CN102732315A - Hydrotreatment and catalytic cracking deeply-combined method for residuum - Google Patents
Hydrotreatment and catalytic cracking deeply-combined method for residuum Download PDFInfo
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Abstract
The invention discloses a hydrotreatment and catalytic cracking deeply-combined method for residuum. The hydrotreatment and catalytic cracking deeply-combined method for residuum comprises the following steps that a residuum raw material, at least part of catalytically cracked heavy recycle oil and at least part of catalytically cracked slurry undergo a hydrotreatment reaction in the presence of hydrogen and a hydrotreatment catalyst in a hydrotreatment device; a hydrotreatment reaction effluent is subjected to gas-liquid separation; a liquid phase directly enters into a catalytic cracking device without passing through a fractionation device and then undergoes a catalytic cracking reaction; a catalytic cracking reaction effluent is treated by the fractionation device so that dry gas, liquefied gas, a catalytically cracked gasoline fraction, a catalytically cracked diesel fraction, catalytically cracked heavy recycle oil and catalytically cracked slurry are separated out; and a part or all of the catalytically cracked heavy recycle oil and the catalytically cracked slurry are fed back to the hydrotreatment device and then undergo a hydrotreatment reaction. Compared with the prior art, the hydrotreatment and catalytic cracking deeply-combined method for residuum can realize maximum-yield production of gasoline, save an equipment investment, fully utilize reaction heat and reduce production energy consumption.
Description
Technical field
The present invention relates to a kind of residual oil lightening method, the residual oil lightening method that specifically the residual hydrocracking technology and the catalytic cracking technology degree of depth is made up.
Background technology
Along with crude oil becomes heavy day by day, becomes bad; Increasing residual oil needs processing treatment; Residual oil refers generally to the hydrocarbon material in crude oil or other source; Removing the remainder after the gasoline fraction, diesel oil distillate, reduced pressure distillate wet goods cut through underpressure distillation, generally have characteristics such as boiling point height, foreign matter content are many, is the most unmanageable raw material in the petroleum refining industry.The processing treatment of residual oil will be not lower boiling product with its cracking still, like petroleum naphtha, intermediate oil and vacuum gas oil etc., but also will improve their hydrogen-carbon ratio, and this just need realize through the method for decarburization or hydrogenation.Wherein decarbonization process comprises coking, solvent deasphalting, RFCC etc.; Hydrogenation comprises hydrogen cracking, unifining etc.Hydrogenation method can hydrocracking residual oil, improves the productive rate of liquid product, and can also remove heteroatoms wherein, and quality product is not bad.But hydrogenation method is the catalysis complete processing, has hydrogenation catalyst inactivation problem, and when especially processing poor quality, heavier hydrocarbon feeds, the catalyst deactivation problem is more serious.At present, in order to reduce heavy, poor residuum cost of processing, increase the oil refining enterprise profit; The technology of processing heavy, poor residuum is main with decarbonization process still at present, but its poor product quality need be carried out aftertreatment and could be utilized; Wherein deasphalted oil and wax tailings cut especially need carry out hydrotreatment; Could continue to use lighting devices such as catalytic cracking or hydrogen cracking 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 residual hydrocracking technology is lower, and main purpose is to supply raw materials for downstream raw material lighting device such as devices such as catalytic cracking or coking.Through hydrotreatment; Sulphur, nitrogen, metal impurities content and carbon residue in the poor residuum are obviously reduced; Thereby obtain the charging that lighting device in downstream can be accepted; Especially therefore CCU is mainstream technology with residue fixed-bed hydrotreatment and catalytic cracking combination technique in the residual hydrogenation modifying process technology at present.
Existing residual hydrocracking and catalytic cracking combined technique; At first be that residual oil is carried out hydrotreatment; Hydrogenated oil is isolated petroleum naphtha and diesel oil distillate; Hydrogenation tail oil carries out catalytic cracking reaction as the RFCC charging, and product is dry gas, liquefied gas, gasoline, diesel oil and coke; Recycle stock carry out the catalysis freshening or with loop back residual hydrogenation equipment and the residual hydrocracking raw materials mix is carried out hydrotreatment, catalytic slurry gets rid of outward or part catalysis freshening or loop back residual hydrogenation equipment.Above-mentioned residual hydrocracking and catalytic cracking combined technique exist yield of gasoline low, and heat energy loss is big, unfavorable factors such as facility investment height.
