CN105647581A - Catalytic gasoline hydrogenation method - Google Patents
Catalytic gasoline hydrogenation method Download PDFInfo
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- CN105647581A CN105647581A CN201410645062.8A CN201410645062A CN105647581A CN 105647581 A CN105647581 A CN 105647581A CN 201410645062 A CN201410645062 A CN 201410645062A CN 105647581 A CN105647581 A CN 105647581A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 239000003381 stabilizer Substances 0.000 claims abstract description 41
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 37
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 8
- 230000011218 segmentation Effects 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 238000007600 charging Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 25
- 238000006477 desulfuration reaction Methods 0.000 claims description 23
- 230000023556 desulfurization Effects 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000087 stabilizing effect Effects 0.000 abstract 2
- 239000005864 Sulphur Substances 0.000 description 24
- 238000005265 energy consumption Methods 0.000 description 22
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- -1 monoolefine Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalytic gasoline hydrogenation method. The catalytic gasoline hydrogenation method comprises the following steps: the full-fraction catalytic gasoline (1) enters a pre-hydrogenation reactor (9), and the reaction product enters a fractionating tower (10) to carry out light-fraction and heavy-fraction gasoline segmentation; heavy fraction gasoline at the bottom of the fractionating tower enters a hydrodesulfurization reactor (14) after heat exchange, and reaction products enter an octane number recovery reactor (17) after heat exchange through an octane number recovery reaction feeding heat exchanger (15) and heating through an octane number recovery feeding heating furnace (16); the reaction product at the outlet of the octane number recovery reactor (17) enters a stabilizer reboiler (25), and then enters a thermal separation tank (18) after heat exchange through an octane number recovery feeding heat exchanger (15) and a hydrodesulfurization feeding heat exchanger (13) in sequence; the liquid phase at the bottom of the thermal separation tank enters a stabilizing tower (24), the gas phase at the top of the tank enters a cold separation tank (20) after heat exchange and cooling, and the liquid phase at the bottom of the cold separation tank enters the stabilizing tower (24) after heat exchange.
Description
Technical field
The present invention relates to a kind of gasoline hydrogenation method.
Background technology
For improving Air quality, improve the ability of automobile tail gas purification system further, reduce Exhaust emission, in December, 2013, China issues and starts to implement five-stage motor spirit national standard (GB17930-2013), in end of the year transitional period to 2017, on January 1st, 2018 plays supply country V standard motor spirit in China, it is desired to sulphur content is not more than 10ppm. Catalytic gasoline, as the main blending component of China's clean vehicle gasoline, accounts for more than the 70% of gasoline concoction pond, and the sulphur content therefore reduced in catalytic gasoline is the key producing super low-sulfur oil. Gasoline hydrogenation be a kind of adopt bed technology that catalytically cracked gasoline is carried out hydrotreatment so that its sulphur content meet country motor spirit emission standard method, because of advantages such as the mitigation of its operational condition, desulfurization degree height, the hydrogen low and loss of octane number of consumption are little, it is widely used in factory of each great oil refining. This technique adopts the technical process of full distillation gasoline pre-hydrotreating-light and heavy fractions gasoline segmentation-last running gasoline hydrodesulfurizationmethod usually, after reaction product and reaction feed heat exchange, through sky cold but after enter separating tank and carry out gas-liquid separation, it is de-except hydrogen sulfide and lighter hydrocarbons that separation tank bottom liquid enters stabilizer tower again after heat exchange heats up, and is finally met the treated gasoline product of requirement. This kind of technical process, major part heat of reaction can not be fully utilized, and cools away by reaction product air cooler, causes power loss. Liquid-phase reaction product is repeatedly through cooling simultaneously, and heat exchange enters stabilizer tower after heating up, and adds the exergy destruction in heat transfer process, causes power loss, and the energy consumption causing gasoline hydrogenation device unnecessary increases so that gasoline hydrogenation plant energy consumption is general higher. Energy-saving and emission-reduction, improve enterprise resource utilization, reduce energy consumption, existence that decreasing pollution is enterprise this, it is achieved the maximized key of enterprise profit. In addition, due to China's catalytic gasoline olefin(e) centent height, being generally greater than 40v%, while adopting gasoline hydrofinishing technology hydrogenating desulfurization, a large amount of alkene, by hydrotreated lube base oil, causes loss of octane number to increase.Therefore, it is necessary to develop a kind of super low sulfur clean gasoline being applicable to domestic catalytic gasoline production sulphur content and being less than 10ppm, and can effectively reduce energy consumption, the novel technique of recovered energy to greatest extent.
