CN101760239B - Utilization method of catalytic cracking diesel - Google Patents
Utilization method of catalytic cracking diesel Download PDFInfo
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- CN101760239B CN101760239B CN 200810240865 CN200810240865A CN101760239B CN 101760239 B CN101760239 B CN 101760239B CN 200810240865 CN200810240865 CN 200810240865 CN 200810240865 A CN200810240865 A CN 200810240865A CN 101760239 B CN101760239 B CN 101760239B
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Abstract
The invention relates to a utilization method of catalytic cracking diesel, wherein the method comprises the following steps: (1) separating the catalytic cracking diesel into a component with the boiling point being less than 230 DEG C and a component with the boiling point being more than 230 DEG C; (2) hydrogenering for the component with the boiling point being more than 230 DEG C obtained inthe step (1) under the condition that poly-aromatic hydrocarbon is inverted into monocyclic aromatic hydrocarbon; (3) separating the component with the boiling point being less than 230 DEG C obtained in the step (1) and hydrogenation product obtained in the step (2) to obtain diesel rich in the monocyclic aromatic hydrocarbon, and catalytically cracking the diesel rich in the monocyclic aromatichydrocarbon. In the method, firstly, the catalytic cracking diesel is separated into the component with the boiling point being less than 230 DEG C and the component with the boiling point being morethan 230 DEG C, and then the poly-aromatic hydrocarbon in the component with the boiling point being more than 230 DEG C can be hydro-fined into the monocyclic aromatic hydrocarbon, therefore, the hydrogenation selectivity can be improved, and the FCC gasoline with high content of aromatic hydrocarbon and high octane number can be obtained.
Description
Technical field
The present invention relates to a kind of method of utilizing of catalytic cracking diesel oil.
Background technology
Along with crude resources poor qualityization, the processing that contains acid oil and the raising of fluid catalystic cracking (FCC) raw material intermingled dregs ratio, cause the character of catalytic cracking diesel oil (LCO) worse and worse, mainly show as cetane value extremely low (＜25).
For the method for LCO upgrading normally behind hydrofining or the hydro-upgrading as diesel product or blend component (Europe Ш diesel oil requires cetane value greater than 51).For the hydro-upgrading of above-mentioned LCO inferior, its cetane value need be improved 25 more than the unit, could satisfy Europe Ш emission request.But the hydro-upgrading of this LCO inferior need consume a large amount of hydrogen and extremely low reaction velocity, and plant construction and process cost are very high.Therefore, LCO inferior (cetane value＜25) hydro-upgrading production diesel oil has not been an economically viable route in some cases.
It is saturated that LCO inferior is carried out hydrogenation earlier, then as the FCC apparatus charging, produces stop bracket gasoline or blend component, is an economically viable route in some cases.
US 5,152, and 883 disclose a kind of LCO, HCO and clarified oil through the hydrogenation freshening method of producing stop bracket gasoline to FCC apparatus again.After this method was heavy oil process FCC apparatus, after LCO, HCO and clarified oil separation in the FCC reaction product, after hydrogenation device for treatment, after will separating greater than the fraction more than 221 ℃, freshening can be produced stop bracket gasoline to FCC apparatus again.This method is HCO and the full freshening of clarified oil, and side reactions such as FCC apparatus carbon deposit increase, and the hydrogenation unit hydrogenation degree of depth does not provide and specifies.
US 5,582, and 711 disclose a kind of FCC and hydrogenation unit combined processing method.This method comprises two or more catalytic cracking reaction parts, wherein exists a hydrogenation reaction part between two reactive moieties.After the raw material process FCC apparatus first cracking reactive moieties, isolate heavy constituent at the bottom of gas, petroleum naphtha, diesel oil and the tower, heavy constituent are through after the hydrogenation device for treatment at the bottom of diesel oil and the tower, hydrogenation reaction product is again through separating, light constituents such as petroleum naphtha and gas are separated, refined diesel oil and heavy constituent again freshening to the FCC apparatus second cracking reactive moieties.To separate again after the FCC apparatus first reactive moieties product, the isolated light constituent of hydrogenation unit and the mixing of the FCC apparatus second reactive moieties product.This technology also is in order to obtain low-molecular olefine and stop bracket gasoline.But because heavy constituent freshening at the bottom of the tower cause the FCC apparatus carbon deposit to increase, and the hydrogenation device for treatment difficulty also increases.
