CN100519705C - Combination technique for removing mercaptans from gasoline - Google Patents
Combination technique for removing mercaptans from gasoline Download PDFInfo
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- CN100519705C CN100519705C CNB2007101235466A CN200710123546A CN100519705C CN 100519705 C CN100519705 C CN 100519705C CN B2007101235466 A CNB2007101235466 A CN B2007101235466A CN 200710123546 A CN200710123546 A CN 200710123546A CN 100519705 C CN100519705 C CN 100519705C
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- gasoline
- mercaptan
- demercaptaning
- alkali
- combination process
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003502 gasoline Substances 0.000 title claims description 81
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 54
- 239000003513 alkali Substances 0.000 claims description 48
- 238000007254 oxidation reaction Methods 0.000 claims description 31
- 238000006477 desulfuration reaction Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000023556 desulfurization Effects 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydrocarbon peroxides Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 229920003240 metallophthalocyanine polymer Polymers 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 239000003208 petroleum Substances 0.000 abstract description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 description 19
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 8
- 239000003518 caustics Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- CCEPFPXUJPGUDT-UHFFFAOYSA-M benzyl-dimethyl-octadecylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CCEPFPXUJPGUDT-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Images
Abstract
A combined process for catalytic petroleum desulfurizing alcohol consists of light and heavy fractions. The process is carried out by pre-alkaline washing for light fraction, liquid-liquid agent extracting by alkaline, desulfurized alcohol treating, hydrogenating for heavy fraction, decreasing alkyl, desulfurizing for heavy fraction, pre-alkaline washing, catalyzing for fixed bed, mixing, oxidizing and removing sulfur alcohol. It's economical and it can decrease total sulfur content in petroleum, have less tail gas containing hydrocarbon discharge and octane loss and no environmental pollution.
Description
Technical field
The present invention relates to a kind of demercaptaning for gasoline technology, relate in particular to a kind of combination process of catalytic gasoline mercaptan removal.
Background technology
Nearly 70% from catalytically cracked gasoline in China's motor spirit, catalytically cracked gasoline the key issue that alkene and desulfurization are the gasoline product quality upgradings falls.To the catalytic gasoline selective hydrogenation realizing falling alkene and desulfurization is present industrial proven technique, and will be along with the raising of content of sulfur in gasoline restriction is constantly popularized.During to the catalytic gasoline selective hydrogenation, be the boundary by 80 ℃ generally, earlier gasoline is divided into two cuts of weight, only high last running imposes hydrogenation and falls the alkene desulfurization to sulfur-bearing, and saturated too much to avoid alkene, loss of octane number is excessive.At present, both at home and abroad developed the technology that alkene falls in some gasoline desulfurs.These technology are not fully paid close attention to the mercaptan removal problem.What have only adopts caustic wash desulfuration alcohol to light gasoline fraction, and described in Chinese patent CN1283762C, and caustic wash desulfuration alcohol can produce a large amount of stench alkaline residues, is unfavorable for environmental protection.The proposition that has is fallen the alkene desulfurization to hydrogenation and is handled the last running of falling after alkene and the desulfurization of catalytically cracked gasoline and impose the secondary hydrogenation again, removes mercaptan wherein, and described in Chinese patent CN1234815C, but investment and process cost are very high.
Alkene and desulfurizer fall in a few cover catalytically cracked gasolines of domestic present enforcement, hydrotreater as the catalytic gasoline of Sinopec Shijiazhuang refinery and Zhenghai refinery, the actual mercaptan removal flow process of taking is that the last running behind the hydrogenation merges with light gasoline fraction again, one plays traditional mixed oxidization sweetening unit, refining qualified gasoline mercaptan.
