CN103059938B - A kind of heavy hydrocarbon hydroprocessing method - Google Patents
A kind of heavy hydrocarbon hydroprocessing method Download PDFInfo
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Abstract
The invention discloses a kind of heavy hydrocarbon hydroprocessing method, comprise following content: up-flow reactor (UFR) is connected with at least one down-type fixed-bed reactor and counter-current reactor and used, heavy hydrocarbon feeds is successively by UFR, down-type fixed-bed reactor and counter-current reactor, and wherein (1) heavy hydrocarbon feeds and hydrogen enter UFR after being blended in the temperature of reaction that process furnace radiation section is heated to needed for UFR; (2) UFR effluent mixes hydrogen with the part heated through process furnace convection zone and mixes, and enters the further hydrotreatment of down-type fixed-bed reactor; (3) down-flow fixed bed reaction effluent enters from counter-current reactor top, has contacted hydrogenation reaction with the mixed hydrogen entered from bottom is reverse.Adopt this kind of technique can control the anti-entrance temperature of reaction of down-flow fixed bed one flexibly, give full play to device fixed bed partially catalyzed agent performance, improve catalyst performance and de-impurity removal percentage further, the extension fixture operational cycle simultaneously.
Description
Technical field
The present invention relates to a kind of hydrocarbons hydrogenation treatment technology, specifically, relate to a kind of hydroprocessing technique comprising 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.Its cracking will be not only lower boiling product by the processing treatment of heavy oil, residual oil, and as petroleum naphtha, intermediate oil and pressure reduction gas wet goods, but also will improve their hydrogen-carbon ratio, this is realized by the method for decarburization or hydrogenation with regard to needing.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, good product quality, have obvious advantage.But hydrogenation technique is catalysis complete processing, there is hydrogenation catalyst deactivation prob, 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 oil refining enterprise's profit, at present, process the technique of more heavy, poor residuum still based on decarbonization process, but its poor product quality, needing to carry out aftertreatment could utilize, wherein deasphalted oil and wax tailings cut especially need to carry out hydrotreatment, could continue to use the lighting such as catalytic cracking or hydrocracking device to process, therefore, each oil refining enterprise all separately has the hydrotreater of deasphalted oil and wax tailings.
The slag oil cracking rate of heavy oil, residual hydrocracking technology is lower, and main purpose is for downstream raw material lighting device such as the device such as catalytic cracking or coking is supplied raw materials.Pass through hydrotreatment, sulphur in poor residuum, nitrogen, metal impurities content and carbon residue are obviously reduced, thus the charging that acquisition downstream raw material lighting device can accept, especially catalytic cracking unit, therefore at present in heavy, residual hydrogenation residua upgrading Technology with residue fixed-bed hydrotreatment and catalytic cracking combination technique for 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 to flow downward mode reactor and upflowing (UFR) reactor.UFR reactor significantly can reduce the metal content in charging; effectively slow down the generation of bed pressure drop; therefore, before UFR reactor is generally arranged on fixed-bed reactor (downward stream mode), protection fixed bed reactor catalyst bed is forced to stop work because running later stage metal deposition causes bed pressure drop to raise rapidly.Up-flow reactor technology characteristics be gas-oil mixture charging from reactor bottom upwards by upflowing beds, and be that liquid phase is continuous in reactor, gas phase is that bubbling form is passed 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 local, played the catalyst performance of each point preferably, slow down the quick growth of beds pressure drop.
Before upflowing (UFR) reactor is generally arranged on fixed-bed reactor (downward stream mode), can significantly reduce the metal content entered in down-type fixed-bed reactor charging, protection fixed bed reactor catalyst, prevents its premature inactivation.Updraft technical characterstic is that reactant flow flows from bottom to top, and make beds slight expansion, therefore Pressure Drop is less, thus initial stage when solving conventional fixed-bed reactor processing poor residuum and terminal pressure fall and change large problem.Up-flow reactor can remove metallic impurity preferably, to protect the fixed-bed reactor in downstream, prolong operating period.This combination process can give full play to upflowing reaction zone and fixed-bed reactor advantage separately.
