CN103773494B - The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment - Google Patents
The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment Download PDFInfo
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- CN103773494B CN103773494B CN201310743967.4A CN201310743967A CN103773494B CN 103773494 B CN103773494 B CN 103773494B CN 201310743967 A CN201310743967 A CN 201310743967A CN 103773494 B CN103773494 B CN 103773494B
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Abstract
The present invention relates to a kind of hydrogen circulation differential catalytic distillation sulfur method and the equipment of producing super low sulfur state V petrol and diesel oil, specifically with the full distillation gasoline of FCC, coker gasoline or diesel oil etc. are stock oil, the method of employing selective hydrogenation circulation catalytic distillation desulfurization removes the S-contained substance in petrol and diesel oil in catalytic distillation tower, production sulphur content is not more than state V petrol and diesel oil of 10ppm, technical process is simple, equipment is few, invest little, workable, effectively can solve the problem of oil quality upgrading, promote industrial upgrading, alleviate motor vehicle exhaust pollution on the environment, there is great social effect and economic benefit.
Description
Technical field
The present invention relates to a kind of production technique and equipment of petrol and diesel oil desulfurization, a kind of hydrogen circulation differential catalytic distillation sulfur method and equipment producing super low sulfur state V petrol and diesel oil, belongs to technical field of petrochemical industry specifically.
Background technology
Increasing along with China's automobile, the pollution that motor vehicle exhaust causes is more and more serious, and the oxynitride that standard vehicle petrol and diesel oil subrogate country IV of state V standard at least will realize 10% reduces discharging, the directly discharge of PM2.5 in minimizing tail gas.Therefore production high-quality super low sulfur petrol and diesel oil has become the megatrend that World modernization petroleum refining industry meets day by day harsh environmental regulation.
Catalytic distillation desulfurization technology, be catalyzed reaction desulfurization and fractionation by distillation are coupled in one, desulphurization reaction carries out with distillation simultaneously, thus improves desulfurization degree, realizes the quality upgrading of petrol and diesel oil.Patent of invention CN1429884A, CN1189183A, it is all the desulfurization technology adopting catalytic distillation principle disclosed in US5597476, difference is that feed gasoline is first entered fixed-bed reactor by hydrodesulfurization disclosed in CN1429884A, reacted gasoline enters distillation tower, base product last running finally enters catalytic distillation tower, whole sweetening process is complicated, the reaction that desulphurization reaction experienced by reactor is separated with the conversion in catalytic distillation tower, conversion in catalytic distillation tower is separated and can not promotes that lower boiling sulfide in reactor above transforms to the reaction of higher sulfide, do not realize being coupled completely of desulphurization reaction and fractionation by distillation, the technical superiority performance of catalytic distillation is not enough, and the technology of Dou Shi U.S. CD-Tech disclosed in CN1189183A, US5597476 (predecessor is CR & L) company, catalytic distillation sulfur removal technology disclosed in CN1189183A stock oil is entered a catalytic distillation tower, but high, the low-sulfur content light gasoline fraction of olefin(e) centent also can contact Hydrobon catalyst, add the chance of light gasoline fraction olefins hydrogenation, larger loss of octane number can be caused, it is more complicated that CDHydro/CDHDS two tower catalytic distillation desulfurization technology disclosed in US5597476 also exists device structure in tower, and catalyst inventory is little, handling difficulty, the shortcomings such as complicated operation, not easily adjusts, and thermal load is larger.
Summary of the invention
Instant invention overcomes the deficiency of above-mentioned existing catalytic distillation desulfurization technology, the present invention specifically directly processes stock oils such as the full distillation gasoline of FCC, coker gasoline, diesel oil, the method of employing selective hydrogenation circulation catalytic distillation desulfurization removes the S-contained substance in petrol and diesel oil in catalytic distillation tower, state V petrol and diesel oil (sulphur content is not more than 10ppm) after desulfurization is obtained at the bottom of catalytic distillation tower, the backflow of an overhead light-end part, a part is containing unreacted H
2with the H that reaction generates
2the petroleum naphtha of S, through reducing valve dehydrogenation desulfurization tower, takes off H
2hydrogen after S is delivered at the bottom of catalytic distillation tower through Recycle hydrogen compressor and is carried out recycle, and hydrogen desulfurization tower top obtains lighter hydrocarbons simultaneously.
