CN103059938A - Heavy hydrocarbon hydrotreating method - Google Patents
Heavy hydrocarbon hydrotreating method Download PDFInfo
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Abstract
The invention discloses a heavy hydrocarbon hydrotreating method. According to the method, an up-flow reactor (UFR) is in series connection with at least one down-flow fixed bed reactor and a counter-flow reactor, a heavy hydrocarbon raw material passes through the UFR, the down-flow fixed-bed reactor and the counter-flow reactor in order. Further, the method includes: (1) mixing the heavy hydrocarbon raw material with hydrogen, heating the mixture to a reaction temperature required by the UFR, then leaving the mixture to enter the UFR: (2) mixing the UFR effluent with part of mixed hydrogen heated by a heating furnace convection section, making the mixture enter the down-flow fixed bed reactor to undergo a further hydrogenation treatment; and (3) introducing the down-flow fixed bed reaction effluent into the counter-flow reactor from the top, making the effluent undergo reverse contact with the mixed hydrogen entering from the bottom so as to complete the hydrogenation reaction. The method can flexibly control the first reactor inlet reaction temperature of the down-flow fixed bed, gives full play to the performance of the catalyst at the fixed bed, simultaneously further improves the catalyst performance and impurity removal rate, as well as prolongs the equipment operation period.
Description
Technical field
The present invention relates to a kind of hydrocarbons hydrogenation treatment technology, specifically, relate to a kind of hydroprocessing technique that comprises long residuum and vacuum residuum heavy hydrocarbon feeds.
Background technology
Along with crude oil day by day becomes heavy, becomes bad, increasing heavy oil, residual oil need processing treatment.The processing treatment of heavy oil, residual oil will be lower boiling product with its cracking not only, such as petroleum naphtha, intermediate oil and pressure reduction gas wet goods, but also will improve their hydrogen-carbon ratio, and this just need to realize by the method for decarburization or hydrogenation.Decarbonization process wherein comprises coking, solvent deasphalting, heavy oil fluid catalytic cracking etc.; Hydrogenation technique comprises hydrocracking, hydrofining, hydrotreatment etc.Hydrogenation technique can hydrocracking residual oil, improves the productive rate of liquid product, and can also remove heteroatoms wherein, and good product quality has obvious advantage.But hydrogenation technique is the catalysis complete processing, has hydrogenation catalyst inactivation problem, and when especially processing poor quality, heavier hydrocarbon feeds, Catalysts Deactivation Problems is more serious.In order to reduce the cost of heavy, poor residuum processing, increase the oil refining enterprise profit, at present, process the technique of more heavy, poor residuum still take decarbonization process as main, but its poor product quality need to be carried out aftertreatment and could be utilized, wherein deasphalted oil and wax tailings cut especially need to carry out hydrotreatment, could continue to use the lighting devices such as catalytic cracking or hydrocracking to process, therefore, each oil refining enterprise all has the hydrotreater of deasphalted oil and wax tailings in addition.
The slag oil cracking rate of heavy oil, residual hydrocracking technology is lower, and main purpose is to supply raw materials for downstream raw material lighting device such as the devices such as catalytic cracking or coking.By hydrotreatment, sulphur, nitrogen, metal impurities content and carbon residue in the poor residuum are obviously reduced, thereby obtain the charging that raw material lighting device in downstream can be accepted, especially catalytic cracking unit, therefore at present in heavy, the residual hydrogenation residua upgrading Technology take residue fixed-bed hydrotreatment and catalytic cracking combination technique as mainstream technology.
In fixed bed residual hydrocracking technology, according to the flow pattern of reactant flow in reactor, type of reactor can be divided into common fixed-bed reactor namely flow downward mode reactor and upflowing (UFR) reactor.The metal content of UFR reactor in can the decrease charging; effectively slow down the generation of bed pressure drop; therefore UFR reactor operated by rotary motion protects the fixed bed reactor catalyst bed to be forced to stop work because running later stage metal deposition causes bed pressure drop to raise rapidly at fixed-bed reactor (downward stream mode) before.The up-flow reactor technology characteristics is that the gas-oil mixture charging is upwards passed through the upflowing beds from reactor bottom, and be that liquid phase is continuous in reactor, gas phase is the bubbling form and passes through, make whole beds slight expansion, the settling such as metal and coke can be deposited on whole beds equably, avoid concentrating on a certain part, brought into play preferably the catalyst performance of each point, slow down the rapid growth of beds pressure drop.
