CN102757809B - Mercaptan removal and lye regeneration device and method for gasoline light fractions - Google Patents
Mercaptan removal and lye regeneration device and method for gasoline light fractions Download PDFInfo
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Abstract
The invention relates to a mercaptan removal and lye regeneration device and a method for gasoline light fractions. The mercaptan removal and lye regeneration device for gasoline light fractions comprises a static mixer, a liquid film alkaline wash reactor, a lye coalescence remover, a lye oxidation separation tower and a liquid film extraction contactor. The mercaptan removal and lye regeneration device and the method for gasoline light fractions have the advantages that pre-alkaline washing is used for removing hydrogen sulfide and phenol, so that the investment is low; the two-stage liquid film alkaline wash reactor and the alkaline wash process are utilized, so that the mercaptan in products can be guaranteed to be below 10 parts per million (ppm), no free lye is carried, and the copper sheet corrosion and water-solutbility acid base detection can be guaranteed to be qualified with no water wash needed; the oxidation rate of mercaptan sodium in the lye is high, two-phase perturbation emulsification is quite slight, and more than 60% of generated disulphide can be separated and recycled; the content of the disulphide in the regenerated lye can be guaranteed to be no more than 100 ppm, and the regenerated lye cannot be re-extracted into products when used for removing mercaptan in a circulation mode; the total sulfur in products can be guaranteed to be stable and not rise without replacing the lye frequently, and compared with other processes, the discharge amount of alkaline residues is reduced by more than 50%.
Description
Technical field
The present invention relates to petrochemical industry, particularly relate to the device and method of a kind of gasoline lighting end mercaptan removal and alkali liquid regeneration.
Background technology
Along with the in poor quality of crude oil and high-sulfurized, and the raising day by day that society requires Fuel Petroleum desulfurization, require that oil refining enterprise improves constantly crude oil processing technology level, update Fuel Petroleum sulfur removal technology, more will pay attention to the Sustainable development need of production of energy-saving and emission-reduction consumption reduction in production process simultaneously.
Namely European and American developed countries start to perform clean gasoline the Europe IV standard as far back as 2005, within 2009, start to perform Europe V standard, China also took the lead in 2011 implementing state IV standard on the ground such as Beijing, Shanghai, require that motor benzine total sulfur is no more than 50ppm, the clean gasoline producing more low sulfur content is the inevitable choices of people to living environment pay attention to day by day.
Tradition alkali cleaning extraction process cannot meet the requirement of current gasoline deep desulfuration, hydrogenating desulfurization is then current Application comparison maturation and the deep desulfuration technology widelyd popularize, but hydrogenating desulfurization exists, and plant investment is huge, complicated operation, the problem that gasoline refining cost is high, but also the shortcoming that there is loss gasoline octane rating.
Fushun Petrochemical Research Institute of SINOPEC is on the basis of hydrogenating desulfurization technology, by selecting, the gasoline that is suitable for is light, last running cut point temperature, the method of the lighting end alkali cleaning extracting that, sulphur content higher to olefin(e) centent is lower carries out desulfurization process, the last running higher to sulphur content carries out hydrogenating desulfurization process with the desulfurization catalyst of special exploitation, and two kinds of distillation gasolines after desulfurization reconcile into gasoline product again.This technique solves full distillation gasoline hydrogenation technique on the one hand to the problem of loss of octane number, and gasoline lighting end adopts the cost of alkali cleaning extraction desulfurization alcohol far below hydrogenating desulfurization cost on the other hand, greatly reduces gasoline refining cost.
Liquefied gas caustic wash desulfuration alcohol technology is very ripe, and what current industrial application was more is packed extraction column and fiber film contactor two class mass transfer apparatus, and gasoline lighting end adopts the experimental study of caustic wash desulfuration alcohol and industrial application not yet to have ripe equipment and technology.
Summary of the invention
The object of this invention is to provide a kind of gasoline lighting end mercaptan removal and alkali liquid regeneration device and method, to solve, the investment of current gasoline lighting end doctor process is huge, complicated operation, gasoline refining cost are high and lose the technical barriers such as gasoline octane rating.
