CN103254936A - Residual oil hydrotreating-catalytic cracking combined process method - Google Patents
Residual oil hydrotreating-catalytic cracking combined process method Download PDFInfo
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Abstract
The invention relates to a residual oil hydrotreating-catalytic cracking combined process method, wherein residual oil and hydrogen enter a residual oil hydrogenation device, and dry gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated residual oil are obtained through separation; the hydrogenated residual oil enters a catalytic cracking device for reaction and is separated into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil; the heavy cycle oil and the oil slurry enter a solvent extraction device; returning the raffinate phase to the catalytic cracking device; the extract phase enters a fractionating tower for separation, the top of the tower is provided with an extraction solvent, the lateral line is provided with middle fraction, and the bottom of the tower is provided with heavy fraction; the extraction solvent is returned to the solvent extraction device; the middle distillate is sent to a residual oil hydrotreater; part of the middle distillate is sent to a lubricating oil device; producing asphalt by using the tower bottom heavy fraction as an asphalt improver; the method increases the aromatic hydrocarbon content of the residual oil hydrotreating raw material, reduces the viscosity, reduces the contents of impurities such as sulfur, nitrogen, metals and the like, and reduces the severity of the operation of the device.
Description
Technical field
Present method belongs to the combined technical method of hydrotreatment, in particular, is a kind of processing method with residual hydrocracking and catalytic cracking combination.
Background technology
Current, oil refining processing industry in the world is being faced with the crude resources severe challenge of heaviness and poor qualityization day by day.2008,3.42 hundred million tons of crude oil in China amount of finish, wherein the heavy crude amount of finish reaches 1.37 hundred million tons, accounts for total amount more than 40%.As everyone knows, residual oil accounts for the crude oil ratio usually 45～75%, and its character significantly is inferior to the lower gas wet goods cut of boiling range, and therefore, the crude oil deep processing is made every effort to maximize the pressure of producing light-end products and industrial chemicals and just dropped on the residual oil naturally.
In the optional technological line of residual oil deep processing, residual hydrogenation and catalytic cracking combined technique are a kind of good technology.Residual oil has improved hydrogen richness after removing impurity such as metal, sulphur, nitrogen through hydrotreatment, can be used as the heavy oil fluid catalytic cracking raw material of high-quality, and residual oil is transformed fully.This technology has obtained increasing application, and constantly developed.US4,713,221 disclose on conventional residual hydrogenation and catalytic cracking combined basis, and the heavy cycle oil of catalytic cracking (comprising gas oil catalytic cracking and heavy oil fluid catalytic cracking) is circulated to residual hydrogenation equipment, with carry out hydrogenation after topped crude mixes, hydrogenated residue enters catalytic cracking unit.The change that this is little can make the benefit of one barrel of crude oil of the every processing in refinery have a net increase of 0.29 dollar.
CN1119397C discloses a kind of residual hydrocracking---catalytic cracking combination process, is that residual oil and clarified oil enter the residual hydrocracking device together, carries out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst; The hydrogenated residue that obtains of reaction enters catalytic cracking unit, carries out cracking reaction in the presence of cracking catalyst, and heavy cycle oil is in the catalytic cracking unit internal recycling, react slurry oil obtain clarified oil through separation, be back to hydrogenation unit.
CN101210200A discloses a kind of residual hydrocracking and catalytic cracking combination process, the thing that steams of residual oil, the heavy catalytic cycle oil that removes solid impurity, optional distillate and optional catalytically cracked oil enters the residual hydrocracking device together, the hydrogenated residue of gained enters catalytic cracking unit with optional vacuum gas oil, obtains various products; The catalytic cracking turning oil that removes impurity is circulated to the residual hydrocracking device; Catalytically cracked oil is carried out fractionation by distillation, and be circulated to the residual hydrocracking device.
