CN103773494A - Production process and equipment of hydrogen circulation differential catalyst distillation and desulfuration - Google Patents
Production process and equipment of hydrogen circulation differential catalyst distillation and desulfuration Download PDFInfo
- Publication number
- CN103773494A CN103773494A CN201310743967.4A CN201310743967A CN103773494A CN 103773494 A CN103773494 A CN 103773494A CN 201310743967 A CN201310743967 A CN 201310743967A CN 103773494 A CN103773494 A CN 103773494A
- Authority
- CN
- China
- Prior art keywords
- catalytic
- differential
- catalytic distillation
- tower
- mass transfer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a hydrogen circulation differential catalyst distillation and desulfuration method and equipment for producing ultra-low sulphur national-V naphtha and diesel oil. Particularly, by using FCC (Fluid Catalytic Cracking) full-fraction gasoline, coker gasoline or diesel as raw material oils, and adopting a selective hydrogenation circulation catalyst distillation method, a sulphur-containing substance in the naphtha and diesel oil is removed in a catalyst distillation tower, and the national-V naphtha and diesel oil with the sulphur content of not more than 10 ppm is produced. The hydrogen circulation differential catalyst distillation and desulfuration method is simple in process, less in equipment, small in investment, and strong in maneuverability, and is capable of effectively solving the problem of quality upgrading and rebuilding of an oil product, promoting industrial upgrading, and lightening the pollution of automobile exhaust emission to the environment, thereby being important in social meaning 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 of producing super low sulfur state V petrol and diesel oil, belongs to petrochemical technology field specifically.
Background technology
Increasing along with China's automobile, the pollution that motor vehicle exhaust causes is more and more serious, and state's V standard vehicle reduces discharging by petrol and diesel oil subrogate country IV standard the oxynitride of at least realizing 10%, directly reduces the discharge of PM2.5 in tail gas.Therefore production high-quality super low sulfur petrol and diesel oil has become World modernization petroleum refining industry and has met a megatrend of the environmental regulation of harshness day by day.
Catalytic distillation desulfurization technology, is that catalyzed reaction desulfurization and fractionation by distillation are coupled in to one, and desulphurization reaction carries out with distillation simultaneously, thereby improves desulfurization degree, realizes the quality upgrading of petrol and diesel oil.Patent of invention CN1429884A, CN1189183A, US5597476 is disclosed is all the desulfurization technology that adopts catalytic distillation principle, difference is that the disclosed hydrodesulfurization of CN1429884A first enters feed gasoline fixed-bed reactor, reacted gasoline enters distillation tower, base product last running finally enters catalytic distillation tower, whole sweetening process complexity, desulphurization reaction has experienced the reaction in reactor and has separated with the conversion in catalytic distillation tower, conversion in catalytic distillation tower separates and can not promote that the interior lower boiling sulfide of reactor transforms to the reaction of higher sulfide above, do not realize the coupling completely of desulphurization reaction and fractionation by distillation, the technical superiority performance of catalytic distillation is not enough, and the technology of the disclosed Dou Shi U.S. CD-Tech of CN1189183A, US5597476 (predecessor is CR & L) company, the disclosed catalytic distillation sulfur removal technology of CN1189183A is that stock oil is entered to a catalytic distillation tower, but high, the low-sulfur content light gasoline fraction of olefin(e) centent also can contact Hydrobon catalyst, the chance that has increased light gasoline fraction olefins hydrogenation, can cause larger loss of octane number, the disclosed CDHydro/CDHDS two tower catalytic distillation desulfurization technologies of US5597476 exist the shortcomings such as the interior device structure of tower is more complicated, and catalyst inventory is little, and handling are difficult, and complicated operation is difficult for adjusting, and thermal load is larger.
Summary of the invention
The present invention has overcome 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, adopt the method for selective hydrogenation circulation catalytic distillation desulfurization in catalytic distillation tower, to remove the S-contained substance in petrol and diesel oil, at the bottom of catalytic distillation tower, obtain the state's V petrol and diesel oil (sulphur content is not more than 10ppm) after desulfurization, an overhead light-end part refluxes, and a part is containing unreacted H
2h with reaction generation
2the petroleum naphtha of S, through reducing valve dehydrogenation desulfurization tower, is taken off H
2hydrogen after S is carried out recycle at the bottom of Recycle hydrogen compressor is delivered to catalytic distillation tower, 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 has realized reaction and the differential contact and the coupling that separate, reaction conversion ratio and separation efficiency are improved, technical process is simple, and catalyst distribution is even, and utilization ratio is high, facility investment is little, simple to operate.