CN102167985B provides a kind of hydro-upgrading method for ungraded gasoline, for the feature of China's catalytic gasoline, adopt the method for modifying of selective hydrodesulfurization, Olefin decrease, recovery octane value, two sections, two device flow processs, gasoline does not carry out weight separation, entirely evaporates and point directly carries out hydro-upgrading. Present method can much slower sulphur and alkene, and loss of octane number is little, but gasoline products sulphur content only can meet state IV motor spirit standard.
CN102010751A relate to the combination production method of a kind of ultra-low sulfur and high-octane number gasoline, full distillation gasoline first carries out directed sulphur transfer, then carrying out weight segmentation, last running gasoline carries out hydrogenating desulfurization and different structure, aromizing, then obtains gasoline products after mixing with lighting end gasoline. Present method production sulphur content can be less than the gasoline products of 10ppm, but severe reaction conditions, reaction product only with untreated last running gasoline heat exchange, heat exchange process is unreasonable, and high-temperature position heat energy can not make full use of, and heat utilization ratio is low.
CN103059957A discloses a kind of Low-energy consumption catalytic gasoline hydrodesulfurizationmethod method, by taking adjustment catalytic cracking unit separation column operation, the former point catalytic gasoline of entirely evaporating is extracted out to be adjusted to and extracted lighting end gasoline and middle gasoline out, and increase last running gasoline and extract line out, lighting end gasoline and middle gasoline are divided into gasoline light, middle after facing hydrogen mercaptan removal, in then, gasoline and last running gasoline carry out hydrogenating desulfurization after mixing. Gasoline product quality can be met the specification of quality that sulphur content is less than 10ppm by this method, and energy consumption is lower. But this method is equivalent to the energy consumption of gasoline hydrogenation device is transferred to catalytic unit, is not low power technology truly.
CN103059946A discloses a kind of Low-energy consumption catalytic gasoline hydrodesulfurizationmethod method, this method and CN103059957A almost all fours, and in just, gasoline and last running gasoline have carried out hydrogenating desulfurization respectively.
Summary of the invention
Goal of the invention
It is an object of the invention to provide a kind of gasoline hydrogenation method, can much slower catalytic gasoline product sulphur content, and loss of octane number is little, and can effectively reduce energy consumption, to greatest extent recovered energy.
Invention general introduction
Described gasoline hydrogenation method comprises the following steps:
Entirely evaporating point catalytic gasoline and enter pre-hydrogenator after pre-hydrogenation feed exchanger and pre-hydrogenation feed preheater heat exchange and heating, reaction product enters that separation column carries out gently, last running gasoline is split, and fractionation cut point is 50��70 DEG C;
Last running gasoline at the bottom of separation column enters hydrodesulphurisatioreactors reactors after hydrogenating desulfurization feed exchanger heat exchange, and reaction product enters octane value recovering reactor after octane value recovering reaction feed interchanger heat exchange and octane value recovering charging process furnace are heated;
Octane value recovering reactor outlet reaction product enters stabilizer tower reboiler, for stabilizer tower provides thermal source, then enters hot knock-out pot hot gas-liquid separation at 175��215 DEG C successively after octane value recovering feed exchanger and hydrogenating desulfurization feed exchanger heat exchange;
It is stable that liquid phase at the bottom of hot knock-out pot goes stabilizer tower to carry out product, tank deck gas phase is through pre-hydrogenation feed exchanger heat exchange, again through cooling after enter the cold gas-liquid separation at 40��55 DEG C of cold separating tank, cold separation tank bottom liquid phase enter after stabilizer tower feed exchanger heat exchange stabilizer tower carry out product stablize;Gasoline at the bottom of stabilizer tower is through stabilizer tower feed exchanger heat exchange and as hydrogenation last running gasoline products after cooling.
