A kind of burnt production method of pin that removes solid particulate in the stock oil
The invention belongs to a kind of under the situation that does not have hydrogen the thermal non-catalytic cracking method of hydrocarbon ils, more particularly, be a kind of method of producing acicular petroleum coke.
The burnt production method of conventional pin is: stock oil is after interchanger and the preheating of process furnace convection zone, be introduced at the bottom of the separation column, with coking oil gas heat exchange in separation column from the coke cat head, pumping into the process furnace radiation section after stock oil at the bottom of the separation column and heavy distillate mixing operates through alternating temperature, the scope of alternating temperature is 430~520 ℃, recycle ratio is 0.2~1.2, stock oil after the heating enters coke drum and carries out pyrogenic reaction, the coke tower top pressure is 0.1~3.0MPa, 380 ℃~460 ℃ of coke tower top temperatures, pin Jiao stays in the coke drum, switches to another coke drum after general 24 hours and continues coking.The coking oil gas that generates from the coke cat head overflow enter separation column bottom and stock oil heat exchange after, obtain gas, gasoline, diesel oil and gas oil caterpillar through fractionation, the heavy distillate that is difficult for gasification with circulate after stock oil mixes.
The burnt production technology of pin is a theoretical basis with the mesophasespherule formation mechanism, and the general raw material that adopts is rich in aromatic hydrocarbons such as catalytically cracked oil, thermal cracking residue, lube oil furfural refining extraction oil or ethylene bottom oil etc.Wherein catalytically cracked oil must be removed solid impurities such as catalyst fines wherein earlier as raw material, otherwise the growth of mesophase ball in the burnt production process of pin is had adverse influence, is unfavorable for that also mesophase ball melts and becomes the wide area intermediate phase.
Remove nearly five kinds of the method for the solid particulate (based on catalyst fines) in the FCC slurry oil: natural sedimentation, flocculation sedimentation, electrostatic separation method, filtering separation method and centrifugal separation.They have mainly utilized in the suspension, and the difference of density is separated between solid particulate and the solution.
USP4,407,707 disclose a kind of method that removes solid particulate in the hydrocarbon ils, and this method is to add sulfonic acid or sulfonate earlier in hydrocarbon ils, isolates solid particulate through washing then.In this method, solid particulate is not to settle from oil, but transfers to sedimentation again in the water.Although it is more effective that water washes out solid particulate, owing to difficulty in process has hindered industrial application.
USP4,686,048 discloses the method for catalyst fines in a kind of FCC of removing slurry oil, be lower than 100 ℃ hydrocarbon ils dilution slurry oil earlier with boiling point, again through the catalyst fines that filters, oil-contg 2% is isolated in washing, go out thinner in the slurry oil by fractionation by distillation, the slurry oil that obtains is as carbon black raw material.
USP4,919, the 792 disclosed methods that remove catalyst fines in the fluid catalytic cracking (FCC) are to add sinking agents such as coal, coke, FCC catalyzer, moving bed catalytic cracking (TCC) catalyzer, aluminum oxide or silicon oxide in the high temperature slurry oil that extract out FCC separation column bottom, and this agent can promote the catalyst fines rapid subsidence, remove.Sedimentation can be carried out in slurry settler or whizzer.
USP5,593,572 disclose the method for spent catalyst powder in a kind of FCC of removing slurry oil, add the aliphatic polymer of the heteroatoms punctuate of capacity in slurry oil, carry out flocculating settling and separate.
USP5,645,711 disclose a kind of combination process, it passes through equipment for separating liquid from solid with coker gas oil, by removing coke powder and the solid particulate in the gas oil, improve coker gas oil character, thereby reach the operational cycle of devices such as improving catalytic cracking and hydrogenation pre-treatment.
WO97/04042 discloses a kind of water-insoluble solid particulate method of separating from hydrocarbon ils.As flocculation agent, the adding effective dose is carried out settlement separate with alkylphenol oxyethyl group thing, and solid content is reduced to below the 500ppm in the slurry oil, and this slurry oil can be used as carbon black raw material.
The purpose of this invention is to provide a kind of burnt production method of pin that removes solid particulate in the stock oil.
Method provided by the invention comprises:
Catalytically cracked oil and coking distillate enter at least one hot settling vessel, settling temperature is 80~200 ℃, settling time is 8~36 hours, the catalytically cracked oil (abbreviation clarified oil) that removes behind the solid particulate carries out preheating with the bottom that the burnt raw material of other optional pin enters coking fractional distillation column, isolates the coking distillate in the clarified oil simultaneously;
The clarified oil that comes out at the bottom of the coking fractional distillation column enters process furnace with the burnt raw material of other optional pin and operates through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 0.1~3.0MPa, filling the burnt time is 16~40 hours, and the pin coke laydown that reaction generates is in coke drum;
The coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil, wherein part gasoline and/or part diesel oil enter hot settling vessel, this part gasoline and/or diesel oil carry out static mixing with catalytically cracked oil after can entering hot settling vessel separately, and also can take action with the catalytically cracked oil advanced person enters hot settling vessel after attitude is mixed again.
