CN101434863B - Oxidative desulfurization method for sulfur-containing diesel - Google Patents
Oxidative desulfurization method for sulfur-containing diesel Download PDFInfo
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- CN101434863B CN101434863B CN2007101583587A CN200710158358A CN101434863B CN 101434863 B CN101434863 B CN 101434863B CN 2007101583587 A CN2007101583587 A CN 2007101583587A CN 200710158358 A CN200710158358 A CN 200710158358A CN 101434863 B CN101434863 B CN 101434863B
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- 238000000034 method Methods 0.000 title claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 40
- 229910052717 sulfur Inorganic materials 0.000 title claims description 21
- 239000011593 sulfur Substances 0.000 title claims description 21
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 21
- 230000023556 desulfurization Effects 0.000 title abstract description 21
- 230000001590 oxidative effect Effects 0.000 title abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002594 sorbent Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000002283 diesel fuel Substances 0.000 claims description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 238000001935 peptisation Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- -1 alkyl sulpholanes Chemical class 0.000 abstract description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000008187 granular material Substances 0.000 description 13
- 150000003462 sulfoxides Chemical class 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 150000003457 sulfones Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- 101100456282 Caenorhabditis elegans mcm-4 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an oxidation desulfurization method of diesel. The method adopts an adsorption method to remove polar sulfur compounds in the diesel after oxidation disposal; wherein, the used sorbent contains mesoporous molecular sieve grains which have the following properties: the specific area is 650-1000m<2>/g, the most probable pore size is 2.3-4.2nm, the acid content of NH3-TPD is 0.3-0.6mmol/g and the granularity is 2mm-3mm. The method selects the mesoporous molecular sieve grains which have rich specific surface, relatively suitable aperture distribution and suitable acidity and have excellent selective adsorption performance on the sulfur compounds in the oxidative diesel such as sulpholanes or sulphoxides, alkyl sulpholanes or sulphoxides, benzo sulfolane or sulphoxides, and the like, and therefore improves the adsorption efficiency of the adsorption device on the one hand and leads the oxidated diesel to have high desulfurization rate on the other hand.
Description
Technical field
The present invention relates to a kind of oxidation desulfurizing method of sulfur-containing diesel, particularly remove the method for sulfocompound in the diesel oil after the oxide treatment with absorption method.
Background technology
Organic sulfide in the fuel oil is a kind of generally acknowledged objectionable impurities, and to influences such as environment, motor car engine life-spans greatly, for example the oxysulfide of its burning back generation is prone to form acid rain; Corrosion mover, the life-span of reducing mover; Strengthen the quantity discharged of obnoxious flavour and PM for particulate matter in the vehicle exhaust etc.In view of above harm, strict more sulfur content in oil products standard has been issued in each major country of the world, area in succession, with the sulfur content in the strictness control fuel oil.
Diesel oil is as a kind of of paramount importance fuel oil, and annual consumption is huge.Simultaneously relative gasoline, the content of sulphur is higher in the diesel oil, and kind is more complicated, and is more difficult when removing.In order to remove the organic sulfide in the diesel oil to greatest extent, reduce sulphur content in the diesel oil, various diesel fuel desulfurization technological development are carried out in high gear.
The diesel fuel desulfurization technology is divided into hydrogenating desulfurization and non-hydrogenating desulfurization two big classes.Traditional hydrogenation technique can satisfy the low-sulfur requirement of diesel oil, also is present most important sulfur method.But the hydrogenation method severe reaction conditions needs HTHP, and facility investment is big, and process cost is high, causes the diesel oil cost significantly to rise.In addition; Sulphur in the diesel oil mainly exists with the form of thiophenes; Account for more than 85% of diesel oil total sulfur greatly, wherein benzo class and dibenzo class thiophene account for more than 70% of thiophene-based again, and benzo class and dibenzo class thiophene sulfide exist owing to steric effect in hydrogenation process; Be not easy fully to contact, thereby be difficult to by hydrogenation and removing with the catalyst desulfurizing active site.