US 5,944,982 is the combination process of FCC technology and hydrogenation technique, wherein the FCC process using is double lifting leg technology, after heavy feed stock reacts through FCC apparatus first riser tube, isolate relatively lighter component and heavier component, advance the hydrogenation unit hydrotreatment than light constituent (heavy naphtha and LCO) after, the hydrogenation products freshening carries out cracking reaction to FCC apparatus second riser tube.Two portions product has independently separating device.This technology is for producing low-carbon alkene and stop bracket gasoline.
US 6,123, and 830 is the combination process of FCC and hydrogenation, raw material at first through after the first cover hydrogenation device for treatment, goes the first cover FCC apparatus, and reaction product is through after separating, at the bottom of diesel oil and the tower heavy constituent go second the cover hydrogenation unit, carry out hydrotreatment after, go again second the cover FCC apparatus.After mixing, the reaction product of two cover FCC apparatus separates.This process using two the cover hydrogenation units and two the cover FCC apparatus, invest higher.
US 6,569, and 315 raw materials are isolated LCO and HCO in the FCC apparatus product through FCC apparatus, and after hydrogenation device for treatment, freshening is produced low-molecular olefine and petroleum naphtha to FCC apparatus again with LCO and HCO.
US 6,811,682 is on the FCC apparatus riser tube two conversion zones and two charging inlets to be arranged, raw material advances first inlet, LCO in the reaction product and HCO are after hydrogenation device for treatment, second inlet (in the upstream of first inlet) of freshening to the FCC apparatus riser tube produced low-molecular olefine and petroleum naphtha again.
US 6,837, on the 989 device riser tubes two conversion zones and two charging inlets are arranged, raw material advances first inlet, LCO in the reaction product is after hydrogenation device for treatment, second inlet (in the upstream of first inlet) of freshening to the FCC apparatus riser tube produced low-molecular olefine and petroleum naphtha again.
It is saturated that aforesaid method carries out hydrogenation earlier with LCO inferior, then as the FCC apparatus charging, though can improve the utilization ratio of LCO inferior to a certain extent, but with the product of the hydrogenation process raw material as FCC apparatus, can cause aromaticity content reduction in the FCC gasoline, and cause the FCC gasoline octane rating to reduce.
Summary of the invention
The method of utilizing that the purpose of this invention is to provide a kind of catalytic cracking diesel oil, this method can make aromaticity content and the high FCC gasoline of octane value.
The present inventor finds, in LCO aromatic hydrocarbons mainly based on mononuclear aromatics, double ring arene, also have part three rings and the above aromatic hydrocarbons of three rings.Their boiling point and carbonatoms depended in the distribution of aromatic hydroxy compound, mononuclear aromatics such as alkylbenzene, indane or naphthane etc. concentrate on (＜230 ℃) in the low boiler cut, double ring arene such as naphthalene, naphthalene class, acenaphthene class and acenaphthylene class then concentrate in the middle runnings section of diesel oil (230～310 ℃), and three rings and the aromatic hydrocarbons more than three rings then concentrate in the last running of diesel oil (＞310 ℃).For the hydrofining LCO of freshening to FCC apparatus, produce the stop bracket gasoline scheme, among the LCO after requiring to make with extra care, should be rich in mononuclear aromatics, do not contain double ring arene and thrcylic aromatic hydrocarbon as far as possible, because these materials can cause the increase of FCC apparatus amount of coke.Existing LCO utilizes method with whole LCO hydrogenation inferior, saturated selectivity is relatively poor in hydrogenation process, makes the part mononuclear aromatics be saturated to cycloalkanes, with the raw material of such hydrogenation products as FCC apparatus, can cause aromaticity content reduction in the FCC gasoline, and cause the FCC gasoline octane rating to reduce.In research LCO, after the composition and distribution, hydrogenation dearomatization and catalytic cracking reaction of aromatic hydrocarbons, technical scheme of the present invention has been proposed.