By the control of fractionation cut point, can guarantee that gained lighting end mercaptan from gasoline and total sulfur content are all not more than 10ppm, meet state V gasoline standard requirement, such lighting end gasoline can directly mix with the refining last running gasoline after hydrogenating desulfurization and octane value recovering, obtain super low sulfur clean gasoline product, it is possible to directly as ether-based device raw material. Lighting end Gasoline On-line sulphur content analyzer can be set, on-line analysis lighting end mercaptan from gasoline and total sulfur content, the cut point of convenient and swift regulation and control lighting end gasoline and quality.
Preferably, pre-hydrotreating reaction adopts Ni-Mo catalyzer, can ensure de-except the diolefine in stock oil and colloid, extend the downstream reaction operational cycle, and ensure that lighting end mercaptan from gasoline and total sulphur are all not more than 10ppm, meet state V gasoline standard requirement. Operation condition is: reaction pressure 2��2.4MPa, temperature of reaction 95��190 DEG C, reaction velocity 2.5��4.0h-1, hydrogen-oil ratio 3��6.
Preferably, hydrodesulfurization reaction adopts Co--Mo catalyst, for the de-sulfide removing relatively macromole in last running gasoline. Operation condition is: reaction pressure 1.9��2.1MPa, temperature of reaction 185��260 DEG C, reaction velocity 3��6h-1, hydrogen-oil ratio 200��300; Octane value recovering reaction employing take molecular sieve as Co��Mo catalyzer of carrier, remove in last running gasoline, relatively small molecules sulfocompound is de-, avoid hydrogen sulfide and alkene to recombine generation mercaptan, and carry out isomerization and aromatization, make up the loss of octane number because olefin saturated causes. Operation condition is: reaction pressure 1.5��1.7MPa, temperature of reaction 250��370 DEG C, reaction velocity 2��6h-1, hydrogen-oil ratio 200��300.
Temperature of reaction of the present invention is reacting initial temperature, and namely each elementary reaction material enters the temperature in of respective reaction device. Owing to described pre-hydrotreating reaction, hydrodesulfurization reaction, octane value recovering reaction are thermopositive reaction, reactor outlet temperature can a little more than temperature in. The difference of reactor outlet temperature and temperature in is called temperature rise. Such as, in above-mentioned preferred version, the temperature of reaction of pre-hydrotreating reaction is 95��190 DEG C, and temperature rise is 2��10 DEG C, and pre-hydrogenator temperature out is 97��200 DEG C; The temperature of reaction of hydrodesulfurization reaction is 185��260 DEG C, and temperature rise is 5��20 DEG C, and the temperature out of hydrodesulphurisatioreactors reactors is 190��280 DEG C; The temperature of reaction of octane value recovering reaction is 250��370 DEG C, and temperature rise is 20��30 DEG C, and the temperature out of octane value recovering reactor is 270��400 DEG C. The change of temperature of reaction and temperature rise is main by the impact of reaction raw materials composition and catalyst performance, and such as, along with the degeneration of catalyst performance, temperature of reaction needs to improve, and this is well known to those skilled in the art.
Preferably, liquid phase at the bottom of hot knock-out pot and cold separation tank bottom liquid phase enter stabilizer tower different pelverized coal feeder positions respectively, decrease cooling, intensification repetitive operation that sub-thread charging causes because of cold and hot material remix, (traditional process only establishes a cold separating tank to reduce power loss, liquid at the bottom of tank is one material only, stabilizer tower is entered, therefore a stabilizer tower only feed entrance point) after heat exchange.