The diesel oil non-hydrogenation sulfur method mainly comprises adsorption desulfurize, abstraction desulfurization, oxidation sweetening etc.Adsorption desulfurize mainly is to utilize the polarity of sulphur in the oil product to separate with abstraction desulfurization.The polarity of thiophene-type sulfide is not strong, and adsorption desulfurize and abstraction desulfurization can only partly remove this type sulfide, thereby these two kinds of sulfur methods exist certain limitation.
Oxidative desulfurization techniques is with oxygenant thiophene-type sulfide to be oxidized to sulfone and the stronger sulfur compound of sulfoxide isopolarity earlier, and then from diesel oil, removes the stronger sulfur compound of these polarity, generally is to adopt methods such as solvent extraction or fractionation by adsorption.Oxidation sweetening has benzo class and dibenzo class thiophene (or the substituted benzo class of alkyl and dibenzo class thiophene) to be selected to remove effect preferably, can be used for diesel deep desulfurization.
In the oxidation desulfurizing method of diesel oil, the used sorbent material of the common fractionation by adsorption that adopts is gac, silica gel or aluminium glue, and such as the sorbent material that CN 1504543A mentions, these sorbent materials can not taken into account aspect loading capacity and the adsorption selectivity.And; Generally be to adopt the sorbent material of single granularity and single kind to adsorb; The problem that can exist the sorbent material in the whole adsorption unit not make full use of like this, reason is following: (1) because the loading capacity of sorbent material is identical with adsorption selectivity, so the sorbent material at the upper reaches reaches capacity earlier than the sorbent material in downstream; (2) if adopt the poor ignition quality fuel raw material; Can contain impurity such as colloid in the diesel oil after oxide treatment, can cause the sorbent material of ingress blocked very soon, and the sorbent material in downstream also not given full play to adsorption.Because the downstream sorbent material can not be fully used, so just reduced the appearance sulfur content of whole adsorption unit, shortened the running period of device, increased replacing and regenerated frequency, influence diesel yield, improve running cost.
Summary of the invention
In order to overcome above-mentioned technical problem, the invention provides a kind of oxidation desulfurizing method of sulfur-containing diesel.The inventive method can increase the adsorption selectivity of whole adsorption unit, improves the desulfurization degree of diesel oil, and has bigger loading capacity, the running period of extension fixture.
Diesel oxidation desulfurizing method of the present invention comprises the steps: sulfur-containing diesel after oxide treatment, removes the polarity sulfur compound in the diesel oil with absorption method, contains the mesoporous molecular sieve particle in the adsorption unit that wherein absorption method adopted.
Described mesoporous molecular sieve particulate is formed as follows: the content of mesoporous molecular sieve accounts for 65-80wt%, and surplus is a tackiness agent.Described mesoporous molecular sieve is one or more among MCM-41, MCM-48 and the SBA-15, is preferably the MCM-41 molecular sieve.Described mesoporous molecular sieve particulate character is following: specific surface is 650～1000m
2/ g, the most probable aperture is 2.3～4.2nm, NH
3-TPD acid amount is 0.3～0.6mmol/g, granularity 2～3mm, and its shape can be sphere.
Described mesoporous molecular sieve particle can be prepared by following method: select the suitable former powder of mesoporous molecular sieve, its character is following: specific surface is 800～1200m
2/ g, the most probable aperture is 2.5～4.5nm, SiO
2/ Al
2O
3Weight ratio is 15～100, preferred 30～80; The former powder of mesoporous molecular sieve is carried out ammonium exchange, roasting earlier, obtains the Hydrogen mesoporous molecular sieve, again the Hydrogen mesoporous molecular sieve with gained mixes with tackiness agent, after the moulding, warp drying and roasting and must the mesoporous molecular sieve particle.Wherein said ammonium give-and-take conditions are: the former powder of sodium type mesoporous molecular sieve is used NH under 70～90 ℃
4 +Concentration is 0.1～0.2mol/mol ammonium salt solution (being preferably an ammonium nitrate and/or ammonium chloride) exchange 2～4 times, behind 100～120 ℃ of down dry 2～4h, at 550～650 ℃ of roasting 2～6h, processes the Hydrogen mesoporous molecular sieve.Above-mentioned tackiness agent is that (pore volume is that 0.3～0.5m/gBET specific surface area is 150～300m by little porous aluminum oxide
2/ g) through with processing behind mineral acid and/or the organic acid peptization; Wherein used mineral acid is one or more in hydrochloric acid, nitric acid, phosphoric acid and the sulfuric acid; Be preferably nitric acid and/or phosphoric acid; Used organic acid is one or more in acetate, oxalic acid, propionic acid and the Hydrocerol A, is preferably acetate and/or Hydrocerol A.In the preparation process, peptization acid is 0.10～0.55 with the mol ratio of little porous aluminum oxide, is preferably 0.20～0.40.Described mesoporous molecular sieve is with after tackiness agent mixes, and 100～120 ℃ of dry 2-4h down are at 550～550 ℃ of roasting 3～5h.
