aromatic saturation cause 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 for the gasoline ultra-deep desulfurization and preparation and application.This adsorbent carries out ultra-deep desulfurization to gasoline can guarantee that the octane number loss is less than 1 unit even slightly increase simultaneously.
A kind of adsorbent 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, under being room temperature to 150 ℃, temperature carries out precipitation reaction, to precipitated product filter, wash, dry, roasting, namely obtain containing VIII group 4 transition metal oxide and have nanoscale take zinc oxide for mainly storing up the sulphur component and containing the adsorbent of other binder component; 2., acidic molecular sieve and alumina dry glue are mixed, add Aci-Jel solvent extruded moulding, after drying, the 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, obtain containing the octane value recovering agent of VIB and/or VIII group 4 transition metal oxide after drying, the roasting; Also can with 1., component in 2. is by the use that becomes one of the Combination of Methods such as kneading, dipping, deposition sedimentation, co-precipitation.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 lower reduction 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; Described precipitating reagent refers to 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 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 ethylene glycol; Described have nanoscale and refer to less than 100nm, preferably less than 50nm; Described molecular sieve refers to 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 refers to nitric acid, phosphoric acid, acetic acid and/or their combination, preferred nitric acid; Described group vib metal refers to 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 refers to 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 adopts fixed-bed operation with the method for above-mentioned absorbent preparation super low-sulfur oil, and the adsorption operations condition is as follows: 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 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)
Following production desulfuration adsorbent: 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 described mixture, continue to grind after 30 minutes, be extruded into the bar that diameter is 2mm at banded extruder, after drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of lower roastings 4 hours, makes 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 ℃ lower dry 12 hours, 500 ℃ of lower roastings 4 hours.
Embodiment 1
The preparation of desulfuration adsorbent among the present invention.
As an illustrative examples, be prepared as follows the agent of storage sulphur: 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 90 ℃ in 8.10g urea and fully stir down 24 hours so that the precipitating reagent complete hydrolysis, after filtration, the deionized water washing obtains wet cake, gets green solid through vacuum drying again, in 500 ℃ of lower 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.Be extruded into the bar that diameter is 2mm at banded extruder.After drying under the room temperature, drying is 10 hours under 120 ℃, 500 ℃ of lower roastings 4 hours, makes 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 ℃ lower dry 12 hours, follow in 500 ℃ of lower 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 and 2g H β, the 1g boehmite that obtain among the embodiment 1 are mixed, put into baking oven in 60 ℃ of dry processing 1 hour, add again extruded moulding after 3% the aqueous solution of nitric acid 3ml kneading; In 120 ℃ of oven dry, after 500 ℃ of roastings, obtain the roasting sample behind the airing; Press again the same procedure load molybdenum of embodiment 2 and phosphorus on above-mentioned roasting sample, namely obtain catalyst C.
Embodiment 4
With embodiment 2, the molecular sieve that just uses 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, reaction is carried out in fixed bed reactors.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 instrument, 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).Evaluation results is listed in the table 1.As can be seen from Table 1, although the Comparative Examples adsorbent can cause a large amount of losses of octane number simultaneously at 370 ℃ of lower organic sulfur compounds that can effectively remove in the gasoline stocks.The desulfuration adsorbent of this patent protection can effectively remove the nearly all sulfide in the 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 processed
Embodiment 16
In the situation that the absorption temperature is lower than 300 ℃, the desulfurized effect when investigating independent use desulfuration adsorbent with different FCC gasoline stocks, reaction is carried out in fixed bed reactors.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 instrument, 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).Evaluation results is listed in the table 2.As can be seen from Table 2, the Comparative Examples adsorbent is under 270 ℃, although can keep less its desulphurizing ability loss of octane number loss larger, namely sulfur capacity is low.The desulfuration adsorbent of this patent protection; still have at a lower temperature desulphurizing activated preferably; can effectively remove the nearly all sulfide in the gasoline; can obtain the super low-sulfur oil product; meanwhile; the sulfur capacity of adsorbent is much higher than the Comparative Examples adsorbent, and octane number loses also less.
The situation of change of table 2, different gasoline stocks its octane number and sulfur content after desulfuration adsorbent is processed
Embodiment 17
Investigate the performance of desulfuration adsorbent and octane value recovering catalyst with different FCC gasoline stocks, reaction is carried out in fixed bed reactors.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 instrument, 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).Evaluation results is listed in the table 3.As can be seen from Table 3; gasoline stocks is contacted with octane value recovering catalyst with the desulfuration adsorbent of this patent protection successively; can effectively remove the nearly all sulfide in the gasoline; can obtain the super low-sulfur oil product that sulfur content is lower than 10ppm; can guarantee simultaneously that the octane number loss is less than a unit; 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 processed
Claims (7)
1. the application of a gasoline desulphurization sorbent is characterized in that, is used for the desulfuration adsorbent of gasoline, adopt fixed-bed operation, the adsorption operations condition is as follows: 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 reduced under as 200-550 ° of C in reaction temperature, and during use, storage sulphur agent and octane value recovering agent mix use;
The preparation method of this gasoline desulphurization sorbent is:
(1) zinc salt, VIII family base metal salt, other salt and precipitating reagent are mixed in containing the polar solvent of proton, under being room temperature to 150 ℃, temperature carries out precipitation reaction, to precipitated product filter, wash, dry, roasting, namely obtain containing VIII group 4 transition metal oxide and have nanoscale take zinc oxide as main component and contain the storage sulphur agent of other binder;
Described other salt refers to 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, the 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, obtain containing the octane value recovering agent of VIB and/or VIII group 4 transition metal oxide after drying, the roasting;
(3) component in (1), (2) being combined into one by kneading, dipping, deposition sedimentation, coprecipitation method uses;
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 application of gasoline desulphurization sorbent according to claim 1 is characterized in that: described VIII family base metal is the combination by any one and/or they of iron, cobalt, nickel.
3. the application of gasoline desulphurization sorbent according to claim 1 is characterized in that: described 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 application of gasoline desulphurization sorbent according to claim 1 is characterized in that: the described solvent that contains proton is the aqueous solution, ethanol, methyl alcohol, isopropyl alcohol, ethylene glycol, glycerine and/or their combination.
5. the application of gasoline desulphurization sorbent according to claim 1 is characterized in that: described molecular sieve is ZSM-5, Y, USY, SAPO-11, ZSM-22, β and/or their mixture.
6. the application of gasoline desulphurization sorbent according to claim 1 is characterized in that: described Aci-Jel solvent is nitric acid, phosphoric acid, acetic acid and/or their combination.
7. the application of gasoline desulphurization sorbent according to claim 1 is characterized in that: described VI B group 4 transition metal is chromium, molybdenum, tungsten and/or their combination.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN112619592A (en) * | 2020-12-21 | 2021-04-09 | 上海灿越化工科技有限公司 | Preparation method of hierarchical pore modified adsorbent for deep desulfurization of gasoline |
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