Preferably, described hot gas liquid separation temperature is 180��190 DEG C. So-called hot gas-liquid separation refer to heat exchange after reaction product directly carry out gas-liquid two-phase separation without cooling further, with the utilization economizing on resources and improving heat.Applicant finds after deliberation, hot gas liquid separation temperature involved in the present invention can not be too high, too high meeting causes pre-hydrogenation charging coking, and (hot gas liquid separation temperature should control to be no more than 215 DEG C, to prevent diene polymerization coking wherein when heating pre-hydrogenation charging), and flash liquid phasor is few, gas phase carries heat surplus, increases cooling load, unfavorable energy-conservation; Hot gas liquid separation temperature can not be too low, and too low flashed vapour phasor is few, and pre-hydrogenation charging can not be made to be heated to high enough temp, can increase the amount that extraneous input adds thermal medium, be unfavorable for energy-conservation. Calculating through applicant's repetition test, when hot gas liquid separation temperature is 180��190 DEG C, effect is ideal, both the material of reactive system can not be caused disadvantageous effect, can reach again good energy-saving effect.
Preferably, cold separating tank top gas is de-mutually recycles in hydrodesulfurization reaction as recycle hydrogen except after hydrogen sulfide. Recycle hydrogen arranges depriving hydrogen sulphide facility, de-except the hydrogen sulfide in recycle hydrogen, prevents the restructuring of the alkene in hydrogen sulfide and last running gasoline from generating sulfide, it is to increase hydrodesulfurization reaction selectivity, reduces reaction severity.
The present invention adopts two sections of combined hydrogenation technology of pre-hydrogenation, hydrogenating desulfurization and octane value recovering, full distillation gasoline carries out pre-hydrotreating reaction, diolefine is converted into monoolefine, reduce downstream hydrogenation desulphurization reaction system coking, guarantee device long-term operation, also carry out the small molecules trechmannite compounds such as mercaptan simultaneously and tautomerize to the reactions such as active monoolefine to heavy sulfide transfer and non-active monoolefine; Hydrogenating desulfurization and octane value recovering reaction, then carry out desulfurization, aromizing and isomerization reaction, is conducive to deep desulfuration and reduces loss of octane number. Described pre-hydrotreating reaction, hydrodesulfurization reaction and octane value recovering reaction are prior art, and used catalyst is also the material being common to described reaction known in this field, and those skilled in the art can select preferred catalyzer and reaction conditions according to practical situation.
Octane value recovering reaction product heat is utilized to low temperature step by step by high temperature. First reaction product provides thermal source for stabilizer tower reboiler, avoids the energy input of external heat medium, decreases energy expenditure; Again, carry out preheating octane value recovering reaction feed, reduce the thermal load of octane value recovering reaction feed process furnace, reduce fuel consumption; Then carry out heat exchange with hydrodesulfurization reaction charging, make charging meet the temperature of reaction requirement of hydrodesulphurisatioreactors reactors; Finally utilize the gas-phase heating pre-hydrotreating reaction charging of thermal separation tank deck, it is achieved heat utilizes step by step. Simultaneously liquid phase at the bottom of hot knock-out pot directly enters stabilizer tower, and the repetitive operation reduce reaction liquid product cooling, heating up, reduces power loss.
Compared with prior art, the present invention has the following advantages:
1. can processing sulphur content and be not more than 2000ppm, olefin(e) centent is not more than the catalytic gasoline inferior of 45v%, and production sulphur content is less than state's V gasoline component of 10ppm, product liquid receipts rate be not less than 99wt% and loss of octane number little.
2. can according to feedstock property and sulphur content characteristic distributions, online regulation and control separation column light and heavy fractions gasoline cut point and lighting end quality of gasoline.