The invention provides a kind of method of utilizing of catalytic cracking diesel oil, wherein, this method may further comprise the steps:
(1) catalytic cracking diesel oil being separated into boiling point is component more than 230 ℃ less than 230 ℃ component and boiling point;
(2) polycyclic aromatic hydrocarbons being converted under the condition of mononuclear aromatics, is that component more than 230 ℃ is carried out hydrogenation to the boiling point that obtains in the step (1);
(3) obtain isolating the diesel oil that is rich in mononuclear aromatics the hydrogenation products of boiling point less than 230 ℃ component and step (2) from step (1), and the diesel oil that is rich in mononuclear aromatics that will obtain carries out catalytic cracking.
It is component more than 230 ℃ less than 230 ℃ component and boiling point that method of the present invention is separated into catalytic cracking diesel oil boiling point earlier, making boiling point then is that polycyclic aromatic hydrocarbons hydrofining in the component more than 230 ℃ is mononuclear aromatics, can improve hydrogenation selectivity, make the high FCC gasoline of aromaticity content and octane value.
Description of drawings
Fig. 1 represents the schema of a kind of preferred implementation of method of the present invention.
Embodiment
The method of utilizing of catalytic cracking diesel oil provided by the invention may further comprise the steps:
(1) catalytic cracking diesel oil being separated into boiling point is component more than 230 ℃ less than 230 ℃ component and boiling point;
(2) polycyclic aromatic hydrocarbons being converted under the condition of mononuclear aromatics, is that component more than 230 ℃ is carried out hydrogenation to the boiling point that obtains in the step (1);
(3) obtain isolating the diesel oil that is rich in mononuclear aromatics the hydrogenation products of boiling point less than 230 ℃ component and step (2) from step (1), and the diesel oil that is rich in mononuclear aromatics that will obtain carries out catalytic cracking.
The boiling range scope of described catalytic cracking diesel oil is 180-400 ℃.Method of the present invention is particularly useful for LCO inferior, and for example cetane value is less than 25 LCO.
According to a kind of preferred implementation of the present invention, can be that further to be separated into boiling point be 230-310 ℃ component and boiling point greater than 310 ℃ component for component more than 230 ℃ with boiling point in step (1), and be that 230-310 ℃ component and boiling point carries out hydrogenation greater than 310 ℃ component to boiling point respectively in step (2), boiling point is that the temperature of 230-310 ℃ component hydrogenation is lower than boiling point greater than the temperature of 310 ℃ component hydrogenation.According to this preferred implementation, boiling point is that 230-310 ℃ component mainly contains di pah, boiling point mainly contains three rings or the above aromatic hydrocarbons of three rings greater than 310 ℃ component, to they difference hydrogenation, can improve hydrogenation selectivity, being conducive to polycyclic aromatic hydrocarbons hydrofining is mononuclear aromatics, thereby further reduces the amount of coke of FCC apparatus.
In step (1), can adopt conventional separation method, for example, described separation can be carried out in separation column, the operational condition of separation column can comprise: feeding temperature is that 180-280 ℃, column bottom temperature are 250-350 ℃, tower top temperature is 120-250 ℃, and tower top pressure is 0.05-1.05MPa (gauge pressure).Tell lighting end section (boiling point less than 230 ℃ component) from the separation column top, tell middle runnings section (boiling point is 230-310 ℃ component) and tell double distilled segmentation (boiling point greater than 310 ℃ component) at the bottom of the tower from the separation column side line.
In step (2), the method for described hydrogenation is included under the existence of Hydrobon catalyst, and the component for the treatment of hydrogenation is contacted with hydrogen.The described component for the treatment of hydrogenation refers to that boiling point is the component more than 230 ℃, component that boiling point is 230-310 ℃ or boiling point greater than 310 ℃ component.The condition of contact can comprise: temperature of reaction is 250-450 ℃, and the hydrogen dividing potential drop is 1-12MPa, and liquid hourly space velocity is 0.3-10h
-1, hydrogen to oil volume ratio is 100-1500Nm
3/ m
3The condition optimization of contact comprises: temperature of reaction is 260-420 ℃, and the hydrogen dividing potential drop is 2-10MPa, and liquid hourly space velocity is 0.5-8.0h
-1, hydrogen to oil volume ratio is 150-1000Nm
3/ m
3In step (2), under the effect of Hydrobon catalyst, carry out hydrogenating desulfurization, hydrodenitrification, alkene is saturated and part aromatic hydrocarbons saturated reaction.Be the condition that 230-310 ℃ component contacts with hydrogen for boiling point, temperature of reaction is preferably 250-400 ℃; For the condition that boiling point contacts with hydrogen greater than 310 ℃ component, temperature of reaction is preferably 280-450 ℃.
