CN103242904A - Combined process method for hydrorefining - Google Patents
Combined process method for hydrorefining Download PDFInfo
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Abstract
The invention discloses a combined process method for hydrorefining. Full-range FCC gasoline is divided into a light fraction and a heavy fraction; the light fraction is subjected to an alkaline-free deodorization process; the heave fraction is mixed with novel hydrogen heated by a heating furnace after the heat transfer so as to carry out hydrodesulfurization; effluent after the reaction is separated; an obtained liquid is blended with the light fraction after the mercaptan-removing process; an obtained hydrogen-rich gas is used as supplemental hydrogen for diesel hydrorefining; crude diesel, recycle hydrogen and the supplemental hydrogen are mixed and then subjected to hydrodesulfurization; and effluents after hydrogenation are separated to obtain a diesel product. In the method, a flow of passing through the novel hydrogen in onetime is employed in the hydrogenation for the heavy fraction, so that the content of mercaptan sulfur generated by hydrogen sulfide and olefins during a hydrogenation process is decreased; and the heavy fraction of the gasoline is firstly exchanged heat and then mixed with hydrogen in a hydrogen furnace outputted from the heating furnace, so that coke caused by local overheating when the heavy fraction of the gasoline is heated by the heating furnace is slowed down, thereby facilitating prolonging an operation period of the device.
Description
Technical field
The invention belongs to a kind of hydrofining combined technique, the processing method of FCC gasoline hydrogenation and diesel oil hydrofining combination is specifically especially produced the Unionfining technological process of low thioalcohol gasoline.
Technical background
Along with the increasingly stringent of sustainable development and the environmental requirement of world economy, the production of low-sulfur, super low sulfur clean gasoline has been trend of the times.From the formation of China's gasoline pool, the FCC gasoline component accounts for 75% ~ 80%.And the sulphur content of FCC gasoline is the highest to the contribution rate of the sulphur content in China's gasoline usually at 100 ~ 2000 μ g/g, reaches more than 98%.And the raw material of processing along with FCC develops to the heaviness direction, will cause the sulphur content in the FCC gasoline further to increase.Therefore, the epoch of complying with need be produced low-sulfur, super low sulfur clean gasoline, and the FCC gasoline desulfur just becomes the epoch and need produce in the clean gasoline technology gordian technique that must solve.
The processing method of alkene falls in the hydrogenating desulfurization that CN1597865A has proposed inferior patrols such as a kind of full cut FCC gasoline.Under the condition that hydrogen exists and temperature raises step by step, contact three reaction zones of formation with three kinds of catalyzer.First reaction zone removes the diolefin in the gasoline, and second reaction zone use selective desulfurization catalyst removes organic sulfide and part alkene wherein, and the 3rd reaction zone uses gasoline reforming catalyst to improve the octane value of gasoline.This processing method catalyst runs cycle is long, the liquid receipts are high, but the degree of depth of gasoline desulfur is limited.
CN101508908A discloses a kind of production method of ultra-clean gasoline, is a kind of ultra-deep desulfurization-recovery octane value hydrogenation modifying process of FCC gasoline inferior.Concrete steps are: the full distillation gasoline of poor quality is cut into lighting end gasoline and last running gasoline; Making lighting end gasoline and selectivity take off the diene catalyzer props up chain isomerism/aromatization catalyzer with desulfurization-hydro carbons list and contacts; Last running gasoline is contacted with catalyst for selectively hydrodesulfurizing, and reaction effluent contacts with additional desulfurization-hydro carbons higly branched chain hydroisomerization catalyst, then lighting end gasoline and the mixing of last running gasoline is obtained the clean gasoline product.This method is applicable to handles FCC gasoline inferior, and improve the octane value of product and kept high product liquid to receive, but the technology relative complex, device hydrogen consumption is higher, and once investment is all relative higher with process cost.
The disclosed gasoline modifying method of US5399258 is, first section saturated through hydrogenation desulfurization and denitrogenation, hydrogenation of olefins after, the intermediate product that obtains directly enters second section and carries out the octane value recovering reaction.First section temperature of reaction is higher, and is fair with second section temperature of reaction.Because first section temperature of reaction is too high, causes final product to produce a large amount of mercaptan sulfurs, temperature is more high, and the mercaptan sulfur of generation is more many.