In the adsorption unit that is adopted, preferred filling scheme is following: the filling mesoporous molecular sieve particle in downstream, one or more in upper reaches filling gac, aluminium glue, silica gel and the amorphous aluminum silicide, preferred gac.
In the inventive method, best filling scheme is following: the sorbent material that the upstream sorbent layer adopts is a gac, accounts for 30～50% of sorbent material TV; The sorbent material that the downstream adsorbent layer adopts is the mesoporous molecular sieve particle, accounts for 50～70% of sorbent material TV.So not only can increase the total volume of sorbent material, and can also reduce investment.
The character of described activated carbon granule is following: specific surface is 800～1000m
2/ g, pore volume are 0.5～0.7ml/g, and granularity is 2mm～4mm, and it is shaped as sphere.Preferably adopt sour modified activated carbon, formic acid and/or acetic acid are generally adopted in described acid, and detailed process is following: with activated carbon granule absorption formic acid and/or acetic acid steam, it is reached capacity, general adsorption time is 8～36h, preferred 15～30h.The present invention preferably adopts the granularity of gac more than or equal to mesoporous molecular sieve particulate granularity; Can not make adhesive and heavy substance only concentrate on the top of adsorption column like this; Can increase the loading capacity of whole adsorption unit, the running period of extension fixture, more help improving the desulfurization degree of diesel oil.
The adsorption conditions of this adsorption unit is following: 20 ℃～40 ℃ of adsorption temps, and pressure is 0.1～0.2MPa, volume space velocity is 0.1～0.5h during diesel feed liquid
-1, be preferably 0.2～0.4h
-1
, before removing the polarity sulfur compound, can select earlier to remove after the segment polarity sulfur compound through the diesel oil after the oxide treatment, remove the polarity sulfur compound of remainder again with absorption method with method of extraction with absorption method.Diesel oil extracted the method for removing sulfone and sulfoxide after described extraction can be adopted conventional oxide treatment; Extraction agent can be selected methyl alcohol, tetramethylene sulfone, furfural, glycol, N-Methyl pyrrolidone, N for use; In the N-N,N-DIMETHYLACETAMIDE one or more; When wherein the polarity of extraction agent is strong,, can directly extract with solvent like methyl alcohol, tetramethylene sulfone, furfural, glycol etc.; When if the polarity of extraction agent is more weak, like N-Methyl pyrrolidone, DMAC N,N etc., then, extract again earlier with behind extraction agent and an amount of water thorough mixing, do like this and can effectively avoid the too much diesel oil of SX.Described extraction is selected 1～3 time, generally extracts 1 time.Described extraction can be carried out under normal condition, is generally at 20 ℃～40 ℃, and pressure is to carry out under 0.1～0.2MPa, and agent oil volume ratio is 0.5: 1～4: 1.
The present invention selects to have abundant specific surface, the pore size distribution that suits and the mesoporous molecular sieve particle of appropriate acid; To the sulfocompound in the oxidated diesel oil; Has good selection absorption property like tetramethylene sulfone (sulfoxide), alkyl tetramethylene sulfone (sulfoxide), benzocyclobutane sulfone (sulfoxide) etc.; Improve on the one hand the adsorption efficiency of adsorption unit, make the diesel oil after the oxide treatment have higher desulfurization degree on the other hand.