In usual fixed-bed reactor, the catalyzer of difference in functionality is divided in different reactors or different beds, packing sequence is: generally first load Hydrodemetalation catalyst, recharge Hydrobon catalyst, last fill depth desulfurization depth carbon residue conversion catalyst.
In conventional up-flow reactor and down-type fixed-bed reactor combination process, heavy hydrocarbon feeds and UFR mix hydrogen and mix, and the logistics of UFR hydrogenation mixes mixing hydrogen with fixed bed.Because fixed bed mixes hydrogen amount greatly, temperature comparatively UFR hydrogenation logistics is low, therefore occurs significantly temperature drop at fixed bed entrance.
Hydrodemetalation catalyst, Hydrobon catalyst and deep conversion beds is passed through at first fixed-bed reactor top successively with downward stream mode after usual updraft reaction effluent mixes with hydrogen.Reaction terminates hydrogenation resultant and carries out gas-liquid separation.But because adding of a large amount of hydrogen of down-flow fixed bed entrance causes temperature in decline, 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, down-type fixed-bed reactor entrance does not have effective temperature raising means, down-flow fixed bed reactive behavior can not give full play to, and is unfavorable for extending running period.
For the hydrodesulfurization reaction of general sulfide, just higher depth of conversion can be reached when pressure is not too high.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 are all complete at fixed bed catalyst bed.And in the fixed bed hydrogenation technique of above-mentioned routine, in reactor, hydrogen dividing potential drop constantly reduces along the direction of logistics, its reason has: hydrogenation reaction consumes hydrogen, and hydrogen molecule number in gas phase is declined; Due to hydrogenation reaction heat release, reaction bed temperature rises, and stock oil vaporization rate increases, and oil gas molecule number increases; Generating the hydrocarbon gas of low carbon number, hydrogen sulfide, ammonia etc. in reaction process makes gas molecula number increase.So just occurred making the hydrogen dividing potential drop of easy hydro-upgrading part (hydrodemetallation (HDM), partial hydro-desulfurization) 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 makes reactor reaction temperature raise gradient greatly, has both increased the cold hydrogen amount of device, too increases 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, there is the prolongation with runtime, UFR reactor and the down-type fixed-bed reactor cycle of operation and the unmatched problem of temperature of reaction, down-flow fixed bed entrance does not have temperature raising means, and the especially last beds of down-flow fixed bed makes its reactive behavior not give full play to due to the reduction of hydrogen dividing potential drop.
In prior art, in the tandem process of UFR and down-type fixed-bed reactor, along with the flowing of reaction mass, concentration of hydrogen sulfide in hydrogen is more and more higher, when reaction mass flows through last down-type fixed-bed reactor, in hydrogen, concentration of hydrogen sulfide peaks, and last reactor mainly carries out deep hydrodesulfurizationof and carbon residue conversion reaction, too high concentration of hydrogen sulfide seriously inhibits the carrying out of reaction, and this foreign matter content also often causing hydrotreatment to generate oil can not meet the feed needs 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 reaction in upstream, generate oil to react with reverse contact of fresh recycle hydrogen in counter-current reactor, because in fresh recycle hydrogen, hydrogen sulfide content is very low, be therefore more conducive to the carrying out of the deep hydrodesulfurizationof reaction generating oil.Simultaneously in counter-current reactor, reaction bed temperature is relatively more even, and catalyst activity can be played more fully.
The inventive method solve UFR and fixed-bed reactor in conjunction with time cannot effectively extend running period deficiency, the temperature distribution of down-type fixed-bed reactor is more reasonable, the performance of the removing impurities matter performance of further raising 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 fixed-bed reactor is raised from back to front successively, what be conducive to that difficulty removes sulphur, carbon residue etc. removes conversion, and reaction bed temperature distribution can be improved, improve decreasing ratio and the device handiness of impurity, decrease the shut-down more catalyst changeout number of times of device, significantly improve the economic benefit of device.
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 adjustment process stream journey, make up-flow reactor, down-type fixed-bed reactor and adverse current fixed-bed reactor cooperation, improve down-flow fixed bed temperature distribution, improve the performance of the removing impurities matter performance of fixed bed catalyst simultaneously further, reduce cold hydrogen and inject, the extension fixture cycle of operation.