Above-mentioned technology has all been done further optimization utilization to catalytic cracking recycle oil and slurry oil, makes that aromatic hydrocarbon content reduces in the catalytically cracked material, and the device operating severity reduces, and simultaneously, the aromatic hydrocarbon in recycle stock and the slurry oil has been brought into play the effect of dilution residual oil raw material.But slurry oil steams excess still not to be fully utilized, and behind the stable hydrocarbon slag input oil device in the recycle stock corresponding cracking reaction can take place simultaneously, generates imperfect component, increases the residual hydrogenation equipment load simultaneously.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can improve the catalytic cracking unit yield of light oil, simultaneously, catalytic cracking recycle oil and slurry oil are fully used, produce residual hydrocracking, catalytic cracking and the solvent extraction group processing method of more high value added products.
Residual hydrocracking provided by the invention, catalytic cracking and solvent extraction group processing method may further comprise the steps:
(1) raw material residual oil separately or and other raw materials enter residual hydrogenation equipment with hydrogen and react, the reaction product separation obtains dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue;
(2) hydrogenated residue with step (1) enters catalytic cracking unit continuation reaction separately or with other catalytically cracked materials together, and product is separated into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil;
(3) with heavy cycle oil and all or part of solvent extraction plant that enters of slurry oil of step (2) gained, heavy cycle oil and slurry oil carry out extracting and separating in solvent extraction plant; The extracting phase that obtains separately or and the part heavy cycle oil that comes out of catalytic cracking unit Returning catalyticing cracking device together;
(4) extraction phase that step (3) is obtained enters the separation that separation column is realized different fractions, and cat head is extraction solvent, and side line is middle runnings, is last running at the bottom of the tower; Extraction solvent is back to solvent extraction plant, realizes recycle; The all or part of cut of middle runnings is delivered to the residual hydrocracking device portal and is entered the residual hydrocracking device with residual oil raw material; The part cut of middle runnings can be delivered to lube plant and produce lubricant base as charging; Last running is produced pitch as the pitch improving agent at the bottom of the tower.
Residual oil in the step (1) is a kind of or mixture in long residuum and the vacuum residuum.The residual hydrocracking device can be fixed bed weight, residual hydrocracking device, moving-bed weight, residual hydrocracking device, ebullated bed weight, residual hydrocracking device, expanded bed weight, residual hydrocracking device, one or more combination in slurry attitude bed weight, the residual hydrocracking device., residual hydrocracking technology heavy with at present industrial ripe fixed bed is example, described reactor or reaction bed comprise a kind of hydrogenation catalyst at least, and the weight of employing, residual oil hydrocatalyst refer to have single catalyst or the combination catalyst of functions such as weight, residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.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 or sulfide are active ingredient, optionally add the catalyzer of other various auxiliary agents such as elements such as P, Si, F.In the present fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Be 5～35MPa in absolute pressure normally, preferred 10～20MPa, temperature is 300 ℃～500 ℃, preferred 350 ℃～450 ℃ operations down.Volume space velocity is 0.1～5hr during liquid
-1, preferred 0.15～2hr
-1Scope in, hydrogen-oil ratio (volume) is 100～5000, preferred 500～3000.
In the step (2), the catalytic cracking technology that uses those skilled in the art of the present technique to be familiar with carries out hydrocarbon raw material catalytic cracking.The gas that the generates body recovery system of can degassing, gasoline fraction is preferably all delivered to the oil product jar.Gas oil often is sent to the further hydrotreatment of downstream hydrofining at least in part, whole or a branch of heavy gas oil, with all or part of of recycle stock, whole introducing solvent extraction plants of slurry oil, the cut point of introducing the solvent extraction plant cut is 200 ℃～600 ℃, preferred 260 ℃～500 ℃, this part cut accounts for 5～40% of total cutting cut weight ratio, and then cutting out partial or all aromatic hydrocarbon and hydrogenating materials are mixed into the residual hydrocracking device.Reason is to contain a large amount of arenes in recycle stock and the slurry oil, these aromatic hydrocarbon have solvability preferably to the condensed-nuclei aromaticss such as bituminous matter in residual oil raw material and the hydrogenated products, in hydrogenation process, the condensed-nuclei aromaticss such as bituminous matter that can reduce or eliminate in residual oil raw material and the hydrogenated products take place to assemble and the probability of coking, make residual hydrogenation equipment can handle the worse residual oil of more character, and can also reduce sedimentation of coke amount on the hydrogenation catalyst, prolong the work-ing life of catalyzer, residual hydrogenation equipment can be turned round under higher transformation efficiency.The operational condition of catalytic cracking unit is: temperature of reaction is 400 ℃～700 ℃, reaction pressure 0.1～0.8MPa, agent-oil ratio (weight) 2～60, reaction raw materials and 0.1～30 second duration of contact of catalyzer.Preferred operational condition is: temperature of reaction is 460 ℃～550 ℃, reaction pressure 0.1～0.4MPa, agent-oil ratio (weight) 2～20, reaction raw materials and 0.1～10 second duration of contact of catalyzer.The catalytic cracking catalyst that adopts comprises the catalyzer that is generally used for catalytic cracking, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5 type, M type, layer post equimolecular sieve cracking catalyst.Described catalytic cracking unit can be that every covering device comprised a reactor, a revivifier and a separation column at least more than a cover or overlapped.Reactor can be the catalyst cracker of various types, and preferably riser tube or riser tube add the bed reactor.