CN101492606A provides a kind of FCC gasoline hydrodesulfurizationmethod method that produces the low thioalcohol product.Comprise: the hydrocarbon stream that will comprise sulfide is fed to the catalytic distillation reactor with one or more hydrodesulfurizationreaction reaction zone; Hydrogen is fed to the catalytic distillation reactor; Simultaneously in the catalytic distillation reactor: hydrocarbon stream is fractionated into last running and lighting end; Make hydrogen contact to form H with lighting end
2The lighting end that S and sulphur content are lowered; Recovery is as lighting end, the H of overhead product
2S and hydrogen; Reclaim last running; Overhead product is heated to 500 ℉ ~ 700 ℉; Overhead product and the hydrogen of heating are fed to the high-temperature low-pressure reactor, to form H
2The reaction effluent that S and sulphur content are lowered; Separating reaction effluent, H
2S and unreacted hydrogen are to form light ends fractionation and to comprise H
2The cut of S and hydrogen; The part of light ends fractionation is recycled to the catalytic distillation reactor.This method can effectively reduce the thio-alcohol sulphur in the product gasoline, but the operation more complicated, control is difficult for stable.
At present, in representational FCC desulfurization process of gasoline technology, abroad mainly be the Prime-G+ technology of IFP (IFP) exploitation and the SCANfining technology of Mobil company; Domestic mainly is the RSDS technology of Sinopec Research Institute of Petro-Chemical Engineering (RIPP) and the OCTM-D technology of Fushun Petrochemical Research Institute (FRIPP) exploitation.The common trait of these technology is exactly will concentrate in the last running at FCC gasoline sulfuration owner, sulfide in the lighting end is based on mercaptan, and high-octane olefin component concentrates on the characteristics in the lighting end, be weight two portions by 70 ℃ ~ 100 ℃ cut-points with the gasoline fractionation, last running uses proprietary catalyzer to carry out selective hydrodesulfurization, method mercaptan removal such as alkali-free sweetening are adopted in lighting end, two kinds of cuts are mixed obtaining product gasoline then.These technology can remove the sulphur content in the FCC gasoline effectively, and guarantee that the gasoline octane rating loss is minimum.Investment is big, plant energy consumption is high, running period is short, the shortcoming of mercaptan reorganization but all exist.
In the prior art, the machinery that gasoline hydrogenation and diesel hydrotreating unit are formed, because the diesel oil hydrogenation treatment capacity is often greater than gasoline hydrogenation, diesel oil hydrogenation adopts the hydrogen recycle flow process, and independently make-up hydrogen compressor and circulating hydrogen compressor are set.Gasoline hydrogenation all arranges hydrogen gas compressor, and gasoline stocks oil process furnace is set, and makes gasoline easily cause local superheating to cause that coking phenomenon is serious, can not get running period guaranteeing; And the product stripping tower adopts the reboiler furnace stripping, and facility investment and the working cost of device are higher.
Summary of the invention
At the deficiencies in the prior art, the invention provides the Unionfining technological process of a kind of FCC deep desulfurization of gasoline, production low thioalcohol gasoline.
Unionfining technological process of the present invention may further comprise the steps:
A, the full distillation gasoline of FCC is divided into lighting end gasoline and last running gasoline, the cutting temperature of described lighting end gasoline and last running gasoline is 50 ℃ ~ 80 ℃;
B, step a gained lighting end gasoline carry out alkali-free sweetening, remove the mercaptan compound that contains;
New hydrogen after c, step a gained last running gasoline and the heating is mixed into the gasoline hydrogenation reactor and carries out hydrodesulfurization reaction, reaction effluent enters separator and carries out gas-liquid separation, the gained hydrogen-rich gas after boosting as the hydrogen make-up of diesel oil hydrofining device, the gained liquid phase through behind the stripping and the lighting end gasoline behind the step b gained mercaptan removal mix as the blended gasoline carrying device;
D, diesel raw material and after recycle hydrogen and step c gained hydrogen make-up are mixed, enter the diesel oil hydrogenation reactor together, reaction effluent enters separator and carries out gas-liquid separation, and the gained hydrogen-rich gas recycles after desulfurization, gained liquid is carrying device behind the stripping tower stripping, obtains diesel product.