The inventive method; In conjunction with the character of the composition and the polarity sulfocompound of diesel oil after oxide treatment, and take all factors into consideration the cost of sorbent material, preferably with activated carbon granule and mesoporous molecular sieve particle layering filling; Can increase the appearance sulfur content of adsorption unit like this, simultaneously the running period of extension fixture.Especially select the gac and the mesoporous molecular sieve particle of appropriate acid to be used, not only can increase the adsorption rate of sorbent material, improve the efficient of whole adsorption unit; Also help the sorbent material that makes full use of in the whole adsorption unit; Increase and hold sulfur content, prolonged the running period of device simultaneously, reduced the replacing and the regeneration frequency of sorbent material; Improve diesel yield, reduce cost.
The inventive method preferably with the diesel oil after the oxide treatment through after extracting most sulfone and sulfoxide, utilize absorption method to remove remaining sulfone and sulfoxide again, with the sulphur in the deep removal diesel oil.Compare with independent employing absorption method, this method can improve the desulfurization degree of diesel oil, reduces the loss of diesel oil.
Embodiment
In the inventive method, the method for oxide treatment diesel oil can adopt disclosed any method for oxidation in the prior art.Such as: used oxygenant is a ydrogen peroxide 50, with formic acid or TS-1 sieve peg-raking catalyst.Generally speaking, the mole number of used ydrogen peroxide 50 is 5～10 times of mole number of sulphur in the diesel oil, preferred 6～8 times.During with formic acid catalysis, formic acid accounts for 80～95w% of ydrogen peroxide 50 and formic acid mixing solutions; During with TS-1 catalysis, the weight ratio of ydrogen peroxide 50 and TS-1 is 8～15, preferred 9～11.After diesel oil was heated to 80～100 ℃ of assigned temperatures, (stir speed (S.S.) was 400～500r/min) to high degree of agitation, slowly adds oxygenant and catalyzer then and carries out oxidizing reaction, and the reaction times is about 5～30min.If have contamination precipitation to exist in the oil phase of reaction back, need remove by filter.
The processing of embodiment 1 gac
(Shanghai Compressor Factory No.2 produces, and its specific surface is 930m with exsiccant 200g activated carbon granule C0
2/ g, pore volume are 0.6ml/g, and particle is the sphere of 2～4mm) be placed on the top of moisture eliminator, the bottom of moisture eliminator is poured acetate (concentration is greater than 99wt%) in advance into, airtight after, the saturated therein absorption of gac 24h obtains acid activated carbon granule C1.
Change the acetate among the acid activated carbon granule C1 of preparation into formic acid, obtain activated carbon granule C2.
The preparation of embodiment 2 MCM-41 sieve particles
Prepare the MCM-41 molecular screen primary powder like the disclosed method of patent CN01125680.X, the following specific surface of character is 960m
2/ g, the most probable aperture is 3.0nm, SiO
2/ Al
2O
3Weight ratio is 40.Under 70 ℃ of situation, 0.1mol/mol aqueous ammonium nitrate solution exchange 2 times, behind 100 ℃ of dry 3h, 550 ℃ of roasting 4h process the HMCM-41 molecular sieve.Then (pore volume is 0.35ml/g, and the BET specific surface area is 175m with little porous aluminum oxide
2/ g) through with processing tackiness agent behind nitric acid (mol ratio of nitric acid and little porous aluminum oxide the is 0.25) peptization; Mix with HMCM-41 then; Moulding, dry 2h under 110 ℃ is in 500 ℃ of following roasting 3h; Processing diameter is the spherical MCM-41 sieve particle M1 of 2-3mm, and wherein the MCM-41 molecular sieve content is 67wt%.Resulting its specific surface of MCM-41 sieve particle is 820m
2/ g, the most probable aperture is 2.8nm, NH
3-TPD acid amount is 0.35mmol/g.
