CN103242904B - A kind of hydrofining combined technique - Google Patents
A kind of hydrofining combined technique Download PDFInfo
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Abstract
The invention discloses a kind of hydrofining combined technique.The full distillation gasoline of FCC is divided into lighting end and last running, alkali-free sweetening is carried out in lighting end, hydrogenating desulfurization is carried out after last running heat exchange and after the new hydrogen mixing of process furnace heating, separating reaction effluent, lighting end after gained liquid and mercaptan removal is in harmonious proportion, and gained hydrogen-rich gas is as the hydrogen make-up of diesel oil hydrofining; Carry out hydrogenating desulfurization after the mixing of gas oil, recycle hydrogen and hydrogen make-up, hydrogenation effluent carries out separation and obtains diesel product.In the inventive method, heavy fractioning hydrogenation adopts new hydrogen once by flow process, decreases the content of the mercaptan sulfur that hydrogen sulfide and alkene generate in hydrogenation process; The first heat exchange of last running gasoline again with process furnace hydrogen furnace out after contaminated product, slow down the gasoline last running coking that local superheating causes when process furnace heats, thus be conducive to the extension fixture cycle of operation.
Description
Technical field
The invention belongs to a kind of hydrofining combined technique, the processing method of specifically FCC gasoline hydrogenation and diesel oil hydrofining combination, especially produces the Unionfining technological process of low thioalcohol gasoline.
Technical background
Along with the sustainable development of world economy and the increasingly stringent of environmental requirement, the production of low-sulfur, super low sulfur clean gasoline has been trend of the times.From the formation of China's gasoline pool, FCC gasoline component accounts for 75% ~ 80%.And the sulphur content of FCC gasoline is usually at 100 ~ 2000 μ g/g, the highest to the contribution rate of the sulphur content in China's gasoline, reach more than 98%.And, along with the raw material of FCC processing is to heaviness future development, increase causing the sulphur content in FCC gasoline further.Therefore, the epoch of complying with need to produce low-sulfur, super low sulfur clean gasoline, and FCC gasoline desulfurization just becomes the epoch to be needed to produce the gordian technique that must solve in clean gasoline technology.
CN1597865A proposes the processing method of the hydrogenating desulfurization Olefin decrease of the inferior patrols such as a kind of full cut FCC gasoline.Under the condition that hydrogen exists and temperature raises step by step, form three reaction zones with three kinds of catalyst exposure.First reaction zone removes the diolefin in gasoline, and second reaction zone uses selective desulfurization catalyst to remove organic sulfide wherein and some olefin, and the 3rd reaction zone uses gasoline reforming catalyst to improve the octane value of gasoline.This processing method catalyst runs cycle is long, 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: complete for poor quality distillation gasoline is cut into lighting end gasoline and last running gasoline; Lighting end gasoline and selectivity is made to take off diene catalyzer and desulfurization-hydro carbons list branched chain isomer/aromatization catalyst exposure; Last running gasoline is contacted with catalyst for selectively hydrodesulfurizing, and reaction effluent contacts with supplementary desulfurization-hydro carbons higly branched chain hydroisomerization catalyst, then lighting end gasoline and last running gasoline is mixed to get clean gasoline product.The method is applicable to process FCC gasoline inferior, improves the octane value of product and maintains higher product liquid and receive, but technique relative complex, and device hydrogen consumption is higher, once investment and process cost all relatively high.
Disclosed in US5399258, gasoline modifying method is, first paragraph is after hydrogenation desulfurization and denitrogenation, olefins hydrogenation, and the intermediate product obtained directly enters second segment and carries out octane value recovering reaction.The temperature of reaction of first paragraph is higher, maintains an equal level with the temperature of reaction of second segment.Because the temperature of reaction of first paragraph is too high, cause final product to produce a large amount of mercaptan sulfur, temperature is higher, and the mercaptan sulfur of generation is more.