In method provided by the invention, the coking distillate boiling spread that enters hot settling vessel is 150~430 ℃.When coking distillate is light when being 150~200 ℃ as boiling point, preferably select lower settling temperature as 80~150 ℃, otherwise lighter distillate can gasify, do not have the effect of diluting catalytically cracked oil; When coking distillate is heavier when being 200~430 ℃ as boiling point, preferably select higher settling temperature as 150~200 ℃, higher settling temperature helps diluting catalytically cracked oil.The weight ratio of this distillate and catalytically cracked oil is 0.01~0.6: 1.
The burnt raw material of other pin is selected from vacuum residuum, long residuum, fluid catalytic cracking decant oil, heavy crude, ethylene bottom oil, lubricating oil and extracts one or more mixture among oil and the thermal cracking residue out.In method provided by the invention, the burnt raw material of other pin can use, and also can.
When the burnt raw material of pin is single catalytically cracked oil, at least adopt two hot settling vessels, be generally two to four, the slurry oil sedimentation in one of them hot settling vessel finishes the back as the burnt raw material use of pin, switching recycles during heat sink the falling, and the slurry oil sedimentation in other hot settling vessel is standby.
When the burnt raw material of pin also has other pin Jiao raw material except catalytically cracked oil, can only use a hot settling vessel, the size of hot settling vessel is determined according to the relative proportion of catalytically cracked oil and the burnt raw material of other pin.Also can use more than one hot settling vessel, its working method is identical with the situation of the burnt raw material of above-mentioned single pin.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is a kind of burnt production method synoptic diagram of pin that removes solid particulate in the stock oil provided by the present invention, but does not limit method provided by the invention.
Catalytic cracked oil pulp enters hot settler 2 through pipeline 1 and coking distillate from pipeline 22, residue oil after the sedimentation goes out device through pipeline 4, the slurry oil that removes behind the solid particle is drawn through pipeline 3, separately or with entering coking plant fractionating column 8 bottoms through pump 6, pipeline 7 successively from the burnt raw material of other pin of pipeline 5. In coking fractional distillation column 8, take off the coking distillate component that miscella contains behind the solid particle and be separated, recycle.
8 out feedstock oils at the bottom of the coking fractional distillation column, enter in the heating furnace 12 through pipeline 9, pump 10, pipeline 11 successively, after being heated to 430~520 ℃, entered by pipeline 13 and to carry out degree of depth heat cracking reaction in the coke drum 14, the inlet operating temperature of coke drum is 460~510 ℃, top of coke tower pressure is 0.1~3.0MPa, and filling the burnt time is 16~40 hours. The pin coke deposits that reaction generates is in coke drum. Behind burnt full the switching, carry out decoking by the delaying coking hydraulic decoking system of routine.
Coking oil gas enters fractionating column 8 through pipeline 15 and is fractionated into gas, gasoline, diesel oil, gas oil, go out device through pipeline 16,17,18,19 respectively, wherein part gasoline enters hot settler 2 through pipeline 20,22 successively, and/or part diesel oil enters hot settler 2 through pipeline 21,22 successively. This part gasoline and/or diesel oil carry out static mixing with slurry oil after can entering separately hot settler, also can with enter again hot settler after the advanced Mobile state of slurry oil mixes. The concrete boiling range of this part gasoline and/or diesel oil and quantity can be determined by practical operation.
Method advantage provided by the invention is:
1, the present invention effectively reduces the raw material oil viscosity by the mixing of low viscosity coking distillate and feedstock oil, has greatly improved the solid removal efficient of hot settler, and the ash removal efficiency reaches more than 80%;
2, the present invention does not need additionally to replenish low viscous distillate component, must low-viscosity substances derive from the self-produced coking distillate of delayed coking unit, saved the demand that component is externally mended in the combined unit operation;
3, the low viscosity coking distillate mixed into feedstock oil of the present invention can be recycled, and enters fractionation at the bottom of the coking fractional distillation column owing to remove behind the solid particle miscella, so wherein contained coking distillate can be separated first, then recycles.
The following examples will give further instruction to present method, but therefore not limit present method.
Comparative Examples 1
This Comparative Examples illustrates catalytically cracked oil without separate solid particles, but directly carries out coking production pin Jiao's situation.
Catalytically cracked oil is introduced at the bottom of the coking fractional distillation column after the coking distillate preheating, entering process furnace operates through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, and the coke tower top pressure is 0.3MPa, and filling the burnt time is 24 hours, the sedimentation of coke that reaction generates is in coke drum, and the coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil.
