CN105733666A - Treatment method for catalytic cracking oil slurry - Google Patents
Treatment method for catalytic cracking oil slurry Download PDFInfo
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Abstract
The invention discloses a treatment method for catalytic cracking oil slurry. The method comprises the steps: adding a hyperoxide cross-linking agent into the catalytic cracking oil slurry so as to form a mixed material; preheating the mixed material, and heating the mixed material to the temperature of 380 DEG C to 420 DEG C; introducing the heated mixed material to the upper part of a reactor, and staying the mixed material for a staged cracking reaction; discharging oil gas of the staged cracking reaction from the top of the reactor; and extracting extract oil of the staged cracking reaction from the bottom of the reactor, carrying out filtering to remove coke, and blending decoked remaining oil with heavy-oil-residue oil so as to produce road asphalt. According to the method, the catalytic cracking oil slurry can be comprehensively treated by a relatively simple process in a low-cost manner, and the utilization benefit of the oil slurry is improved.
Description
Technical field
The present invention relates to oil refining and petrochemical industry processing method, particularly relate to the processing method of the externally extracting oil raw material of a kind of catalytic cracking process units.
Background technology
China's catalytic cracking year processing capacity is more than 1.5 hundred million t, and outside annual partially catalyzed cracking slurry oil, the amount of getting rid of is more than 7,500,000 t.Owing to catalytic cracked oil pulp having catalyst dust, colloid, asphalitine, alkene and condensed-nuclei aromatics, bring many difficulties to the comprehensive utilization of catalytic cracked oil pulp.
Big (the 965kg/m of the slurry oil density of catalytic cracked oil pulp3), carbon residue high (6%), fragrance point content high (45%), saturated point of content be below 45%, and containing a certain amount of colloid, asphalitine, and the heavy metal such as S and Ni, V；In aromatic hydrocarbon, single, double cyclic aromatics content is relatively low, and three rings, four cyclic aromatics content are higher, and this illustrates to also have in slurry oil some olefin.If directly as catalytically cracked material freshening, its chemical constituent and structure is by difficulty of processing affecting catalytic cracking and products thereof character.Otherwise, slurry oil is easily separated, these heavy arenes, saturated hydrocarbons can be made into high value-added product.
Existing catalytic cracked oil pulp utilization ways has: catalytic cracked oil pulp (FCC slurry) freshening, active additive, as coking raw material, produce white carbon black, carbon fiber material, production heavy-duty road asphalt, solvent deasphalting hardening agent, RX and filling oil, produce petroleum aromatic plasticizer etc..
Catalytic cracked oil pulp utilization and one of FCC slurry usage technical scheme that road asphalt production combination is current most study.The lean wax of catalytic cracked oil pulp, rich in aromatic hydrocarbons, is the active component improving asphalt quality.But owing to the condensation level of slurry oil is low, produce asphalt for high grade road usually used as a kind of soft component with other high softening-point components (de-oiled asphalt such as solvent deasphalting) blending, limit the application of catalytic cracked oil pulp.Research shows by condensation catalytic cracked oil pulp, namely in slurry oil, add appropriate cross-linking agent and catalyst, so as to react under certain temperature and time, making polycyclic aromatic hydrocarbon condensation in catalytic cracked oil pulp is the compound of more macromole, utilizes the distillation Residual oil after the light fraction in distillation elimination catalytic slurry can concoct out qualified road asphalt with decompression residuum simultaneously.The character of condensation slurry oil is main relevant with chemical composition, and it forms, any change of chemical constitution all can change the character of slurry oil.
In prior art, what CN103044932 mainly introduced is the raw material preparation method for modified pitch of a kind of low asphalt content, but for getting rid of the slurry oil of generation outside catalytic cracking unit, it contains a certain amount of catalyst fines, processed is relatively difficult, catalytic slurry is processed by the technology utilizing CN103044932, it is impossible to obtain qualified modified pitch.
CN201010602664 (CN102559250) proposes to add a certain amount of auxiliary agent such as vapor partial pressure regulator and oxidant etc. in catalytic cracked oil pulp raw material, by oil pump, material is delivered to heat exchanger and preheats.Material enters heating furnace after preheating, sends into distillation column and be easily separated after being heated to 360～420 DEG C.The plug light oil that can arrive at tower top and the mixture of vapor partial pressure regulator, if vapor partial pressure regulator is insoluble in light oil, can obtain light oil after standing separation.Wax oil is distillated from tower centre exit.The high boiling point heavy oil containing a small amount of catalyst microparticle is obtained from tower bottom, can as mixing asphalt oil.High-temperature filter can also be passed through if desired for the high boiling point heavy oil without powder and remove the microparticle of residual, the high boiling point heavy oil relatively cleaned, but the introducing due to vapor partial pressure regulator, easy aging equipment, it is not easy large-scale production, and it is unfavorable for the cleaning of equipment, improve producing cost, be unfavorable for industrialization.