The invention provides for achieving the above object following technical scheme:
Hydrogen circulation differential catalytic distillation sulfur method and an equipment of producing super low sulfur state V petrol and diesel oil, is characterized in that being undertaken by following step:
The stock oil such as FCC gasoline or coker gasoline, diesel oil that carrys out catalytic cracking enters catalytic distillation tower middle and upper part after preheater preheating, carries out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower, and reaction generates H
2s, obtains state's V vapour (bavin) oil (sulphur content the is not more than 10ppm) product after desulfurization at the bottom of catalytic distillation tower, overhead light-end enters catalytic distillation tower top return tank through condensation, and a part refluxes, and a part is containing unreacted H
2h with reaction generation
2light vapour (bavin) oil of S, through reducing valve dehydrogenation desulfurization tower, at the bottom of entering hydrogen thionizer tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, takes off H
2hydrogen after S enters overhead condensation tank after Recycle hydrogen compressor, distillates at the bottom of being back to catalytic distillation tower and carries out recycle from tank deck, simultaneously at the bottom of tank, obtains light hydrocarbon product.
Wherein catalytic distillation tower operational condition is: working pressure 0.3～2.5MPa; Service temperature is 100～350 ℃; 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 stock oil such as FCC gasoline or coker gasoline, diesel oil that carrys out catalytic cracking enters catalytic distillation tower (2) middle and upper part after preheater (1) is preheated to 80～300 ℃, in tower, carry out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis distillation tower (2) end charging, it is upper that reaction mainly occurs in differential catalytic rectifying column internals (4), and H is produced in reaction
2s, catalytic distillation tower (2) end, obtains state's V vapour (bavin) oil (sulphur content the is not more than 10ppm) product after desulfurization, overhead light-end enters catalytic distillation tower top return tank (7) after condenser (6) is condensed to 20～250 ℃, and a part refluxes, and a part is containing unreacted H
2h with reaction generation
2light vapour (bavin) oil of S, through reducing valve (8) dehydrogenation desulfurization tower (9), at the bottom of entering hydrogen thionizer (9) tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, takes off 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 from tank deck, obtains light hydrocarbon product at the bottom of tank simultaneously.
Wherein catalytic distillation tower operational condition is: working pressure 0.3～2.5MPa; Service temperature is 100～350 ℃; Operating reflux ratio is 0.5～3.0; Operation air speed 2～6h
-1.
Catalytic distillation tower in device (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, can be also 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 and mass transfer sepn process in differential catalytic rectifying column internals (4) are as follows: the stock oil on plane differential column plate (15) enters the mobile passage of gas-liquid two-phase through mass transfer unit (13) from stock oil entrance, under the effect of mass transfer unit (13), be injected on catalytic unit (14) through the collision of gas-liquid separation plate, after the reaction of catalytic unit (14), get back on plane differential column plate (15), then under the effect of mass transfer unit (13), incoming stock oil-in is promoted and is injected on catalytic unit (14) by mass transfer unit (13), so move in circles, when having improved catalyst utilization, increase the effect of mass transmitting between gas-liquid, improve sweetening effectiveness.
The present invention is compared with existing sulfur method, and the advantage having is:
(1) realized catalyzed reaction and contacted and be coupled with the differential of fractionation by distillation, catalytic unit and mass transfer unit are staggered, and have avoided catalyzed reaction and have separated the segmentation of mass transfer process subregion and carry out, and have improved 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, has embodied the technological merit of catalytic distillation.
Maximum feature of the present invention is: realized the height coupling of catalyzed reaction and fractionation by distillation, improve the utilization ratio of catalyzer, simplify technical process, the investment of minimizing equipment, reduce operation easier, solve the high problem of petrol and diesel oil sulfur-bearing, be conducive to accelerate comprehensive quality upgrading of 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 variation 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) %, and sulphur content 800ppm, is preheated to 260 ℃ 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, 250～300 ℃ of service temperatures, 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.
At the bottom of catalytic distillation tower after art breading of the present invention, product gasoline sulphur content 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) %, and sulphur content 1040ppm, is preheated to 270 ℃ 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, 250～320 ℃ of service temperatures, 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.
At the bottom of catalytic distillation tower after art breading of the present invention, product gasoline sulphur content 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) %, and sulphur content 750ppm, is preheated to 250 ℃ 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, 250～320 ℃ of service temperatures, 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.
At the bottom of catalytic distillation tower after art breading of the present invention, product gasoline sulphur content 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 (7)
1. hydrogen circulation differential catalytic distillation sulfur method and equipment, is characterized in that:
Stock oil enters catalytic distillation tower middle and upper part after preheater preheating, carries out differential catalytic distillation desulphurization reaction with the hydrogen of autocatalysis base product charging in tower, and reaction generates H
2s, obtains state's V vapour (bavin) oil (sulphur content the is not more than 10ppm) product after desulfurization at the bottom of catalytic distillation tower, overhead light-end enters catalytic distillation tower top return tank through condensation, and a part refluxes, and a part is containing unreacted H
2h with reaction generation
2light vapour (bavin) oil of S, through reducing valve dehydrogenation desulfurization tower, at the bottom of entering hydrogen thionizer tower, with the poor amine liquid counter current contact adsorption desulfurize from tower top charging, takes off H
2hydrogen after S enters overhead condensation tank after Recycle hydrogen compressor, distillates at the bottom of being back to catalytic distillation tower and carries out recycle from tank deck, simultaneously at the bottom of tank, obtains light hydrocarbon product.