In the step (3), the solvent extraction technology that adopts those skilled in the art of the present technique to be familiar with, can use rotating disc contactor or tray column, distillate enters from the tower item, and extraction solvent enters at the bottom of tower, the spe medium that adopts can be alkanes, as propane, butane, Trimethylmethane, pentane, iso-pentane, hexane or two or more mixture wherein; Also can be ketone such as acetone, butanone, pimelinketone or two or more mixture wherein; Also can be alcohols, as ethanol, propyl alcohol, ethylene glycol, fourth octanol or two or more mixture wherein; Also can be amides, as methane amide, ethanamide, diethylamide or two or more mixture wherein; Also can be alkane, alcohol, ketone, acid amides or one or more mixture of solvent wherein.Operational condition is: total extraction solvent and distillate weight ratio are 1～8: 1, and pressure is 0～5MPa, and temperature is 0 ℃～250 ℃.Extracting phase loops back catalytic cracking unit with the distillate of choosing wantonly, and the extracting phase cut accounts for 3～30% of catalytic cracking unit combined feed total feed weight ratio, enters catalytic cracking unit with hydrogenated residue and reacts.Not containing in the extracting phase or contain a spot of aromatic hydrocarbon, is the high quality raw material of catalytic cracking unit.
In the step (4), cat head is that overhead product is extraction solvent, and side stream is middle runnings, and the bottomsstream is last running; Extraction solvent is back to solvent extraction plant, realizes recycle; The all or part of lighter fraction of middle runnings can be delivered to the residual hydrocracking device portal and enter the residual hydrocracking device with residual oil raw material, the amount of middle runnings accounts for 2～20% of residual hydrogenation equipment combined feed total feed weight ratio, accounts for 10～100% of the total middle runnings weight ratio of separation column.Middle runnings all or part of can be delivered to lube plant than last running and produce lubricant base as charging, the cut point of middle runnings is 350 ℃～550 ℃.Last running carries a certain amount of catalytic cracking catalyst fine powder at the bottom of the tower, need not to separate, and can produce pitch as the pitch improving agent together with distillate.
Middle runnings in the distillation tower has very high aromaticity, help the bituminous matter in the residual oil to dissociate into littler structure, this has increased the speed that the residual oil molecular diffusion enters the catalyzer micropore, thereby can improve the metal impurities decreasing ratio, improves residual hydrocracking device air speed and treatment capacity.Simultaneously, the adding of middle runnings has reduced the viscosity of residual hydrocracking raw material, can improve the flow state of logistics in reactor, overcomes the operational difficulty and the hidden danger that cause because of pulsation.And the adding of middle runnings can improve the aromaticity of solvent on every side, increases bitum peptizing power, reduces its deposition on the catalyzer of rear portion.Simultaneously, the partial hydrogenation product of polycyclic aromatic hydrocarbons is very strong hydrogen supply agent in the middle runnings, can reduce the condensation of residual oil hot radical, suppresses the generation of coking precursor.The carbon deposit that these all can significantly reduce catalyzer has reduced deactivation rate, the extension fixture operational cycle.