CN201110237462 proposes a kind of technique utilizing catalytic slurry decompression distillation coproduction aromatic naphtha, Colophonium, fuel oil, the steps include: first to be stored among head tank by the by-product catalytic slurry of RFCC, adopt again and be pumped in heating furnace to heat to 350～380 DEG C, continuously enter among vacuum distillation tower, vacuum distillation tower evacuation is maintained at below 40mmHg post, and by reducing pressure continuously, distillation is sequentially obtaining fuel oil, aromatic naphtha and Colophonium at the bottom of distillation column side line and tower.This technological process of the present invention is briefly direct and continuous, operating condition relaxes easily-controllable, and production scale scalability is strong, and for the catalytic slurry that aboundresources overstocks, coproduction can obtain high added value, the high marketization aromatic naphtha of demand, fuel oil and Colophonium, improve the comprehensive utilization ratio of catalytic slurry；This joint production process does not result in noxious gas emission simultaneously, and cooling water circulation utilization, discharge of wastewater is limited.But the aromatic naphtha mechanical admixture that this technology obtains is more, it is necessary to process further, economic worth is little, and the Colophonium condensation degree obtained is not high, and as Colophonium blend component, incorporation is less than 10%, and the Colophonium trade mark of production is low, and physical and chemical index is difficult to qualified.
In a word, the comprehensive utilization aspect of catalytic cracked oil pulp also has substantial amounts of work to do.How to process catalytic cracked oil pulp in a simple and efficient manner, overcome defect of the prior art, become those skilled in the art's problem demanding prompt solution.
Summary of the invention
Present invention aim at providing the processing method of a kind of catalytic cracked oil pulp so that it is the utilization benefit of slurry oil with relatively simple process low cost integrated treatment catalytic cracked oil pulp, can be improved.
For achieving the above object, the present invention provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) in catalytic cracked oil pulp, add peroxide cross-linking agent and form mixed material；
2) this mixed material is preheated, be then heated to 380～420 DEG C；
3) this mixed material after heating is passed into reactor top so that it is stop and carry out segmentation cracking reaction；
4) segmentation cracking reaction oil gas is discharged by reactor head；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；
Wherein, in step 3) in, this mixed material after heating stops 1～30min in described reactor, carries out described segmentation cracking reaction under 0.3～5.0MPa reaction pressure, 460～490 DEG C of reaction temperatures.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, described catalytic cracked oil pulp is catalytic cracking unit externally extracting oil.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, the addition of described peroxide cross-linking agent is the 0.01～0.09% of described catalytic cracked oil pulp quality；
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, the addition of described peroxide cross-linking agent, it is more preferred from the 0.04～0.06% of described catalytic cracked oil pulp quality.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, described peroxide cross-linking agent is the combination of one or more in cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide.
In step 1) in, it is the compound of more macromole that the effect of peroxide cross-linking agent mainly can make the further condensation of condensed-nuclei aromatics in catalytic cracked oil pulp at relatively high temperatures, increases product viscosity.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 2) in, the temperature that this mixed material is preheated is 50～90 DEG C.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 2) in, use tubular heater to carry out preheating to mixed material and heat.
In step 2) in, use tubular heater that mixed material carries out warm-up operation and heating operation；The fire box temperature of heating furnace controls between 530～600 DEG C, mixed material is preheating to 50～90 DEG C in head tank, deliver to heat exchanger to preheat, distillate the abundant heat exchange of steam again to elevate the temperature with fractionator overhead and middle part, reduce the load of heating furnace, saving energy expenditure, material controls at 380～420 DEG C in furnace outlet temperature.Production process regulates furnace temp according to operation conditions, it may be achieved produce continuously.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 3) in, described reactor is the one in sky barrel reactor, circulation bed bioreactor, visbreaking reactor.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 3) in, this mixed material after heating stops 15～25min in described reactor, carries out described segmentation cracking reaction under 0.5～3.0MPa reaction pressure, 470～480 DEG C of reaction temperatures.