The cut point of the lighting end gasoline described in the step a and last running gasoline is distributed to determine by the sulphur in the FCC gasoline and olefin(e) centent, is generally 50 ℃ ~ 80 ℃.
Alkali-free sweetening described in the step b is the technology of knowing in this area.Condition as alkali-free sweetening is generally: reactor operating pressure 0.1 ~ 1.0MPa, 20 ℃ ~ 70 ℃ of temperature of reaction, charging air speed 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.Catalyst system therefor and promotor are this area catalyzer commonly used, can select the commercial goods or are prepared according to the knowledge of this area.
Gasoline hydrodesulfurizationmethod reactor described in the step c adopts new hydrogen once to pass through flow process.
The operational condition of the described gasoline hydrogenation reactor of step c is: reaction pressure 1.0 MPa ~ 4.0 MPa, 250 ℃ ~ 300 ℃ of temperature ins of reaction, volume space velocity 2.0h
-1~ 12.0h
-1, hydrogen to oil volume ratio 200: 1 ~ 600: 1, preferred 400: 1 ~ 500: 1.Hydrogen to oil volume ratio suitably increases, and is beneficial to guarantee the hydrogenator temperature in and has certain turndown ratio.
Among the step c, described new hydrogen can enter independent process furnace and heat, and perhaps enters charging process furnace or the heating of its convection zone of diesel oil hydrofining device, controls new hydrogen heater outlet temperature by the bypass of process furnace hydrogen.
The described new hydrogen of step c can directly be sent here by new hydrogen pipe network, or sent here by the outlet of the hydrogen make-up compressor one-level of the described diesel hydrotreating unit of step b, behind gasoline hydrodesulfurizationmethod reactor, gas-liquid separator, the gained hydrogen-rich gas can turn back to the secondary entrance of the hydrogen make-up compressor of diesel oil hydrofining device, again after overdraft as the hydrogen make-up of diesel oil hydrogenation.
The catalyzer that uses in the reactor of gasoline hydrogenation described in the step c adopts catalyst for selectively hydrodesulfurizing.Catalyst for selectively hydrodesulfurizing is carrier with aluminum oxide or siliceous aluminum oxide generally, and reactive metal generally is selected from one or more among W, Mo, Ni and the Co, can also contain conventional auxiliary agent, as among K, Ca, P, Si, F, B, Ti and the Zr one or more.Weight with catalyzer is benchmark, and active metallic content is counted 8.0wt%～20.0wt% with oxide compound, is preferably 10.0wt%～18.0wt%; Auxiliary agent content is 1.0wt%～6.0wt%, is preferably 1.5wt%～5.0wt%.Hydrobon catalyst can be selected existing commercial Hydrobon catalyst, FGH-21, FGH-31 catalyzer as Fushun Petrochemical Research Institute's development, the gasoline hydrogenation catalysts such as RSDS-1 of Beijing Research Institute of Petro-Chemical Engineering development perhaps can be as required be prepared according to the existing method of this area.
The described last running gasoline of step c enters the logistics of the preceding elder generation of hydrogenator and the suitable potential temperature of diesel oil hydrofining device, normally with diesel oil hydrogenation reaction effluent heat exchange to 180 ℃ ~ 230 ℃, preferred 200 ℃ ~ 210 ℃, preventing the diolefine component polymerization coking at high temperature in the last running gasoline, thereby guarantee this interchanger long-term operation.Last running gasoline after the heat exchange is mixed into hydrogenator with the new hydrogen that process furnace heats again.The temperature of hydrogenator parallel feeding realizes by tandem control hydrogen furnace outlet temperature.
Doing of the described diesel raw material of steps d is generally 330 ~ 380 ℃, is generally boiling range and is 170 ℃ ~ 380 ℃ diesel component.Diesel raw material can be one or more in coker gas oil, catalytic diesel oil or the straight-run diesel oil.