Description of drawings
Fig. 1 residual hydrocracking, catalytic cracking and solvent extraction group processing method schematic flow sheet.
Embodiment
Enter residual hydrogenation equipment 18 through preheating after mixing from the hydrogen of pipeline 1 with from the residual oil of pipeline 2, contact with hydrogenation catalyst and carry out hydrotreatment and react; Product after the separation is respectively gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue, wherein gas, hydrotreated naphtha, hydrogenated diesel oil are respectively through pipeline 3,4,5 caterpillars, hydrogenated residue enters heavy oil catalytically cracking equipment 19 through pipeline 6 with the raffinate oil from pipeline 12, contact with catalytic cracking catalyst and react, obtain dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil, dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil are respectively by pipeline 7,8,9,10 caterpillars.Heavy cycle oil and slurry oil enter solvent extraction plant 20 through pipeline 11, heavy cycle oil and slurry oil and connect solution from the solvent of pipeline 14 and carry out extraction process in extraction plant, extracting phase contains a certain amount of catalytic cracking catalyst fine powder, be back to catalytic cracking unit 19 through pipeline 12 with hydrogenated residue, extraction phase enters separation column 21 through pipeline 13 to be separated, obtain the overhead fraction extraction solvent, middle runnings and tower bottom distillate, the overhead fraction extraction solvent is back to extraction plant 20 through pipeline 14 and recycles, middle runnings is back to residual hydrocracking device 18 through pipeline 15 or pipeline 16, or carry through pipeline 16 and to make the top-grade lubricating oil base oil, tower bottom distillate is carried through pipeline 17 and is made the pitch improving agent.
The invention has the advantages that:
1, in the catalytic cracking unit isolated heavy cycle oil and slurry oil after extracting and separating, the middle runnings of being rich in aromatic hydrocarbon in the extraction phase adds in the residual oil raw material, can significantly reduce charging viscosity, improve the diffusibility of reactant and take off the impurity speed of reaction, reduced foreign matter contents such as the sulphur that generates in the oil, nickel, vanadium.
2, in the catalytic cracking unit isolated heavy cycle oil and slurry oil after extracting and separating, do not contain or contain a spot of aromatic hydrocarbon in the extracting phase, major part is stable hydrocarbon, they are catalytically cracked materials of high-quality, be back to catalytic cracking and can improve light oil yield (the yield sum that refers to liquefied gas, gasoline and diesel oil), reduce the green coke amount; Simultaneously, extracting phase contains a certain amount of catalytic cracking catalyst fine powder, need not to separate, and can loop back catalytic cracking unit and use.
3, in the catalytic cracking unit isolated heavy cycle oil and slurry oil after extracting and separating, being rich in aromatic hydrocarbon in the extraction phase middle runnings, is the raw material on the top-grade lubricating oil basis of high-quality, but the high product of production added value, simultaneously, at the bottom of the extraction phase tower oil as asphalt modifier.
Embodiment
One liter of four anti-pilot plant of fixed bed residual hydrogenation that the residual hydrogenation equipment that uses in embodiment and the Comparative Examples is produced as U.S. Xytel company; device is totally four reactors; load protective material, metal remover, sweetening agent and denitrfying agent respectively; it is 5: 40: 30 that catalyst property sees Table 1 grade of mixing ratio: 25, and catalyzer is that independently develop in the laboratory.The small-sized riser reactor pilot plant that FCC tests designs voluntarily in the laboratory in embodiment and the Comparative Examples carries out, the catalyzer that uses as shown in the table 1.