CN101492606A provides a kind of FCC gasoline hydrodesulfurizationprocess process producing low thioalcohol product.Comprise: the hydrocarbon stream comprising sulfide is fed to the catalytic distillation reactor with one or more hydrodesulfurizationreaction reaction zone; Hydrogen is fed to catalytic distillation reactor; Simultaneously in catalytic distillation reactor: hydrocarbon stream is fractionated into last running and lighting end; Hydrogen is made to contact to form H with lighting end
2the lighting end that S and sulphur content are lowered; Reclaim as the lighting end of overhead product, H
2s and hydrogen; Reclaim last running; Overhead product is heated to 500 ℉ ~ 700 ℉; The overhead product of heating and hydrogen are fed to 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, to form light ends fractionation and to comprise H
2the cut of S and hydrogen; A part for light ends fractionation is recycled to catalytic distillation reactor.The method effectively can reduce the thio-alcohol sulphur in product gasoline, but operation more complicated, control not easily to stablize.
At present, in representational FCC gasoline sulfur removal technology technology, the SCANfining technique of mainly the Prime-G+ technique developed of IFP (IFP) and Mobil company abroad; The OCTM-D technique that the RSDS technique of domestic mainly Sinopec Research Institute of Petro-Chemical Engineering (RIPP) and Fushun Petrochemical Research Institute (FRIPP) develop.The common trait of these technology mainly concentrates in last running for FCC gasoline sulfide exactly, sulfide in lighting end is based on mercaptan, and high-octane olefin component concentrates on the feature in lighting end, be weight two portions by 70 DEG C ~ 100 DEG C cut-points by gasoline fractionation, last running uses proprietary catalyzer to carry out selective hydrodesulfurization, lighting end adopts the method mercaptan removal such as alkali-free sweetening, then two kinds of cuts is mixed to get product gasoline.These technology can remove the sulphur content in FCC gasoline effectively, and ensure gasoline octane rating loss reduction.But all there is the shortcoming that investment is comparatively large, plant energy consumption is high, running period is short, mercaptan is recombinated.
In the prior art, the machinery of gasoline hydrogenation and diesel hydrotreating unit composition, because diesel oil hydrogenation treatment capacity is often greater than gasoline hydrogenation, diesel oil hydrogenation adopts hydrogen recycle flow process, arranges independently make-up hydrogen compressor and circulating hydrogen compressor.Gasoline hydrogenation all arranges hydrogen gas compressor, and arranges gasoline stocks oil process furnace, and make gasoline easily cause local superheating to cause coking phenomenon serious, running period can not be guaranteed; And product stripping tower adopts reboiler furnace stripping, and facility investment and the working cost of device are higher.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of FCC gasoline deep desulfuration, produce the Unionfining technological process of low thioalcohol gasoline.
Unionfining technological process of the present invention comprises the following steps:
A, complete for FCC distillation gasoline is divided into lighting end gasoline and last running gasoline, the cutting temperature of described lighting end gasoline and last running gasoline is 50 DEG C ~ 80 DEG C;
B, step a gained lighting end gasoline carry out alkali-free sweetening, remove the mercaptan compound contained;
C, step a gained last running gasoline and the new hydrogen after heating are mixed into gasoline hydrogenation reactor and carry out hydrodesulfurization reaction, reaction effluent enters separator and carries out gas-liquid separation, gained hydrogen-rich gas is as the hydrogen make-up of Diesel Oil Hydrofining Unit after boosting, and the lighting end gasoline mixing of gained liquid phase after stripping and after step b gained mercaptan removal is as blended gasoline carrying device;
After d, diesel raw material mix with recycle hydrogen and step c gained hydrogen make-up, enter diesel oil hydrogenation reactor together, reaction effluent enters separator and carries out gas-liquid separation, and gained hydrogen-rich gas uses through desulfurization Posterior circle, gained liquid is carrying device after stripping tower stripping, obtains diesel product.
The cut point of the lighting end gasoline described in step a and last running gasoline is distributed by the sulphur in FCC gasoline and olefin(e) centent and determines, is generally 50 DEG C ~ 80 DEG C.