Upflowing (UFR) reactor operated by rotary motion can decrease enters the metal content in the down-type fixed-bed reactor charging at fixed-bed reactor (downward stream mode) before, and the protection fixed bed reactor catalyst prevents its too early inactivation.Updraft technical characterstic is that reactant flow flows from bottom to top, make the beds slight expansion, so Pressure Drop is less, thereby the large problem of variation falls in the initial stage when solving conventional fixed-bed reactor processing poor residuum and terminal pressure.Up-flow reactor can remove metallic impurity preferably, with the fixed-bed reactor in protection downstream, prolong operating period.This combination process can be given full play to upflowing reaction zone and fixed-bed reactor advantage separately.
Usually in the fixed-bed reactor catalyzer of difference in functionality is divided in different reactors or the different bed, packing sequence is: generally load first Hydrodemetalation catalyst, Hydrobon catalyst, at last fill depth desulfurization depth carbon residue conversion catalyst recharge.
In the conventional up-flow reactor and down-type fixed-bed reactor combination process, heavy hydrocarbon feeds mixes with the mixed hydrogen of UFR, and the logistics of UFR hydrogenation is mixing with the mixed hydrogen of fixed bed.Because the mixed hydrogen amount of fixed bed is large, temperature is low than the logistics of UFR hydrogenation, therefore significantly temperature drop occurs at the fixed bed entrance.
After mixing with hydrogen, common updraft reaction effluent passes through successively Hydrodemetalation catalyst, Hydrobon catalyst and deep conversion beds at first fixed-bed reactor top with downward stream mode.Reaction finishes the hydrogenation resultant and carries out gas-liquid separation.But because the adding of a large amount of hydrogen of down-flow fixed bed entrance causes temperature in to descend, especially with the prolongation of runtime, UFR reactor and the down-type fixed-bed reactor cycle of operation and the unmatched problem of temperature of reaction, the down-type fixed-bed reactor entrance does not have effective temperature raising means, the down-flow fixed bed reactive behavior can not be given full play to, and is unfavorable for prolonging running period.
For the hydrodesulfurization reaction of general sulfide, when pressure is not too high, just can reach higher depth of conversion.And large for reaction hydrogenation difficulty such as the conversion of deep desulfuration, hydrodenitrification, carbon residue and the bitum hydrocrackings of macromole, need higher reaction pressure, and these reactions all are to finish at the fixed bed catalyst bed.And in the fixed bed hydrogenation technique of above-mentioned routine, the hydrogen dividing potential drop constantly reduces along the direction of logistics in the reactor, and its reason has: hydrogenation reaction consumes hydrogen, so that the hydrogen molecule number descends in the gas phase; Because the hydrogenation reaction heat release, reaction bed temperature rises, and the stock oil vaporization rate increases, and the oil gas molecule number increases; The hydrocarbon gas of generation low carbon number, hydrogen sulfide, ammonia etc. increase gas molecula number in the reaction process.So just occurred so that easily the hydrogen dividing potential drop of hydro-upgrading part (hydrodemetallation (HDM), partial hydrogenation desulfurization) is high, and the hydrogen of difficult hydro-upgrading part (deep hydrodesulfurizationof, hydrodenitrification, removal of ccr by hydrotreating) divides and forces down, and causes the low reaction rate of whole hydrogenation reaction.Hydrogenation reaction is thermopositive reaction in addition, and the concurrent flow of charging has both increased the cold hydrogen amount of device so that reactor reaction temperature rising gradient is large, has also increased cracking reaction and the coking reaction of stock oil, improves the hydrogen consumption of device.