Described Hydrobon catalyst can be the various Hydrobon catalysts of routine.Hydrobon catalyst contains hydrogenation activity composition and carrier.Described hydrogenation activity composition is VI family and/or group VIII metal, and described carrier is heat-resistant inorganic oxide carrier, is preferably one or more mixtures in aluminum oxide, silicon oxide, titanium oxide, zirconium white and the molecular sieve.
The preferred hydrofining activeconstituents of the present invention comprises nickel oxide, molybdenum oxide, Tungsten oxide 99.999, fluorine and phosphorus oxide, and carrier is silica-alumina.Total amount with catalyzer is benchmark, the content of each composition can for: nickel oxide 1～10 weight %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 weight %, fluorine 1～10 weight %, phosphorus oxide 0.5～8 weight %, silica-alumina 40-85 weight %.Be benchmark with described carrier, preferably, the content of the silicon oxide in the silica-alumina is 2-45 weight %, and the content of aluminum oxide is 55-98 weight %; The content of further preferred silicon oxide is 5-40 weight %, and the content of aluminum oxide is 60-95 weight %.Described silica-alumina has specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of silica-alumina is preferably 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of silica-alumina is preferably 0.4～1ml/g, more preferably 0.5～0.8ml/g.
Described Hydrobon catalyst can also contain organic additive, and this organic additive can be oxygen-containing organic compound and/or itrogenous organic substance.Preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be one or more in the ammonium salt of quadrol, ethylenediamine tetraacetic acid (EDTA) (EDTA) and ethylenediamine tetraacetic acid (EDTA).Described organism is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound, is preferably 0.08-1.5.
After the hydrofining, can cool off hydrotreated product, carry out gas-liquid separation then, liquid phase stream is cut.Gas-liquid separation can utilize conventional method, for example uses high-pressure separator and light pressure separator successively.
Obtain isolating the diesel oil that is rich in mononuclear aromatics the hydrogenation products of boiling point less than 230 ℃ component and step (2) from step (1).Can be respectively from the hydrogenation products of boiling point less than 230 ℃ component and step (2), isolate the diesel oil that is rich in mononuclear aromatics, perhaps boiling point is mixed less than 230 ℃ component and the hydrogenation products of step (2), from mixture, isolate the diesel oil that is rich in mononuclear aromatics then.
Described being separated in the separation column carried out, and the operational condition of separation column can comprise: feeding temperature is that 180-280 ℃, column bottom temperature are 250-350 ℃, and tower top temperature is 120-250 ℃, and tower top pressure is 0.05-1.05MPa (gauge pressure).Gasoline fraction (less than 200 ℃ of cuts) is extracted from cat head, obtains being rich in the diesel oil distillate of mononuclear aromatics at the bottom of the tower.
Catalytic cracking can be adopted the catalyst cracking method of this area routine.The condition of catalytic cracking can comprise: temperature of reaction is 450-600 ℃, and agent-oil ratio is 1-20, and the reaction times is 0.2-8 second, and atomized water steam accounts for the 1-20 weight % of inlet amount, and reaction pressure is normal pressure-300 kPa (gauge pressure).The condition optimization of catalytic cracking comprises: temperature of reaction is 490-560 ℃, and agent-oil ratio is 3-12, and the reaction times is 1-2 second, and atomized water steam accounts for the 4-8 weight % of inlet amount, and reaction pressure is 100-300 kPa (gauge pressure).
The device of described catalytic cracking reaction can be generally the combination of riser reactor or riser tube and bed reactor for well known in the art.It for example can be fluid catalytic cracking of heavy oil (RFCC), also can be catalytic pyrolysis (DCC, the combination of riser tube and dense-phase bed reactor), voluminous isoparaffin catalytic cracking (MIP, riser tube the connect combination of quick bed reactor, i.e. reactor described in the Chinese patent 99105903.4) etc. in the device one or more.