Table 1 the present invention uses the main physico-chemical property of residual oil hydrocatalyst
Residual oil, (quality group becomes 100: 9 to the separation column intermediate oil, character sees Table 2) and hydrogen directly enter the residual hydrogenation pilot plant after mixing, react according to the condition in the table 3, reaction product is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue, and product distributes and running condition sees Table 4; (quality group becomes 98: 9 for hydrogenated residue and extraction tower raffinate oil, character sees Table 2) enter catalytic cracking unit together, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil, reaction conditions sees Table 3, and product distributes and running condition sees Table 5.Catalytic cracking turning oil and slurry oil enter the extracting and separating tower, extraction solvent is the mixture (volume ratio is 1: 1: 1) of furfural, ring fourth maple and hexanolactam, and extraction solvent and distillate weight ratio are 2: 1, and pressure is normal pressure, temperature is 50 ℃, and extracting phase character sees Table 6.Extracting phase is back to catalytic cracking unit, and extraction phase enters separation column, and solvent overhead is back to extraction tower and recycles, and side stream oil and residual oil raw material enter residual hydrogenation equipment together, and the bottomsstream is as asphalt modifier, and distillate character sees Table 7.The total light oil yield of residual hydrogenation equipment and catalytic cracking unit sees Table 8.
Table 2 residual hydrogenation equipment feed properties
| Comparative Examples | Embodiment | |
| Density (20 ℃), kg/m 3 | 0.977 | 0.980 |
| S，wt％ | 4.43 | 4.05 |
[0031]
| N，wt％ | 0.37 | 0.34 |
| Carbon residue (MCR), wt% | 13.2 | 12.0 |
| Metal (Ni+V), ppm | 78.5 | 71.7 |
| Stable hydrocarbon, wt% | 24.5 | 22.8 |
| Aromatic hydrocarbon, wt% | 40.7 | 45.3 |
| Colloid, wt% | 30.7 | 28.2 |
| Bituminous matter, wt% | 4.1 | 3.7 |
The main operational condition of table 3 residual hydrogenation and catalytic cracking
| Comparative Examples | Embodiment | |
| The hydrogenation unit test conditions | ||
| Hydrogen partial pressure, MPa | 16 | 16 |
| Volume space velocity (residual oil), hr -1 | 0.27 | 0.30 |
| Temperature of reaction, ℃ | 390 | 390 |
| Hydrogen-oil ratio, v/v | 1000 | 1000 |
| The catalytic cracking unit operational condition | ||
| Agent-oil ratio | 6 | 6 |
| Temperature of reaction, ℃ | 507 | 507 |
| Reaction times, second | 2 | 2 |
Table 4 residual hydrogenation product data situation
| The residual hydrogenation product distributes, wt% | Comparative Examples | Embodiment |
| C1～C4 | 1.47(1.47) | 1.43(1.56) |
| Hydrotreated naphtha (C5～180 ℃) | 0.96(0.96) | 0.95(1.04) |
| Hydrogenated diesel oil (180 ℃～350 ℃) | 7.25(7.25) | 7.70(8.4) |
| Hydrogenated residue (＞350 ℃) | 87.55(87.55) | 89.92(98.0) |
| Hydrogenated residue character | ||
| Density (20 ℃), kg/m 3 | 0.933 | 0.941 |
| S，wt％ | 0.32 | 0.28 |
[0036]
| N，wt％ | 0.14 | 0.11 |
| Carbon residue (MCR), wt% | 4.1 | 3.5 |
| Metal (Ni+V), ppm | 5.2 | 4.6 |
| Stable hydrocarbon, wt% | 58.5 | 56.9 |
| Aromatic hydrocarbon, wt% | 26.7 | 27.3 |
| Colloid, wt% | 13.2 | 13.7 |
| Bituminous matter, wt% | 1.6 | 2.1 |
Annotate: numerical value is the product yield of residual oil relatively in the table bracket
Table 5 catalytic cracking product data situation
| Comparative Examples | Embodiment | |
| The catalytic cracking product distributes, wt% | ||
| Dry gas | 1.72(1.73) | 1.74(1.88) |
| Liquefied gas | 10.47(10.50) | 10.56(11.40) |
| Catalytic gasoline | 44.01(44.16) | 46.57(50.30) |
| Catalytic diesel oil | 15.43(15.48) | 15.38(16.61) |
| Catalytic cracking turning oil | 12.78(12.82) | 11.99(12.95) |
| Slurry oil | 8.02(8.05) | 6.55(7.07) |
| Coke | 8.68(8.71) | 7.21(7.79) |
Annotate: numerical value is the product yield of residual oil relatively in the table bracket
Table 6 extracting phase character
| Project | Extracting phase |
| Density (20 ℃), kg/m 3 | 0.970 |
| S，wt％ | 0.15 |
| N，wt％ | 0.05 |
| Carbon residue (MCR), wt% | 0.21 |
| Metal (Ni+V), ppm | 2.5 |
| Stable hydrocarbon, wt% | 97.8 |
| Aromatic hydrocarbon, wt% | 2.2 |
| Colloid, wt% | 0 |
[0043]
| Bituminous matter, wt% | 0 |
Table 7 side stream, tower bottom distillate main character
| Project | Side stream | Tower bottom distillate |
| Density (20 ℃), kg/m 3 | 0.985 | 1.097 |
| S，wt％ | 0.29 | 0.89 |
| N，wt％ | 0.10 | 0.25 |
| Carbon residue (MCR), wt% | 0.31 | 23.65 |