The reaction conditions of the described diesel oil hydrogenation reactor of steps d is: reaction pressure 6.0 MPa ~ 18.0 MPa, 230 ℃ ~ 300 ℃ of temperature ins of reaction, volume space velocity 0.2h
-1~ 8.0 h
-1, hydrogen to oil volume ratio 200: 1 ~ 1000: 1.The catalyzer that diesel oil hydrogenation uses can be conventional diesel oil hydrofining catalyst.Conventional diesel oil hydrofining catalyst is active ingredient with VI B family and/or group VIII metal generally, is carrier with aluminum oxide or siliceous aluminum oxide.The group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Weight with catalyzer is benchmark, and the group VIB metal content is counted 8wt% ~ 28wt% with oxide compound, and group VIII metal content is counted 2wt% ~ 15wt% with oxide compound, and its physical properties is as follows: specific surface is 100 ~ 650m
2/ g, pore volume are 0.15 ~ 0.8 mL/g.Can adopt the common hydrofining commercial catalysts of this area, or the grading composition of several suitable catalyzer.As FH-98, FH-DS, the FH-UDS of Fushun Petrochemical Research Institute's development, or Hydrobon catalysts such as RN-10, the RN-1 of the development of Beijing Research Institute of Petro-Chemical Engineering, RN-10B, perhaps the existing method according to this area is prepared.
Compared with prior art, this processing method is united by hydrogenation unit, optimizes technical process, has realized that different material obtains desirable comprehensive process effect under optimum, have the following advantages:
1, by Unionfining technology, adopt the heat supply of the high potential temperature reactant flow of diesel refining device to give the logistics of gasoline refining reaction feed, the coking of having avoided the last running of FCC gasoline to cause because of local superheating when process furnace heats is conducive to the extension fixture cycle of operation.
2, by Unionfining technology, make the heat exchanger network potential temperature coupling between device more reasonable, be conducive to the utilization of the low potential temperature heat of device, thereby reduce the machinery energy consumption.
3, the full cut of FCC gasoline is divided into light gasoline fraction and heavy naphtha by certain cut point, thiophenic sulfur is not entered in the lighting end, the heavy naphtha higher to sulphur content carries out deep desulfuration, guarantees that blend gasoline product sulphur content drops to 5 ~ 50 μ g/g; Simultaneously, the loss of octane number of product gasoline＜2 unit.
4, adopt new hydrogen once by the flow process of gasoline refining reactor, reduced in the prior art hydrogen recycle and used caused H
2S becomes the possibility of mercaptan with the alkene recombination, also be conducive to the desulfurization of gasoline refining reaction depth.
5, adopt hydrogen once by the gasoline refining reactor, cancellation naphtha-treating plant circulating hydrogen compressor and desulphurization of recycle hydrogen system are conducive to reduce plant energy consumption and reduce plant investment.
6, contaminated product technology behind the naphtha-treating plant employing stove has effectively prevented the coking of charging heating furnace tube and reactor head carbon deposit, prolong operating period greatly.
7, technical process of the present invention is short, technology is advanced rationally, advantages such as saving equipment is many, facility investment is few, process cost is low, plant energy consumption is low, the cycle of operation is long, production assurance, for new design or new device have plant investment few, take up an area of few, the plant energy consumption advanced person, product satisfies characteristics such as index; It is low to have an improvement expenses for old plant modification, reduces plant energy consumption, characteristics such as prolong operating period.
Description of drawings
Fig. 1 is Unionfining technological process schematic flow sheet provided by the invention.
Wherein 1 is FCC gasoline, 2 is Cutting Tap, 3 is diesel refining resultant of reaction/gasoline refining reaction raw materials oil heat exchanger, and 4 are the gasoline refining reactor, and 5 is the hydrogen process furnace, 6 is make-up hydrogen compressor, 7 are gasoline refining Reaction Separation device, and 8 is the treated gasoline stripping tower, and 9 is product gasoline, 10 is gas oil, 11 is diesel refining reaction feed process furnace, and 12 is the diesel refining reactor, and 13 is diesel refining Reaction Separation device, 14 is the refined diesel oil stripping tower, 15 is new hydrogen, and 16 for the diesel oil stripping tower ejects material, and 17 eject material for gasoline stripping tower, 18 is refined diesel oil, and 19 is circulating hydrogen compressor.