2. sulfur method according to claim 1 and equipment, wherein catalytic distillation tower operational condition is: working pressure 0.3～2.5MPa; Service temperature is 100～350 ℃; Operating reflux ratio is 0.5～3.0; Operation air speed 2～6h
-1.
3. comprise stripping section column internals, differential catalytic rectifying column internals and rectifying section column internals according to the catalytic distillation tower described in claim 1 and 2.
4. stripping section column internals according to claim 3 and rectifying section column internals can be filler internals, can be also column plate internals.
5. differential catalytic rectifying column internals according to claim 3 are made up of plane differential column plate, mass transfer unit and catalytic unit.
6. differential catalytic rectifying column internals according to claim 5, it is characterized in that described catalyzed reaction and mass transfer sepn process are: the stock oil on plane differential column plate enters the mobile passage of gas-liquid two-phase through mass transfer unit from stock oil entrance, under the effect of mass transfer unit, be injected on catalytic unit through the collision of gas-liquid separation plate, after the reaction of catalytic unit, get back on plane differential column plate, then under the effect of mass transfer unit, incoming stock oil-in is promoted and is injected on catalytic unit by mass transfer unit (13), so move in circles, when having improved catalyst utilization, increase the effect of mass transmitting between gas-liquid, improve sweetening effectiveness.
7. according to sulfur method and equipment described in claim 1-6, having it is characterized in that realizing catalyzed reaction contacts and is coupled with the differential of fractionation by distillation, catalytic unit and mass transfer unit are staggered, avoid catalyzed reaction and separated the segmentation of mass transfer process subregion and carry out, improved reaction conversion ratio and separation efficiency.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310743967.4A CN103773494B (en) | 2013-12-24 | 2013-12-24 | The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310743967.4A CN103773494B (en) | 2013-12-24 | 2013-12-24 | The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103773494A true CN103773494A (en) | 2014-05-07 |
| CN103773494B CN103773494B (en) | 2016-01-20 |
Family
ID=50566262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310743967.4A Expired - Fee Related CN103773494B (en) | 2013-12-24 | 2013-12-24 | The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103773494B (en) |
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 |
-
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103773494B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101787307B (en) | Gasoline hydrodesulfurization method | |
| CN101921611B (en) | Catalytic cracking method and system for reducing sulphur content of petrol | |
| CN101313053A (en) | Selective naphtha hydrodesulfurization with high temperature mercaptan decomposition | |
| CN101492609A (en) | Method for deep desulfurization olefin hydrocarbon reduction of gasoline | |
| CN102337153B (en) | Hydrotreatment method of gasoline distillate oil | |
| CN106147839B (en) | A kind of method for reducing content of sulfur in gasoline | |
| CN112662427B (en) | Gasoline fraction desulfurization method, method for producing low-sulfur gasoline and reaction system | |
| CN1176189C (en) | Catalytic conversion method and apparatus for upgrading poor gasoline | |
| CN101294108B (en) | Combination method of catalytic cracking production separation and hydrogen refining | |
| CN102443432A (en) | Method for producing low-sulfur gasoline by non-hydroforming sulfur and alcohol removal | |
| CN103540359B (en) | A kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and yield of gasoline | |
| CN102533321A (en) | Catalytic conversion method and device for reducing sulphur content in gasoline | |
| CN103059946B (en) | Low-energy consumption catalytic gasoline hydrodesulfurizationmethod method | |
| CN102443433A (en) | Method for producing low-sulfur gasoline | |
| CN101993725A (en) | Method for producing low-sulfur gasoline | |
| CN201154953Y (en) | System for preparing high quality gasoline by catalytic hydrocarbon recombination | |
| CN1204231C (en) | Desulfurization process of gasoline | |
| CN103540356B (en) | A kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and diesel yield | |
| CN103773494B (en) | The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment | |
| CN104726132A (en) | Process For The Hydrodesulphurization Of Hydrocarbon Cuts | |
| CN101492610A (en) | Method for deep desulfurization olefin hydrocarbon reduction of gasoline | |
| CN103450935B (en) | A kind of method of producing super low-sulfur oil | |
| CN103059965B (en) | Catalytic gasoline deep hydrodesulfurizationmethod method | |
| CN1171977C (en) | Method and device for reducing olefine in gasoline | |
| CN101429442A (en) | System and method for catalyzing hydrocarbon for recombinant production of high-quality gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 300308 1114, Hua Ying building, Central Avenue, Airport Economic Zone, Tianjin Binhai New Area Applicant after: Tianjin Hao Yong chemical engineering company limited Address before: 300308 1114, Hua Ying building, Central Avenue, Airport Economic Zone, Tianjin Binhai New Area Applicant before: Tianjin Haoyong Chemical Technology Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20171224 |