3., under the prerequisite of the sulphur content and octane value that ensure gasoline products, the condition of pre-hydrogenation, hydrogenating desulfurization and octane value recovering reaction is optimized coupling, to reduce energy consumption.
4. hydrodesulfurization reaction product heat is utilized to low temperature step by step by high temperature. First reaction product provides thermal source for stabilizer tower reboiler, avoids the energy input of external heat medium, decreases energy expenditure; Again, carry out preheating octane value recovering reaction feed, reduce the thermal load of octane value recovering charging process furnace, reduce fuel consumption; Then carry out heat exchange with hydrodesulfurization reaction charging, make charging meet the temperature of reaction requirement of hydrodesulphurisatioreactors reactors; Finally utilize the gas-phase heating pre-hydrotreating reaction charging of thermal separation tank deck, it is achieved heat utilizes step by step.
5. compared with conventional catalyst gasoline hydrogenation device, the unique distinction of the present invention arranges reaction product heat, cold separating tank, octane value recovering reaction product first carries out hot gas, liquid separation, hot knock-out pot top gas is for heating pre-hydrotreating reaction charging, empty more cold but enter gas-liquid separation in cold separating tank afterwards, cold separating tank top gas is enter stabilizer tower after recycle hydrogen oil heat exchange at the bottom of the use of desulfurization Posterior circle, cold separation tank bottom liquid phase and stabilizer tower mutually;Liquid phase at the bottom of hot knock-out pot directly enters stabilizer tower. The repetitive operation decrease reaction liquid product cooling, heating up, reduces power loss. Hot knock-out pot is vertical vessel, and opening for feed and tank wall are tangential, make the gas phase flashed off increase at tank internal screw, produce centrifugation, under the pressure effect of centrifugal force, the drop carried in gas is thrown toward container inner wall, and relies on self gravitation to carry out being settled down at the bottom of tank along container inner wall. Compared with tradition separating tank, liquid separation efficiency is higher, and required shell of tank size is less, saves facility investment.
6., compared with conventional catalyst gasoline hydrogenation device, plant energy consumption can reduce by 4��7 kgoe/t chargings.
Accompanying drawing explanation
Fig. 1 is less energy-consumption gasoline hydrogenation device technique schematic flow sheet of the present invention.
Wherein: 1 is catalytic gasoline charging, 2 supplement fresh hydrogen (hereinafter referred to as new hydrogen), 3 is charging strainer, 4 is charging surge tank, 5 is pre-hydrogenation fresh feed pump, 6 is make-up hydrogen compressor, 7 is pre-hydrogenation feed exchanger, 8 is pre-hydrogenation feed preheater, 9 is pre-hydrogenator, 10 is separation column, 11 is separation column reboiler furnace, 12 is hydrogenating desulfurization fresh feed pump, 13 is hydrogenating desulfurization feed exchanger, 14 is hydrodesulphurisatioreactors reactors, 15 is octane value recovering feed exchanger, 16 is octane value recovering charging process furnace, 17 is octane value recovering reactor, 18 is reaction product hot knock-out pot, 19 is reaction product air cooler, 20 is the cold separating tank of reaction product, 21 is desulphurization of recycle hydrogen system, 22 is circulating hydrogen compressor, 23 is stabilizer tower feed exchanger, 24 is stabilizer tower, 25 is stabilizer tower reboiler, 26 is gasoline products air cooler, 27 is gasoline products water cooler, 28 is note vulcanizing agent facility, 29 is note inhibiter facility, 30 is hydrogenation last running gasoline products, 31 is lighting end gasoline products.
Embodiment
The inventive method will be described in detail by the following examples, but the present invention is not by the restriction of embodiment.