Heavy hydrocarbon hydroprocessing method of the present invention comprises following content: up-flow reactor (hereinafter referred to as UFR), at least one down-type fixed-bed reactor are connected successively with countercurrent hydrogenation reactor and used, heavy hydrocarbon feeds passes through UFR, down-type fixed-bed reactor and counter-current reactor successively, wherein:
(1) radiation section that heavy hydrocarbon feeds and hydrogen are blended in process furnace enters UFR after being heated to the temperature of reaction needed for UFR, and the hydrogen to oil volume ratio of UFR entrance is 150: 1 ~ 300: 1;
(2) UFR reactor effluent and the down-flow fixed bed heated through process furnace convection zone mix after hydrogen mixes and enter the further hydrotreatment of down-type fixed-bed reactor, and down-type fixed-bed reactor hydrogen to oil volume ratio is 400: 1 ~ 1200: 1;
(3) down-type fixed-bed reactor effluent enters the top of counter-current reactor, hydrogen enters bottom counter-current reactor, be separated with down-flow fixed bed reaction effluent the generation oil obtained to carry out reversely having contacted hydrogenation reaction, the hydrogen to oil volume ratio in 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 carries out being separated and fractionation, obtains light-end products and hydrogenation tail oil, and gained gaseous product enters cold high score and is separated.
In the methods of the invention, described up-flow reactor is the reactor that gas and liquid also flow to upper flowing.Described down-type fixed-bed reactor is gas and liquid and stream passes downwardly through the reactor of fixed bed catalyst bed.And described counter-current reactor is hydrogen upwards flows, the reactor of downward liquid flow and hydrogen counter current contact.
In the inventive method, counter-current reactor gained generates oil and first carries out gas-liquid separation, obtain hydrogen depleted gas and hydrogenation heavy oil, hydrogen depleted gas goes cold low separator to continue to be separated, 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 counter-current reactor top is mainly containing light hydrocarbons, so cold high pressure separator directly can be entered isolate hydrogen-rich gas and light ends, hydrogen-rich gas Returning reactor after purifying continues to use, and light ends then goes cold low separator to continue to be separated.
In the inventive method, UFR generally introduces cold oil, and down-type fixed-bed reactor generally introduces cold hydrogen, to adjust temperature distribution, prevents local temperature too high.Down-type fixed-bed reactor can be arranged in series 1 ~ 5, preferably 2 ~ 3.In UFR and down-type fixed-bed reactor, can one or more beds be set as required.And counter-current reactor generally arranges 1,1 ~ 3 beds is set in counter-current reactor equally.
In the inventive method; the catalyzer used in UFR, down-type fixed-bed reactor and 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; as hydrogenation protecting agent; Hydrodemetalation catalyst; Hydrobon catalyst; hydrodenitrogenation catalysts etc., catalyzer is generally followed successively by hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst by the flow direction of reaction mass.Catalyzer can adopt commercial goods, as the residual hydrogenation catalyst series etc. of Sinopec Fushun Petrochemical Research Institute development and production, and also can according to the existing method preparation in this area.The catalyzer that UFR uses is generally spherical, and the catalyzer that down-type fixed-bed reactor and counter-current reactor use can be any suitable shape, as spherical, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc.
In the inventive method, the reaction effect that reaction conditions can reach according to the character of raw material and requirement is determined by this area general knowledge.In general UFR reaction conditions is, reaction pressure 8 ~ 25MPa, temperature of reaction 350 ~ 400 DEG C, volume space velocity 0.2 ~ 2.0h during liquid
-1; Down-type fixed-bed reactor reaction conditions is, reaction pressure identical with UFR (disregarding the pressure-losses of Flow of Goods and Materials), temperature of reaction 370 ~ 430 DEG C, volume space velocity 0.2 ~ 1.0 h during liquid
-1; The reaction conditions of counter-current reactor is: reaction pressure 8 ~ 25MPa, temperature of reaction 370 ~ 450 DEG C, volume space velocity 0.2 ~ 2.0h during liquid
-1, concrete technology condition can be optimized on demand and determines.