Object of the present invention is achieved through the following technical solutions:
A kind of gasoline lighting end mercaptan removal and alkali liquid regeneration device, comprise static mixer, one-level liquid film alkali cleaning reactor, secondary liquid film alkali cleaning reactor, alkali lye coalescer, alkali liquor oxidized knockout tower and liquid film extracting contactor, described static mixer is connected with caustic prescrub tank by pipeline, described caustic prescrub tank is connected with one-level alkali cleaning separating tank by one-level liquid film alkali cleaning reactor, described one-level liquid film alkali cleaning reactor is arranged on one-level alkali cleaning separating tank, the outlet of one-level alkali cleaning separating tank is connected with secondary alkali cleaning separating tank by secondary liquid film alkali cleaning reactor, secondary alkali cleaning separating tank is externally connected with alkali lye coalescer, circulation alkali liquor pump is provided with outside described one-level liquid film alkali cleaning reactor, the circulation alkali liquid pump the other end is separated alkali lye and exports and be connected with secondary alkali cleaning, described secondary liquid film alkali cleaning reactor is connected with the outlet of regenerating alkali liquid pump with extracting slurry tank alkali lye, and described regenerating alkali liquid pump is externally connected with fresh alkali lye feed-pipe, the alkali lye outlet of described one-level alkali cleaning separating tank is outer is provided with alkali lye preheater and catalyst injector, and be connected with the alkali lye import of described alkali liquor oxidized knockout tower, gas distributor, alkali liquor oxidized separation dividing plate and coalescent pack is provided with in described alkali liquor oxidized knockout tower, disulphide discharge nozzle and tail gas discharge nozzle is provided with outside described alkali liquor oxidized knockout tower, tail gas discharge nozzle is provided with tail gas and divides flow container, is provided with compressed air pipe outside described gas distributor, described alkali liquor oxidized knockout tower alkali lye outlet is connected with extracting slurry tank with liquid film extracting contactor by petroleum naphtha pipe, described liquid film extracting contactor is connected with the petroleum naphtha outlet of petroleum naphtha pump and liquid film extracting slurry tank, in described extracting slurry tank, coalescing-plate and dividing plate are installed, described petroleum naphtha pipe is provided with naphtha feed pipe and petroleum naphtha coalescer, and described petroleum naphtha coalescer is provided with Containing-sulfur Naphtha discharge nozzle and alkaline residue delivery pipe.
Further, be connected bottom described alkali lye coalescer with alkaline residue tank, top is provided with clean petroleum product outlet; Coalescing-plate and dividing plate is provided with in described extracting slurry tank.
A method for gasoline lighting end mercaptan removal and alkali liquid regeneration, comprises the following steps:
1) in static mixer, fresh alkali lye is inputted by caustic prescrub pump, pending gasoline stocks and alkali lye carry out shear-mixed reaction 0.1 ~ 2min in static mixer, alkali lye mass rate is the 20-60%wt of quality of gasoline flow, the two settlement separate 10 ~ 30min in caustic prescrub tank, obtain be separated caustic prescrub after gasoline and alkali lye, alkali lye recycles, according to hydrogen sulfide in product and the periodic replacement of phenol content;
2) after caustic prescrub gasoline by alkali lye after output tube and the alkali cleaning of secondary liquid film, with membrane-membrane contact Laminar Flow in one-level liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains one-level treated gasoline and one-level alkali lye at the settlement separate 30 ~ 60min of one-level alkali cleaning separating tank;
3) one-level treated gasoline is by output tube and regeneration alkali lye, with membrane-membrane contact Laminar Flow in secondary liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains secondary treated gasoline and secondary alkali lye at the settlement separate 30 ~ 60min of secondary alkali cleaning separating tank;