In the combination process of existing UFR reactor and down-type fixed-bed reactor, exist the prolongation with runtime, UFR reactor and the down-type fixed-bed reactor cycle of operation and the unmatched problem of temperature of reaction, the down-flow fixed bed entrance does not have the temperature raising means, and the beds that down-flow fixed bed is especially last is because the reduction of hydrogen dividing potential drop can not be given full play to its reactive behavior.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of heavy-hydrocarbon raw material hydrogenation treatment method, the inventive method is by adjusting the material technical process, make up-flow reactor, down-type fixed-bed reactor and adverse current fixed-bed reactor cooperation, improve the down-flow fixed bed temperature distribution, further improve simultaneously the performance of the removing impurities matter performance of fixed bed catalyst, reduce cold hydrogen and inject the extension fixture cycle of operation.
Heavy hydrocarbon hydroprocessing method of the present invention comprises following content: the use of connecting successively of up-flow reactor (hereinafter referred to as UFR), at least one down-type fixed-bed reactor and countercurrent hydrogenation reactor, heavy hydrocarbon feeds is successively by UFR, down-type fixed-bed reactor and counter-current reactor, wherein:
(1) enter UFR after heavy hydrocarbon feeds and the hydrogen radiation section that is blended in process furnace is heated to the required temperature of reaction of UFR, the hydrogen to oil volume ratio of UFR entrance is 150: 1～300: 1;
(2) the UFR reactor effluent mixes with the down-flow fixed bed that heats through the process furnace convection zone and enters the further hydrotreatment of down-type fixed-bed reactor after hydrogen mixes, and the down-type fixed-bed reactor hydrogen to oil volume ratio is 400: 1～1200: 1;
(3) the down-type fixed-bed reactor effluent enters the top of counter-current reactor, hydrogen enters from the counter-current reactor bottom, separate the generation oil that obtains with the down-flow fixed bed reaction effluent and carry out reverse contact and finish hydrogenation reaction, the hydrogen to oil volume ratio in the adverse current fixed-bed reactor is 500: 1～1500: 1.
According to heavy hydrocarbon hydroprocessing method of the present invention, wherein also comprise step (4): step (3) gained liquid phase stream separates and fractionation, obtains light-end products and hydrogenation tail oil, and the gained gaseous product enters cold high score to be separated.
In the methods of the invention, described up-flow reactor is gas and liquid and flows to the upper reactor that flows.Described down-type fixed-bed reactor is gas and liquid and flows to lower reactor by the fixed bed catalyst bed.And described counter-current reactor to be hydrogen upwards flow the reactor of downward liquid flow and hydrogen counter current contact.
In the inventive method, the counter-current reactor gained generates oil and at first carries out gas-liquid separation, obtain hydrogen-depleted gas body and hydrogenation heavy oil, the hydrogen-depleted gas body goes the cold low separator to continue to separate, and hydrogenation heavy oil then removes atmospheric fractional tower or directly goes the further lighting of catalytic cracking unit.The gas-phase product of being discharged by the counter-current reactor top mainly contains light hydrocarbons, isolate hydrogen-rich gas and light ends so can directly enter cold high pressure separator, hydrogen-rich gas Returning reactor after purifying continues to use, and light ends then goes the cold low separator to continue to separate.
In the inventive method, UFR generally introduces cold oil, and down-type fixed-bed reactor is generally introduced cold hydrogen, to adjust temperature distribution, prevents that local temperature is too high.Down-type fixed-bed reactor can be connected and be arranged 1～5, preferred 2～3.In UFR and the down-type fixed-bed reactor one or more beds can be set as required.And 1 of counter-current reactor operated by rotary motion arranges 1～3 beds equally in the counter-current reactor.
In the inventive method; the catalyzer that uses in UFR, down-type fixed-bed reactor and the counter-current reactor can be the common heavy hydrocarbons hydrotreating catalyst in this area; optimum catalyst character can be optimized according to feedstock property; catalyzer generally comprises multiple; such as the hydrogenation protecting agent; Hydrodemetalation catalyst; Hydrobon catalyst; hydrodenitrogenation catalysts etc., catalyzer generally are followed successively by hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst by the flow direction of reaction mass.Catalyzer can adopt the commercial goods, such as the residual hydrogenation catalyst series of Sinopec Fushun Petrochemical Research Institute development and production etc., and also can be according to the existing method preparation in this area.The catalyzer that UFR uses is generally sphere, and the catalyzer that down-type fixed-bed reactor and counter-current reactor use can be any suitable shape, such as sphere, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc.