In the inventive method, by the Flow of Goods and Materials feature of UFR and down-type fixed-bed reactor, hydrogen needed for reaction is divided into three parts, a part of radiation section through process furnace enters UFR reactor after being heated to the temperature of reaction needed for UFR, and another part enters down-type fixed-bed reactor after the preheating facility heating arranged in process furnace convection zone.Part III enters bottom counter-current reactor.The program material be conducive on the one hand in dissimilar reactor distributes and fluid distributes, the temperature in of down-type fixed-bed reactor can be controlled on the other hand flexibly, make the reaction conditions of UFR and down-type fixed-bed reactor can flexible on demand, solve the problem that down-type fixed-bed reactor temperature of reaction is limited to UFR, make both fully coordinate, reach desirable combined reaction effect.Particularly later stage in the reaction, UFR can not fully temperature raising cause down-type fixed-bed reactor reactivity worth to decline, 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 raising of hydrogen dividing potential drop is conducive to the deep hydrogenation conversion of impurity.The inventive method fully studies the reaction characteristics of UFR, down-type fixed-bed reactor and counter-current reactor, solve three kinds of reactors in conjunction with time cannot effectively extend running period deficiency, the temperature distribution of down-type fixed-bed reactor is more reasonable, give full play to the performance of down-type fixed-bed reactor catalyzer, improve catalyst utilization and impurity removal percentage, decrease the shut-down more catalyst changeout number of times of device, significantly improve the economic benefit of device.
For the hydrodesulfurization reaction of general sulfide, just higher depth of conversion can be reached when pressure is not too high.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 are all complete at fixed bed catalyst bed.And in the fixed bed hydrogenation technique of above-mentioned routine, in reactor, hydrogen dividing potential drop constantly reduces along the direction of logistics, its reason has: hydrogenation reaction consumes hydrogen, and hydrogen molecule number in gas phase is declined; Due to hydrogenation reaction heat release, reaction bed temperature rises, and stock oil vaporization rate increases, and oil gas molecule number increases; Generating the hydrocarbon gas of low carbon number, hydrogen sulfide, ammonia etc. in reaction process makes gas molecula number increase.So just occurred making the hydrogen dividing potential drop of easy hydro-upgrading part (hydrodemetallation (HDM), partial hydro-desulfurization) 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 makes reactor reaction temperature raise gradient greatly, has both increased the cold hydrogen amount of device, too increases cracking reaction and the coking reaction of stock oil, increases the hydrogen consumption of device.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
In UFR and fixed-bed reactor combined process flow technique, easily there is focus in UFR in operational process, and especially having arrived and having run the middle and later periods is the position that focus easily produces at UFR upper catalyst bed layer.When UFR occurs focus and can not promote temperature of reaction further, and declining because the activity of down-flow fixed bed catalyzer is existing, reactivity worth does not reach requirement, and now just needs are stopped work more catalyst changeout.Now, down-flow fixed bed catalyzer does not make full use of.Simultaneously because hydrogen sulfide content in last reactor is very high, the carrying out that also seriously inhibit deep hydrodesulfurizationof to react, have impact on the hydrogenating desulfurization degree of depth.
In the inventive method, increase preheating facility at Reaktionsofen convection zone, hydrogen needed for partial reaction is heated, the funnel temperature of process furnace is down to less than 250 DEG C, then send air preheater centralized recovery heat.
In the inventive method, upflowing hydrogenation reaction refers to that residual oil and pre-hydrogenation effluent are mixed into and is filled with upflowing hydrogenation catalyst as carried out hydrogenation reaction in FZC10U type upflowing hydrogenator, up-flow reactor adopts multi-catalyst bed, cold oil is squeezed between beds, to control bed temperature, carry bed heat.FZC10U type upflowing hydrogenation catalyst is produced by catalyzer branch office of Sinopec Group.