USP 4; 565; 620, US4,713,221 grades disclose on the residual hydrogenation of routine and catalytic cracking combined basis; Merge from the recycle stock of heavy oil catalytically cracking equipment and wax catalysis cracking unit and vacuum residuum from crude oil unit and to send residual hydrogenation equipment processing to, the hydrogenation tail oil carrying device that obtains from residual hydrogenation equipment product fractionating system is as downstream heavy oil catalytically cracking equipment (with the wax catalysis cracking unit) charging.But catalytically cracked oil is not utilized effectively, and this method is limited to reduction coke yield, raising product yield.
CN1119397C discloses a kind of hydrogenation and catalystic cracking combined process for residual oil; In this method; Residual oil and clarified oil get into residual hydrogenation equipment together, in the presence of hydrogen and hydrogenation catalyst, react, and heavy cycle oil circulates in CCU inside; The slurry oil of reaction gained obtains clarified oil through separator separates, is back to hydrogenation unit.But slurry oil gets into the residual hydrocracking device, and the easy green coke thing in the slurry oil will increase the carbon deposit of hydrogenation catalyst, has reduced the hydrogenation activity and the operational cycle of hydrogenation catalyst, and heavy cycle oil is inner at CCU.Therefore, this method is limited to reducing coke yield, improving the quality of products.
CN1382776A discloses the method for a kind of residual hydrocracking and catalytically cracking heavy oil, and this method is carried out hydrogenation reaction with residual oil at hydrotreater, and reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.The hydrogenated residue of gained gets into CCU with optional vacuum gas oil and carries out cracking reaction, and the heavy cycle oil of catalytic cracking returns hydrotreater, and the thing that steams that the distillation slurry oil obtains returns hydrotreater.This method is organically joined together two devices, can residual oil, heavy cycle oil and slurry oil be converted into clean cargo.A kind of residual hydrocracking and catalytic cracking combination process are disclosed among the CN101210200A.In this process method; The thing that steams of residual oil, the heavy catalytic cycle oil that removes solid impurity, optional distillate and optional catalytically cracked oil gets into the residual hydrocracking device together; The hydrogenated residue of gained gets into CCU together with optional vacuum gas oil, obtains various products; The heavy catalytic cycle oil that removes solid impurity is circulated to the residual hydrocracking device; Catalytically cracked oil is carried out fractionation by distillation, and catalytically cracked oil to steam thing capable of circulation to the residual hydrocracking device.But aforesaid method all is provided with fractionating system in hydrotreatment and catalytic cracking process, increased investment cost; Because the process heat exchange, heat-energy losses is more.
Simultaneously, existing residual hydrocracking device is equipped with the product fractionating system, obtains main purpose product--hydrogenated residue, and by-product 1%～2% (quality) hydrotreated naphtha and 5%～8% (quality) diesel oil distillate from the product fractionating system.Residual hydrogenation equipment product fractionating system is except that separation column; Need nearly 20 covers of equipment such as other pump, interchanger, reboiler, air cooler, various containers; And material is had relatively high expectations, and not only construction investment is bigger, and ordinary production when operation energy consumption is also higher.
In addition, hydrotreater and CCU all have diesel product, and comparatively speaking, the total recovery of gasoline products will reduce.In addition, the slag oil cracking rate of residual hydrocracking device is lower, and it is limited that hydrogenated oil carries out petroleum naphtha, diesel yield that fractionation obtains, and the diesel oil distillate that the residual hydrocracking process obtains still can not satisfy the high-quality diesel requirement of products.Foreign matter contents such as catalytic cracking diesel oil sulphur are higher, and character is relatively poor, also need further hydrotreatment just to can be used as qualified diesel product.