In the inventive method, reaction conditions can be determined by this area general knowledge according to the reaction effect that raw material properties and requirement reach.In general the UFR reaction conditions is, reaction pressure 8～25MPa, 350～400 ℃ of temperature of reaction, volume space velocity 0.2～2.0h during liquid
-1The down-type fixed-bed reactor reaction conditions is reaction pressure identical with UFR (disregarding the pressure-losses of Flow of Goods and Materials), 370～430 ℃ of temperature of reaction, volume space velocity 0.2～1.0 h during liquid
-1The reaction conditions of counter-current reactor is: reaction pressure 8～25MPa, 370～450 ℃ of temperature of reaction, volume space velocity 0.2～2.0h during liquid
-1, the concrete technology condition can be optimized definite on demand.
In the inventive method, press the Flow of Goods and Materials characteristics of UFR and down-type fixed-bed reactor, the required hydrogen of reaction is divided into three parts, a part enters the UFR reactor after the radiation section of process furnace is heated to the required temperature of reaction of UFR, another part enters down-type fixed-bed reactor after heating through the preheating facility that arranges in the process furnace convection zone.Third part enters the counter-current reactor bottom.The material that this scheme is conducive in the dissimilar reactors on the one hand distributes and the fluid distribution, can control flexibly on the other hand the temperature in of down-type fixed-bed reactor, the reaction conditions that makes UFR and down-type fixed-bed reactor is flexible on demand, solved the problem that the down-type fixed-bed reactor temperature of reaction is subject to UFR, both are fully coordinated, reach desirable combined reaction effect.Particularly in the reaction middle and later periods, UFR fully temperature raising causes the down-type fixed-bed reactor reactivity worth to descend, affect the problem of running period, simultaneously because counter-current reactor beds catalyst activity levels is the highest, the hydrofining degree of depth is maximum, and the deep hydrogenation that the raising of hydrogen dividing potential drop is conducive to impurity transforms.The inventive method is fully studied the reaction characteristics of UFR, down-type fixed-bed reactor and counter-current reactor, solved three kinds of reactors in conjunction with the time can't effectively prolong running period deficiency, the temperature distribution of down-type fixed-bed reactor is more reasonable, given full play to the performance of down-type fixed-bed reactor catalyzer, catalyst utilization and impurity removal percentage have been improved, the shut-down that has reduced device is the catalyst changeout number of times more, has obviously improved the economic benefit of device.
For the hydrodesulfurization reaction of general sulfide, when pressure is not too high, just can reach higher depth of conversion.And large for reaction hydrogenation difficulty such as the conversion of deep desulfuration, hydrodenitrification, carbon residue and the bitum hydrocrackings of macromole, need higher reaction pressure, and these reactions all are to finish at the fixed bed catalyst bed.And in the fixed bed hydrogenation technique of above-mentioned routine, the hydrogen dividing potential drop constantly reduces along the direction of logistics in the reactor, and its reason has: hydrogenation reaction consumes hydrogen, so that the hydrogen molecule number descends in the gas phase; Because the hydrogenation reaction heat release, reaction bed temperature rises, and the stock oil vaporization rate increases, and the oil gas molecule number increases; The hydrocarbon gas of generation low carbon number, hydrogen sulfide, ammonia etc. increase gas molecula number in the reaction process.So just occurred so that easily the hydrogen dividing potential drop of hydro-upgrading part (hydrodemetallation (HDM), partial hydrogenation desulfurization) is high, and the hydrogen of difficult hydro-upgrading part (deep hydrodesulfurizationof, hydrodenitrification, removal of ccr by hydrotreating) divides and forces down, and causes the low reaction rate of whole hydrogenation reaction.Hydrogenation reaction is thermopositive reaction in addition, and the concurrent flow of charging has both increased the cold hydrogen amount of device so that reactor reaction temperature rising gradient is large, has also increased cracking reaction and the coking reaction of stock oil, increases the hydrogen consumption of device.