| Metal (Ni+V), ppm | 3.5 | 5.1 |
| Stable hydrocarbon, wt% | 5.8 | 3.4 |
| Aromatic hydrocarbon, wt% | 92.2 | 50.7 |
| Colloid, wt% | 3.0 | 28.2 |
| Bituminous matter, wt% | 0 | 12.7 |
Table 8 residual hydrogenation, catalytic cracking total yield of products
| Project, wt% (residual oil relatively) | Comparative Examples | Embodiment |
| Liquefied gas | 10.50 | 11.40 |
| Gasoline | 45.12 | 51.34 |
| Diesel oil | 22.73 | 25.01 |
| Light oil (liquefied gas+gasoline+diesel oil) | 78.35 | 87.75 |
Comparative Examples
Residual oil raw material (character sees Table 2) and hydrogen enter the residual hydrogenation pilot plant after mixing, and react according to the condition in the table 3, carry out reaction product and are separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue, and product distributes and running condition sees Table 4; Hydrogenated residue and recycle stock enter catalytic cracking unit together, catalytic cracking recycle oil adopts and filters the back heavy catalytic cycle oil, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil and slurry oil, and reaction conditions sees Table 3, and product distributes and running condition sees Table 5.The total light oil yield of residual hydrogenation equipment and catalytic cracking unit sees Table 8.
As can be seen from Table 8, combination process of the present invention is compared with the existing technology in the Comparative Examples, and yield of liquefied gas has improved 0.9 percentage point, and yield of gasoline has improved 6.22 percentage points, and diesel yield has improved 2.28 percentage points, and light oil yield has improved 9.4%.Present embodiment can also adopt the of the present invention part of middle runnings extraction in the extraction phase is used as to produce lubricant base, produces more high value added products.
Claims (10)
1. hydrogenation and catalystic cracking combined process for residual oil, it is characterized in that: step comprises:
(1) raw material residual oil separately or and other raw material enter residual hydrogenation equipment with hydrogen and react, the reaction product separation obtains dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue;
The residual hydrogenation condition is: hydrogen partial pressure 10～22MPa, and temperature of reaction is 300 ℃～435 ℃, volume space velocity is 0.1～4.5hr
-1, hydrogen to oil volume ratio 500～3000;
Catalyzer is to be carrier with porous refractory inorganic oxides aluminum oxide, and the oxide compound of W, Mo, Co, Ni or sulfide are active ingredient, adds P, Si or/and the catalyzer of F element;
(2) hydrogenated residue with step (1) enters catalytic cracking unit continuation reaction separately or with other catalytically cracked materials together, and product is separated into dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil; Temperature of reaction is 400 ℃～700 ℃, and reaction pressure 0.1～0.8MPa, agent weight of oil be than 2～60, reaction raw materials and 0.1～30 second duration of contact of catalyzer;
Catalyzer is silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5 type, M type, layered molecular sieve catalytic cracking catalyst;
(3) with heavy cycle oil and all or part of solvent extraction plant that enters of slurry oil of step (2) gained, heavy cycle oil and slurry oil carry out extracting and separating in solvent extraction plant; The extracting phase that obtains separately or and the part heavy cycle oil that comes out of catalytic cracking unit Returning catalyticing cracking device together; Total extraction solvent and distillate weight ratio are 1～8: 1, and pressure is 0～5MPa, and temperature is 0 ℃～250 ℃; Spe medium is one or more the mixture in alkanes, ketone, alcohols, the amides;
(4) extraction phase that step (3) is obtained enters the separation that separation column is realized different fractions, and cat head is extraction solvent, and side line is middle runnings, is last running at the bottom of the tower; The cut point of the middle runnings in the separation column is 200 ℃～550 ℃; Extraction solvent is back to solvent extraction plant, realizes recycle; The all or part of cut of middle runnings is delivered to the residual hydrocracking device portal and is entered the residual hydrocracking device with residual oil raw material; The part cut of middle runnings is delivered to lube plant and is produced lubricant base as charging; Last running is produced pitch as the pitch improving agent at the bottom of the tower.