In residual hydrocracking and the catalytic cracking combined technique, the energy consumption of fractionation plant accounts for bigger ratio, and the energy consumption that how to reduce fractionation plant also is the content that needs emphasis to consider.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of residual hydrocracking and catalytic cracking degree of depth combined technical method, can improve the quality and the quantity of gasoline products, and technological process is simple simultaneously, and whole energy consumption reduces.
Residual hydrocracking of the present invention and catalytic cracking degree of depth combined technical method; Comprise hydrotreater and CCU; Residual oil raw material, at least the part heavy catalytic cycle oil and at least the part catalytically cracked oil in hydrotreater, in the presence of hydrogen and hydrotreating catalyst, carry out hydrotreatment reaction; The hydrotreatment reaction effluent carries out gas-liquid separation; The gas phase circulation is used for the hydrotreatment reaction; Liquid phase directly gets into CCU without fractionation plant and carries out catalytic cracking reaction; The catalytic cracking reaction elute is isolated dry gas, liquefied gas, catalytically cracked gasoline cut, catalytic cracking diesel oil cut, heavy catalytic cycle oil (also being referred to as catalytic cracking recycle oil) and catalytically cracked oil in fractionation plant, the hydrotreater that partly or entirely loops back of heavy catalytic cycle oil carries out the hydrotreatment reaction, and the hydrotreater that partly or entirely loops back of catalytically cracked oil carries out the hydrotreatment reaction.
In the inventive method; Residual oil raw material comprises long residuum or vacuum residuum; It also can be the residual oil raw material in other source; Also can contain part straight-run gas oil (VGO simultaneously in the residual oil raw material; Be vacuum distillate), in wax tailings (CGO, the i.e. vacuum distillate that obtains of coker), deasphalted oil (DAO, the i.e. heavy distillate of residual oil behind solvent deasphalting), solvent-extracted oil, ethylene cracking tar, shale oil, coal tar, biomass high-temperature thermo-cracking tar, animal-plant oil etc. one or more.Specifically can specifically confirm according to the raw material supply situation.
In the inventive method; The heavy catalytic cycle oil and the catalytically cracked oil that get into hydrotreater can be heavy catalytic cycle oil and the catalytically cracked oils that CCU obtains in residual hydrocracking of the present invention and the catalytic cracking combination method, also can comprise heavy catalytic cycle oil and catalytically cracked oil that other CCU obtains.In existing CCU, heavy catalytic cycle oil is directly to loop back CCU.The heavy catalytic cycle oil that CCU obtains in residual hydrocracking of the present invention and the catalytic cracking combination method can all or part of entering hydrotreater; The heavy catalytic cycle oil that gets into hydrotreater generally accounts for CCU at least and obtains more than 50% of heavy catalytic cycle oil weight, is preferably more than 80%.The heavy catalytic cycle oil of remainder can loop back CCU.The catalytic cracking diesel oil cut that CCU obtains can get into hydrotreater, get into CCU or discharge, and the ratio between the three is regulated arbitrarily as required.The entering hydrotreater more than at least 30% of catalytically cracked oil weight; The preferred hydrotreater that gets into more than 50% according to the form of hydrogenator in the hydrotreater, confirms whether catalytically cracked oil need remove the solid dust operation; When in general hydrogenator is fixed bed or moving-bed; The solid dust in the catalytically cracked oil need be removed,, also the solid dust in the catalytically cracked oil can be do not removed if when hydrogenator is liquid bed or suspension bed.The cut point of various cuts can specifically be confirmed as required in the CCU.
In the inventive method, hydrotreater can be provided with the hydrogenator of suitable number according to the needs of processing treatment scale, and hydrogenator is provided with one at least, also can be provided with 2 ~ 6.The residual oil raw material hydrotreatment generally needs lower air speed, and a plurality of hydrogenators are set, and can solve the problem of ultra-large hydrogenator processing difficulties.When a plurality of hydrogenator was set, the heavy catalytic cycle oil that gets into hydrotreater can get into hydrotreater from arbitrary hydrogenator with catalytically cracked oil, also can get into different hydrogenators respectively in the ratio that suits.Specifically can be by those skilled in the art by conventional knowledge or carry out simple experiment and confirm.