In the prior art, in the tandem process of UFR and down-type fixed-bed reactor, along with flowing of reaction mass, concentration of hydrogen sulfide in the hydrogen is more and more higher, when reaction mass is flowed through last down-type fixed-bed reactor, concentration of hydrogen sulfide peaks in the hydrogen, and last reactor mainly carries out deep hydrodesulfurizationof and carbon residue conversion reaction, too high concentration of hydrogen sulfide severe inhibition the carrying out of reaction, this foreign matter content that also often causes hydrotreatment to generate oil can not satisfy the charging requirement of catalytic cracking unit.And in the methods of the invention, change last down-type fixed-bed reactor into countercurrent hydrogenation reactor, after a series of hydrogenation reactions through the upstream, generating oil reacts with reverse contact of fresh recycle hydrogen in counter-current reactor, because hydrogen sulfide content is very low in the fresh recycle hydrogen, therefore more be conducive to generate the carrying out of oily deep hydrodesulfurizationof reaction.In counter-current reactor, reaction bed temperature is more even simultaneously, and catalyst activity can access more fully performance.
The inventive method solved UFR and fixed-bed reactor in conjunction with the time can't effectively prolong running period deficiency, the temperature distribution of down-type fixed-bed reactor is more reasonable, further improve the performance of the removing impurities matter performance of down-flow fixed bed catalyzer, improve the utilising efficiency of catalyzer, the extension fixture cycle of operation.The reaction formation that last fixed-bed reactor take fluid countercurrent current to flow, hydrogen dividing potential drop in the fixed-bed reactor is raise from back to front successively, be conducive to the conversion that removes that difficulty removes sulphur, carbon residue etc., and can improve the reaction bed temperature distribution, decreasing ratio and the device handiness of impurity have been improved, the shut-down that has reduced device is the catalyst changeout number of times more, has obviously improved the economic benefit of device.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
In UFR and fixed-bed reactor combined process flow technique, focus appears in UFR easily in operational process, especially to the later stage in service be the position that focus produces easily at UFR upper catalyst bed layer.When UFR focus occurs and can not further promote temperature of reaction the time, and because the existing institute of the activity of down-flow fixed bed catalyzer descends, reactivity worth does not reach requirement, the more catalyst changeout of just need to stopping work at this moment.At this moment, the down-flow fixed bed catalyzer does not take full advantage of.Simultaneously since in last reactor hydrogen sulfide content very high, also severe inhibition the carrying out of deep hydrodesulfurizationof reaction, affected the hydrogenating desulfurization degree of depth.
In the inventive method, increase the preheating facility at the Reaktionsofen convection zone, the required hydrogen of partial reaction is heated, the funnel temperature of process furnace is down to below 250 ℃, send again air preheater centralized recovery heat.
In the inventive method, the upflowing hydrogenation reaction refers to that residual oil is mixed into to be filled with in upflowing hydrogenation catalyst such as the FZC10U type upflowing hydrogenator with pre-hydrogenation effluent and carries out hydrogenation reaction, up-flow reactor adopts the multi-catalyst bed, between beds, squeeze into cold oil, with the control bed temperature, carry the bed heat.FZC10U type upflowing hydrogenation catalyst is produced by catalyzer branch office of Sinopec Group.
The down-type fixed-bed reactor that relates to and counter-current reactor are the trickle bed hydrogen addition technology, single catalyst or the combination catalyst of the function such as the catalyst for hydrotreatment of residual oil of employing refers to have residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.These catalyzer generally all are as carrier take porous refractory inorganic oxides such as aluminum oxide; group vib and/or VIII family metal such as W; Mo; Co; the oxide compound of Ni etc. is active ingredient; optionally add other various auxiliary agents such as P; Si; F; the catalyzer of the elements such as B; the FZC series residual oil hydrocatalyst produced of Sinopec Group's catalyzer branch office for example; specifically comprise protective material; catalyst for demetalation; desulfurization catalyst; denitrification catalyst etc.; filling order generally be make stock oil successively with protective material; hydrodemetallation (HDM); hydrogenating desulfurization; the hydrodenitrogenation catalyst contact also has the technology with these several catalyst mix fillings certainly.The technology contents that above-mentioned catalyst loading technology is well known to those skilled in the art.