The invention solves the problem that catalytic distillation tower desulphurization reaction and fractionation by distillation segmentation are carried out, described catalytic distillation tower only need load a kind of catalyst for selectively hydrodesulfurizing, catalyzer is evenly distributed on every layer of column plate, and catalytic unit and mass transfer unit are staggered, and achieves reaction and the differential contacts be separated and coupling, improve reaction conversion ratio and separation efficiency, technical process is simple, and catalyst distribution is even, and utilization ratio is high, facility investment is little, simple to operate.
The invention provides following technical scheme for achieving the above object:
Produce hydrogen circulation differential catalytic distillation sulfur method and the equipment of super low sulfur state V petrol and diesel oil, it is characterized in that being undertaken by following step:
The FCC gasoline or the stock oil such as coker gasoline, diesel oil that carry out catalytic cracking enter catalytic distillation tower middle and upper part after preheater preheats, carry out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower, and reaction generates H
2s, obtain oil (sulphur content the is not more than 10ppm) product of the state V vapour (bavin) after desulfurization at the bottom of catalytic distillation tower, overhead light-end enters catalytic distillation tower top return tank through condensation, and part backflow, a part is containing unreacted H
2with the H that reaction generates
2light vapour (bavin) oil of S, through reducing valve dehydrogenation desulfurization tower, enters at the bottom of hydrogen thionizer tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, and de-H
2hydrogen after S enters overhead condensation tank after Recycle hydrogen compressor, distillates to be back at the bottom of catalytic distillation tower and carries out recycle, obtain light hydrocarbon product simultaneously at the bottom of tank from tank deck.
Wherein catalytic distillation tower operational condition is: working pressure 0.3 ~ 2.5MPa; Service temperature is 100 ~ 350 DEG C; Operating reflux ratio is 0.5 ~ 3.0; Operation air speed 2 ~ 6h
-1.
The more detailed art treatment of the present invention is as follows:
The FCC gasoline or the stock oil such as coker gasoline, diesel oil that carry out catalytic cracking enter catalytic distillation tower (2) middle and upper part after preheater (1) is preheated to 80 ~ 300 DEG C, in tower, differential catalytic distillation desulphurization reaction is carried out with the hydrogen of autocatalysis distillation tower (2) end charging, reaction mainly occurs in differential catalytic rectifying column internals (4), and H is produced in reaction
2s, catalytic distillation tower (2) end, obtains oil (sulphur content the is not more than 10ppm) product of the state V vapour (bavin) after desulfurization, overhead light-end enters catalytic distillation tower top return tank (7) after condenser (6) is condensed to 20 ~ 250 DEG C, and part backflow, a part is containing unreacted H
2with the H that reaction generates
2light vapour (bavin) oil of S, through reducing valve (8) dehydrogenation desulfurization tower (9), enters at the bottom of hydrogen thionizer (9) tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, and de-H
2hydrogen after S enters thionizer top drainer (11) after Recycle hydrogen compressor (10), distillates and is back to the implementation recycle of catalytic distillation tower (2) end, obtain light hydrocarbon product simultaneously at the bottom of tank from tank deck.
Wherein catalytic distillation tower operational condition is: working pressure 0.3 ~ 2.5MPa; Service temperature is 100 ~ 350 DEG C; Operating reflux ratio is 0.5 ~ 3.0; Operation air speed 2 ~ 6h
-1.
In device, catalytic distillation tower (2) comprises stripping section column internals (3), differential catalytic rectifying column plate (4) and rectifying section column internals (5).
In device, stripping section column internals (3) and rectifying section column internals (5) can be filler internals, also can be column plate internals.
Catalytic distillation tower (2) interior differential catalytic rectifying column plate (4) is the core component of this device, as shown in Figure 2.Differential catalytic rectifying column internals (4) are made up of plane differential column plate (15), mass transfer unit (13) and catalytic unit (14).
Catalyzed reaction in differential catalytic rectifying column internals (4) and mass transfer sepn process as follows: the stock oil on plane differential column plate (15) enters gas liquid two-phase flow passage through mass transfer unit (13) from stock oil entrance, be injected on catalytic unit (14) through the collision of gas-liquid separation plate under the effect of mass transfer unit (13), get back on plane differential column plate (15) after the reaction of catalytic unit (14), then under the effect of mass transfer unit (13), incoming stock oil-in is injected on catalytic unit (14) by mass transfer unit (13) lifting, so move in circles, the effect of mass transmitting between gas-liquid is added while improve catalyst utilization, improve sweetening effectiveness.