In the inventive method; The hydrotreatment reaction effluent at first carries out gas-liquid separation; (being commonly referred to as high pressure separates) generally carried out in this gas-liquid separation under the condition identical with the reaction pressure grade; Separate the gas phase that obtains and be mainly hydrogen, handle the back circulation through selectable depriving hydrogen sulphide and be used for hydrogenation reaction, the hydrotreatment reaction process need be replenished the consumption of new hydrogen with the postreaction process simultaneously.The liquid phase that obtains after the gas-liquid separation of hydrotreatment reaction effluent gets into light pressure separator, directly gets into CCU without fractionation then, and light pressure separator can flash off a small amount of light hydrocarbons and dissolved hydrogen sulfide and hydrogen etc.
The residual hydrocracking technology can be any technology of the present invention that is applicable to, like fixed bed residual hydrocracking technology, suspension bed residual oil hydrogenation treatment technology, boiling bed residual oil hydrotreatment technology, moving-bed residual hydrocracking technology etc.At present normally used is fixed bed residual hydrocracking technology and boiling bed residual oil hydrotreatment technology.With the most sophisticated fixed bed residual hydrocracking technology in the present industry is example, the catalyst for hydrotreatment of residual oil of employing be meant have residuum hydrogenating and metal-eliminating, the single catalyst or the combination catalyst of function such as hydrogenating desulfurization, hydrodenitrification and hydrogen cracking.These catalyzer generally all are to be carrier with porous refractory inorganic oxides such as aluminum oxide; The oxide compound of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. is an active ingredient; The catalyzer that optionally adds elements such as other various auxiliary agents such as P, Si, F, B; The CEN that for example produces, FZC, ZTN, ZTS series residual oil hydrocatalyst by catalyzer branch office of Sinopec Group, the ZTN that produces by Qilu Petrochemical company, ZTS catalyst series etc.At present in fixed bed residual hydrogenation technology; It often is the supporting use of multiple catalyzer; Protective material, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst etc. are wherein arranged, and the filling order generally is that raw oil is contacted with protective material, HDM, hydrogenating desulfurization, hydrodenitrogenation catalyst successively.Technology with these several kinds of catalyst mix fillings is also arranged certainly.The a plurality of reactor drums of hydrotreatment operated by rotary motion are to improve amount of finish.Hydroprocessing condition is 5MPa-35MPa in absolute pressure normally, and preferably 10MPa-20MPa, temperature are 300 ℃-500 ℃, preferably 350 ℃-450 ℃ operations down.Volume space velocity and hydrogen dividing potential drop are to select according to the characteristic of treating material and the hydrotreatment degree of depth of requirement during liquid.Volume space velocity is generally at 0.1h during liquid
-1-5.0h
-1, 0.15h preferably
-1-2.0h
-1Scope in, total hydrogen to oil volume ratio is 100-5000, is preferably 300-3000.The present invention is applicable to normal pressure and vacuum residuum hydrotreatment, is particularly useful for the hydrocracking of heavy hydrocarbon oil.The actual conditions of residual hydrocracking process can specifically be confirmed according to the requirement of raw material properties and CCU charging.
In the inventive method, catalytic cracking can be adopted this area routine techniques.CCU can be more than a cover or overlaps; Every cover CCU should comprise a reactor drum and a revivifier at least; CCU need be provided with separation column, can separation column be set every cover CCU respectively, also can shared separation column.Separation column is dry gas, liquefied gas, catalytically cracked gasoline cut, catalytic cracking diesel oil cut, heavy catalytic cycle oil and catalytically cracked oil etc. with the fractionation of catalytic cracking reaction elute.Also can heavy catalytic cycle oil and catalytically cracked oil be drawn separation column as an overhead product, can simplify the structure of separation column like this, reduce fractionating tower equipment cost and process cost.Catalytic cracking fractionating tower can be by conventional knowledge design.