Under 90 ℃ of situation, 0.2mol/mol ammonium chloride solution exchange 4 times is washed with distilled water to no cl ions existence in the washings with above-mentioned MCM-41 molecular screen primary powder, 100 ℃ of dryings 4 hours, and the HMCM-41 molecular sieve is processed in 650 ℃ of roastings 3 hours.Then (pore volume is 0.45ml/g, and the BET specific surface area is 291m with little porous aluminum oxide
2) through with processing tackiness agent behind nitric acid (nitric acid and aperture alumina molar ratio the are 0.40) peptization; Then to mix with the proportioning of HMCM-41; Moulding, dry 2h under 110 ℃ is in 500 ℃ of following roasting 5h; Processing diameter is the spheric MCM-41 sieve particle M2 of 2-3mm, and wherein MCM-41 content is 78wt%.Resulting its specific surface of MCM-41 sieve particle is 875m
2/ g, the most probable aperture is 2.9nm, NH
3-TPD acid amount is 0.54mmol/g.
The preparation of embodiment 3 SBA-15 sieve particles
Prepare the SBA-15 molecular screen primary powder like the disclosed method of patent CN200510050090.6, character is following: specific surface is 885m
2/ g, the most probable aperture is 3.9nm, SiO
2/ Al
2O
3Weight ratio is 62.Under 85 ℃ of situation, 0.15mol/mol aqueous ammonium nitrate solution exchange 2 times, 100 ℃ of dryings are after 3 hours, and the HSBA-15 molecular sieve is processed in 600 ℃ of roastings 4 hours.Then (pore volume is 0.42ml/g, and the BET specific surface area is 235m with little porous aluminum oxide
2/ g) through with processing tackiness agent behind nitric acid (mol ratio of nitric acid and little porous aluminum oxide the is 0.30) peptization; Then to mix with HSBA-15; Moulding, dry 2h under 110 ℃ is in 500 ℃ of following roasting 4.5h; Processing diameter is the spherical SBA-15 sieve particle S1 of 2～3mm, and wherein the SBA-15 molecular sieve content is 70wt%.Resulting its specific surface of SBA-15 sieve particle is 720m
2/ g, the most probable aperture is 2.8nm, NH
3-TPD acid amount is 0.45mmol/g.
The oxidation of embodiment 4 sulfur-containing diesels
(Yangzhou Petrochemical Plant provides with 200g straight-run diesel oil; Sulphur content is 422 μ g/g) add reactor drum, be heated to 90 ℃, under agitation condition, add 2.5g ydrogen peroxide 50 (purity is 34wt%), 26.5g formic acid (purity is 99wt%) and 2.9g water then; Reaction 8min obtains the diesel oil A after the oxidation.
The desulfurization of diesel oil is handled after embodiment 5 oxide treatment
Add 250ml extraction agent methyl alcohol among the diesel oil A after oxidation, with the diesel oil thorough mixing, sulfone under the normal temperature and pressure in the extraction oil and sulfoxide.The extraction back diesel oil recovery is seen table 2.
Then with adsorption column up and down volume ratio be 3: 7 ratio, the MCM-41 sieve particle M1 that the embodiment 2 of packing into earlier in the adsorption unit bottom is prepared, again with the activated carbon granule C1 of adsorber acid among the embodiment 1 be placed on MCM-4 1 sieve particle M1 above.200ml diesel oil after the extraction is volume space velocity 0.25h during with liquid
-1Get into adsorption unit, normal temperature absorption.The sulphur content determination result sees table 1 in the diesel oil of absorption back.
The oxidation of embodiment 6 sulfur-containing diesels
Employing has the shock flow type reactor for treatment sulfur-containing diesel of two stirring rakes; Used sulfur-containing diesel is straight-run diesel oil and the catalytic cracking diesel oil mixing oil of being produced by Yangzhou Petrochemical Plant (catalytic diesel oil accounts for 40wt%); Sulphur content wherein is 1480.6 μ g/g, and the diesel oil add-on is 1205g.After slowly stirring under the normal pressure and being warming up to 90 ℃, the stirring rake revolution is decided to be 500r/min, load weighted 3gTS-1 sieve catalyst (Chengdu organic chemistry ltd system) is added in the diesel oil.Then 36.0g ydrogen peroxide 50 and 3.2g water droplet are added to and react 25min in the diesel oil, obtain the diesel oil B after the oxidation.