4) one-level alkali lye force feed enters in alkali liquor oxidized knockout tower, pressurized air is scattered in the alkali lye in liquid oxidation knockout tower by gas distributor by with microvesicle form simultaneously, air consumption is 1-5 times of sodium mercaptides oxidation theory demand, sodium mercaptides oxide catalyst content in alkali lye is 50-200ppm, alkali liquor oxidized temperature is 20-70 DEG C, oxygen in air fully contacts with the sodium mercaptides in alkali lye and reacts and generates sodium hydroxide and disulphide, and sodium hydroxide is dissolved in alkali lye and alkali lye is regenerated; Disulphide density is little floats over alkali lye upper strata, through disengaging zone, hydrophilic coalescent pack forms alkali lye liquid film to alkali lye, alkali lye fully contacts with the disulphide of layering, and in alkali lye, the disulphide of emulsification is extracted in the disulphide of layering, and in alkali lye, disulphide content reduces further;
5) alkali lye and the low sulfur naphtha that are oxidized separation disulphide pass through liquid film extracting contactor, alkali lye mass rate is the 20-100%wt of petroleum naphtha mass rate, two-phase contacts Laminar Flow with membrane-membrane in liquid film extracting contactor, two-phase fully contacts, disulphide residual in alkali lye is extracted in petroleum naphtha, alkali lye and petroleum naphtha are at the settlement separate 30 ~ 90min of extracting slurry tank, obtain regeneration alkali lye and Containing-sulfur Naphtha, regeneration alkali lye delivers to secondary liquid film reactor by regenerating alkali liquid pump, Containing-sulfur Naphtha 30-80% recycles, 70-20% must remove carrying device after alkali lye by petroleum naphtha coalescer,
6) low sulfur naphtha described in can be low-sulphur oil, chemical industry light oil, solvent oil or diesel oil.
Accompanying drawing explanation
The structural representation that Fig. 1 is a kind of gasoline lighting end mercaptan removal described in the embodiment of the present invention and alkali liquid regeneration device.
In figure:
1, static mixer; 2, caustic prescrub tank; 3, caustic prescrub pump; 4, one-level liquid film alkali cleaning reactor; 5, one-level alkali cleaning separating tank; 6, secondary liquid film alkali cleaning reactor; 7, secondary alkali cleaning separating tank; 8, alkali lye coalescer; 9, circulation alkali liquid pump; 10, alkali lye preheater; 11, catalyst injector; 12, alkali liquor oxidized knockout tower; 13, gas distributor; 14, coalescent pack; 15, liquid film extracting contactor; 16, extracting slurry tank; 17, coalescing-plate; 18, dividing plate; 19, regenerating alkali liquid pump; 20, petroleum naphtha pump; 21, petroleum naphtha coalescer; 22, alkali liquor oxidized separation dividing plate; 23, tail gas divides flow container.
Embodiment
As shown in Figure 1, a kind of gasoline lighting end mercaptan removal described in the embodiment of the present invention and alkali liquid regeneration device, comprise static mixer 1, one-level liquid film alkali cleaning reactor 4, secondary liquid film alkali cleaning reactor 6, alkali lye coalescer 8, alkali liquor oxidized knockout tower 12 and liquid film extracting contactor 15, described static mixer 1 is connected with caustic prescrub tank 2 by pipeline, , described caustic prescrub tank 2 is connected with one-level alkali cleaning separating tank 5 by one-level liquid film alkali cleaning reactor 4, described one-level liquid film alkali cleaning reactor 4 is arranged on one-level alkali cleaning separating tank 5, the outlet of one-level alkali cleaning separating tank 5 is connected with secondary alkali cleaning separating tank 7 by secondary liquid film alkali cleaning reactor 6, secondary alkali cleaning separating tank 7 is externally connected with alkali lye coalescer 8, circulation alkali liquor pump 9 is provided with outside described one-level liquid film alkali cleaning reactor 4, circulation alkali liquid pump 9 the other end exports with secondary alkali cleaning separating tank 7 alkali lye and is connected, described secondary liquid film alkali cleaning reactor 6 is connected with the outlet of regenerating alkali liquid pump 19 with extracting slurry tank 16 alkali lye, and described regenerating alkali liquid pump 19 is externally connected with fresh alkali lye feed-pipe, the alkali lye outlet of described one-level alkali cleaning separating tank 5 is outer is provided with alkali lye preheater 10 and catalyst injector 11, and be connected with the alkali lye import of described alkali liquor oxidized knockout tower 12, gas distributor 13, alkali liquor oxidized separation dividing plate 22 and