Alkali-free sweetening described in step b is technology well known in the art.Condition as alkali-free sweetening is generally: reactor operating pressure 0.1 ~ 1.0MPa, temperature of reaction 20 DEG C ~ 70 DEG C, Feed space velocities 0.5 ~ 2.0h
-1, air flow quantity/inlet amount volume ratio is 0.1 ~ 1.0.Used catalyst and promotor are the catalyzer that this area is commonly used, and can select commercial goods or be prepared according to the knowledge of this area.
Gasoline hydrodesulfurizationmethod reactor described in step c adopts new hydrogen once to pass through flow process.
The operational condition of the gasoline hydrogenation reactor described in step c is: reaction pressure 1.0 MPa ~ 4.0 MPa, reaction temperature in 250 DEG C ~ 300 DEG C, volume space velocity 2.0h
-1~ 12.0h
-1, hydrogen to oil volume ratio 200: 1 ~ 600: 1, preferably 400: 1 ~ 500: 1.Hydrogen to oil volume ratio suitably increases, and is beneficial to ensure hydrogenator temperature in and have certain turndown ratio.
In step c, described new hydrogen can enter independent heating stove and heat, or enters charging process furnace or the heating of its convection zone of Diesel Oil Hydrofining Unit, controls new hydrogen heater outlet temperature by the bypass of process furnace hydrogen.
New hydrogen described in step c directly can be sent here by new hydrogen pipe network, or sent here by the hydrogen make-up compressor primary outlet of diesel hydrotreating unit described in step b, after gasoline hydrodesulfurizationmethod reactor, gas-liquid separator, gained hydrogen-rich gas can turn back to the secondary inlet of the hydrogen make-up compressor of Diesel Oil Hydrofining Unit, then as the hydrogen make-up of diesel oil hydrogenation after overdraft.
The catalyzer used in the reactor of gasoline hydrogenation described in step c adopts catalyst for selectively hydrodesulfurizing.Catalyst for selectively hydrodesulfurizing generally with aluminum oxide or silicon-containing alumina for carrier, active metal is generally selected from one or more in W, Mo, Ni and Co, can also contain conven-tional adjuvants, as one or more in K, Ca, P, Si, F, B, Ti and Zr.With the weight of catalyzer for benchmark, active metallic content take oxide basis as 8.0wt% ~ 20.0wt%, is preferably 10.0wt% ~ 18.0wt%; Auxiliary agent content is 1.0wt% ~ 6.0wt%, is preferably 1.5wt% ~ 5.0wt%.Hydrobon catalyst can select existing business Hydrobon catalyst, as FGH-21, FGH-31 catalyzer of Fushun Petrochemical Research Institute's development, the gasoline hydrogenation catalysts such as the RSDS-1 of Beijing Research Institute of Petro-Chemical Engineering development, or can be prepared according to the existing method of this area as required.
Last running gasoline described in step c enters the logistics of the front elder generation of hydrogenator and the suitable potential temperature of Diesel Oil Hydrofining Unit, normally with the heat exchange of diesel oil hydrogenation reaction effluent to 180 DEG C ~ 230 DEG C, preferably 200 DEG C ~ 210 DEG C, to prevent the diene component at high temperature polymerization coking in last running gasoline, thus ensure this interchanger long-term operation.The new hydrogen that last running gasoline after heat exchange heats with process furnace is again mixed into hydrogenator.The temperature of hydrogenator parallel feeding is realized by serials control hydrogen furnace outlet temperature.
Doing of diesel raw material described in steps d is generally 330 ~ 380 DEG C, is generally the diesel component that boiling range is 170 DEG C ~ 380 DEG C.Diesel raw material can be one or more in coker gas oil, catalytic diesel oil or straight-run diesel oil.
Described in steps d, the reaction conditions of diesel oil hydrogenation reactor is: reaction pressure 6.0 MPa ~ 18.0 MPa, reaction temperature in 230 DEG C ~ 300 DEG C, 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 common diesel Hydrobon catalyst.Common diesel Hydrobon catalyst generally with VI B race and/or group VIII metal for active ingredient, with aluminum oxide or silicon-containing alumina for carrier.Group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 8wt% ~ 28wt%, and group VIII metal content take oxide basis as 2wt% ~ 15wt%, and its physical properties is as follows: specific surface is 100 ~ 650m
2/ g, pore volume is 0.15 ~ 0.8 mL/g.The common hydrofining commercial catalysts of this area can be adopted, or the grading composition of several appropriate catalysts.As FH-98, FH-DS, FH-UDS of Fushun Petrochemical Research Institute's development, or the Hydrobon catalyst such as RN-10, RN-1, RN-10B of Beijing Research Institute of Petro-Chemical Engineering development, or be prepared according to the existing method of this area.