The desulfurization of diesel oil is handled after embodiment 7 oxide treatment
Add 250ml extraction agent methyl alcohol among the diesel oil B after oxidation, with the diesel oil thorough mixing, sulfone under the normal temperature and pressure in the extraction oil and sulfoxide.
Then with adsorption column up and down volume ratio be 5: 5 ratio, the MCM-41 sieve particle M1 that the embodiment 2 of in adsorption unit, packing into earlier is prepared, again with the activated carbon granule C1 of adsorber acid among the embodiment 1 be placed on MCM-41 sieve particle M1 above.200ml diesel oil after the extraction is volume space velocity 0.25h during with liquid
-1Get into adsorption unit, normal temperature absorption.The sulphur content determination result sees table 1 in the diesel oil of absorption back.
The desulfurization of the diesel oil after embodiment 8 oxide treatment is handled
Add 250ml methyl alcohol among the diesel oil A after the 250ml oxidation, with the diesel oil thorough mixing, sulfone under the normal temperature and pressure in the extraction oil and sulfoxide.
Then with adsorption column up and down volume ratio be 7: 3 ratio, the MCM-41 sieve particle M2 that the embodiment 2 of in adsorption unit, packing into earlier is prepared, again with activated carbon granule C2 be placed on MCM-41 sieve particle M2 above.200ml diesel oil after the extraction is volume space velocity 025h during with liquid
-1Getting into adsorption unit adsorbs at normal temperatures and pressures.The sulphur content determination result sees table 1 in the diesel oil of absorption back.
Embodiment 9 is without directly absorption of extraction
Compare with embodiment 5, do not extract, directly get into adsorption column absorption.The sulphur content determination result sees table 1 in the diesel oil of absorption back.The adsorption efficiency of sorbent material descended 90% o'clock, and the adsorbed diesel oil and the volume ratio of sorbent material are seen table 3.
Embodiment 10
Like embodiment 8 steps diesel oil is carried out oxidation and absorption.Just the MCM-41 sieve particle M2 in the instance 8 is changed to the SBA-15 sieve particle S1 of preparation in the instance 3.The sulphur content determination result sees table 1 in the diesel oil of absorption back.
Embodiment 11
Compare with embodiment 5, with the activated carbon granule C1 of adsorber acid all be changed among the embodiment 1 without acid-treated activated carbon granule C0, the sulphur content determination result sees table 1 in the diesel oil of absorption back.
Embodiment 12
Compare with embodiment 5, the C1 sorbent material all is changed to molecular sieve M1 among the embodiment 2, the sulphur content determination result sees table 1 in the diesel oil of absorption back.The adsorption efficiency of sorbent material descended 90% o'clock, and the adsorbed diesel oil and the volume ratio of sorbent material are seen table 3.
Embodiment 13
Compare with embodiment 7, the activated carbon granule C1 of adsorber acid all is changed to molecular sieve M1 among the embodiment 2, the sulphur content determination result sees table 1 in the diesel oil of absorption back.