Described catalytic cracking catalyst can be any one or a few the combination that is provided by prior art.These catalytic cracking catalysts contain zeolite, inorganic oxide and optional clay usually, and each components contents is respectively: zeolite 5～50 weight %, inorganic oxide 5～95 weight %, clay 0～70 weight %.
Described zeolite is selected from large pore zeolite and optional mesopore zeolite as active ingredient, and large pore zeolite accounts for 25～100 weight % of active ingredient, and preferred 50～100 weight %, mesopore zeolite account for 0～75 weight % of active ingredient, preferred 0～50 weight %.
Described large pore zeolite is selected from one or more the mixture in y-type zeolite, rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), ultrastable Y (USY), the extremely steady y-type zeolite of rare earth (REUSY).
Described mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as non-metallic element such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the ZSM series zeolite be selected among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures any or appoint several mixtures.
Described inorganic oxide is selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).
Described clay is as matrix, and namely carrier is selected from kaolin and/or halloysite.
About catalyzed cracking processing technology and the catalyzer that adopts thereof at US 6,495,028, all is described respectively among CN110116C, CN1072032C, CN1814705A, CN1814707A, CN1854251A and the CN1854254A etc., quotes as a reference in the lump here.
Fig. 1 represents the schema of a kind of preferred implementation of method of the present invention.With after hydrogenated diesel oil from hydrogenated diesel oil pipeline 2 mixes, enter catalytic cracking unit 3 from the catalytically cracked stock (wax oil or residual oil) of stock oil pipeline 1.The reaction product of coming out from catalytic cracking unit 3 enters fractionation and absorbing-stabilizing system 5 through pipeline 4, can obtain dry gas 6, liquefied gas 7, stop bracket gasoline 8, poor ignition quality fuel 9 and heavy oil 10.Poor ignition quality fuel 9 enters first separation column 11, tell diesel oil lighting end section (＜230 ℃) 12 from cat head, tell diesel oil middle runnings section (230～3 10 ℃) 13 from the tower side line, be rich in double ring arene, at the bottom of tower, tell diesel oil double distilled segmentation (＞310 ℃) 14, be rich in thrcylic aromatic hydrocarbon.Diesel oil middle runnings section 13 is entered the first hydrogenation reaction zone 15, and double ring arene is saturated to mononuclear aromatics.Diesel oil double distilled segmentation 14 enters the second hydrogenation reaction zone 16, and thrcylic aromatic hydrocarbon is saturated to mononuclear aromatics.The liquid product 17 in the first hydrogenation reaction zone, the liquid product 18 in the second hydrogenation reaction zone and the first fractionation cat head diesel oil lighting end section 12 are mixed, mixing oil 19 enters after-fractionating tower 20, cat head is extracted gasoline fraction 21, is refined diesel oil 22 at the bottom of the tower, is rich in mononuclear aromatics.Refined diesel oil mixes as the catalytic cracking unit charging with catalytically cracked material.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
The trade names of used Hydrobon catalyst are RS-1000 among the embodiment, are produced by catalyzer Chang Ling branch office of China Petrochemical Corp..Catalytic cracking catalyst is the MLC-500 poiser, is produced, is provided by catalyzer Shandong branch office of China Petrochemical Corp., and its specific nature is shown in Table 6.
Used stock oil A is a kind of conventional inferior heavy oil among the embodiment, and its main character is as shown in table 1.
Embodiment 1
Stock oil A enters catalytic cracking unit, behind reaction product process main fractionating tower and the absorbing-stabilizing system, obtains dry gas, liquefied gas, stop bracket gasoline, heavy oil and LCO (cetane value is 24).Wherein the LCO of gained be divided into after through first separation column light, in, weigh three cut sections, middle runnings section and double distilled segmentation enter first hydrogenation zone and second hydrogenation zone respectively.Liquid product, the second hydrogenation zone liquid product of benzoline, first hydrogenation zone are entered the after-fractionating tower after mixing.In the after-fractionating tower gasoline fraction is extracted, the refined diesel oil freshening is to catalytic cracking unit.The character of present embodiment stock oil A sees Table 1, and the character of the freshening refined diesel oil B behind the process hydrogenation sees Table 2, and the operational condition of machinery sees Table 3.Product distributes and sees Table 7, and main character sees Table 8.