The present invention is compared with existing sulfur method, and the advantage had is:
(1) achieve the differential contacts of catalyzed reaction and fractionation by distillation and be coupled, catalytic unit and mass transfer unit are staggered, and avoid catalyzed reaction and are separated the segmentation of mass transfer process subregion and carry out, and improve reaction conversion ratio and separation efficiency.
(2) technical process is simple, and catalyst distribution is even, and utilization ratio is high, and facility investment is little, simple to operate, embodies the technological merit of catalytic distillation.
Maximum feature of the present invention is: achieve catalyzed reaction and be coupled with the height of fractionation by distillation, improve the utilization ratio of catalyzer, simplify technical process, the investment of minimizing equipment, reduce operation easier, solve the problem that petrol and diesel oil sulfur-bearing is high, be conducive to the comprehensive quality upgrading accelerating China's petrol and diesel oil.
Accompanying drawing explanation
Fig. 1 is the production process technology schema of hydrogen circulation differential catalytic distillation of the present invention desulfurization
Fig. 2 is differential catalytic rectifying column plate operation operating mode schematic diagram
Wherein 1-preheater, 2-catalytic distillation tower, 3-catalytic distillation tower stripping section internals, 4-differential catalytic rectifying column plate, 5-catalytic distillation tower rectifying section internals, 6-catalytic distillation tower top condenser, 7-catalytic distillation tower top return tank, 8-reducing valve, 9-hydrogen thionizer, 10-hydrogen circulator, 11-desulfurization tower top drainer, 12-tower body; 13-mass transfer unit, 14-catalytic unit, 15-plane differential column plate.
Embodiment
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, these described improvement and change all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.
Embodiment 1
Stock oil is catalytically cracked gasoline, and olefin(e) centent is 36.54 (wt) %, sulphur content 800ppm, is preheated to 260 DEG C and enters catalytic distillation tower, carries out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower.
Catalytic distillation working pressure 2.0MPa, service temperature 250 ~ 300 DEG C, operation air speed 3h
-1, operating reflux ratio 2.0, described catalytic distillation tower stripping section column internals, rectifying section column internals are 3 meters of filler internals, and centre is 30 layers of differential catalytic rectifying column plate.
Product gasoline sulphur content at the bottom of catalytic distillation tower after present invention process process is 9ppm, and research octane number (RON) (RON) loss is 0.5, and chemistry consumption hydrogen is 0.19, and liquid yield reaches 99.5%.
Embodiment 2
Stock oil is coker gasoline, and olefin(e) centent is 40.14 (wt) %, sulphur content 1040ppm, is preheated to 270 DEG C and enters catalytic distillation tower, carries out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower.
Catalytic distillation working pressure 2.2MPa, service temperature 250 ~ 320 DEG C, operation air speed 4h
-1, operating reflux ratio 1.5, described catalytic distillation tower stripping section column internals is 18 layers of valve tray, and rectifying section column internals is 3 meters of filler internals, and centre is 30 layers of differential catalytic rectifying column plate.
Product gasoline sulphur content at the bottom of catalytic distillation tower after present invention process process is 10ppm, and research octane number (RON) (RON) loss is 0.7, and chemistry consumption hydrogen is 0.21, and liquid yield reaches 99.71%.
Embodiment 3
Stock oil is catalytically cracked gasoline, and olefin(e) centent is 33.87 (wt) %, sulphur content 750ppm, is preheated to 250 DEG C and enters catalytic distillation tower, carries out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower.
Catalytic distillation working pressure 2.1MPa, service temperature 250 ~ 320 DEG C, operation air speed 5h
-1, operating reflux ratio 2.5, described catalytic distillation tower stripping section column internals, rectifying section column internals are 18 layers of valve tray, and centre is 30 layers of differential catalytic rectifying column plate.
Product gasoline sulphur content at the bottom of catalytic distillation tower after present invention process process is 8ppm, and research octane number (RON) (RON) loss is 0.9, and chemistry consumption hydrogen is 0.3, and liquid yield reaches 99.40%.