coalescent pack 14 is provided with in described alkali liquor oxidized knockout tower 12, disulphide discharge nozzle and tail gas discharge nozzle is provided with outside described alkali liquor oxidized knockout tower 12, tail gas discharge nozzle is provided with tail gas and divides flow container 23, is provided with compressed air pipe outside described gas distributor 13, described alkali liquor oxidized knockout tower 12 alkali lye outlet is connected with extracting slurry tank 16 with liquid film extracting contactor 15 by petroleum naphtha pipe, described liquid film extracting contactor 15 is connected with the petroleum naphtha outlet of petroleum naphtha pump 20 and liquid film extracting slurry tank 16, coalescing-plate 17 and dividing plate 18 are installed in described extracting slurry tank 16, described petroleum naphtha pipe is provided with naphtha feed pipe and petroleum naphtha coalescer 21, and described petroleum naphtha coalescer 21 is provided with Containing-sulfur Naphtha discharge nozzle 42 and alkaline residue delivery pipe 43.Be connected with alkaline residue tank bottom described alkali lye coalescer 8, top is provided with clean petroleum product outlet; Coalescing-plate 17 and dividing plate 18 is provided with in described extracting slurry tank 16.
Gasoline lighting end mercaptan removal described in the embodiment of the present invention and the method for alkali liquid regeneration, comprise the following steps:
1) in static mixer, fresh alkali lye is inputted by caustic prescrub pump, pending gasoline stocks and alkali lye carry out shear-mixed reaction 0.1 ~ 2min in static mixer, alkali lye mass rate is the 20-60%wt of quality of gasoline flow, the two settlement separate 10 ~ 30min in caustic prescrub tank, obtain be separated caustic prescrub after gasoline and alkali lye, alkali lye recycles, according to hydrogen sulfide in product and the periodic replacement of phenol content;
2) after caustic prescrub gasoline by alkali lye after output tube and the alkali cleaning of secondary liquid film, with membrane-membrane contact Laminar Flow in one-level liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains one-level treated gasoline and one-level alkali lye at the settlement separate 30 ~ 60min of one-level alkali cleaning separating tank;
3) one-level treated gasoline is by output tube and regeneration alkali lye, with membrane-membrane contact Laminar Flow in secondary liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains secondary treated gasoline and secondary alkali lye at the settlement separate 30 ~ 60min of secondary alkali cleaning separating tank;
4) one-level alkali lye force feed enters in alkali liquor oxidized knockout tower, pressurized air is scattered in the alkali lye in liquid oxidation knockout tower by gas distributor by with microvesicle form simultaneously, air consumption is 1-5 times of sodium mercaptides oxidation theory demand, sodium mercaptides oxide catalyst content in alkali lye is 50-200ppm, alkali liquor oxidized temperature is 20-70 DEG C, oxygen in air fully contacts with the sodium mercaptides in alkali lye and reacts and generates sodium hydroxide and disulphide, and sodium hydroxide is dissolved in alkali lye and alkali lye is regenerated; Disulphide density is little floats over alkali lye upper strata, through disengaging zone, hydrophilic coalescent pack forms alkali lye liquid film to alkali lye, alkali lye fully contacts with the disulphide of layering, and in alkali lye, the disulphide of emulsification is extracted in the disulphide of layering, and in alkali lye, disulphide content reduces further;
5) alkali lye and the low sulfur naphtha that are oxidized separation disulphide pass through liquid film extracting contactor, alkali lye mass rate is the 20-100%wt of petroleum naphtha mass rate, two-phase contacts Laminar Flow with membrane-membrane in liquid film extracting contactor, two-phase fully contacts, disulphide residual in alkali lye is extracted in petroleum naphtha, alkali lye and petroleum naphtha are at the settlement separate 30 ~ 90min of extracting slurry tank, obtain regeneration alkali lye and Containing-sulfur Naphtha, regeneration alkali lye delivers to secondary liquid film reactor by regenerating alkali liquid pump, Containing-sulfur Naphtha 30-80% recycles, 70-20% must remove carrying device after alkali lye by petroleum naphtha coalescer,
6) low sulfur naphtha described in can be low-sulphur oil, chemical industry light oil, solvent oil or diesel oil.