CCU is operated by this area general condition: temperature of reaction is 450～600 ℃, preferably 480～550 ℃; Regeneration temperature is 600-800 ℃, is preferably 650-750 ℃, and the agent weight of oil is than 2～30, preferably 4～10; With 0.1～15 second duration of contact of catalyzer, best 0.5～5 second; Pressure 0.1～0.5MPa.The catalytic cracking catalyst that is adopted comprises the catalyzer that is generally used for catalytic cracking; Like silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5, M type, layer post equimolecular sieve cracking catalyst; Molecular sieve cracking catalyst preferably, this is because molecular sieve cracking catalyst active high, green coke is few; Gasoline yield is high, and transformation efficiency is high.The reactor drum of described CCU can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor drum.Technical process is generally: raw oil injects from the riser reactor bottom; Contact with high-temperature regenerated catalyst from revivifier; The oil gas that cracking reaction generates and the catalyst mixture of deposit coke move up along riser reactor, accomplish the catalytic cracking reaction of whole raw oil.
The concrete operations condition of residual hydrocracking and catalytic cracking can be obtained through simple experiment according to feedstock property and product quality indicator by the technician.
Existing with have compared with techniques advantage of the present invention to comprise the following aspects.
1, in whole combination process; Main products is high octane number catalytic cracking gasoline, LPG liquefied petroleum gas and a small amount of dry gas; And volume production goes out catalytic cracking diesel oil on demand; Can guarantee to improve gasoline output, and the quality of catalytically cracked gasoline obviously improves, the quality of the catalytic cracking diesel oil that obtains also can obviously improve.
2, from whole combination process; Need not establish fractionating system in the hydrotreater; Hydrotreatment generates oil and directly gets into catalyst cracker, need not establish fresh feed pump, has cancelled nearly 20 complete equipments of fractionating system simultaneously; Facility investment is greatly reduced, and process cost also significantly reduces simultaneously.
3, heavy catalytic cycle oil plays diluting effect to fresh residual oil raw material, and oil property improves, and has reduced the hydrogenation reaction difficulty and processing severity of residual hydrocracking parallel feeding; In addition; Heavy catalytic cycle oil can reduce the viscosity of residual oil raw material; Improve logistics distribution and the mass transfer of raw material in reactive system; Reduce to be diffused in the influence in the residual hydrocracking process, improve the deposition distribution of poisonous metal in catalytic reaction system such as nickel, vanadium, prolong the work-ing life of catalyzer; Simultaneously, the reduction of viscosity is more prone to the conveying and the filtration of mixing raw material oil.
4, heavy catalytic cycle oil can remove impurity in the Residue Hydrotreating Technology process, and aromatic hydrocarbons is saturated, becomes better catalytically cracked material and forms, and has further improved catalytic cracking high value added product yield.
5, because hydrotreater is not established fractionating system, hydrogenated oil directly gets into catalyst cracker, can reduce the loss of heat greatly, has significantly reduced the required energy of fractionation process simultaneously, thereby has reduced the energy consumption of whole technological process.
6, can make full use of catalytically cracked oil; Further utilize being worth low catalytically cracked oil; When catalysis heavy cycle oil and catalyzer cracking slurry oil recycle jointly simultaneously, can reduce the viscosity of catalytically cracked oil, help removing the solid dust in the catalytically cracked oil.
Embodiment
Further specify the technique effect of process of the present invention, operational condition and acquisition below.
Technical process is described in detail as follows:Catalytically cracked oil is through after removing solid dust; Mix with residual oil raw material and heavy catalytic cycle oil; Be mixed into hydrotreating reactor with recycle hydrogen after boosting; Through contacting with the hydrotreating catalyst bed, remove impurity such as metal in the mixing raw material, sulphur, nitrogen, the carbon residue that reduces raw material simultaneously satisfies the charging requirement of downstream catalytic cracking unit.Hydrotreating reactor outlet reaction effluent gets into HP separator and carries out gas-liquid separation; Isolated gaseous stream carries out being recycled to the hydrotreating reactor inlet after the laggard recycle compressor of processing such as depriving hydrogen sulphide boosts; The new hydrogen that replenishes also can be introduced after recycle compressor; Isolated liquid phase stream gets into light pressure separator more further to be separated; Isolated liquid phase stream (being hydrogenated oil) is without heat exchange and fractionation, and the pressure of adjustment light pressure separator makes liquid phase stream under the situation of not using feedstock pump, directly get into the catalytic-cracking reaction system of CCU through pipeline.