In step 3) in, the temperature in reactor is 460～490 DEG C, and pressure is 0.3～5.0MPa, and the reaction mass time of staying in reactor is 1～30min, the preferably control condition of this temperature, pressure and time and segmentation cracking reaction.This mixed material after heating carries out the segmentation cracking reaction between coking and visbreaking in reactor, little molecule condensed-nuclei aromatics condensation in material generates macromole condensed-nuclei aromatics, catalyst fines, as green coke center, assembles green coke, and a small amount of coke of generation can be filtered to remove.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, decoking excess oil is 10～70:90～30 with heavy oil residual oil blending mass ratio；
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, decoking excess oil is preferably 40～60:60～40 with heavy oil residual oil blending mass ratio.
In step 4) in, fractionating column fractionates out gas and can be used to hydrogen manufacturing or as fuel, gasoline, diesel oil can as fuel oil blending component or solvent naphtha, wax oil can as the freshening component of catalytic unit, or as rubber production auxiliary agent；Reactor bottom tapped oil (segmentation cracking reaction tapped oil) obtains decoking excess oil after being filtered to remove a small amount of coke, decoking excess oil is because component boiling point is high, there is bigger viscosity, higher fragrance divides and colloid, asphalitine, and wax content is relatively low, it is possible to be used as road asphalt blending component.
For solving problem of the prior art, the present invention provides the processing method of a kind of catalytic cracked oil pulp, and for processing the externally extracting oil of catalytic cracking process units, its know-why and prominent technique effect are as follows:
1) present invention adds appropriate peroxide cross-linking agent in catalytic cracked oil pulp, and carry out the segmentation cracking reaction between coking and visbreaking in the reactor, making polycyclic aromatic hydrocarbon condensation in catalytic cracked oil pulp is the compound of more macromole, light oil is as light diesel fuel component, and decoking excess oil produces qualified road asphalt with the blending of heavy oil residual oil.The present invention, with relatively simple process low cost integrated treatment catalytic cracked oil pulp, improves the utilization benefit of slurry oil, it is adaptable to catalytic cracked oil pulp produces light oil double product Colophonium.Compared with CN102559250, the condensation degree that the heat cracking reaction of the present invention generates oil is higher, and as Colophonium blend component, incorporation is higher；Compared with CN103044932, the present invention is directed to the characteristic of catalytic slurry, carried out processed, cost-effective catalytic slurry has been utilized.
2) this technological process is briefly direct and continuous, operating condition relaxes easily-controllable, and production scale scalability is strong, and for resourceful catalytic slurry, coproduction can obtain high added value, the light-weight fuel oil of high marketization demand and Colophonium, effectively raise the comprehensive utilization ratio of catalytic slurry；And decrease equipment investment, simplify operation sequence, reduce operating cost and production cost；The method does not result in noxious gas emission simultaneously, and cooling water circulation utilization, discharge of wastewater is limited.And, the present invention is not while introducing vapor partial pressure regulator, by reducing the addition (< 0.1%) of peroxide, adopt the reactions such as visbreaking that catalytic slurry decomposes cracking further, cost can reduced, while reducing the Degree of Ageing of equipment, improve the performance of product bitumen product；Compared with CN102559250, the light diesel fuel component that the present invention produces is more, and the condensation degree that heat cracking reaction generates oil is higher, and as Colophonium blend component, incorporation is higher, and economic benefit becomes apparent from.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of the processing method of a kind of catalytic cracked oil pulp of the present invention.
Wherein, accompanying drawing labelling:
1 slurry oil tank
2 heating furnaces
3 reactors
4 fractionating columns
A entrance
B, C, D, E, F export
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail, in order to be easier to understand the purpose of the present invention, technology contents, feature and performance, and what listed illustrative embodiments was only used as to illustrate, it is not intended as the restriction of the present invention.