Table 1 catalytic cracking unit feed properties
| The stock oil numbering | A |
| Density (20 ℃), g/cm 3 | 0.9025 |
| Viscosity (80 ℃), mm 2/s | 24.38 |
| Viscosity (100 ℃), mm 2/s | 13.88 |
| Condensation point, ℃ | 37 |
| Carbon residue, weight % | 3.82 |
| Elementary composition, weight % | |
| C | 86.86 |
| H | 12.86 |
| S | 0.13 |
| N | 0.26 |
| Metal content, μ g/g | |
| Fe/Na | 8.9/7.1 |
| Ni/V | 5.2/.9 |
| Ca | 9.9 |
| Form weight % | |
| Stable hydrocarbon | 67.6 |
| Aromatic hydrocarbons | 21.1 |
| Colloid | 10.5 |
| Bituminous matter | 0.8 |
| Boiling range, ℃ | |
| HK | 307 |
| 50％ | 479 |
| 70％ | 551 |
Table 2 freshening refined diesel oil character
| The freshening refined diesel oil | B |
| Density, g/cm 3 | 0.8605 |
| Refractive power, (20 ℃) | 1.4820 |
| Sulphur content, μ g/g | 33.7 |
| Nitrogen content, μ g/g | 18.6 |
| Form | |
| Paraffinic hydrocarbons | 35.3 |
| Total naphthenic hydrocarbon | 7.7 |
| Total stable hydrocarbon | 43 |
| Total mononuclear aromatics | 54.1 |
| Total double ring arene | 2.6 |
| Thrcylic aromatic hydrocarbon | 0.3 |
| Total aromatic hydrocarbons | 57 |
| Boiling range D-86, ℃ | |
| HK，℃ | 187 |
| 50％ | 248 |
| KK，℃ | 358 |
Table 3 device principal reaction parameter
| Numbering | Embodiment 1 |
| First hydroconversion reaction zone | |
| The hydrogen dividing potential drop, MPa | 6.4 |
| Temperature of reaction, ℃ | 310 |
| Volume space velocity during liquid, h -1 | 2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 400 |
| Second hydroconversion reaction zone | |
| The hydrogen dividing potential drop, MPa | 6.4 |
| Temperature of reaction, ℃ | 320 |
| Volume space velocity during liquid, h -1 | 2.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 |
| Catalytic cracking reaction zone | |
| The reactor pattern | The MIP reactor |
| Riser tube outlet temperature of reaction, ℃ | 510 |
| The second fast bed reaction zone temperature, ℃ | 490 |
| Regeneration temperature, ℃ | 698 |
| The refined diesel oil recycle ratio, weight % | 20-25 |
| The slurry oil recycle ratio, weight % | 5-8 |
Table 4 FCC tests catalyst property
| The catalyzer title | The MLC-500 poiser |
| Chemical constitution,, weight % | |
| Al 2O 3 | 54.5 |
| Na 2O | 0.33 |
| RE 2O 3 | 0.2 |
| Physical properties: | |
| Pore volume, ml/g | 0.12 |
| Specific surface area, m 2/g | 94 |
| Tap density, g/cm 3 | 0.84 |
Comparative Examples 1
Stock oil A enters catalytic cracking unit after mixing, and behind reaction product process main fractionating tower and the absorbing-stabilizing system, obtains dry gas, liquefied gas, stop bracket gasoline, heavy oil and LCO (cetane value is 24).Wherein the LCO of gained directly enters hydrogenator and reacts, and gasoline fraction is extracted, and the refined diesel oil freshening is to catalytic cracking unit.Character through the freshening refined diesel oil C behind the hydrogenation sees Table 5.The operational condition of machinery sees Table 6.Product distributes and sees Table 7, and main character sees Table 8.