The demercaptaning for gasoline technology is continued to use Merox catalytic oxidation desulfurization alcohol principle always for many years, utilizes the slightly acidic of mercaptan and these two characteristics of the easy oxidized generation disulfide of mercaptan negative ion to remove mercaptan.Principal reaction is:
RSH+NaOH→RSNa+H
2O (1)
2RSNa+1/2O
2+H
2O→RSSR+2NaOH (2)
According to above-mentioned identical principle, the application method of practical sulphur removal alcohol is divided into two kinds of extracting and oxidizing method and mixed oxidization methods, and object all is full distillation gasoline.Two reactions of extracting and oxidizing method mercaptan removal are carried out respectively: extracting is in alkali lye from gasoline with mercaptan earlier, and oily alkali imposes oxidation to the mercaptan in the alkali lye after separating again, is fit to removing of small molecules mercaptan.Two reactions of oxidation desulfurization alcohol are carried out simultaneously: the oxidation while mixing of oily alkali; Remove (see " petroleum refining engineering " third edition for details, the woods generation ruler of great talent and bold vision compiles, the 598th～600 page) that is fit to macromole mercaptan.
Mercaptan situation in the weight gasoline is just the opposite: the mercaptans content height in the petroleum naphtha, the alkyl sulfhydryl of the overwhelming majority for easily removing; And the mercaptan in the heavy naphtha is benzothiophene kind conversion or alkene and hydrogen sulfide effect formation in the hydrogenation process, though content seldom, generally has only 20～30ppm, removes very difficulty.
The doctor process that adopts has the deficiency of two aspects at present: the one, and the mercaptan in the light gasoline fraction is converted into disulphide in mixed oxidization mercaptan removal process, still be retained in the gasoline fraction, does not reduce total sulfur content; The 2nd, increased the air injection amount of mercaptan removal process in oil, increased the hydrocarbonaceous tail gas discharging, unfavorable safety and environmental protection.
Summary of the invention
Gasoline is any cut between each course of processing of refinery produce 30～205 ℃, is mainly used in vehicle fuel.The combination of alkene sulfur removal technology falls in technology of the present invention and catalytic gasoline hydrogenation, identical falling under the total sulfur level, can reduce the hydrogenating desulfurization degree of depth of last running, reduces loss of octane number.Also can match with petroleum naphtha etherificate technology.
The present invention is on the basis of the characteristics of mercaptan in analysing in depth catalytic gasoline weight cut, executes respectively and controls.Described technological process comprises the steps: pending gasoline stocks is separated into light gasoline fraction and heavy naphtha; Adopt liquid-liquor alkali extraction process to carry out mercaptan removal to light gasoline fraction then,, adopt fixed-bed catalytic mixed oxidization method mercaptan removal to the heavy naphtha process or without hydrotreatment.
Technology of the present invention is particularly useful for catalytic cracking or catalytic cracking gasoline, and described light gasoline fraction is meant to be done at 150 ℃ with interior gasoline fraction.
Extracting has the agent alkali behind the mercaptan, can mercaptan be removed regeneration or by air catalytic oxidation mercaptan is converted into disulphide by heating to remove regeneration, and the agent alkali after the regeneration recycles, and can avoid the generation of a large amount of alkaline residues.
Light gasoline fraction mixes the blend component as gasoline product separately as the blend component of gasoline product or with the heavy naphtha that removes mercaptan through fixed-bed catalytic mixed oxidization method behind liquid-liquor alkali extraction desulfurization alcohol.
Light gasoline fraction wherein can also mix with heavy naphtha earlier, and then remove mercaptan through fixed-bed catalytic mixed oxidization method together behind liquid-liquor alkali extraction desulfurization alcohol.
In fixed-bed catalytic mixed oxidization method, can be carrier with activated alumina, gac, porous resin, molecular sieve and/or charcoal fiber adsorbability material, load C o, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine are catalyzer; And with air, oxygen, dissolved oxygen, oxygen-rich air, hydrocarbon peroxides and/or H
2O
2Be oxygenant, employed hydrocarbon peroxides for example is tertbutyl peroxide and/or hydrogen phosphide cumene etc.
Described extractant alkali is the alkali lye that alkali lye or adding help extracting functional agent and regenerated catalyst, and wherein regenerated catalyst is Co, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine.
Described alkali lye is the alkaline aqueous solution such as NaOH, KOH and quaternary ammonium hydroxide.
In order to improve extraction efficiency, can in alkali lye, add and help the extracting functional agent, what add helps the extracting functional agent to have hydrotropy and helps catalytic function, the extracting functional agent that helps that uses for example is in ethylene glycol, isopropylformic acid, thanomin and the quaternary amines material one or more, and wherein the quaternary amines material for example is dodecyl dimethyl benzyl ammonium chloride, hydroxide octadecyl dimethyl benzyl ammonium etc.