The technical process of accompanying drawings following examples 1��3:
As shown in Figure 1, entirely evaporate point catalytic gasoline 1 to filter through charging strainer 3, enter charging surge tank 4, mix with the new hydrogen 2 coming from make-up hydrogen compressor 6 through pre-hydrogenation fresh feed pump 5, enter pre-hydrogenator 9 through pre-hydrogenation feed exchanger 7 and the heat exchange of pre-hydrogenation feed preheater 8 and after being heated to suitable temperature of reaction, carry out diolefine and be converted into the reaction that the trechmannite compound such as monoolefine, mercaptan transforms sulfide of attaching most importance to. Supplement new hydrogen through make-up hydrogen compressor 6 supercharging. Reaction product enters that separation column 10 carries out gently, the segmentation of last running gasoline, in lighting end gasoline 31, mercaptan and total sulfur content meet state V gasoline standard requirement, can directly as gasoline blending component, also can directly as ether-based device raw material carrying device, last running gasoline removes deep hydrodesulfurizationof, and separation column 10 is heated by separation column reboiler furnace 11. At the bottom of separation column, last running gasoline mixes with recycle hydrogen through hydrogenating desulfurization fresh feed pump 12, after hydrogenating desulfurization feed exchanger 13 heat exchange to temperature of reaction, enter hydrodesulphurisatioreactors reactors 14 carry out hydrogenating desulfurization and part olefin saturation, reaction product enters octane value recovering reactor 17 after octane value recovering feed exchanger 15 heat exchange and octane value recovering charging process furnace 16 are heated to temperature of reaction, carry out mercaptan removal, aromizing and isomerization reaction, it is achieved while meeting product desulfurization requirement, keep less loss of octane number.Octane value reactor 17 exports reaction product and enters stabilizer tower reboiler 25, for stabilizer tower 24 provides thermal source, then enters the hot gas-liquid separation of reaction product hot knock-out pot 18 after octane value recovering feed exchanger 15 and hydrogenating desulfurization feed exchanger 13 heat exchange successively. Liquid phase at the bottom of hot knock-out pot removes stabilizer tower 24, tank deck gas phase enters the cold separating tank 20 of reaction product again through the heat exchange of pre-hydrogenation feed exchanger 7 after reaction product air cooler 19 condensing cooling, cold separating tank top gas mutually namely recycle hydrogen through desulphurization of recycle hydrogen system 21 de-except carrying out mixing with the new hydrogen 2 supplemented after hydrogen sulfide and compress boosting Posterior circle use through circulating hydrogen compressor 22. Cold separation tank bottom liquid phase enter after stabilizer tower feed exchanger 23 heat exchange stabilizer tower 24 carry out product stablize. Gasoline heat exchange at the bottom of tower also delivers to storage tank as hydrogenation last running gasoline products 30 after gasoline products air cooler 26 and gasoline products water cooler 27 cool. Device arranges note vulcanizing agent facility 28, initially goes into operation presulfiding of catalyst for device. Note inhibiter facility 29 is set on stabilizer tower 24 top, to reduce equipment corrosion.
Embodiment 1
Taking catalytic gasoline A as raw material, its character is such as table 1. Catalyzer is commercial goods, and composition is in table 2. Fractionation cut point is 70 DEG C. Operational condition is in table 3, and product property is in table 4, and plant energy consumption is in table 5. Adopt this technology that sulphur content in product can be made to be less than 10ppm as can be seen from Table 4, loss of octane number 1.0 units, find out by table 5, plant energy consumption is 15.76kgoe/t charging, 5.99 units lower than comparative example 1,3.84 units lower than comparative example 2.
Embodiment 2
Taking catalytic gasoline B as raw material, its character is such as table 1. Catalyzer is commercial goods, and composition is in table 2. Fractionation cut point is 65 DEG C. Operational condition is in table 3, and product property is in table 4, and plant energy consumption is in table 5. Adopt this technology that sulphur content in product can be made to be less than 10ppm as can be seen from Table 4, loss of octane number 0.5 unit, find out by table 5, plant energy consumption is 14.95kgoe/t charging, 6.8 units lower than comparative example 1,4.65 units lower than comparative example 2.