The down-type fixed-bed reactor related to and counter-current reactor are trickle bed hydrogen addition technology, and the catalyst for hydrotreatment of residual oil of employing refers to the single catalyst or combination catalyst with functions such as residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.These catalyzer are all generally if aluminum oxide is for carrier with porous refractory inorganic oxide, group vib and/or group VIII metal are as W, Mo, Co, the oxide compound of Ni etc. is active ingredient, optionally add other various auxiliary agent as P, Si, F, the catalyzer of the elements such as B, the FZC series residual oil hydrocatalyst that such as Sinopec Group's catalyzer branch office produces, specifically comprise protective material, catalyst for demetalation, desulfurization catalyst, denitrification catalyst etc., filling order be generally make stock oil successively with protective material, hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst contacts, certainly also have the technology of this several catalyst mix filling.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, after heating, oil gas 5 enters from the bottom of up-flow reactor 6, hydrotreatment reaction is carried out under upflowing hydrogenation catalyst exists, hydrogenated oil 7 obtains high-temperature oil gas 8 from the outflow of up-flow reactor top and enters down-type fixed-bed reactor after mixing through the hydrogen 17 of convection zone preheating, in fixed-bed reactor, reactant flow is that flow pattern from top to bottom carries out hydrotreatment under fixed bed residual oil hydrocatalyst exists.First high-temperature oil gas 8 enters anti-9 tops of fixed bed one, one anti-hydrogenation effluent 10 enters counter-current reactor 11 top, in counter-current reactor, liquid phase is flow pattern from top to bottom, gas phase and hydrogen 22 are flow pattern from bottom to up in fixed-bed reactor, under fixed bed residual oil hydrocatalyst exists, carry out hydrotreatment.Counter-current reactor liquid phase stream 12 is discharged from bottom, and obtain main purpose hydrogenation of net product through separator 13 and generate oil 15 and lighter hydrocarbons 14, counter-current reactor gaseous stream 16 obtains recycle hydrogen 18 through separator 17 separating-purifying.Recycle hydrogen 18 obtains mixed hydrogen 22 for each reactor after compressor 19 mixes with new hydrogen 21, and the distribution of hydrogen is determined by requirements such as reaction conditions and temperature of reactor controls.
Embodiment
Test at the residual hydrogenation pilot plant of UFR, down-flow fixed bed and counter-current reactor composition, comprise a UFR reactor, a down-type fixed-bed reactor and a counter-current reactor and be composed in series.
Raw materials used is typical Middle East residual oil, and used catalyst is FZC-10U type upflowing hydrogenation catalyst, and temperature of reaction 387 DEG C, 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, after mainly removing the impurity such as metal and sulfide, obtain upflowing hydrogenated oil.Character refers to table 1.
Upflowing hydrogenated oil mixes hydrogen from the outflow of up-flow reactor top with the down-flow fixed bed through further heat exchange and is mixed into down-flow fixed bed hydrotreating unit, and down-flow fixed bed mixes hydrogen temperature and is elevated to 282 DEG C from original 253 DEG C.Under down-flow fixed bed residual oil hydrocatalyst exists, carry out hydrotreatment reaction, down-flow fixed bed comprises main fill depth catalyst for demetalation, and desulfurization catalyst; Down-flow fixed bed effluent enters counter-current reactor and counter-current reactor mixes the reverse contact reacts of hydrogen, further hydro-upgrading, deep removal metal and sulphur, and degree of depth carbon residue transforms, main filling high reactivity desulfurization catalyst and denitrification catalyst and degree of depth carbon residue conversion catalyst.Temperature of reaction 394 DEG C, volume space velocity: 0.39h
-1, hydrogen-oil ratio volume (v/v) 552.Be fixed bed hydroprocessing reaction through further hydrotreatment and generate oil.Technological condition refers to table 3.
For UFR, down-type fixed-bed reactor and counter-current reactor, the condition adopted also should be different.
comparative example
Adopt identical raw material to adopt identical catalyzer to carry out hydrogenation reaction with identical processing condition at up-flow reactor, obtain upflowing hydrogenated oil.Generate oil nature and refer to table 2.