Claims (4)
1. hydrogen circulation differential catalytic distillation sulfur method, it is characterized in that: stock oil enters on the differential catalytic rectifying column plate of catalytic distillation tower middle and upper part after preheater preheats, carry out differential catalytic distillation desulphurization reaction with on differential catalytic rectifying column plate in tower of the hydrogen of autocatalysis base product charging, reaction generates H
2s, after obtaining desulfurization at the bottom of catalytic distillation tower, sulphur content is not more than the state's V vapour/diesel product of 10ppm, and overhead light-end enters catalytic distillation tower top return tank through condensation, and part backflow, a part is containing unreacted H
2with the H that reaction generates
2light vapour/the diesel oil of S, through reducing valve dehydrogenation desulfurization tower, enters at the bottom of hydrogen thionizer tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, and de-H
2hydrogen after S enters overhead condensation tank after Recycle hydrogen compressor, distillates to be back at the bottom of catalytic distillation tower and carries out recycle, obtain light hydrocarbon product simultaneously at the bottom of tank from tank deck; Described catalytic distillation tower comprises stripping section column internals, differential catalytic rectifying column internals and rectifying section column internals, and differential catalytic rectifying column internals are made up of plane differential column plate, mass transfer unit and catalytic unit.
2. method according to claim 1, it is characterized in that: described catalyzed reaction and rectifying separation principle of work are: the stock oil on plane differential column plate enters gas liquid two-phase flow passage through mass transfer unit from stock oil entrance, turning back through the collision of gas-liquid separation plate under the effect of mass transfer unit is injected on catalytic unit, get back on plane differential column plate after the reaction of catalytic unit, then under the effect of mass transfer unit, incoming stock oil-in is injected on catalytic unit by mass transfer unit lifting again, so move in circles, the effect of mass transmitting between gas-liquid is added while improve catalyst utilization, improve reaction conversion ratio and sweetening effectiveness.
3. method according to claim 2, it is characterized in that: achieve the differential contacts of catalyzed reaction and fractionation by distillation and be coupled, catalytic unit and mass transfer unit are staggered, solve the problem that catalyzed reaction and the segmentation of rectifying separation process subregion are carried out, improve reaction conversion ratio and separation efficiency.
4. method according to claim 1, is characterized in that: stripping section column internals and rectifying section column internals can be filler internals, also can be column plate internals.
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Citations (6)
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|---|---|---|---|---|
| CN1412279A (en) * | 2001-10-20 | 2003-04-23 | 中国石化集团齐鲁石油化工公司 | Petroleum hydrocarbon hydrogenation desulfurization catalytic distillation process and its catalytic distillation equipment |
| US7122114B2 (en) * | 2003-07-14 | 2006-10-17 | Christopher Dean | Desulfurization of a naphtha gasoline stream derived from a fluid catalytic cracking unit |
| CN1895715A (en) * | 2006-04-25 | 2007-01-17 | 河北工业大学 | Catalytic rectification tower plate |
| CN101108983A (en) * | 2006-07-19 | 2008-01-23 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
| WO2009097191A1 (en) * | 2008-01-29 | 2009-08-06 | Catalytic Distillation Technologies | Process for desulfurization of cracked naphtha |
| CN102516036A (en) * | 2011-12-14 | 2012-06-27 | 河北工业大学 | Process method for preparing methyl tert-butyl ether by differential reaction rectification and equipment for same |
-
2013
- 2013-12-24 CN CN201310743967.4A patent/CN103773494B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412279A (en) * | 2001-10-20 | 2003-04-23 | 中国石化集团齐鲁石油化工公司 | Petroleum hydrocarbon hydrogenation desulfurization catalytic distillation process and its catalytic distillation equipment |
| US7122114B2 (en) * | 2003-07-14 | 2006-10-17 | Christopher Dean | Desulfurization of a naphtha gasoline stream derived from a fluid catalytic cracking unit |
| CN1895715A (en) * | 2006-04-25 | 2007-01-17 | 河北工业大学 | Catalytic rectification tower plate |
| CN101108983A (en) * | 2006-07-19 | 2008-01-23 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
| WO2009097191A1 (en) * | 2008-01-29 | 2009-08-06 | Catalytic Distillation Technologies | Process for desulfurization of cracked naphtha |
| CN102516036A (en) * | 2011-12-14 | 2012-06-27 | 河北工业大学 | Process method for preparing methyl tert-butyl ether by differential reaction rectification and equipment for same |
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