Hydrogenated oil gets into the reactive system of CCU; Contact with the high temperature regeneration catalytic cracking catalyst and carry out catalytic cracking reaction; Reacted oil gas logistics gets into the separation column of catalytic unit; In separation column, isolate gas, catalytically cracked gasoline cut, catalytic cracking diesel oil cut, heavy catalytic cycle oil and catalytically cracked oil; Gas and catalytically cracked gasoline cut discharger; CCU etc. is discharged, looped back to the catalytic cracking diesel oil cut on demand, and partly or entirely (all preferred) and the residual oil raw material of heavy catalytic cycle oil are mixed into hydrotreater and carry out the hydrotreatment reaction, and catalytically cracked oil is mixed into the hydrotreatment system with residual oil raw material after removing solid dust (also can mix with part or all of heavy catalytic cycle oil and remove solid dust jointly).
Following embodiment will further specify method provided by the invention, but therefore not limit the present invention.Reaction is on small-sized lifting tubular type CCU and pilot scale residual hydrocracking device, to carry out.Used raw oil is normal slag in the sand in embodiment and the Comparative Examples, and its character is listed in table 1.The type of used catalyst for hydrotreatment of residual oil and volume are identical in embodiment and the Comparative Examples; All are CEN, FZC, ZTN, ZTS series residual oil hydrocatalysts that catalyzer branch office of Sinopec Group produces; Specifically comprise protective material; Catalyst for demetalation, desulfurization catalyst, denitrification catalyst etc.; The filling order generally is that raw oil is contacted with protective material, HDM, hydrogenating desulfurization, hydrodenitrogenation catalyst successively, and the technology with these several kinds of catalyst mix fillings is also arranged certainly.The technology contents that above-mentioned catalyst loading technology is well known to those skilled in the art.Catalytic cracking catalyst used in embodiment and the Comparative Examples is identical, is the catalyzer that 3,500,000 tons of/year heavy oil catalytically cracking equipments of Dalian Company use, and is industrial equilibrium catalyst.Its fresh dose consists of: 95wt%LBO-16 olefine lowering catalyst+5wt%LBO-A boosting of octane rating auxiliary agent.
Comparative Examples
This Comparative Examples adopts conventional residual hydrocracking-catalyst cracking method, and promptly residual oil carries out hydrogenation reaction at hydrotreater, and reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.The hydrogenated residue of gained gets into CCU and carries out cracking reaction, and heavy catalytic cycle oil is handled at the CCU internal recycle.Table 2, table 3, table 4 are respectively processing condition, product distributes and main products character.
Embodiment
This embodiment adopts residual hydrocracking provided by the invention and catalytic cracking combination method; All liquid products of hydrotreatment (being hydrogenated oil) directly get into CCU without fractionation; The catalytic cracking reaction elute fractionates out dry gas, liquefied gas, catalytically cracked gasoline cut, catalytic cracking diesel oil cut, catalytic cracking turning oil and catalytic slurry; Heavy catalytic cycle oil that wherein obtains and catalytic slurry all circulate and get into hydrotreater and carry out hydrotreatment; And heavy catalytic cycle oil and slurry oil that other CCU obtains have been introduced; Make total heavy catalytic cycle oil and slurry oil reach 30% of resid feed, saved the thinning oil of straight-run gas oil as residual oil.Residual hydrogenation raw oil is Middle East mixing subtracting slag for Middle East mixed residue oil: heavy catalytic cycle oil and slurry oil=70:30 (quality %).Table 2, table 3, table 5 are respectively processing condition, product distributes and main products character.