Table 5 freshening refined diesel oil character
| The freshening refined diesel oil | C |
| Density, g/cm3 | 0.8569 |
| Refractive power, (20 ℃) | 1.4799 |
| Sulphur content, μ g/ |
18 |
| Nitrogen content, μ g/g | 9.6 |
| Form | |
| Paraffinic hydrocarbons | 35.2 |
| Total naphthenic hydrocarbon | 27.8 |
| Total stable hydrocarbon | 53 |
| Total mononuclear aromatics | 34.0 |
| Total double ring arene | 2.7 |
| Thrcylic aromatic hydrocarbon | 0.3 |
| Total aromatic hydrocarbons | 37 |
| Boiling range D-86, ℃ | |
| HK，℃ | 185 |
| 50％ | 246 |
| KK，℃ | 357 |
Table 6 device principal reaction parameter
| Numbering | Comparative Examples 1 |
| Hydroconversion reaction zone | |
| The hydrogen dividing potential drop, MPa | 6.4 |
| Temperature of reaction, ℃ | 340 |
| Volume space velocity during liquid, h -1 | 1.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 400 |
| Catalytic cracking reaction zone | |
| The reactor pattern | The MIP reactor |
| Riser tube outlet temperature of reaction, ℃ | 505 |
| The second fast bed reaction zone temperature, ℃ | 490 |
| Regeneration temperature, ℃ | 698 |
| The refined diesel oil recycle ratio, weight % | 20-25 |
| The slurry oil recycle ratio, weight % | 5-8 |
Table 7 catalytic cracking unit product distributes
| Products distribution, weight % | Embodiment 1 | Comparative Examples 1 |
| Dry gas | 4.50 | 5.00 |
| Liquefied gas | 17.00 | 17.50 |
| Gasoline | 62.00 | 62.60 |
| Slurry oil | 6.50 | 5.50 |
| Coke | 9.50 | 8.90 |
| Loss | 0.5 | 0.50 |
| Add up to | 100.00 | 100.00 |
Table 8 catalytically cracked gasoline main character
| Gasoline products is formed, weight % | Embodiment 1 | Comparative Examples 1 |
| Paraffinic hydrocarbons | 38.82 | 42.32 |
| Alkene | 28.00 | 28.50 |
| Naphthenic hydrocarbon | 9.80 | 10.20 |
| Aromatic hydrocarbons | 23.38 | 19.98 |
| Octane value RON | 92.1 | 90.7 |
As can be seen from Table 8, the aromaticity content of the FCC gasoline of embodiment 1 is 23.38 weight %, octane value is 92.1, the aromaticity content of the FCC gasoline of Comparative Examples 1 only is 19.98 weight %, octane value is 90.7 only also, illustrates to adopt method of the present invention can significantly improve aromaticity content and the octane value of FCC gasoline.With the contrast of the result in table 2 and the table 5 as can be seen, method of the present invention can also significantly improve the aromaticity content of refined diesel oil.
Claims (9)
- A catalytic cracking diesel oil utilize method, it is characterized in that this method may further comprise the steps:(1) catalytic cracking diesel oil being separated into boiling point is component more than 230 ℃ less than 230 ℃ component and boiling point;(2) polycyclic aromatic hydrocarbons being converted under the condition of mononuclear aromatics, is that component more than 230 ℃ is carried out hydrogenation to the boiling point that obtains in the step (1);(3) obtain isolating the diesel oil that is rich in mononuclear aromatics the hydrogenation products of boiling point less than 230 ℃ component and step (2) from step (1), and the diesel oil that is rich in mononuclear aromatics that will obtain carries out catalytic cracking; Wherein, the cetane value of described catalytic cracking diesel oil is less than 25.
- 2. method according to claim 1, wherein, the boiling range scope of described catalytic cracking diesel oil is 180-400 ℃.
- 3. method according to claim 1, wherein, in step (1) be that further to be separated into boiling point be 230-310 ℃ component and boiling point greater than 310 ℃ component for component more than 230 ℃ with boiling point, and be that 230-310 ℃ component and boiling point carries out hydrogenation greater than 310 ℃ component to boiling point respectively in step (2), boiling point is that the temperature of 230-310 ℃ component hydrogenation is lower than boiling point greater than the temperature of 310 ℃ component hydrogenation.