Slurry oil and coke nature are as shown in table 1, and as can be seen from Table 1, the viscosity of slurry oil is 51.24mm
2/ s, ash content (the method test that provides according to GB/T 508, down with) be 3300ppm, the thermal expansivity of coke (being called for short CTE, according to 1000 ℃ of carbon rod sample preparation methods tests, down together) is 2.71 * 10
-6/ ℃, be underproof as the burnt product of pin.
Comparative Examples 2
This Comparative Examples explanation catalytically cracked oil does not dilute the situation of producing pin Jiao through separate solid particles but add coking distillate.
Catalytically cracked oil is introduced in two hot settling vessels, 150 ℃ of following sedimentations 24 hours, removing catalytically cracked oil behind the solid particulate enters at the bottom of the coking fractional distillation column after the coking distillate preheating again, entering process furnace operates through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 0.3MPa, filling the burnt time is 24 hours, the sedimentation of coke that reaction generates is in coke drum, and the coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil.
Clarified oil and coke nature are as shown in table 1, and as can be seen from Table 1, the clarification oil viscosity still is 51.24mm
2/ s, ash content is reduced to 690ppm, and the ash decreasing ratio is 79.1%; The CTE of coke is 2.63 * 10
-6/ ℃, be underproof as the burnt product of pin.
Embodiment 1
Catalytically cracked oil and coker gas oil entered in two hot settling vessels by weight 10: 1, settling temperature is 150 ℃, settling time is 24 hours, removes the bottom that catalytically cracked oil behind the solid particulate enters coking fractional distillation column and carries out preheating, isolates the coker gas oil in the clarified oil simultaneously; Come out at the bottom of the coking fractional distillation column clarified oil enter process furnace and operate through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 0.7MPa, filling the burnt time is 24 hours, and the pin coke laydown that reaction generates is in coke drum; The coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil, and wherein part diesel oil enters hot settling vessel.
Test-results is listed in table 2, as can be seen from Table 2, and the 51.24mm of clarification oil viscosity before the sedimentation
2/ s drops to 30.18mm
2/ s, the ash content of the clarified oil 3300ppm before the sedimentation drops to 580ppm, and the ash decreasing ratio is 82.4%; The CTE of coke is 2.58 * 10
-6/ ℃, can be used as the burnt product of qualified pin.And Comparative Examples 2 is not owing to adding the coking distillate dilution, so do not obtain the burnt product of qualified pin when heat sink falling.
Embodiment 2
Catalytically cracked oil and coker gas oil entered in two hot settling vessels by weight 10: 2, settling temperature is 90 ℃, settling time is 32 hours, removes the bottom that catalytically cracked oil behind the solid particulate enters coking fractional distillation column and carries out preheating, isolates the coker gas oil in the clarified oil simultaneously; Come out at the bottom of the coking fractional distillation column clarified oil enter process furnace and operate through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 0.7MPa, filling the burnt time is 24 hours, and the pin coke laydown that reaction generates is in coke drum; The coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil, and wherein part diesel oil enters hot settling vessel.
Test-results is listed in table 2, as can be seen from Table 2, and the 51.24mm of clarification oil viscosity before the sedimentation
2/ s drops to 19.30mm
2/ s, the ash content of the clarified oil 3300ppm before the sedimentation drops to 420ppm, and the ash decreasing ratio is 87.3%; The CTE of coke is 2.56 * 10
-6/ ℃, can be used as the burnt product of qualified pin.
Embodiment 3
Catalytically cracked oil and coker gas oil entered in two hot settling vessels by weight 10: 3, settling temperature is 90 ℃, settling time is 16 hours, removes the bottom that catalytically cracked oil behind the solid particulate enters coking fractional distillation column and carries out preheating, isolates the coker gas oil in the clarified oil simultaneously; Come out at the bottom of the coking fractional distillation column clarified oil enter process furnace and operate through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 1.0MPa, filling the burnt time is 24 hours, and the pin coke laydown that reaction generates is in coke drum; The coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil, and wherein part diesel oil enters hot settling vessel.
Test-results is listed in table 3, as can be seen from Table 3, and the 51.24mm of clarification oil viscosity before the sedimentation
2/ s drops to 12.73mm
2/ s, the ash content of the clarified oil 3300ppm before the sedimentation drops to 280ppm, and the ash decreasing ratio is 91.5%; The CTE of coke is 2.54 * 10
-6/ ℃, can be used as the burnt product of qualified pin.