Table 1 residual oil raw material oiliness matter.
| Project | The Middle East subtracts slag | Straight-run gas oil | Heavy catalytic cycle oil | Catalytically cracked oil | Comparative Examples | Embodiment |
| S, quality % | 3.62 | 2.99 | 1.22 | 0.46 | 3.32 | 2.67 |
| N, μg/g | 4251 | 1302 | 2153 | 1492 | 3566 | 3427 |
| Carbon residue (CCR), quality % | 18.04 | 0.84 | / | 8.55 | 13.55 | 14.15 |
| Density (20 ℃), kg/m 3 | 1024.9 | 936.3 | 1059.6 | 999.9 | 987.6 | 1012.9 |
| Viscosity (100 ℃), mm 2/s | 1387 | 12.65 | 8.88 | 35.86 | 133.8 | 204.5 |
| Ni+V, μg/g | 172.86 | / | / | 6.30 | 110.89 | 112.56 |
Table 2 hydrotreatment and catalytic cracking process condition.
| Title | Comparative Examples | Embodiment |
| The hydroprocessing technique condition | ? | ? |
| Raw material | Residual oil+straight-run gas oil | Residual oil+heavy catalytic cycle oil+slurry oil |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 |
| Temperature of reaction, ℃ | 385 | 385 |
| ?Volume space velocity, h -1 | 0.20 | 0.20 |
| Hydrogen-oil ratio | 600 | 600 |
| The catalytic cracking process condition | ? | ? |
| Raw material | Hydrogenated residue | The mixing oil hydrogenated oil |
| Temperature of reaction, ℃ | 505 | 505 |
| Agent-oil ratio | 7.5 | 7.5 |
Table 3 product distributes.
| Title | Comparative Examples | Embodiment |
| The hydrotreatment product distributes ●: quality % | ? | ? |
| Chemistry hydrogen consumption | 1.3 | 1.52 |
| Gas | 4.39 | 4.04 |
| Petroleum naphtha | 1.14 | 0 |
| Diesel oil | 5.35 | 0 |
| Hydrogenation tail oil | 90.42 | 97.48 |
| The catalytic cracking product distributes ●: quality % | ||
| Dry gas | 1.58 | 1.48 |
| Liquefied gas | 12.82 | 10.31 |
| Gasoline | 44.01 | 41.01 |
| Diesel oil | 19.72 | 19.86 |
| Recycle stock+slurry oil | 14.72 | 18.97 |
| Coke | 7.15 | 8.37 |
| Two covering devices add up to ●●, quality % | ||
| Chemistry hydrogen consumption | 1.3 | 1.52 |
| Gas | 5.82 | 5.48 |
| Liquefied gas | 11.59 | 10.05 |
| Gasoline (comprising hydrotreated naphtha) | 40.93 | 39.98 |
| Diesel oil | 23.18 | 19.36 |
| Recycle stock+slurry oil (looping back residual hydrogenation equipment) | 0 | 18.49 |
| Heavy oil | 13.31 | 0 |
| Coke | 6.47 | 8.16 |
In the table 3: ● with the device inlet amount is 100% calculating, ● ● with fresh residual oil raw material is 100% calculating.
The conventional hydrogenation and catalystic cracking main products of table 4 character
●
| Product | Hydrogenated diesel oil | The normal slag of hydrogenation | Catalytically cracked gasoline | Catalytic cracking diesel oil |
| Density (20 ℃), g/cm 3 | 0.9095 | 0.9464 | 0.765 | 0.928 |
| S, μg/g | 160 | 5000 | 165 | 1703 |
| N, μg/g | 30 | 2096 | 37 | 378 |
| Carbon residue, quality % | / | 5.50 | / | / |
| Condensation point, ℃ | －11 | 23 | / | -36 |
| Cetane value | 45 | / | / | 26.1 |
| RON | / | / | 90.5 | / |
In the table 4, ● the normal slag of hydrogenation is intermediates in the present invention.
Table 5 main products character of the present invention.
| Product | Catalytically cracked gasoline |
| Density (20 ℃), g/cm 3 | 0.767 |
| S, μg/g | 125 |
| N, μg/g | 51 |
| RON | 89 |
Comparing result shows that after heavy catalytic cycle oil and slurry oil and the processing of fresh residual oil raw material mixed hydrogenation, the catalytically cracked gasoline yield is 39.98 percentage points, 10.05 percentage points of liquefied gas yields.Can save straight-run gas oil as the residual hydrogenation thinning oil, it is produced high value added product as hydrocracking raw material.The inventive method can satisfy the enterprise that hopes raising the output gasoline well.