Compared with prior art, this processing method is combined by hydrogenation unit, optimization technological process, achieves different material under optimum, obtains desirable comprehensive process effect, have the following advantages:
1, by Unionfining technique, adopt the heat supply of diesel refining device high-temperature position reactant flow to the logistics of gasoline refining reaction feed, avoid FCC gasoline last running when process furnace heats because of the coking that local superheating causes, be conducive to the extension fixture cycle of operation.
2, by Unionfining technique, the heat exchanger network potential temperature between device is mated more reasonable, be conducive to the utilization of device low-temperature level heat, thus reduce machinery energy consumption.
3, complete for FCC gasoline cut is divided into light gasoline fraction and heavy naphtha by certain cut point, thiophenic sulfur is not entered in lighting end, the heavy naphtha higher to sulphur content carries out deep desulfuration, ensures that blend gasoline product sulphur content drops to 5 ~ 50 μ g/g; Meanwhile, loss of octane number < 2 units of product gasoline.
4, adopt new hydrogen once by the flow process of gasoline refining reactor, decrease the H caused by hydrogen recycle use in prior art
2s becomes the possibility of mercaptan with alkene recombination, be also conducive to the desulfurization of gasoline refining reaction depth.
5, adopt hydrogen once by gasoline refining reactor, cancel naphtha-treating plant circulating hydrogen compressor and desulphurization of recycle hydrogen system, be conducive to reducing plant energy consumption and reducing plant investment.
6, contaminated product technique after naphtha-treating plant employing stove, effectively prevent the coking of charging heating furnace tube and reactor head carbon deposit, greatly prolong operating period.
7, present invention process flow process is short, technique is advanced rationally, save the advantages such as 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 few, plant energy consumption is advanced, and product meets the features such as index; For old plant modification, there is improvement expenses low, reduce plant energy consumption, the features such as prolong operating period.
Accompanying drawing explanation
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, 4 is gasoline refining reactor, 5 is hydrogen process furnace, 6 is make-up hydrogen compressor, 7 is gasoline refining Reaction Separation device, 8 is treated gasoline stripping tower, 9 is product gasoline, 10 is gas oil, 11 is diesel refining reaction feed process furnace, 12 is diesel refining reactor, 13 is diesel refining Reaction Separation device, 14 is refined diesel oil stripping tower, 15 is new hydrogen, 16 eject material for diesel oil stripping tower, 17 eject material for gasoline stripping tower, 18 is refined diesel oil, 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 DEG C through diesel refining resultant of reaction/gasoline refining reaction raw materials oil heat exchanger 3 heat exchange, with export out from make-up hydrogen compressor 6 one stage of compression and new hydrogen after heating to 350 DEG C ~ 550 DEG C through hydrogen process furnace 5 is mixed into gasoline refining reactor 4, carry out the reactions such as desulfurization, diolefine be saturated.Reaction effluent enters gasoline refining Reaction Separation device 7 after heat exchange cooling, and the gas phase hydrogen-rich gas after separation removes the secondary inlet of make-up hydrogen compressor 6; Liquid phase after separation goes treated gasoline stripping tower 8 to carry out stripping, removes H wherein
2s and lighter hydrocarbons, then mix as gasoline products 9 carrying device with the light gasoline fraction of Cutting Tap tower top through alkali cleaning.
After gas oil 10 heat exchange heats up and the mixed hydrogen mixed heat transfer sent here of make-up hydrogen compressor 6 and circulating hydrogen compressor 19 heat up after enter diesel refining reaction feed process furnace 11, enter diesel refining reactor 12 after heating to 230 DEG C ~ 300 DEG C, carry out the reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrotreated lube base oil.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, uses after the desulfurization of isolated gas phase hydrogen-rich gas through 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 device from refined diesel oil stripping tower 14.