Embodiment 4
Catalytically cracked oil and coker gasoline entered in the hot settling vessel by weight 10: 5, settling temperature is 90 ℃, settling time is 24 hours, remove the bottom that catalytically cracked oil behind the solid particulate and ethylene bottom oil (weight ratio of the former with the latter is 10: 1) enter coking fractional distillation column and carry out preheating, isolate the coker gasoline in the clarified oil simultaneously; Come out at the bottom of the coking fractional distillation column clarified oil enter process furnace and operate through alternating temperature, the scope of alternating temperature is 430~520 ℃, enter then and carry out degree of depth heat cracking reaction in the coke drum, the temperature in of coke drum is 460~510 ℃, the coke tower top pressure is 1.0MPa, filling the burnt time is 24 hours, and the pin coke laydown that reaction generates is in coke drum; The coking oil gas that comes out from the coke drum top enters the separation column separation and obtains gas, gasoline, diesel oil, gas oil, and wherein part gasoline enters hot settling vessel.
Test-results is listed in table 3, as can be seen from Table 3, and the 51.24mm of clarification oil viscosity before the sedimentation
2/ s drops to 7.2mm
2/ s, the ash content of the clarified oil 3300ppm before the sedimentation drops to 267ppm, and the ash decreasing ratio is 91.9%; The CTE of coke is 2.57 * 10
-6/ ℃, can be used as the burnt product of qualified pin.
Table 1
| | Comparative Examples 1 | Comparative Examples 2 |
| Operational condition | | |
| Heat sink falling | | |
| Coker gas oil/catalytically cracked oil | ?????- | ??????- |
| Temperature, ℃ | ?????- | ?????150 |
| Time, h | ?????- | ?????24 |
| Delayed coking | | |
| The furnace outlet temperature, ℃ | ???430~520 | ???430~520 |
| The coke tower top pressure, MPa | ?????0.3 | ?????0.3 |
| Recycle ratio | ?????0.7 | ?????0.7 |
| Slurry oil/clarified oil | | |
| Kinematic viscosity (100 ℃), mm
2/s
| ????51.24 | ????51.24 |
| Ash, ppm | ????3300 | ????690 |
| The ash decreasing ratio, % | ?????- | ????79.1 |
| Coke | | |
| Ash, heavy % | ????0.71 | ????0.7 |
| Fugitive constituent, heavy % | ????0.9 | ????0.8 |
| Sulphur content, heavy % | ????0.48 | ????0.32 |
| True density, gram per centimeter
3 | ????2.12 | ????2.12 |
| CTE,×10
-6/℃
| ????2.71 | ????2.63 |
Table 2
| | Embodiment 1 | Embodiment 2 |
| Operational condition | | |
| Heat sink falling | | |
| Coker gas oil/catalytically cracked oil | ?????0.1 | ?????0.2 |
| Temperature, ℃ | ?????150 | ?????90 |
| Time, h | ?????24 | ?????32 |
| Delayed coking | | |
| The furnace outlet temperature, ℃ | ????430~520 | ???430~520 |
| The coke tower top pressure, MPa | ?????0.7 | ?????0.7 |
| Recycle ratio | ?????0.3 | ?????0.3 |
| Clarified oil | | |
| Kinematic viscosity (100 ℃), mm
2/s
| ?????30.18 | ?????19.30 |
| Ash, ppm | ?????580 | ?????420 |
| The ash decreasing ratio, % | ?????82.4 | ?????87.3 |
| Pin Jiao | | |
| Ash, heavy % | ?????0.11 | ?????0.08 |
| Fugitive constituent, heavy % | ?????0.6 | ?????0.7 |
| Sulphur content, heavy % | ?????0.53 | ?????0.38 |
| True density, gram per centimeter
3 | ?????2.15 | ?????2.13 |
| CTE,×10
-6/℃
| ?????2.58 | ?????2.56 |
Table 3
| | Embodiment 3 | Embodiment 4 |
| Operational condition | | |
| Heat sink falling | | |
| Coking bavin (vapour) oil/catalytically cracked oil | ?????0.3 | ?????0.5 |
| Temperature, ℃ | ?????90 | ?????90 |
| Time, h | ?????16 | ?????12 |
| Delayed coking | | |
| The furnace outlet temperature, ℃ | ???430~520 | ???430~520 |
| The coke tower top pressure, MPa | ????1.0 | ?????1.0 |
| Recycle ratio | ????0.10 | ?????0.15 |
| Clarified oil | | |
| Kinematic viscosity (100 ℃), mm
2/s
| ????12.73 | ?????7.2 |
| Ash, ppm | ????280 | ?????267 |
| The ash decreasing ratio, % | ????91.5 | ?????91.9 |
| Pin Jiao | | |
| Ash, heavy % | ????0.07 | ?????0.06 |
| Fugitive constituent, heavy % | ????0.8 | ?????0.7 |
| Sulphur content, heavy % | ????0.28 | ?????0.36 |
| True density, gram per centimeter
3 | ????2.14 | ?????2.18 |
| CTE,×10
-6/℃
| ????2.54 | ?????2.57 |