Embodiment 3
Taking catalytic gasoline C as raw material, its character is such as table 1. Catalyzer is commercial goods, and composition is in table 2. Fractionation cut point is 60 DEG C. Operational condition is in table 3, and product property is in table 4, and plant energy consumption is in table 5. Adopt this technology that sulphur content in product can be made to be less than 10ppm as can be seen from Table 4, loss of octane number 1.2 units, find out by table 5, plant energy consumption is 15.32kgoe/t charging, 6.43 units lower than comparative example 1,4.28 units lower than comparative example 2.
Comparative example 1
Taking catalytic gasoline A as raw material, first raw material is carried out pre-hydrogenation dialkene removal and sulphur transfer, then in separation column, carry out light and heavy fractions cutting, cut point is 70 DEG C, after last running gasoline mixes with recycle hydrogen, with enter hydrodesulphurisatioreactors reactors after octane value recovering reaction product heat exchange to 240 DEG C and carry out desulphurization reaction, reaction product enters octane value recovering reactor again after octane value recovering reaction heating furnace is heated to 340 DEG C and contacts with octane value recovering catalyst and carry out mercaptan removal, isomerization and aromatization, octane value recovering reaction product successively with hydrodesulfurization reaction charging, pre-hydrotreating reaction charging heat exchange again through sky cold but after enter reaction product separating tank and carry out gas-liquid separation, enter stabilizer tower after oil heat exchange at the bottom of liquid and stabilizer tower to stablize, last running gasoline and lighting end gasoline after stable are mixed to get gasoline products. catalyzer is commercial goods, and composition is in table 2.Operational condition is in table 3, and product property is in table 4, and plant energy consumption is in table 5. Adopt this technology that sulphur content in product can be made to be less than 10ppm as can be seen from Table 4, loss of octane number 1.5 units, find out by table 5, plant energy consumption is 21.75kgoe/t charging, is about 6-7 unit higher than embodiment.
Comparative example 2
Taking catalytic gasoline A as raw material, first raw material is carried out pre-hydrogenation dialkene removal and sulphur transfer, then in separation column, carry out light and heavy fractions cutting, cut point is 70 DEG C, after last running gasoline mixes with recycle hydrogen, with enter hydrodesulphurisatioreactors reactors after hydrodesulfurization reaction product heat exchange to 240 DEG C and carry out desulphurization reaction, reaction product enters hydrogenation aftertreatment reactor and carries out sweetening reaction after entering stabilizer tower reboiler heat exchange to 330 DEG C after process furnace is heated to 355 DEG C, hydrogenation aftertreatment reaction product successively with hydrodesulfurization reaction charging, pre-hydrotreating reaction charging heat exchange again through sky cold but after enter reaction product separating tank and carry out gas-liquid separation, enter stabilizer tower after oil heat exchange at the bottom of liquid and stabilizer tower to stablize, stable gasoline and lighting end gasoline are mixed to get gasoline products last running gasoline. catalyzer is commercial goods, and composition is in table 2. operational condition is in table 3, and product property is in table 4, and plant energy consumption is in table 5. adopt this technology that sulphur content in product can be made to be less than 10ppm as can be seen from Table 4, loss of octane number 1.2 units, find out by table 5, plant energy consumption is 19.6kgoe/t charging, is about 4-5 unit higher than embodiment.