- 4. method according to claim 3, wherein, be that the method that 230-310 ℃ component is carried out hydrogenation is included under the existence of Hydrobon catalyst to boiling point, the component that with boiling point is 230-310 ℃ contacts with hydrogen, the condition of contact comprises: temperature of reaction is 250-400 ℃, the hydrogen dividing potential drop is 1.0-12.0MPa, and liquid hourly space velocity is 0.3-10.0h -1, hydrogen to oil volume ratio is 100-1500Nm 3/ m 3The method that boiling point is carried out hydrogenation greater than 310 ℃ component is included under the existence of Hydrobon catalyst, the component of boiling point greater than 310 ℃ contacted with hydrogen, the condition of contact comprises: temperature of reaction is 280-450 ℃, and the hydrogen dividing potential drop is 1.0-12.0MPa, and liquid hourly space velocity is 0.3-10.0h -1, hydrogen to oil volume ratio is 100-1500Nm 3/ m 3
- 5. method according to claim 3, wherein, in step (1), described being separated in the separation column carried out, tell boiling point from the separation column top less than 230 ℃ component, to tell boiling point be 230-310 ℃ component and tell boiling point at the bottom of the tower greater than 310 ℃ component from the separation column side line, the operational condition of separation column comprises: feeding temperature is that 180-280 ℃, column bottom temperature are 250-350 ℃, and tower top temperature is 120-250 ℃, and tower top pressure is 0.05-1.05MPa.
- 6. method according to claim 1, wherein, in step (2), the method of described hydrogenation is included under the existence of Hydrobon catalyst, be that component more than 230 ℃ contacts with hydrogen with boiling point, the condition of contact comprises: temperature of reaction is 250-450 ℃, and the hydrogen dividing potential drop is 1-12MPa, and liquid hourly space velocity is 0.3-10h -1, hydrogen to oil volume ratio is 100-1500Nm 3/ m 3
- 7. method according to claim 6, wherein, the condition of contact comprises: temperature of reaction is 260-420 ℃, and the hydrogen dividing potential drop is 2-10MPa, and liquid hourly space velocity is 0.5-8h -1, hydrogen to oil volume ratio is 150-1000Nm 3/ m 3
- 8. method according to claim 1, wherein, in step (3), described being separated in the separation column carried out, at the bottom of tower, tell the diesel oil that is rich in mononuclear aromatics, the operational condition of separation column comprises: feeding temperature is that 180-280 ℃, column bottom temperature are 250-350 ℃, and tower top temperature is 120-250 ℃, and tower top pressure is 0.05-1.05MPa.
- 9. method according to claim 1, wherein, in step (3), the condition of catalytic cracking comprises: temperature of reaction is 450-600 ℃, and agent-oil ratio is 1-20, and the reaction times is 0.2-8 second, atomized water steam accounts for the 1-20 weight % of inlet amount, and reaction pressure is normal pressure-300 kPa.
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| CN103525458B (en) * | 2012-07-06 | 2015-04-29 | 中国石油化工股份有限公司 | Catalytic conversion method |
| CN103805247B (en) * | 2012-11-07 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of combined technical method processing poor ignition quality fuel |
| CN105273745B (en) * | 2014-05-29 | 2017-02-15 | 中国石油化工股份有限公司 | Low-grade diesel oil selective hydrogenation aromatic hydrocarbon removing method |
| CN106467759B (en) * | 2015-08-21 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of heavy oil pretreatment and the combined method of catalytic cracking |
| CN106467761B (en) * | 2015-08-21 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method that heavy oil separation is combined with catalytic cracking |
| CN106467758B (en) * | 2015-08-21 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method of group technology processing heavy oil |
| CN106467757B (en) * | 2015-08-21 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of heavy oil separation-hydrogenation and catalystic cracking combined method |
| CN108102703B (en) * | 2016-11-24 | 2020-06-09 | 中国石油化工股份有限公司 | Processing method of catalytic diesel oil |
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| CN108795495B (en) * | 2017-05-03 | 2020-09-18 | 中国石油化工股份有限公司 | Method for treating diesel raw material |
| CN107286989A (en) * | 2017-06-19 | 2017-10-24 | 中国海洋石油总公司 | A kind of method that the high-knock rating gasoline rich in BTX is produced by heavy aromatics |
| CN109423335B (en) * | 2017-08-30 | 2021-07-09 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing gasoline yield |
| CN110551525B (en) * | 2018-05-31 | 2021-10-08 | 中国石油化工股份有限公司 | Method for producing BTX fraction by catalytically cracking diesel oil |
| CN116515524A (en) * | 2022-07-25 | 2023-08-01 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon by secondary hydrogenation of inferior diesel oil |
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