Claims (13)
1. residual hydrocracking and catalytic cracking degree of depth combined technical method; Comprise hydrotreater and CCU; It is characterized in that: residual oil raw material, at least the part heavy catalytic cycle oil and at least the part catalytically cracked oil in hydrotreater, in the presence of hydrogen and hydrotreating catalyst, carry out hydrotreatment reaction; The hydrotreatment reaction effluent carries out gas-liquid separation; The gas phase circulation is used for the hydrotreatment reaction; Liquid phase directly gets into CCU without fractionation plant and carries out catalytic cracking reaction; The catalytic cracking reaction elute is isolated dry gas, liquefied gas, catalytically cracked gasoline cut, catalytic cracking diesel oil cut, heavy catalytic cycle oil and catalytically cracked oil in fractionation plant, the hydrotreater that partly or entirely loops back of heavy catalytic cycle oil carries out the hydrotreatment reaction, and the hydrotreater that partly or entirely loops back of catalytically cracked oil carries out the hydrotreatment reaction.
2. according to the described method of claim 1; It is characterized in that: residual oil raw material comprises long residuum or vacuum residuum, can selectively contain in straight-run gas oil, wax tailings, deasphalted oil, solvent-extracted oil, ethylene cracking tar, shale oil, coal tar, biomass high-temperature thermo-cracking tar, the animal-plant oil one or more in the residual oil raw material.
3. according to the described method of claim 1, it is characterized in that: the heavy catalytic cycle oil that gets into hydrotreater accounts for CCU and obtains more than 50% of heavy catalytic cycle oil weight; The catalytically cracked oil that gets into hydrotreater accounts for CCU and obtains more than 30% of catalytically cracked oil weight.
4. according to the described method of claim 1, it is characterized in that: the heavy catalytic cycle oil that gets into hydrotreater accounts for CCU and obtains more than 80% of heavy catalytic cycle oil weight; The catalytically cracked oil that gets into hydrotreater accounts for CCU and obtains more than 50% of catalytically cracked oil weight.
5. according to the described method of claim 1, it is characterized in that: hydrotreater is provided with 1 hydrogenator, and 2 ~ 6 hydrogenators perhaps are set.
6. according to the described method of claim 5; It is characterized in that: when a plurality of hydrogenator is set; The heavy catalytic cycle oil and the catalytically cracked oil that get into hydrotreater get into hydrotreater from arbitrary hydrogenator, perhaps get into different hydrogenators respectively in suitable ratio.
7. according to claim 1 or 5 described methods, it is characterized in that: the residual hydrocracking technology is used fixed bed residual hydrocracking technology, suspension bed residual oil hydrogenation treatment technology, boiling bed residual oil hydrotreatment technology or moving-bed residual hydrocracking technology.
8. according to the described method of claim 1, it is characterized in that: the absolute pressure of hydroprocessing condition is 5MPa-35MPa, and temperature is 300 ℃-500 ℃, and volume space velocity is 0.1h during liquid
-1-5.0h
-1, total hydrogen to oil volume ratio is 100-5000.
9. according to the described method of claim 1, it is characterized in that: the absolute pressure of hydroprocessing condition is 10MPa-20MPa, and temperature is 350 ℃-450 ℃, and volume space velocity is 0.15h during liquid
-1-2.0h
-1, total hydrogen to oil volume ratio is 300-3000.
10. according to the described method of claim 1, it is characterized in that: catalytically cracked oil gets into hydrotreater after removing solid dust.
11. according to the described method of claim 1; It is characterized in that: CCU is more than a cover or overlaps; Every cover CCU should comprise a reactor drum and a revivifier at least; CCU need be provided with separation column, and every cover CCU is provided with separation column respectively, perhaps shared separation column.
12. according to the described method of claim 1, it is characterized in that the CCU temperature of reaction is 450～600 ℃, regeneration temperature is 600-800 ℃, the agent weight of oil is than 2～30, with 0.1～15 second duration of contact of catalyzer, and pressure 0.1～0.5MPa.
13. according to the described method of claim 1, it is characterized in that the CCU temperature of reaction is 480～550 ℃, regeneration temperature is 650-750 ℃, the agent weight of oil is than 4～10, with catalyzer duration of contact be 0.5～5 second.
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