2. in accordance with the method for claim 1, it is characterized in that the reactor in the residual hydrocracking device in the described step (1) is to be one or more combination in fixed bed, moving-bed, ebullated bed, the prize attitude bed.
3. in accordance with the method for claim 1; it is characterized in that; reactor in the residual hydrocracking device in the described step (1) is fixed-bed reactor; it is one or more combinations; adopt the catalyzer grading loading; filling simultaneously comprises protective material; metal remover; sweetening agent is at three interior classes or the above catalyzer of three classes; sweetening agent is desulfurization demetalization transition agent; in sweetening agent and the highly active desulfurization agent one or more; different catalysts is divided the bed filling; be contained in a reactor or a plurality of reactor, the protective material bed adopts fixed-bed reactor or up-flow reactor.
4. in accordance with the method for claim 1, it is characterized in that the operational condition of the catalytic cracking unit in the described step (2) is: temperature of reaction is 460 ℃～550 ℃, reaction pressure 0.1～0.4MPa, the agent weight of oil is than 2～20, reaction raw materials and 0.1～10 second duration of contact of catalyzer.
5. in accordance with the method for claim 1, it is characterized in that solvent extraction technology uses rotating disc contactor or tray column in the described step (3), distillate enters from the tower item, and extraction solvent enters at the bottom of tower.
6. in accordance with the method for claim 1, it is characterized in that the extracting phase cut from extraction tower that is back to catalytic cracking unit in the described step (3) accounts for 3～30% of catalytic cracking unit combined feed total feed weight ratio.
7. in accordance with the method for claim 1, it is characterized in that the cut point of delivering to the middle runnings that the separation column of residual hydrocracking device separates in the described step (4) is 200 ℃～500 ℃.
8. in accordance with the method for claim 1, it is characterized in that, deliver to the middle runnings that the separation column of residual hydrocracking device separates in the described step (4) and account for 2～20% of residual hydrogenation equipment combined feed total feed weight ratio.
9. in accordance with the method for claim 1, it is characterized in that, deliver to the middle runnings that the separation column of residual hydrocracking device separates in the described step (4) and account for 10～100% of the total middle runnings weight ratio of separation column.
10. in accordance with the method for claim 1, it is characterized in that the cut point of delivering to the middle runnings that the separation column of lube plant separates in the described step (4) is 350 ℃～550 ℃.
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| CN106367113A (en) * | 2015-07-23 | 2017-02-01 | 中国石化扬子石油化工有限公司 | Residual oil hydrotreating method |
| CN111394122A (en) * | 2020-03-05 | 2020-07-10 | 北京中科诚毅科技发展有限公司 | Hydrogenation tailing treatment process and application and design method thereof |
| CN114437770A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process method for regenerating asphalt activator by using refined oil slurry |
| CN114437771A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process for regenerating asphalt activator by using refined oil slurry |
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| CN104593062A (en) * | 2013-10-31 | 2015-05-06 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined processing method for residual oil |
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| CN114437770A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process method for regenerating asphalt activator by using refined oil slurry |
| CN114437771A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Process for regenerating asphalt activator by using refined oil slurry |
| CN114437771B (en) * | 2020-10-19 | 2024-02-27 | 中国石油化工股份有限公司 | Process method for regenerating asphalt activator by utilizing refined oil slurry |
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