Comparative example 1
Compare with embodiment 5, carry out three extractions, diesel oil does not adsorb afterwards.The sulphur content determination result sees table 1 in the diesel oil of extraction back.The extraction back diesel oil recovery is seen table 2
The desulfurization result of diesel oil (data unit is μ g/g in the table) after the oxidation among table 1 embodiment
| The raw oil sulphur content | Extraction back diesel oil sulphur content | Diesel oil absorption back sulphur content | |
| Embodiment 5 | 422 | 270 | 19.3 |
| Embodiment 7 | 1480 | 927 | 66.3 |
| Embodiment 8 | 422 | 270 | 38.6 |
| Embodiment 9 | 422 | - | 56.1 |
| Embodiment 10 | 422 | 270 | 42.5 |
| Embodiment 11 | 422 | 270 | 35.9 |
| Embodiment 12 | 422 | 270 | 14.1 |
| Embodiment 13 | 1480 | 927 | 47.8 |
| Comparative example 1 | 422 | 270 | 133.0 |
The table 2 diesel oil recovery
| The extraction back diesel oil recovery | |
| Embodiment 5 | 90％ |
| Comparative example 1 | 73％ |
The volume ratio of table 3 diesel oil and sorbent material
| The descend volume ratio of 90% used diesel oil and sorbent material of desulfurization degree | |
| Embodiment 9 | 49 |
| Embodiment 12 | 93 |
Claims (9)
1. the oxidation desulfurizing method of a sulfur-containing diesel comprises the steps: sulfur-containing diesel after oxide treatment, removes the polarity sulfur compound in the diesel oil with absorption method; In the adsorption unit that wherein absorption method adopted; Adopt two adsorbent layers, wherein the sorbent material of upstream sorbent layer employing is a gac, accounts for 30～50% of sorbent material TV; The sorbent material that the downstream adsorbent layer adopts is the mesoporous molecular sieve particle, accounts for 50～70% of sorbent material TV; Said mesoporous molecular sieve particulate is formed as follows: the content of mesoporous molecular sieve accounts for 65～80wt%, and surplus is a tackiness agent; Described mesoporous molecular sieve particulate character is following: specific surface area is 650～1000m
2/ g, the most probable aperture is 2.3～4.2nm, NH
3-TPD acid amount is 0.3～0.6mmol/g, granularity 2～3mm; The character of described gac is following: specific surface area is 800～1000m
2/ g, pore volume are 0.5～0.7ml/g, and granularity is 2mm～4mm.
2. according to the described method of claim 1, it is characterized in that described mesoporous molecular sieve is one or more among MCM-41, MCM-48, the SBA-15.
3. according to the described method of claim 1, it is characterized in that said mesoporous molecular sieve is the MCM-41 molecular sieve.
4. according to the described method of claim 1, it is characterized in that described mesoporous molecular sieve particle is prepared by following method: select the suitable former powder of mesoporous molecular sieve, its character is following: specific surface area is 800～1200m
2/ g, the most probable aperture is 2.5～4.5nm, SiO
2/ Al
2O
3Weight ratio is 15～100; The former powder of mesoporous molecular sieve is carried out ammonium exchange, roasting earlier, obtains the Hydrogen mesoporous molecular sieve, again the Hydrogen mesoporous molecular sieve with gained mixes with tackiness agent, after the moulding, warp drying and roasting and must the mesoporous molecular sieve particle.
5. according to the described method of claim 4, it is characterized in that described tackiness agent is through with processing behind mineral acid and/or the organic acid peptization by little porous aluminum oxide; Wherein acid is 0.10～0.55 with the mol ratio of little porous aluminum oxide.
6. according to the described method of claim 1, it is characterized in that described granularity of activated carbon is more than or equal to mesoporous molecular sieve particulate granularity.
7. according to the described method of claim 1; It is characterized in that described gac is to adopt sour modified activated carbon, formic acid and/or acetic acid are adopted in described acid, and detailed process is following: with charcoal absorption formic acid and/or acetic acid steam; It is reached capacity, and adsorption time is 8～36h.
8. according to the described method of claim 1, it is characterized in that the adsorption conditions of this adsorption unit is following: 20 ℃～40 ℃ of adsorption temps, pressure is 0.1～0.2MPa, volume space velocity is 0.1～0.5h during diesel feed liquid
-1
9. according to the described method of claim 1; It is characterized in that through the diesel oil after the oxide treatment before removing the polarity sulfur compound with absorption method; Elder generation removes after the segment polarity sulfur compound with method of extraction, removes the polarity sulfur compound of remainder again with absorption method; Described extraction conditions is at 20 ℃～40 ℃, and pressure is to carry out under 0.1～0.2MPa, and agent oil volume ratio is 0.5: 1～4: 1; Extraction times is 1～3 time.
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| CN105219430B (en) * | 2015-09-21 | 2017-01-25 | 广西大学 | The Method of Insulin Applied in Desulfurization of Coked Diesel Oil |
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| CN1952050A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Oxidation sweetening method of hydrogenated diesel oil |
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| CN1952050A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Oxidation sweetening method of hydrogenated diesel oil |
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