Embodiment 1 ~ 4
600,000 tons/year, certain refinery FCC gasoline hydro-refining unit and 2,500,000 tons/year of catalytic cracking diesel oil hydro-refining units form machinery.
The full distillation gasoline of FCC enters Cutting Tap through filtration, stage-by-stage heat exchange after heating up, and is divided into light gasoline fraction and heavy naphtha.After heavy naphtha boosting and the reaction effluent heat exchange of the suitable potential temperature of diesel refining device to 200 DEG C, send with make-up hydrogen compressor the hydrogen being heated to 510 DEG C through hydrogen process furnace here to be mixed into gasoline hydrofinishing reactor and to carry out the chemical reactions such as desulfurization, reaction effluent through heat exchange, be cooled to about 40 DEG C after enter reaction product separator, separation obtains hydrogen-rich gas and is sent to make-up hydrogen compressor secondary inlet and divides flow container, after boosting, be sent to diesel refining device; Be separated the liquid phase obtained and enter product stripping tower, obtain overhead gas at stripper overhead, at the bottom of stripping tower tower, extract treated gasoline out, stripping tower adopts reboiler stripping, and its thermal source is provided by the diesel oil of the suitable potential temperature of machinery diesel refining device.Treated gasoline after stripping mixes as gasoline blending component carrying device with the light gasoline fraction through alkali-free sweetening.
The heat exchange of catalytic cracking gas oil heat up after mixes with mixed hydrogen, through heat exchange, heat to 325 DEG C after enter diesel refining reactor, carry out the reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrotreated lube base oil.Reaction effluent enters diesel refining Reaction Separation device and carries out gas-liquid separation after heat exchange, cooling, uses after the desulfurization of isolated gas phase hydrogen-rich gas through compression cycle; Isolated liquid phase obtains refined diesel oil carrying device after stripping.
Adopt diesel oil hydrogenation reaction effluent to be warmed up to about 200 DEG C to 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 make-up hydrogen compressor primary outlet.
Adopt above-mentioned technical process.The wherein alkali-free sweetening alkali-free sweetening II type technique that adopts Chinese Petroleum Univ. to develop, catalyzer is the AFS-12 prefabrication type catalyzer of Chinese Petroleum Univ.'s research and development.Gasoline hydrodesulfurizationcatalyst catalyst is FGH-21, 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 DEG C, obtains lighting end and last running.Lighting end enters alkali-free sweetening unit, removes mercaptan sulfur.Heavy naphtha is through hydrogenating desulfurization, and treated gasoline and the mixing of alkali-free sweetening lighting end gasoline are as product gasoline carrying device.FCC raw gasline character is in table 1; The processing condition of alkali-free sweetening condition are in table 2; The processing condition of heavy naphtha hydrogenating desulfurization are in table 3; Product gasoline character is in 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 DEG C), 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), DEG C | ||||
| 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, DEG C | 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, DEG C | 265 | 265 | 260 | 255 |
| 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 DEG C), 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), DEG C | ||||
| 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 |
Diesel oil hydrogenation catalyzer adopts 3936 or FH-UDS hydrogenation catalyst of Fushun Petrochemical Research Institute's development, and diesel oil carries out the reactions such as hydrogenating desulfurization, hydrodenitrification, hydrogenation deoxidation and hydrotreated lube base oil in refining reaction device.The character of diesel raw material is in table 5; The hydrorefined operational condition of catalytic cracking diesel oil is in table 6, and refined diesel oil product property is in 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 DEG C) g/cm 3 | 0.8549 | 0.8159 | 0.8506 | 0.8517 |
| Boiling range, DEG C | ||||
| 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, DEG C | 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 DEG C 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, DEG C | ||||
| 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 |
Gasoline and the diesel product of equal quality is produced by same materials, the present invention compared with prior art, machinery of the present invention decreases naphtha-treating plant circulating hydrogen compressor, adopt hydrogen once by gasoline refining reactor, the technique of contaminated product after hydrogen heating-furnace, and utilize the reaction effluent gasoline feed refined material oil heat exchange of machinery diesel refining high-temperature position to heat up.Under the prerequisite obtaining same hydrofining result, save the one-time investment of device, reduce plant energy consumption, and extend the cycle of operation of device.