Refer to Fig. 1, it is the device schematic diagram of processing method of a kind of catalytic cracked oil pulp of the present invention.For with relatively simple process low cost integrated treatment catalytic cracked oil pulp, improving the utilization benefit of slurry oil, the present invention provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) in catalytic cracked oil pulp, add peroxide cross-linking agent and form mixed material；
2) this mixed material is preheated, be then heated to 380～420 DEG C；
3) this mixed material after heating is passed into reactor top so that it is stop and carry out segmentation cracking reaction；
4) segmentation cracking reaction oil gas is discharged by reactor head；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；
Wherein, in step 3) in, this mixed material after heating stops 1～30min in described reactor, carries out described segmentation cracking reaction under 0.3～5.0MPa reaction pressure, 460～490 DEG C of reaction temperatures.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, described catalytic cracked oil pulp is catalytic cracking unit externally extracting oil.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, the addition of described peroxide cross-linking agent is the 0.01～0.09% of catalytic cracked oil pulp quality；
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, the addition of described peroxide cross-linking agent, it is more preferred from the 0.04～0.06% of described catalytic cracked oil pulp quality.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 1) in, described peroxide cross-linking agent is the combination of one or more in cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide.
In step 1) in, it is the compound of more macromole that the effect of peroxide cross-linking agent mainly can make the further condensation of condensed-nuclei aromatics in catalytic cracked oil pulp at relatively high temperatures, increases product viscosity.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 2) in, the temperature that this mixed material is preheated is 50～90 DEG C.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 2) in, use tubular heater to carry out preheating to mixed material and heat.
In step 2) in, use tubular heater that mixed material carries out warm-up operation and heating operation；The fire box temperature of heating furnace controls between 530～600 DEG C, mixed material is preheating to 50～90 DEG C in head tank, deliver to heat exchanger to preheat, distillate the abundant heat exchange of steam again to elevate the temperature with fractionator overhead and middle part, reduce the load of heating furnace, saving energy expenditure, material controls at 380～420 DEG C in furnace outlet temperature.Production process regulates furnace temp according to operation conditions, it may be achieved produce continuously.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 3) in, described reactor is the one in sky barrel reactor, circulation bed bioreactor, visbreaking reactor.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 3) in, this mixed material after heating stops 15～25min in described reactor, carries out described segmentation cracking reaction under 0.5～3.0MPa reaction pressure, 470～480 DEG C of reaction temperatures.
In step 3) in, the temperature in reactor is 460～490 DEG C, and pressure is 0.3～5.0MPa, and the reaction mass time of staying in reactor is 1～30min, the preferably control condition of this temperature, pressure and time and segmentation cracking reaction.This mixed material after heating carries out the segmentation cracking reaction between coking and visbreaking in reactor, little molecule condensed-nuclei aromatics condensation in material generates macromole condensed-nuclei aromatics, catalyst fines, as green coke center, assembles green coke, and a small amount of coke of generation can be filtered to remove.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil.
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, decoking excess oil is 10～70:90～30 with heavy oil residual oil blending mass ratio；
Wherein, in processing method one preferred embodiment of the catalytic cracked oil pulp of the present invention, in step 4) in, decoking excess oil is preferably 40～60:60～40 with heavy oil residual oil blending mass ratio.
In step 4) in, fractionating column fractionates out gas and can be used to hydrogen manufacturing or as fuel, gasoline, diesel oil can as fuel oil blending component or solvent naphtha, wax oil can as the freshening component of catalytic unit, or as rubber production auxiliary agent；Reactor bottom tapped oil (segmentation cracking reaction tapped oil) obtains decoking excess oil after being filtered to remove a small amount of coke, decoking excess oil is because component boiling point is high, there is bigger viscosity, higher fragrance divides and colloid, asphalitine, and wax content is relatively low, it is possible to be used as road asphalt blending component.
Embodiment a
The present embodiment provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) adding peroxide cross-linking agent (cumyl peroxide) in catalytic cracked oil pulp (catalytic cracking unit externally extracting oil), addition is the 0.01% of catalytic cracked oil pulp quality, forms mixed material；
2) use tubular heater that this mixed material is preheated (50 DEG C), be then heated to 380 DEG C；
3) this mixed material after heating is passed into reactor (empty barrel reactor) top, make it stop and carry out segmentation cracking reaction, concrete reaction condition is: stops 1min in described reactor, carries out described segmentation cracking reaction under 0.3MPa reaction pressure, 460 DEG C of reaction temperatures.
4) segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；Decoking excess oil is 10:90 with heavy oil residual oil blending mass ratio.
Embodiment b
The present embodiment provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) adding peroxide cross-linking agent (di-isopropylbenzene hydroperoxide) in catalytic cracked oil pulp (catalytic cracking unit externally extracting oil), addition is the 0.09% of catalytic cracked oil pulp quality, forms mixed material；
2) use tubular heater that this mixed material is preheated (90 DEG C), be then heated to 420 DEG C；
3) this mixed material after heating is passed into reactor (visbreaking reactor) top, make it stop and carry out segmentation cracking reaction, concrete reaction condition is: stops 30min in described reactor, carries out described segmentation cracking reaction under 5.0MPa reaction pressure, 490 DEG C of reaction temperatures.
4) segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；Decoking excess oil is 70:30 with heavy oil residual oil blending mass ratio.
Embodiment c
The present embodiment provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) adding peroxide cross-linking agent (benzoyl peroxide) in catalytic cracked oil pulp (catalytic cracking unit externally extracting oil), addition is that the 0.04% of catalytic cracked oil pulp quality forms mixed material；
2) use tubular heater that this mixed material is preheated (65 DEG C), be then heated to 390 DEG C；
3) this mixed material after heating is passed into reactor (circulation bed bioreactor) top, make it stop and carry out segmentation cracking reaction, concrete reaction condition is: stops 15min in described reactor, carries out described segmentation cracking reaction under 0.5MPa reaction pressure, 470 DEG C of reaction temperatures.
4) segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；Decoking excess oil is 40:60 with heavy oil residual oil blending mass ratio.
Embodiment d
The present embodiment provides the processing method of a kind of catalytic cracked oil pulp, and the method includes:
1) adding peroxide cross-linking agent (di-tert-butyl peroxide) in catalytic cracked oil pulp (catalytic cracking unit externally extracting oil), addition is the 0.06% of catalytic cracked oil pulp quality, forms mixed material；
2) use tubular heater that this mixed material is preheated (80 DEG C), be then heated to 410 DEG C；
3) this mixed material after heating is passed into reactor (circulation bed bioreactor) top, make it stop and carry out segmentation cracking reaction, concrete reaction condition is: stops 25min in described reactor, carries out described segmentation cracking reaction under 3.0MPa reaction pressure, 480 DEG C of reaction temperatures.
4) segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；Decoking excess oil is 60:40 with heavy oil residual oil blending mass ratio.
Below by the embodiment under different technology conditions and experimental data thereof, the invention will be further described, to clearly show that its technique effect.
1, the analysis method of primary quality measure and standard in production process of the present invention:
1. viscosity GB/T265
2. flash-point and burning-point GB/T267
3. density GB/T1884
4. asphalt softening point GB/T4507
5. bitumen ductility GB/T4508
6. Asphalt Penetration GB/T4509
2, embodiment 1～5 produces mixing asphalt oil
As it is shown in figure 1, be the process unit schematic diagram of the processing method of catalytic cracked oil pulp of the present invention.From illustrating: the present invention, with the externally extracting oil of catalytic cracking unit for raw material, by the segmentation cracking reaction between coking and visbreaking, obtains light-weight fuel oil and the asphaltic products of high added value.
Its concrete technology flow process is:
Adding a certain amount of peroxide cross-linking agent (material can be entered by the entrance A of slurry oil tank 1) in catalytic cracked oil pulp, addition is 0.01～0.09 (quality) %, and addition is counted with catalytic slurry addition for 100 mass %；
Mixed material passes through heating furnace 2 after being preheating to 50～90 DEG C, enters reactor 3 top in heating furnace 2 after being heated to 380～420 DEG C；
Stopping 1～30min in reactor 3, in reactor 3, temperature controls at 460～490 DEG C, and pressure is 0.3～5.0MPa；
Reaction oil gas is entered fractionating column 4 by reactor 3 top, (gas is discharged by fractionating column 4 top exit C to fractionate out gas, gasoline, diesel oil and wax oil, gasoline and diesel oil are discharged by fractionating column 4 upper outlet D, E respectively, wax oil is discharged by fractionating column 4 lower part outlet F), bottom reactor 3, tapped oil is discharged by outlet at bottom B, for devoking excess oil after being filtered to remove a small amount of coke, decoking excess oil with heavy oil residual oil with blending ratio for 10:90 to 70:30 (quality), can produce qualified road asphalt.
According to process above flow process, to catalytic slurry (density: 0.9687g.cm-3, kinematic viscosity V100℃: 24.9mm2.s-1, flash-point: 166 DEG C) carry out pilot plant test, result shows stable production process, good separation, as shown in table 1.