Embodiment
Below in conjunction with Fig. 1 method provided by the present invention is further detailed:
FCC gasoline 1 enters Cutting Tap 2 and carries out fractionation, obtains light gasoline fraction and heavy naphtha.Wherein heavy naphtha is warmed up to about 200 ℃ through diesel refining resultant of reaction/gasoline refining reaction raw materials oil heat exchanger 3 heat exchange, be mixed into gasoline refining reactor 4 with the new hydrogen that exports out and heat to after 350 ℃ ~ 550 ℃ through hydrogen process furnace 5 from make-up hydrogen compressor 6 one-levels compressions, carry out reactions such as desulfurization, diolefine be saturated.Reaction effluent enters gasoline refining Reaction Separation device 7 after the heat exchange cooling, the gas phase hydrogen-rich gas after the separation removes the secondary entrance of make-up hydrogen compressor 6; Liquid phase after the separation goes treated gasoline stripping tower 8 to carry out stripping, removes H wherein
2S and lighter hydrocarbons mix as gasoline products 9 carrying devices with the light gasoline fraction of Cutting Tap cat head through alkali cleaning then.
After heating up, the mixed hydrogen mixed heat transfer of sending here with make-up hydrogen compressor 6 and circulating hydrogen compressor 19 after gas oil 10 heat exchange heat up enters diesel refining reaction feed process furnace 11, enter diesel refining reactor 12 after heating to 230 ℃ ~ 300 ℃, carry out reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrogenation are saturated.Reaction effluent enters diesel refining Reaction Separation device 13 and carries out gas-liquid separation after diesel refining resultant of reaction/gasoline refining reaction raw materials oil heat exchanger 3 heat exchange, cooling, the desulfurization of isolated gas phase hydrogen-rich gas is used by circulating hydrogen compressor 19 compression cycle; Isolated liquid phase enters refined diesel oil stripping tower 14 and carries out stripping tower, obtains refined diesel oil 18 carrying devices from refined diesel oil stripping tower 14.
Embodiment 1 ~ 4
Certain refinery's 600,000 tons of/year FCC gasoline hydrofinishings device and 2,500,000 tons of/year catalytic cracking diesel oil hydro-refining units are formed machinery.
The full distillation gasoline of FCC is divided into light gasoline fraction and heavy naphtha through filtering, entering Cutting Tap after the heat exchange intensification step by step.Heavy naphtha boost back and the reaction effluent heat exchange to 200 of the suitable potential temperature of diesel refining device ℃, send here with make-up hydrogen compressor and to be heated to 510 ℃ hydrogen through the hydrogen process furnace and to be mixed into the gasoline hydrofinishing reactor and to carry out chemical reactions such as desulfurization, reaction effluent enters the reaction product separator through heat exchange, after being cooled to about 40 ℃, separate to obtain hydrogen-rich gas and be sent to make-up hydrogen compressor secondary entrance and divide flow container, after boosting, be sent to the diesel refining device; Separate the liquid phase that obtains and enter the product stripping tower, obtain overhead gas at the stripping tower cat head, extract treated gasoline out at the bottom of the stripping Tata, stripping tower adopts the reboiler stripping, and its thermal source is provided by the diesel oil of the suitable potential temperature of machinery diesel refining device.Treated gasoline behind stripping mixes as gasoline blend component carrying device with the light gasoline fraction of process alkali-free sweetening.
Mix with mixed hydrogen the catalytic cracking gas oil heat exchange back of heating up, and enters the diesel refining reactor through heat exchange, after heating to 325 ℃, carries out reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrogenation are saturated.Reaction effluent enters diesel refining Reaction Separation device and carries out gas-liquid separation after heat exchange, cooling, the desulfurization of isolated gas phase hydrogen-rich gas is used by compression cycle; Isolated liquid phase obtains the refined diesel oil carrying device behind stripping.
Adopt the diesel oil hydrogenation reaction effluent to be warmed up to about 200 ℃ for the heat exchange of gasoline hydrogenation stock oil in this machinery, gasoline hydrogenation device hydrogen and diesel oil hydrogenation charging share a process furnace, and the hydrogen make-up of gasoline hydrogenation is drawn by the outlet of make-up hydrogen compressor one-level.