Claims (9)
1. a hydrofining combined technique, comprises the following steps:
A, complete for FCC distillation gasoline is divided into lighting end gasoline and last running gasoline, the cutting temperature of described lighting end gasoline and last running gasoline is 50 DEG C ~ 80 DEG C;
B, step a gained lighting end gasoline carry out alkali-free sweetening, remove the mercaptan compound contained;
C, step a gained last running gasoline and new hydrogen are mixed into gasoline hydrogenation reactor and carry out hydrodesulfurization reaction, reaction effluent enters separator and carries out gas-liquid separation, gained hydrogen-rich gas is as the hydrogen make-up of Diesel Oil Hydrofining Unit after boosting, and the lighting end gasoline mixing of gained liquid phase after stripping and after step b gained mercaptan removal is as blended gasoline carrying device; Wherein, described new hydrogen is sent here by the hydrogen make-up compressor primary outlet of Diesel Oil Hydrofining Unit; Described hydrogen-rich gas returns the secondary inlet of the hydrogen make-up compressor of Diesel Oil Hydrofining Unit, as the hydrogen make-up of diesel oil hydrogenation after overdraft;
After d, diesel raw material mix with recycle hydrogen and step c gained hydrogen make-up, enter diesel oil hydrogenation reactor together, reaction effluent enters separator and carries out gas-liquid separation, and gained hydrogen-rich gas uses through desulfurization Posterior circle, gained liquid is carrying device after 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 step c adopts new hydrogen once by flow process, after last running gasoline first carries out heat exchange intensification with diesel oil hydrogenation effluent, then mixes with the new hydrogen after process furnace heats.
3. in accordance with the method for claim 1, it is characterized in that, the operational condition of the gasoline hydrogenation reactor described in step c is: reaction pressure 1.0 MPa ~ 4.0 MPa, reaction temperature in 250 DEG C ~ 300 DEG C, 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, new hydrogen described in step c enters independent heating stove and heats, or new hydrogen enters charging process furnace or the heating of its convection zone of Diesel Oil Hydrofining Unit, 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 catalyst for selectively hydrodesulfurizing used in the reactor of gasoline hydrogenation described in step c with aluminum oxide or silicon-containing alumina for carrier, active metal is selected from one or more in W, Mo, Ni and Co, also containing one or more in K, Ca, P, Si, F, B, Ti and Zr as auxiliary agent; With the weight of catalyzer for benchmark, active metallic content take oxide basis as 8.0wt% ~ 20.0wt%, and auxiliary agent content is 1.0wt% ~ 6.0wt%.
6. in accordance with the method for claim 1, it is characterized in that, last running gasoline described in step c with the mixing of new hydrogen before first and the heat exchange of diesel oil hydrogenation reaction effluent to 180 DEG C ~ 230 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, doing of the diesel raw material described in steps d is 330 ~ 380 DEG C.
8. in accordance with the method for claim 1, it is characterized in that, described in steps d, the reaction conditions of diesel oil hydrogenation reactor is: reaction pressure 6.0 MPa ~ 18.0 MPa, reaction temperature in 270 DEG C ~ 400 DEG C, volume space velocity 0.2h
-1~ 8.0 h
-1with hydrogen to oil volume ratio 200: 1 ~ 1000: 1.
9. in accordance with the method for claim 1, it is characterized in that, diesel oil hydrofining catalyst with VI B race and/or group VIII metal for active ingredient, with aluminum oxide or silicon-containing alumina for carrier; With the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 8wt% ~ 28wt%, and group VIII metal content take oxide basis as 2wt% ~ 15wt%, and its physical properties is as follows: specific surface is 100 ~ 650m
2/ g, pore volume is 0.15 ~ 0.8 mL/g.
Priority Applications (1)
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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 |
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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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