Below in conjunction with drawings and Examples the present invention is described in further details.
As shown in Figure 1, heavy hydrocarbon kind of raw materials 1 mixes with recycle hydrogen 22 after feedstock pump 2 boosts, mixed oil and gas 3 enters the radiation section heating of process furnace 4, oil gas 5 enters from the bottom of up-flow reactor 6 after the heating, in the presence of the upflowing hydrogenation catalyst, carry out the hydrotreatment reaction, hydrogenated oil 7 flows out from the up-flow reactor top and obtains high-temperature oil gas 8 after hydrogen 17 through the convection zone preheating mixes and enter down-type fixed-bed reactor, and reactant flow is that from top to bottom flow pattern is carried out hydrotreatment in the presence of the fixed bed residual oil hydrocatalyst in fixed-bed reactor.High-temperature oil gas 8 at first enters fixed bed one anti-9 tops, one anti-hydrogenation effluent 10 enters counter-current reactor 11 tops, liquid phase is flow pattern from top to bottom in counter-current reactor, gas phase is that hydrogen 22 is flow pattern from bottom to up in fixed-bed reactor, carries out hydrotreatment in the presence of the fixed bed residual oil hydrocatalyst.Counter-current reactor liquid phase stream 12 is discharged from the bottom, obtains the main purpose hydrogenation of net product through separator 13 and generates oil 15 and lighter hydrocarbons 14, and counter-current reactor gaseous stream 16 obtains recycle hydrogen 18 through separator 17 separating-purifyings.Recycle hydrogen 18 through compressors 19 with obtain mixed hydrogen 22 for each reactor after new hydrogen 21 mixes, the distribution of hydrogen is definite by requirements such as reaction conditions and temperature of reactor controls.
Embodiment
Test at the residual hydrogenation pilot plant that UFR, down-flow fixed bed and counter-current reactor form, comprise that a UFR reactor, a down-type fixed-bed reactor and a counter-current reactor are composed in series.
Raw materials used is typical Middle East residual oil, and catalyst system therefor is FZC-10U type upflowing hydrogenation catalyst, and 387 ℃ of temperature of reaction, the reaction total pressure is 15.7MPa, volume space velocity: 0.50h
-1, under the processing condition of hydrogen-oil ratio volume (v/v) 230, in upflowing residual hydrogenation reactor, carry out hydro-upgrading reaction, obtain the upflowing hydrogenated oil after mainly removing the impurity such as metal and sulfide.Character sees table 1 for details.
The upflowing hydrogenated oil flows out from the up-flow reactor top and is mixed into the down-flow fixed bed hydrotreating unit through the mixed hydrogen of the down-flow fixed bed of further heat exchange, and the mixed hydrogen temperature of down-flow fixed bed is elevated to 282 ℃ from original 253 ℃.Carry out the hydrotreatment reaction in the presence of the down-flow fixed bed residual oil hydrocatalyst, down-flow fixed bed comprises main fill depth catalyst for demetalation, and desulfurization catalyst; The down-flow fixed bed effluent enters counter-current reactor and the mixed reverse contact reacts of hydrogen of counter-current reactor, further hydro-upgrading, deep removal metal and sulphur, and the conversion of degree of depth carbon residue mainly load high reactivity desulfurization catalyst and denitrification catalyst and degree of depth carbon residue conversion catalyst.394 ℃ of temperature of reaction, volume space velocity: 0.39h
-1, hydrogen-oil ratio volume (v/v) 552.Be fixed the bed hydroprocessing reaction through further hydrotreatment and generate oil.Technological condition sees table 3 for details.
For UFR, down-type fixed-bed reactor and counter-current reactor, the condition that adopts also should be different.
Comparative Examples
Adopt identical raw material to adopt identical catalyzer to carry out hydrogenation reaction with identical processing condition at up-flow reactor, obtain the upflowing hydrogenated oil.Generate oil nature and see table 2 for details.