Adopt above-mentioned technical process.Wherein alkali-free sweetening adopts the alkali-free sweetening II type technology of Chinese Petroleum Univ.'s exploitation, and catalyzer is the AFS-12 prefabrication type catalyzer of Chinese Petroleum Univ.'s research and development.The gasoline hydrodesulfurizationmethod catalyzer is FGH-21, the FGH-31 hydrogenation catalyst of Fushun Petrochemical Research Institute's development and production.
FCC raw gasline cutting and separating in Cutting Tap, the cutting temperature of lighting end and last running is 75 ℃, obtains lighting end and last running.Lighting end enters the alkali-free sweetening unit, removes mercaptan sulfur.Heavy naphtha is through hydrogenating desulfurization, and treated gasoline and alkali-free sweetening lighting end gasoline mix as the product gasoline carrying device.FCC raw gasline character sees Table 1; The processing condition of alkali-free sweetening condition see Table 2; The processing condition of heavy naphtha hydrogenating desulfurization see Table 3; Product gasoline character sees Table 4.
Table 1 FCC raw gasline character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Stock oil 1 | Stock oil 2 | Stock oil 3 | Stock oil 4 |
| Density (20 ℃), g/cm 3 | 0.7344 | 0.7236 | 0.7300 | 0.7317 |
| Sulphur content, μ g/g | 480 | 580 | 900 | 1150 |
| Mercaptan sulfur, μ g/g | 53 | 78 | 88 | 96 |
| Alkene, v% | 27.3 | 34.4 | 43.5 | 33.0 |
| RON | 93.6 | 93.3 | 92 | 94.5 |
| Boiling range (D 86), ℃ | ? | ? | ? | ? |
| IBP/10% | 23/44 | 27/47 | 42/56 | 32/51 |
| 30%/50% | 68/99 | 64/92 | 68/97 | 67/101 |
| 70%/90% | 136/172 | 130/163 | 131/163 | 140/176 |
| 95%/ FBP | 186/191 | 177/188 | 185/193 | 187/201 |
Table 2 alkali-free sweetening processing condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Lighting end gasoline | Lighting end gasoline | Lighting end gasoline | Lighting end gasoline |
| Catalyzer | AFS-12 | AFS-12 | AFS-12 | AFS-12 |
| Temperature, ℃ | 40 | 40 | 45 | 50 |
| Pressure, MPa | 0.6 | 0.6 | 0.7 | 0.7 |
| Volume space velocity, h -1 | 2.0 | 2.0 | 1.8 | 1.8 |
| Gas/oil ratio, v/v | 0.7 | 0.7 | 0.85 | 0.85 |
Table 3 hydrogenating desulfurization cell process condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Last running gasoline | Last running gasoline | Last running gasoline | Last running gasoline |
| Catalyzer | FGH-21 | FGH-21 | FGH-21/FGH-31 | FGH-31 |
| Temperature of reaction, ℃ | 265 | 265 | 260 | 255 |
| The hydrogen dividing potential drop, MPa | 1.8 | 1.8 | 1.6 | 1.6 |
| Volume space velocity, h -1 | 3.0 | 3.0 | 2.5 | 2.5 |
| Hydrogen-oil ratio (always), v/v | 420 | 420 | 400 | 400 |
Table 4 product gasoline character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Density (20 ℃), g/cm 3 | 0.7257 | 0.7200 | 0.7216 | 0.7243 |
| Sulphur content, μ g/g | 9 | 10 | 8 | 8 |
| Mercaptan sulfur, μ g/g | <5 | <5 | <5 | <5 |
| RON | 92.5 | 91.9 | 90.3 | 92.4 |
| Boiling range (D 86), ℃ | ? | ? | ? | ? |
| IBP/10% | 40/64 | 33/54 | 45/63 | 41/65 |
| 30%/50% | 86/116 | 75/105 | 78/113 | 84/117 |
| 70%/90% | 138/175 | 132/168 | 139/179 | 143/179 |
| 95%/ FBP | 188/199 | 178/190 | 191/200 | 191/206 |
The diesel oil hydrogenation catalyzer adopts 3936 or FH-UDS hydrogenation catalyst of Fushun Petrochemical Research Institute's development, and diesel oil carries out reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrogenation are saturated in the refining reaction device.The character of diesel raw material sees Table 5; The hydrorefined operational condition of catalytic cracking diesel oil sees Table 6, and the refined diesel oil product property sees Table 7.