Be used for the extractive contact reacts equipment of liquid-liquor alkali and be one or more of static mixer, tray column or packing tower, tunica fibrosa contact reactor, wherein several comprise being used in combination of two or more.
Mercaptans content in the heavy naphtha is not high, and it is difficult to remove; And during the hydrotreatment heavy naphtha, though original mercaptan removed, but generate a small amount of extremely difficult mercaptan that removes.So the mercaptan in the heavy naphtha need adopt the mixed oxidization method to remove.Because of this part mercaptans content generally has only 20～30ppm, little to the influence of product total sulfur, so this part purified emphasis is that mercaptan is converted into the less disulphide of harm.
The present invention preferably adopts H
2O
2, hydrocarbon peroxides or dissolved oxygen replace conventional air as oxygenant, thereby can in gasoline, not annotate wind, eliminate hydrocarbonaceous tail gas, safe and environmentally friendly.
Description of drawings
Accompanying drawing is the process flow sheet of the embodiment of the invention 1.Each Reference numeral is respectively among the figure: 1. gasoline splitter; 2. the alkene desulfurization unit falls in the heavy naphtha hydrogenation; 3. the first caustic prescrub jar; 4. first static mixer; 5. light gasoline fraction agent alkali extraction desulfurization alcohol tower; 6. extractant alkali regenerator column; 7. extractant alkali surge tank; 8. the second caustic prescrub jar; 9. second static mixer; 10. heavy naphtha mixed oxidization mercaptan removal tower; 11. settlement separate jar of heavy petrol.
Embodiment
The enforcement that matches of fall the present invention and catalytic gasoline hydrogenation alkene desulfurization technology or petroleum naphtha etherificate technology.
Catalytic gasoline alkene and sulphur content are all higher, in order to reduce the loss of octane value as far as possible, need earlier gasoline to be divided into two cuts of weight in falling the alkene sweetening process.
After gasoline was cut apart, light gasoline fraction entered liquid-liquor alkali extraction desulfurization alcohol section.This section comprises caustic prescrub, pure and mild dose of alkali oxidation regeneration three parts of extraction desulfurization.In order to strengthen extraction rate was acquired, in agent alkali, add have hydrotropy and help catalysis help the extracting functional agent.Mercaptan is qualified after the extracting, and light gasoline fraction is carrying device separately, also can merge carrying device with the qualified heavy naphtha of mercaptan removal; Mercaptan can not be qualified after the extracting, merges to advance fixed-bed catalytic mixed oxidization sweetening unit with heavy naphtha again and handle.
Heavy naphtha does not carry out hydrotreatment, directly advances fixed-bed catalytic mixed oxidization sweetening unit.
Heavy naphtha needs hydrotreatment, carries out hydrogenation earlier and falls alkene desulfurization processing.Heavy naphtha after the hydrotreatment advances fixed-bed catalytic mixed oxidization mercaptan removal section.This section generally comprises caustic prescrub, fixed-bed catalytic mixed oxidization mercaptan removal two portions, but when adopting the dissolved oxygen oxidation, special agent alkali regeneration section need be arranged also.Fixed-bed catalytic mixed oxidization mercaptan removal part can have been taked the circulation of agent alkali or not have the operation of agent alkali circulation dual mode; When adopting the dissolved oxygen oxidation, must adopt has the operation of agent alkali Recycle design.The composition of agent alkali is used in this place, with the used agent bases of extracting part like or identical.
Before concrete device design, need weight gasoline fraction and mercaptans content characteristic thereof are analyzed, remove difficulty according to mercaptan and determine suitable device type, size and process conditions.
Embodiment 1
Fall the alkene example with reference to Figure of description and certain factory's desulfurization, the narration implementing procedure is as follows:
Total sulfur content is that the catalytically cracked gasoline of 620ppm at first is divided into two cuts of weight in gasoline splitter 1.With 80 ℃ of cut-points is example, and the lighting end yield is about about 45wt%, and the sulphur that is distributed in the lighting end is about 13% of full cut total sulfur, and sulphur content is about 180ppm, wherein is mercaptan sulfur about 50wt%.Light gasoline fraction removes the H of trace at the first caustic prescrub jar 3
2S mixes with circulation agent alkali at first static mixer 4 then, in light gasoline fraction agent alkali extraction desulfurization alcohol tower 5 with the mercaptan extracting in agent alkali, the sulphur content of the mercaptan removal light gasoline fraction that comes out has dropped to 90～100ppm from 180ppm.And adopt former flow process, the sulphur content of light gasoline fraction still is 180ppm.