Different from embodiment is, comprises that a UFR reactor, two down-type fixed-bed reactors are composed in series, and wherein the counter-current reactor size of last reactor and embodiment is identical.The upflowing hydrogenated oil is from being mixed into the fixed bed hydrogenation processing unit with the mixed hydrogen of fixed bed, and the mixed hydrogen of this fixed bed is original 253 ℃ without heat-exchange temperature.Carry out the hydrotreatment reaction in the presence of the fixed bed residual oil hydrocatalyst, fixed bed comprises two reactors, main fill depth catalyst for demetalation, and the carbon residue catalyzer is taken off in desulfurization.391 ℃ of temperature of reaction, volume space velocity: 0.39h
-1, hydrogen-oil ratio volume (v/v) 552.Be fixed the bed hydroprocessing reaction through further hydrotreatment and generate oil.Technological condition sees table 3 for details.
The main operational condition of table 1 embodiment and Comparative Examples
| Project | Embodiment | Comparative Examples |
| One anti-inlet pressure, MPa | 16.0 | 16.0 |
| The cumulative volume air speed, h -1 | 0.22 | 0.22 |
| The UFR operational condition | ? | ? |
| Volume space velocity, h -1 | 0.50 | 0.50 |
| The entrance gas oil ratio | 228 | 228 |
| Temperature in, ℃ | 375 | 375 |
| Temperature out, ℃ | 398 | 398 |
| Medial temperature, ℃ | 387 | 387 |
| The down-flow fixed bed operational condition | ? | (downflow system one is anti-) |
| Volume space velocity, h -1 | 1.0 | 1.0 |
| Total gas-oil ratio | 460 | 550 |
| Entrance mixes the hydrogen temperature, ℃ | 282 | 253 |
| Temperature in, ℃ | 389 | 384 |
| Medial temperature, ℃ | 394 | 391 |
| Temperature rise, ℃ | 9 | 5 |
| The counter-current reactor operational condition | ? | (downflow system two is anti-) |
| Volume space velocity, h -1 | 0.75 | 0.75 |
| The bottom inlet gas oil ratio | 90 | — |
| Bottom inlet mixes the hydrogen temperature, ℃ | 253 | — |
Table 2 embodiment raw material, upflowing and fixed bed hydrogenation generate oily main character
| Project | Raw material | The upflowing hydrogenated oil | Counter-current reactor generates oil |
| S, wt% | 3.10 | 1.22 | 0.42 |
| N, μg/g | 3220 | 2260 | 1602 |
| Carbon residue (CCR), wt% | 12.55 | 7.6 | 4.60 |
| Density (20 ℃), kg/m 3 | 986.1 | 955.0 | 936.2 |
| Viscosity (100 ℃), mm 2/s | 120.4 | 45.5 | 23.2 |
| Ni+V,μg/g | 97.0 | 35.0 | 11.5 |
Table 3 Comparative Examples raw material, upflowing and fixed bed hydrogenation generate oily main character
| Project | Raw material | The upflowing hydrogenated oil | The downflow reactor two anti-oil that generate |
| S, wt% | 3.10 | 1.22 | 0.54 |
| N, μg/g | 3220 | 2260 | 2020 |
| Carbon residue (CCR), wt% | 12.55 | 7.6 | 5.74 |
| Density (20 ℃), kg/m 3 | 986.1 | 955.0 | 940.0 |
| Viscosity (100 ℃), mm 2/s | 120.4 | 45.5 | 36.3 |
| Ni+V,μg/g | 97.0 | 35.0 | 15.6 |
The residual hydrogenation stability test
In order further to investigate Technology of the present invention to the impact of activity, stability and the fixed bed catalyst temperature rise of the follow-up fixed bed catalyst bed catalyzer of up-flow reactor, respectively embodiment and Comparative Examples have been carried out stable longevity test, the up-flow reactor condition is consistent with reaction result in the simultaneous test, and fixed bed reaction the results are shown in Table 4.