Table 1 embodiment 1～5
3, mixing asphalt oil application examples
Choose needle penetration (25 DEG C): 86.4, softening point: 44.1 DEG C, the decompression residuum of ductility: 34cm (10 DEG C) is raw material, and embodiment 2 gained mixing asphalt oil by 43:57 and 51:49 mass ratio concoct obtain needle penetration respectively 67 and 74 Colophonium.Its quality meets standard GB/T/T15180-2010 " heavy-duty road asphalt ".
Choose needle penetration (25 DEG C): 116.1, softening point: 43.3 DEG C, the decompression residuum of ductility: 47cm (10 DEG C) is raw material, and embodiment 2 gained mixing asphalt oil by 53:47 and 59:41 mass ratio concoct obtain needle penetration respectively 73 and 77 Colophonium.Its quality meets standard GB/T/T15180-2010 " heavy-duty road asphalt ".
Comparative example 1
Being raw material with identical catalytic slurry, 420 DEG C of decompression distillations obtain residue oil, concoct with decompression residuum, and tune ratio mixed by catalytic slurry vacuum bottoms oil, and < when 10%, gained blend asphalt just can meet standard GB/T/T15180-2010 " heavy-duty road asphalt ".
Comparative example 2
Being raw material with identical catalytic slurry, 500 DEG C of decompression distillations obtain residue oil, concoct with decompression residuum, and tune ratio mixed by catalytic slurry vacuum bottoms oil, and < when 12%, gained blend asphalt just can meet standard GB/T/T15180-2010 " heavy-duty road asphalt ".
Comparative example 3
Being raw material with identical catalytic slurry, furnace outlet temperature is 380 DEG C, adds cumyl peroxide 0.5% (quality), toluene 5% (quality), and the yield of decoking excess oil is 76.8%；
Needle penetration (25 DEG C): 86.4, softening point: 44.1 DEG C, the blending of the decompression residuum of ductility: 34cm (10 DEG C) and above-mentioned decoking excess oil produces road asphalt, gained mixing asphalt oil concoct by the mass ratio of 77:23 and 85:15 obtain needle penetration respectively 61 and 73 Colophonium.Its quality meets standard GB/T/T15180-2010 " heavy-duty road asphalt "
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (10)
1. the processing method of a catalytic cracked oil pulp, it is characterised in that the method includes:
1) in catalytic cracked oil pulp, add peroxide cross-linking agent and form mixed material；
2) this mixed material is preheated, be then heated to 380～420 DEG C；
3) this mixed material after heating is passed into reactor top so that it is stop and carry out segmentation cracking reaction；
4) segmentation cracking reaction oil gas is discharged by reactor head；Segmentation cracking reaction tapped oil is extracted out by reactor bottom, is filtered to remove coke, then with the blending of heavy oil residual oil, decoking excess oil is produced road asphalt；
Wherein, in step 3) in, this mixed material after heating stops 1～30min in described reactor, carries out described segmentation cracking reaction under 0.3～5.0MPa reaction pressure, 460～490 DEG C of reaction temperatures.
2. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 1) in, described catalytic cracked oil pulp is catalytic cracking unit externally extracting oil.
3. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 1) in, the addition of described peroxide cross-linking agent is the 0.01～0.09% of catalytic cracked oil pulp quality.
4. the processing method of catalytic cracked oil pulp according to claim 1, it is characterized in that, in step 1) in, described peroxide cross-linking agent is the combination of one or more in cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide.
5. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 2) in, the temperature that this mixed material is preheated is 50～90 DEG C.
6. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 2) in, use tubular heater to carry out preheating to mixed material and heat.
7. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 3) in, described reactor is the one in sky barrel reactor, circulation bed bioreactor, visbreaking reactor.
8. the processing method of catalytic cracked oil pulp according to claim 1, it is characterized in that, in step 3) in, this mixed material after heating stops 15～25min in described reactor, carries out described segmentation cracking reaction under 0.5～3.0MPa reaction pressure, 470～480 DEG C of reaction temperatures.
9. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 4) in, segmentation cracking reaction oil gas enters fractionating column after being discharged by reactor head, fractionates out gas, gasoline, diesel oil and wax oil.
10. the processing method of catalytic cracked oil pulp according to claim 1, it is characterised in that in step 4) in, decoking excess oil is 10～70:90～30 with heavy oil residual oil blending mass ratio.
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| CN107778887A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of modified pitch and preparation method thereof |
| CN110760334A (en) * | 2019-11-12 | 2020-02-07 | 中国石油化工股份有限公司 | Deep processing method of catalytic slurry oil |
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| CN105733666B (en) | 2018-01-05 |
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