Table 5 diesel raw material character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Catalytic diesel oil | Coker gas oil | Urge bavin/burnt bavin=86/14 | Urge bavin/burnt bavin=90/10 |
| Density (20 ℃) g/cm 3 | 0.8549 | 0.8159 | 0.8506 | 0.8517 |
| Boiling range, ℃ | ? | ? | ? | ? |
| IBP/10% | 170/200 | 162/212 | 172/204 | 169/202 |
| 30%/50% | 221/252 | 244/273 | 228/261 | 224/259 |
| 70%/90% | 301/352 | 300/328 | 300/349 | 301/350 |
| 95%/EBP | 371/378 | 338/347 | 368/374 | 370/376 |
| Existent gum, mg/100mL | 245 | 62.4 | 229 | 237 |
| Cetane value | 39.4 | 47 | 39.9 | 39.7 |
| S/N，μg/g | 800/836 | 1130/968 | 945/845 | 978/832 |
Table 6 diesel oil hydrofining operational condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Catalytic diesel oil | Coker gas oil | Urge bavin/burnt bavin=86/14 | Urge bavin/burnt bavin=90/10 |
| Catalyzer | 3936 | FH-UDS | FH-UDS | FH-UDS |
| Temperature of reaction, ℃ | 330 | 350 | 350 | 350 |
| Reaction pressure, MPa | 6.5 | 6.8 | 6.8 | 6.8 |
| Volume space velocity, h-1 | 0.8 | 1.54 | 1.54 | 1.54 |
| Hydrogen-oil ratio (always), v/v | 700 | 360 | 360 | 360 |
Table 7 refined diesel oil product property
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Density (20 ℃ of) ㎏/m 3 | 847 | 801 | 840 | 841 |
| Sulphur, μ g/g | 15 | 50 | 50 | 50 |
| Cetane value | 52.6 | 51 | 53 | 53.2 |
| Boiling range, ℃ | ? | ? | ? | ? |
| IBP/10% | 187/214 | 167/214 | 237（5%）/246 | 185/212 |
| 30%/50% | 231/258 | 229/255 | 271/280 | 230/261 |
| 70%/90% | 296/320 | 289/315 | 312/336 | 302/324 |
| 95%EBP | 354/362 | 335/345 | 355/365 | 356/365 |
Produce gasoline and the diesel product of equal quality with same materials, the present invention compared with prior art, machinery of the present invention has reduced the naphtha-treating plant circulating hydrogen compressor, adopt hydrogen once by the gasoline refining reactor, the technology of contaminated product behind the hydrogen heating-furnace, and utilize the refining stock oil heat exchange of reaction effluent gasoline feed of the high potential temperature of machinery diesel refining to heat up.Under the prerequisite that obtains same hydrofining result, saved the one-time investment of device, reduce plant energy consumption, and prolonged the cycle of operation of device.
Claims (11)
1. hydrofining combined technique may further comprise the steps:
A, the full distillation gasoline of FCC is divided into lighting end gasoline and last running gasoline, the cutting temperature of described lighting end gasoline and last running gasoline is 50 ℃ ~ 80 ℃;
B, step a gained lighting end gasoline carry out alkali-free sweetening, remove the mercaptan compound that contains;
C, step a gained last running gasoline are mixed into the gasoline hydrogenation reactor with new hydrogen and carry out hydrodesulfurization reaction, reaction effluent enters separator and carries out gas-liquid separation, the gained hydrogen-rich gas after boosting as the hydrogen make-up of diesel oil hydrofining device, the gained liquid phase through behind the stripping and the lighting end gasoline behind the step b gained mercaptan removal mix as the blended gasoline carrying device;
D, diesel raw material and after recycle hydrogen and step c gained hydrogen make-up are mixed, enter the diesel oil hydrogenation reactor together, reaction effluent enters separator and carries out gas-liquid separation, and the gained hydrogen-rich gas recycles after desulfurization, gained liquid is carrying device behind the stripping tower stripping, obtains diesel product.