With embodiment unlike, comprise a UFR reactor, two down-type fixed-bed reactors are composed in series, wherein last reactor is identical with the counter-current reactor size of embodiment.Upflowing hydrogenated oil is mixed into fixed bed hydrogenation processing unit from mixing hydrogen with fixed bed, and it is original 253 DEG C that this fixed bed mixes hydrogen without heat-exchange temperature.Under fixed bed residual oil hydrocatalyst exists, carry out hydrotreatment reaction, fixed bed comprises two reactors, main fill depth catalyst for demetalation, and desulfurization takes off carbon residue catalyzer.Temperature of reaction 391 DEG C, volume space velocity: 0.39h
-1, hydrogen-oil ratio volume (v/v) 552.Be fixed bed hydroprocessing reaction through further hydrotreatment and generate oil.Technological condition refers to table 3.
Table 1 embodiment and comparative example prevailing operating conditions
| Project | Embodiment | Comparative example |
| One anti-inlet pressure, MPa | 16.0 | 16.0 |
| Cumulative volume air speed, h -1 | 0.22 | 0.22 |
| UFR operational condition | ||
| Volume space velocity, h -1 | 0.50 | 0.50 |
| Entrance gas oil ratio | 228 | 228 |
| Temperature in, DEG C | 375 | 375 |
| Temperature out, DEG C | 398 | 398 |
| Medial temperature, DEG C | 387 | 387 |
| 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 hydrogen temperature, DEG C | 282 | 253 |
| Temperature in, DEG C | 389 | 384 |
| Medial temperature, DEG C | 394 | 391 |
| Temperature rise, DEG C | 9 | 5 |
| Counter-current reactor operational condition | (downflow system two is anti-) | |
| Volume space velocity, h -1 | 0.75 | 0.75 |
| Bottom inlet gas oil ratio | 90 | — |
| Bottom inlet mixes hydrogen temperature, DEG C | 253 | — |
Table 2 embodiment raw material, upflowing and fixed bed hydrogenation generate oily main character
| Project | Raw material | 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 DEG C), kg/m 3 | 986.1 | 955.0 | 936.2 |
| Viscosity (100 DEG C), mm 2/s | 120.4 | 45.5 | 23.2 |
| Ni+V,μg/g | 97.0 | 35.0 | 11.5 |
Table 3 comparative example raw material, upflowing and fixed bed hydrogenation generate oily main character
| Project | Raw material | Upflowing hydrogenated oil | Downflow reactor two is counter generates oil |
| 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 DEG C), kg/m 3 | 986.1 | 955.0 | 940.0 |
| Viscosity (100 DEG C), mm 2/s | 120.4 | 45.5 | 36.3 |
| Ni+V,μg/g | 97.0 | 35.0 | 15.6 |
Residual hydrogenation stability test
In order to investigate the impact of Technology of the present invention on the activity of the follow-up fixed bed catalyst bed catalyst of up-flow reactor, stability and fixed bed catalyst temperature rise further, respectively stability longevity test is carried out to embodiment and comparative example, in simultaneous test, up-flow reactor condition is consistent with reaction result, 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 example | 0.54 | 0.58 | 0.63 | 0.67 |
| Generate oily CCR, wt% | ||||
| Embodiment | 4.60 | 4.68 | 5.07 | 5.40 |
| Comparative example | 5.75 | 5.84 | 6.55 | 6.82 |
The present invention has had obvious improvement than the generation oil nature of technique existing in comparative example as can be seen from Table 4, and the present invention than comparative example hydrogenation activity and stability better.In addition, as can be seen from Table 4, Technology of the present invention effectively can improve the temperature rise of fixed-bed reactor, especially the temperature rise that fixed bed one is anti-is significantly improved, the raising of counter-current reactor hydrogen dividing potential drop and hydrogen purity is most important to the performance playing fixed bed catalyst in addition, and can reaction environment be improved, improve hydrogenation activity and the stability of monolithic catalyst system, thus the work-ing life of extending catalyst.