The agent alkali that extracting has mercaptan is with after petroleum naphtha separates, and to the 6 oxidized regeneration of extractant alkali regenerator column, wherein mercaptan is oxidized to disulphide, and deviates from from agent alkali in extractant alkali surge tank 7 in, and agent alkali obtains the reprocessing cycle use.
High sulfur-bearing heavy naphtha arrives first the heavy naphtha hydrogenation and falls and fall the alkene desulfurization in the alkene desulfurization unit 2.For the sulphur content that makes full cut finished product is lower than 150ppm, sulphur content must be lower than 125ppm after the former scheme last running desulfurization, and after adopting flow process of the present invention, it is just passable that the desulfurization depth of heavy petrol reaches 190ppm, greatly reduce the degree of depth of hydrogenation, related data infers that the RON loss of octane number of heavy petrol will reduce by 1.35 units.
After the alkene desulfurization falls in the heavy naphtha hydrogenation, slough the H of trace at the second caustic prescrub jar 8
2S mixes with circulation agent alkali in second static mixer 9, and the difficult mercaptan removal that hydrogenation process generates in heavy naphtha mixed oxidization mercaptan removal tower 10 is direct oxidation into disulphide.Gasoline separates with agent alkali in the settlement separate jar 11 of heavy petrol, and the petroleum naphtha that heavy petrol that mercaptan removal is qualified and extraction desulfurization alcohol are qualified merges device, and agent alkali recycles.
In heavy naphtha mixed oxidization mercaptan removal tower 10, can adopt traditional notes little air as oxygenant, also can adopt H
2O
2Or hydrocarbon peroxides replaces the oxygenant that conventional air is done mixed oxidization, can also adopt circulation agent alkali to separate back scheme such as regeneration separately with gasoline, avoids in gasoline directly air injection, causes oil product to lose and topsoil.
The invention effect
1, take 80 ℃ of cut points as example, the total sulfur mass content of light petrol can reduce by 50～60%.
2, calculate every minimizing 1Nm according to the vapour pressure of gasoline3Air Injection reduces 1.1kg's in theory The gasoline loss. 10,000 tons of gasoline of every processing lose gasoline 1254kg less. The actual specific gross data is bigger.
3, the hydrodesulfurization degree of depth of heavy petrol can correspondingly alleviate, reduce operating cost, heavy petrol RON octane Value is lost 1.35 units less.
Claims (11)
1. the combination process of a demercaptaning for gasoline comprises the steps: pending gasoline stocks is separated into light gasoline fraction and heavy naphtha; Adopt liquid-liquor alkali extraction process to carry out mercaptan removal to light gasoline fraction then,, adopt fixed-bed catalytic mixed oxidization method mercaptan removal to the heavy naphtha process or without hydrotreatment.
2. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: extracting is had agent alkali behind the mercaptan, mercaptan is removed regeneration or by air catalytic oxidation mercaptan is converted into disulphide and removes regeneration by heating, the agent alkali after the regeneration recycles.
3. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: described light gasoline fraction mixes the blend component as gasoline product separately as the blend component of gasoline product or with the heavy naphtha that removes mercaptan through fixed-bed catalytic mixed oxidization method behind liquid-liquor alkali extraction desulfurization alcohol.
4. the combination process of demercaptaning for gasoline as claimed in claim 1 is characterized in that: described light gasoline fraction mixes with heavy naphtha earlier, and then removes mercaptan through fixed-bed catalytic mixed oxidization method together behind liquid-liquor alkali extraction desulfurization alcohol.
5. as the combination process of claim 3 or 4 described demercaptaning for gasoline, it is characterized in that: in fixed-bed catalytic mixed oxidization method, with activated alumina, gac, porous resin, molecular sieve and/or charcoal fiber adsorbability material is carrier, and load C o, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine are catalyzer; With air, oxygen, dissolved oxygen, oxygen-rich air, hydrocarbon peroxides and/or H
2O
2Be oxygenant.
6. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: pending gasoline stocks is catalytic cracking or catalytic cracking gasoline.
7. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: described light gasoline fraction is meant to be done at 150 ℃ with interior gasoline fraction.
8. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: described extractant alkali is alkali lye.
9. the combination process of demercaptaning for gasoline as claimed in claim 1, it is characterized in that: described extractant alkali is for adding the alkali lye that helps extracting functional agent and regenerated catalyst, and wherein regenerated catalyst is Co, Fe, Mo, V, Ni and/or Cu metallo phthalocyanine.
10. the combination process of demercaptaning for gasoline as claimed in claim 8 is characterized in that: the described extracting functional agent that helps is in ethylene glycol, isopropylformic acid, thanomin and the quaternary amines material one or more.
11. the combination process of demercaptaning for gasoline as claimed in claim 8 or 9, it is characterized in that: described alkali lye is KOH, NaOH and/or the quaternary ammonium hydroxide aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101235466A CN100519705C (en) | 2007-04-29 | 2007-07-02 | Combination technique for removing mercaptans from gasoline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710098891 | 2007-04-29 | ||
| CN200710098891.9 | 2007-04-29 | ||
| CNB2007101235466A CN100519705C (en) | 2007-04-29 | 2007-07-02 | Combination technique for removing mercaptans from gasoline |
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| CN100519705C true CN100519705C (en) | 2009-07-29 |
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| CNB2007101235466A Expired - Fee Related CN100519705C (en) | 2007-04-29 | 2007-07-02 | Combination technique for removing mercaptans from gasoline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9523047B2 (en) | 2014-06-12 | 2016-12-20 | Uop Llc | Apparatuses and methods for treating mercaptans |
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|---|---|---|---|---|
| CN101705108B (en) * | 2009-12-11 | 2012-09-05 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
| CN101993750B (en) * | 2010-11-29 | 2013-09-04 | 中国石油大学(北京) | Method for refining liquefied petroleum gas |
| CN101993751B (en) * | 2010-11-29 | 2014-09-03 | 中国石油大学(北京) | Sweetening agent combination |
| CN102851068B (en) * | 2011-06-29 | 2015-02-25 | 中国石油化工股份有限公司 | Gasoline desulfurization method |
| CN103059950B (en) * | 2011-10-21 | 2015-07-22 | 中国石油化工股份有限公司 | Catalytic gasoline hydrodesulfurization method |
| CN103059965B (en) * | 2011-10-21 | 2015-09-30 | 中国石油化工股份有限公司 | Catalytic gasoline deep hydrodesulfurizationmethod method |
| CN103740407B (en) * | 2014-01-21 | 2015-07-01 | 武汉工程大学 | Alkali cleaning-extraction-washing-hydrogenation combined process for producing low-sulfur-content gasoline |
| CN103740405B (en) * | 2014-01-21 | 2015-07-01 | 长江大学 | Alkali cleaning-extraction-hydrogenation combined process for producing low-sulfur-content gasoline |
| CN105542853A (en) * | 2016-01-13 | 2016-05-04 | 山东联星能源集团有限公司 | Selective hydrodesulfurization process for preparing ultra-low sulfur clean gasoline |
| CN105670687A (en) * | 2016-01-13 | 2016-06-15 | 山东联星能源集团有限公司 | Catalytically cracked gasoline desulphurization method |
| CN106520198B (en) | 2016-11-16 | 2018-08-10 | 郝天臻 | A kind of catalytic gasoline sulfur method having both olefine selective remove |
| CN108905951A (en) * | 2018-07-11 | 2018-11-30 | 济南开发区星火科学技术研究院 | A kind of preparation method of demercaptaning for gasoline adsorbent |
| CN114672341A (en) * | 2021-12-30 | 2022-06-28 | 山东东明石化集团有限公司 | Bed activation process for gasoline fixed bed sweetening reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9523047B2 (en) | 2014-06-12 | 2016-12-20 | Uop Llc | Apparatuses and methods for treating mercaptans |
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| CN101100616A (en) | 2008-01-09 |
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