Table 1 feedstock property
| Project | Catalytic gasoline A | Catalytic gasoline B | Catalytic gasoline C |
| Proportion | 0.731 | 0.725 | 0.71 |
| Boiling range, DEG C | 37��185 | 36��202 | 40��205 |
| Sulphur content, ppm | 400 | 200 | 624 |
| Alkene, v% | 45 | 29 | 39.9 |
| Octane value (RON) | 89.7 | 90 | 90.8 |
Table 2 catalyzer composition wt%
Table 3 operational condition
Table 4 product property
Table 5 device consumption
Claims (7)
1. gasoline hydrogenation method, it is characterised in that, comprise the following steps:
Entirely evaporate a point catalytic gasoline (1) and enter pre-hydrogenator (9) after pre-hydrogenation feed exchanger (7) and pre-hydrogenation feed preheater (8) heat exchange and heating, reaction product enters that separation column (10) carries out gently, the segmentation of last running gasoline, and fractionation cut point is 50��70 DEG C;
Last running gasoline at the bottom of separation column enters hydrodesulphurisatioreactors reactors (14) after hydrogenating desulfurization feed exchanger (13) heat exchange, and reaction product enters octane value recovering reactor (17) after octane value recovering reaction feed interchanger (15) heat exchange and octane value recovering charging process furnace (16) are heated;
Octane value recovering reactor (17) outlet reaction product enters stabilizer tower reboiler (25), for stabilizer tower (24) provides thermal source, after octane value recovering feed exchanger (15) and hydrogenating desulfurization feed exchanger (13) heat exchange, then enter hot knock-out pot (18) hot gas-liquid separation at 175��215 DEG C successively;
It is stable that liquid phase at the bottom of hot knock-out pot goes stabilizer tower (24) to carry out product, tank deck gas phase is through the heat exchange of pre-hydrogenation feed exchanger (7), again through cooling after enter cold separating tank (20) cold gas-liquid separation at 40��55 DEG C, cold separation tank bottom liquid phase enter after stabilizer tower feed exchanger (23) heat exchange stabilizer tower (24) carry out product stablize; Gasoline at the bottom of stabilizer tower is through (23) heat exchange of stabilizer tower feed exchanger and as hydrogenation last running gasoline products (30) after cooling.
2. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, pre-hydrotreating reaction adopts Ni-Mo catalyzer, reaction pressure 2��2.4MPa, temperature of reaction 95��190 DEG C, reaction velocity 2.5��4.0h-1, hydrogen-oil ratio 3��6.
3. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, hydrodesulfurization reaction adopts Co--Mo catalyst, reaction pressure 1.9��2.1MPa, temperature of reaction 185��260 DEG C, reaction velocity 3��6h-1, hydrogen-oil ratio 200��300; Octane value recovering reaction employing take molecular sieve as Co��Mo catalyzer of carrier, reaction pressure 1.5��1.7MPa, temperature of reaction 250��370 DEG C, reaction velocity 2��6h-1, hydrogen-oil ratio 200��300.
4. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, liquid phase at the bottom of hot knock-out pot and cold separation tank bottom liquid phase enter stabilizer tower different pelverized coal feeder positions respectively.
5. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, cold separating tank top gas is de-mutually to be recycled in hydrodesulfurization reaction as recycle hydrogen except after hydrogen sulfide.
6. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, hot gas liquid separation temperature is 180��190 DEG C.
7. gasoline hydrogenation method as claimed in claim 1, it is characterised in that, fractionation cutting gained lighting end mercaptan from gasoline and total sulfur content are all not more than 10ppm.
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| CN108359493A (en) * | 2018-02-08 | 2018-08-03 | 中国石油大学(北京) | The method that catalytically cracked gasoline is modified |
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| CN108315053A (en) * | 2018-02-08 | 2018-07-24 | 中国石油大学(北京) | The method that quality upgrading is carried out to catalytically cracked gasoline |
| CN108359493A (en) * | 2018-02-08 | 2018-08-03 | 中国石油大学(北京) | The method that catalytically cracked gasoline is modified |
| CN108359495A (en) * | 2018-02-08 | 2018-08-03 | 中国石油大学(北京) | The method that high Olefinic catalytic cracking gasoline is modified |
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| CN114874808A (en) * | 2021-05-17 | 2022-08-09 | 德明·罗曼·尼古拉耶维奇 | Catalytic processing method and device for light hydrocarbon fraction |
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