2. in accordance with the method for claim 1, it is characterized in that, gasoline hydrodesulfurizationmethod reactor described in the step c adopts new hydrogen once by flow process, and last running gasoline mixes after carrying out the heat exchange intensification with the diesel oil hydrogenation effluent earlier again with through the new hydrogen after the process furnace heating.
3. in accordance with the method for claim 1, it is characterized in that the operational condition of the described gasoline hydrogenation reactor of step c is: reaction pressure 1.0 MPa ~ 4.0 MPa, 250 ℃ ~ 300 ℃ of temperature ins of reaction, volume space velocity 2.0h
-1~ 12.0h
-1With hydrogen to oil volume ratio 200: 1 ~ 600: 1.
4. in accordance with the method for claim 2, it is characterized in that, the described new hydrogen of step c enters independent process furnace and heats, and perhaps new hydrogen enters charging process furnace or the heating of its convection zone of diesel oil hydrofining device, controls new hydrogen heater outlet temperature by the bypass of process furnace hydrogen.
5. in accordance with the method for claim 1, it is characterized in that the described new hydrogen of step c is directly sent here by the hydrogen pipe network, or sent here by the hydrogen make-up compressor one-level outlet of the described diesel hydrotreating unit of step b.
6. in accordance with the method for claim 1, it is characterized in that step c) gained hydrogen-rich gas returns the secondary entrance of the hydrogen make-up compressor of diesel oil hydrofining device, after overdraft as the hydrogen make-up of diesel oil hydrogenation.
7. in accordance with the method for claim 1, it is characterized in that, the catalyst for selectively hydrodesulfurizing that uses in the reactor of gasoline hydrogenation described in the step c is carrier with aluminum oxide or siliceous aluminum oxide, reactive metal is selected from one or more among W, Mo, Ni and the Co, also contains among K, Ca, P, Si, F, B, Ti and the Zr one or more as auxiliary agent; Weight with catalyzer is benchmark, and active metallic content is counted 8.0wt%～20.0wt% with oxide compound, and auxiliary agent content is 1.0wt%～6.0wt%.
8. in accordance with the method for claim 1, it is characterized in that, the described last running gasoline of step c before mixing with new hydrogen earlier and diesel oil hydrogenation reaction effluent heat exchange to 180 ℃～230 ℃.
9. in accordance with the method for claim 1, it is characterized in that doing of the described diesel raw material of steps d is 330～380 ℃.
10. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the described diesel oil hydrogenation reactor of steps d is: reaction pressure 6.0 MPa ~ 18.0 MPa, 270 ℃ ~ 400 ℃ of temperature ins of reaction, volume space velocity 0.2h
-1~ 8.0 h
-1With hydrogen to oil volume ratio 200: 1 ~ 1000: 1.
11. in accordance with the method for claim 1, it is characterized in that diesel oil hydrofining catalyst is active ingredient with VI B family and/or group VIII metal, is carrier with aluminum oxide or siliceous aluminum oxide; Weight with catalyzer is benchmark, and the group VIB metal content is counted 8wt% ~ 28wt% with oxide compound, and group VIII metal content is counted 2wt% ~ 15wt% with oxide compound, and its physical properties is as follows: specific surface is 100 ~ 650m
2/ g, pore volume are 0.15 ~ 0.8 mL/g.
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| US6334948B1 (en) * | 1998-11-18 | 2002-01-01 | Institut Francais Du Petrole | Process for producing gasoline with a low sulphur content |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
| CN101307255A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101724455A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Combined hydrogenation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334948B1 (en) * | 1998-11-18 | 2002-01-01 | Institut Francais Du Petrole | Process for producing gasoline with a low sulphur content |
| CN1465668A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline |
| CN101307255A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101724455A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Combined hydrogenation method |
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| CN111019696A (en) * | 2018-10-09 | 2020-04-17 | 中石化广州工程有限公司 | Hydrotreater |
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