Application example
Certain company adopts the technology of the present invention, has built up a set of gasoline lighting end mercaptan removal and alkali liquid regeneration device:
Gasoline lighting end processing power: 25.8t/h; Turndown ratio: 50-110%; Gasoline lighting end distillation point: 30-68 DEG C; Gasoline lighting end main character: hydrogen sulfide <30ppm, mercaptan <210ppm, total sulfur <270ppm, enter device pressure 0.6-0.8MPaG, temperature 30-45 DEG C; Process operation parameter: caustic prescrub flux of alkaline liquor 6t/h, mercaptan removal alkali lye circular flow 4t/h, catalyst content 100-150ppm, alkaline residue oxidizing temperature 30-50 DEG C, compressed air require 30-40Nm
3/ h, petroleum naphtha circular flow 12-16t/h, flow 2-3t/h changed by petroleum naphtha; Plant running result: refining petroleum naphtha: hydrogen sulfide does not measure, mercaptans content 2-8ppm, doctor test are detected as without, copper corrosion 1a by, water-soluble soda acid, other situation: caustic prescrub is monthly changed alkali lye 15 tons, run and do not change mercaptan removal agent alkali, monthly recovery disulphide 2 tons half a year.
Although above only describes the specific embodiment of the present invention example, it will be understood by those of skill in the art that these only illustrate, protection scope of the present invention is defined by the appended claims.Those skilled in the art, under the prerequisite not deviating from principle of the present invention and essence, can make various changes or modifications to these embodiments, but these change or amendment all falls into protection scope of the present invention.
Claims (3)
1. a gasoline lighting end mercaptan removal and alkali liquid regeneration device, comprise static mixer (1), one-level liquid film alkali cleaning reactor (4), secondary liquid film alkali cleaning reactor (6), alkali lye coalescer (8), alkali liquor oxidized knockout tower (12) and liquid film extracting contactor (15), it is characterized in that: described static mixer (1) is connected with caustic prescrub tank (2) by pipeline, caustic prescrub tank (2) is connected with one-level alkali cleaning separating tank (5) by one-level liquid film alkali cleaning reactor (4), described one-level liquid film alkali cleaning reactor (4) is arranged on one-level alkali cleaning separating tank (5), the outlet of one-level alkali cleaning separating tank (5) is connected with secondary alkali cleaning separating tank (7) by secondary liquid film alkali cleaning reactor (6), secondary alkali cleaning separating tank (7) is externally connected with alkali lye coalescer (8), circulation alkali liquor pump (9) is provided with outside described one-level liquid film alkali cleaning reactor (4), circulation alkali liquid pump (9) the other end exports with secondary alkali cleaning separating tank (7) alkali lye and is connected, described secondary liquid film alkali cleaning reactor (6) is connected with the outlet of regenerating alkali liquid pump (19) with extracting slurry tank (16) alkali lye, and described regenerating alkali liquid pump (19) is externally connected with fresh alkali lye feed-pipe, the alkali lye outlet of described one-level alkali cleaning separating tank (5) is outer to be provided with alkali lye preheater (10) with catalyst injector (11) and to be connected with the alkali lye import of described alkali liquor oxidized knockout tower (12), gas distributor (13), alkali liquor oxidized separation dividing plate (22) and coalescent pack (14) is provided with in described alkali liquor oxidized knockout tower (12), disulphide discharge nozzle and tail gas discharge nozzle is provided with outside described alkali liquor oxidized knockout tower (12), this tail gas discharge nozzle is provided with tail gas and divides flow container (23), and described gas distributor is provided with compressed air pipe outside (13), the alkali lye outlet of described alkali liquor oxidized knockout tower (12) is connected with extracting slurry tank (16) with liquid film extracting contactor (15) by petroleum naphtha pipe, described liquid film extracting contactor (15) connects the petroleum naphtha outlet of petroleum naphtha pump (20) and liquid film extracting slurry tank (16), coalescing-plate (17) and dividing plate (18) are installed in described extracting slurry tank (16), described petroleum naphtha pipe is provided with naphtha feed pipe and petroleum naphtha coalescer (21), described petroleum naphtha coalescer (21) is provided with Containing-sulfur Naphtha discharge nozzle (42) and alkaline residue delivery pipe (43).