Claims (11)
1. a heavy hydrocarbon hydroprocessing method, comprise following content: up-flow reactor, at least one down-type fixed-bed reactor are connected successively with countercurrent hydrogenation reactor and used, heavy hydrocarbon feeds passes through up-flow reactor, down-type fixed-bed reactor and countercurrent hydrogenation reactor successively, wherein:
(1) radiation section that heavy hydrocarbon feeds and hydrogen are blended in process furnace enters up-flow reactor after being heated to the temperature of reaction needed for up-flow reactor, and the hydrogen to oil volume ratio of up-flow reactor entrance is 150: 1 ~ 300: 1;
(2) up-flow reactor effluent and the down-type fixed-bed reactor heated through process furnace convection zone mix after hydrogen mixes and enter the further hydrotreatment of down-type fixed-bed reactor, and the hydrogen to oil volume ratio of down-type fixed-bed reactor is 400: 1 ~ 1200: 1;
(3) down-type fixed-bed reactor effluent enters the top of countercurrent hydrogenation reactor, hydrogen enters bottom countercurrent hydrogenation reactor, be separated with down-type fixed-bed reactor reaction effluent the generation oil obtained to carry out reversely having contacted hydrogenation reaction, in countercurrent hydrogenation reactor, hydrogen to oil volume ratio is 500: 1 ~ 1500: 1.
2. in accordance with the method for claim 1, it is characterized in that, also comprise step (4): step (3) gained generates oil to carry out being separated and fractionation, and obtain light-end products and hydrogenation tail oil, gained gaseous product enters cold high score and is separated.
3. in accordance with the method for claim 1, it is characterized in that, in the inventive method, the gas-phase product that step (3) countercurrent hydrogenation reactor top is discharged 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 cold low separator to continue to be separated.
4. in accordance with the method for claim 1, it is characterized in that, described down-type fixed-bed reactor is arranged in series 1 ~ 5, arranges one or more beds in reactor.
5. in accordance with the method for claim 1, it is characterized in that, described countercurrent hydrogenation reactor arranges 1, arranges 1 ~ 3 beds in reactor.
6. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of step (1) described up-flow reactor is, reaction pressure 8 ~ 25MPa, temperature of reaction 350 ~ 400 DEG C, 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 reaction conditions of step (2) described down-type fixed-bed reactor is that reaction pressure is identical with up-flow reactor, temperature of reaction 370 ~ 430 DEG C, 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 step (3) described countercurrent hydrogenation reactor is: reaction pressure 8 ~ 25MPa, temperature of reaction 370 ~ 450 DEG C, volume space velocity 0.2 ~ 2.0h during liquid
-1.
9. according to the method described in claim 4 or 5, it is characterized in that, described catalyzer refers to have residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, the single catalyst of hydrodenitrification and hydrocracking function or combination catalyst.
10. in accordance with the method for claim 9, it is characterized in that, described catalyzer is with porous refractory inorganic oxide for carrier, and the oxide compound of group vib and/or group VIII metal is active ingredient.
11. in accordance with the method for claim 1; it is characterized in that, the catalyzer used in up-flow reactor, down-type fixed-bed reactor and countercurrent hydrogenation reactor is followed successively by protective material, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst by the flow direction of stock oil.
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| CN104232154B (en) * | 2013-06-21 | 2016-04-06 | 中国石油天然气股份有限公司 | A kind of distillate hydrogenation method for modifying |
| CN105316041B (en) * | 2014-07-30 | 2018-04-10 | 中国石化工程建设有限公司 | A kind of residual hydrogenation method |
| CN111100675A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Process for treating heavy hydrocarbon feedstocks using upflow reactors |
| CN111100677A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for processing heavy hydrocarbon raw material by adopting up-flow reactor |
| CN111100678A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for hydrotreating residual oil by using up-flow reactor |
| CN111298722B (en) * | 2018-12-12 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
| CN114479933B (en) * | 2020-10-28 | 2023-03-24 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reaction system and hydrogenation method |
| CN114479925B (en) * | 2020-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method |
| CN115960625B (en) * | 2021-10-08 | 2024-03-05 | 中国石油化工股份有限公司 | Fixed bed heavy oil hydrogenation process |
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| CN1393516A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Process and reactor for hydrogenating heavy hydrocarbon kind of raw materials |
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