The stability test of table 4 residual hydrogenation
| Runtime | 500h | 1000h | 2000h | 3000h |
| Generate oily S, wt% | ? | ? | ? | ? |
| Embodiment | 0.42 | 0.42 | 0.44 | 0.45 |
| Comparative Examples | 0.54 | 0.58 | 0.63 | 0.67 |
| Generate oily CCR, wt% | ? | ? | ? | ? |
| Embodiment | 4.60 | 4.68 | 5.07 | 5.40 |
| Comparative Examples | 5.75 | 5.84 | 6.55 | 6.82 |
The present invention has had obvious improvement than the generation oil nature of existing technique in the Comparative Examples as can be seen from Table 4, and the present invention is better than Comparative Examples hydrogenation activity and stability.In addition, as can be seen from Table 4, Technology of the present invention can effectively be improved the temperature rise of fixed-bed reactor, especially fixed bed one anti-temperature rise is significantly improved, the raising of counter-current reactor hydrogen dividing potential drop and hydrogen purity is most important to the performance of performance fixed bed catalyst in addition, and can improve reaction environment, and improve hydrogenation activity and the stability of monolithic catalyst system, thus the work-ing life of extending catalyst.
Claims (11)
1. heavy hydrocarbon hydroprocessing method, comprise following content: the use of connecting successively of up-flow reactor, at least one down-type fixed-bed reactor and countercurrent hydrogenation reactor, heavy hydrocarbon feeds is successively by UFR, down-type fixed-bed reactor and counter-current reactor, wherein:
(1) enter UFR after heavy hydrocarbon feeds and the hydrogen radiation section that is blended in process furnace is heated to the required temperature of reaction of UFR, the hydrogen to oil volume ratio of UFR entrance is 150: 1～300: 1;
(2) the UFR reactor effluent mixes with the down-flow fixed bed that heats through the process furnace convection zone and enters the further hydrotreatment of down-type fixed-bed reactor after hydrogen mixes, and the down-type fixed-bed reactor hydrogen to oil volume ratio is 400: 1～1200: 1;
(3) the down-type fixed-bed reactor effluent enters the top of counter-current reactor, hydrogen enters from the counter-current reactor bottom, separate the generation oil that obtains with the down-flow fixed bed reaction effluent and carry out reverse contact and finish hydrogenation reaction, hydrogen to oil volume ratio is 500: 1～1500: 1 in the adverse current fixed-bed reactor.
2. in accordance with the method for claim 1, it is characterized in that, also comprise step (4): step (3) gained generates oil to be separated and fractionation, obtains light-end products and hydrogenation tail oil, and the gained gaseous product enters cold high score to be separated.
3. in accordance with the method for claim 1, it is characterized in that, in the inventive method, the gas-phase product that discharge at step (3) counter-current reactor top directly enters cold high pressure separator and isolates hydrogen-rich gas and light ends, hydrogen-rich gas Returning reactor after purifying continues to use, and light ends then goes the cold low separator to continue to separate.
4. in accordance with the method for claim 1, it is characterized in that described down-type fixed-bed reactor series connection arranges 1～5, and one or more beds are set in the reactor.
5. in accordance with the method for claim 1, it is characterized in that described counter-current reactor arranges 1,1～3 beds is set in the reactor.
6. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the described UFR of step (1) is reaction pressure 8～25MPa, 350～400 ℃ of temperature of reaction, volume space velocity 0.2～2.0h during liquid
-1
7. in accordance with the method for claim 1, it is characterized in that the described down-type fixed-bed reactor reaction conditions of step (2) is that reaction pressure is identical with UFR, 370～430 ℃ of temperature of reaction, volume space velocity 0.2～1.0 h during liquid
-1
8. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the described counter-current reactor of step (3) is: reaction pressure 8～25MPa, 370～450 ℃ of temperature of reaction, volume space velocity 0.2～2.0h during liquid
-1
9. in accordance with the method for claim 1, it is characterized in that single catalyst or the combination catalyst of the functions such as the catalyst for hydrotreatment of residual oil that uses in step (2) and the step (3) refers to have residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.
10.1 in accordance with the method for claim 9, it is characterized in that described catalyzer is take porous refractory inorganic oxides such as aluminum oxide as carrier, the oxide compound of group vib and/or VIII family metal is active ingredient.
11. in accordance with the method for claim 1, it is characterized in that the catalyzer that uses in UFR, down-type fixed-bed reactor and the counter-current reactor is followed successively by protective material, hydrodemetallation (HDM), hydrogenating desulfurization and hydrodenitrogenation catalyst by the flow direction of stock oil.
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