2. a kind of gasoline lighting end mercaptan removal according to claim 1 and alkali liquid regeneration device, is characterized in that: described alkali lye coalescer (8) bottom is connected with alkaline residue tank, and described alkali lye coalescer (8) top is provided with clean petroleum product outlet; Coalescing-plate (17) and dividing plate (18) is provided with in described extracting slurry tank (16).
3. a method for gasoline lighting end mercaptan removal and alkali liquid regeneration, is characterized in that, comprises the following steps:
1) in static mixer, fresh alkali lye is inputted by caustic prescrub pump, pending gasoline stocks and alkali lye carry out shear-mixed reaction 0.1 ~ 2min in static mixer, alkali lye mass rate is the 20-60%wt of quality of gasoline flow, the two settlement separate 10 ~ 30min in caustic prescrub tank, obtain be separated caustic prescrub after gasoline and alkali lye, alkali lye recycles, according to hydrogen sulfide in product and the periodic replacement of phenol content;
2) after caustic prescrub gasoline by alkali lye after output tube and the alkali cleaning of secondary liquid film, with membrane-membrane contact Laminar Flow in one-level liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains one-level treated gasoline and one-level alkali lye at the settlement separate 30 ~ 60min of one-level alkali cleaning separating tank;
3) one-level treated gasoline is by output tube and regeneration alkali lye, with membrane-membrane contact Laminar Flow in secondary liquid film reactor, two-phase fully contacts and reacts, alkali lye mass rate is the 10-40%wt of quality of gasoline flow, the two obtains secondary treated gasoline and secondary alkali lye at the settlement separate 30 ~ 60min of secondary alkali cleaning separating tank;
4) one-level alkali lye force feed enters in alkali liquor oxidized knockout tower, pressurized air is scattered in the alkali lye in liquid oxidation knockout tower by gas distributor by with microvesicle form simultaneously, air consumption is 1-5 times of sodium mercaptides oxidation theory demand, sodium mercaptides oxide catalyst content in alkali lye is 50-200ppm, alkali liquor oxidized temperature is 20-70 DEG C, oxygen in air fully contacts with the sodium mercaptides in alkali lye and reacts and generates sodium hydroxide and disulphide, and sodium hydroxide is dissolved in alkali lye and alkali lye is regenerated; Disulphide density is little floats over alkali lye upper strata, through disengaging zone, hydrophilic coalescent pack forms alkali lye liquid film to alkali lye, alkali lye fully contacts with the disulphide of layering, and in alkali lye, the disulphide of emulsification is extracted in the disulphide of layering, and in alkali lye, disulphide content reduces further;
5) alkali lye and the low sulfur naphtha that are oxidized separation disulphide pass through liquid film extracting contactor, alkali lye mass rate is the 20-100%wt of petroleum naphtha mass rate, two-phase contacts Laminar Flow with membrane-membrane in liquid film extracting contactor, two-phase fully contacts, disulphide residual in alkali lye is extracted in petroleum naphtha, alkali lye and petroleum naphtha are at the settlement separate 30 ~ 90min of extracting slurry tank, obtain regeneration alkali lye and Containing-sulfur Naphtha, regeneration alkali lye delivers to secondary liquid film reactor by regenerating alkali liquid pump, Containing-sulfur Naphtha 30-80% recycles, 70-20% must remove carrying device after alkali lye by petroleum naphtha coalescer,
6) low sulfur naphtha described in is low-sulphur oil, chemical industry light oil, solvent oil or diesel oil.
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| CN102492464A (en) * | 2011-12-02 | 2012-06-13 | 甘肃蓝科石化高新装备股份有限公司 | Gasoline desulfuration and deodorization process |
| CN202808717U (en) * | 2012-08-03 | 2013-03-20 | 宁波中一石化科技有限公司 | Gasoline light fraction mercaptan removal and alkali liquid regeneration device |
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