CN101987961B - Coking delaying method - Google Patents
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- CN101987961B CN101987961B CN200910157464.2A CN200910157464A CN101987961B CN 101987961 B CN101987961 B CN 101987961B CN 200910157464 A CN200910157464 A CN 200910157464A CN 101987961 B CN101987961 B CN 101987961B
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Abstract
The invention relates to a coking delaying method. The method comprises the following steps of: carrying out a coking reaction on hydrocarbon oil in a coking tower; introducing coked oil gas generated in the reaction into a coking fractionating tower to contact and exchange heat with a first part coking raw material in an oil and gas heat-exchanging area; enabling condensed coked oil gas and the first part coking raw material to enter a circular oil stripping zone of the coking fractionating tower, reversely contact with water vapor introduced below the circular oil stripping zone and then enter a liquid-phase material buffer stacking area at the bottom of the coking fractionating tower; and mixing the water vapor left from the circular oil stripping zone and distillate obtained through stripping with non-condensed coked oil gas and separating by the coking fractionating tower to obtain a coked gas product and coked distillate, wherein the total weight ratio of the water vapor to the coking raw material is 0.5-5 to 100. The coking delaying method provided by the invention can improve the yield of coked diesel.
Description
Technical field
The present invention relates to a kind of hydrocarbon ils delayed coking method.
Background technology
Delayed coking is the important process of heavy oil lighting.Industry delayed coking method, as shown in Figure 1, the bottom that coking raw material heats laggard coking fractional distillation column 11 and air-fuel mixture from coke drum, the oil gas being condensed is that coking recycle oil is heated to coking temperature through radiation fresh feed pump, coking heater and enters coke drum and carry out pyrogenic reaction together with raw material, the coke generating is stayed in coke drum, the cooking gas and the coking distillate that generate go out coke drum, enter coking fractional distillation column.At the bottom of coking fractional distillation column comprises tower and tower body, the main fractionation that rises of tower body part, for fractionating out cooking gas, coker gasoline, coker gas oil, wax tailings; Tower bottom divides as shown in Figure 2, refer to that from wax tailings, to extract oil header out following to Fractionator Bottom liquid material exit portion, generally divide ，Zhe Sange region, region that three functions are different from lower to upper successively: liquid phase material cushions stacking area 11-1, oil gas heat transfer zone 11-2, backflow rectification zone 11-3.The entrance 3-1 of part coking raw material between backflow rectification zone 11-3 and oil gas heat transfer zone 11-2 enters separation column, then through oil gas heat transfer zone, enter liquid phase material buffering stacking area 11-1, coking oil gas from coke drum (7 or 9) enters separation column through the coking oil gas entrance 10 between oil gas heat transfer zone 11-2 and liquid phase material buffering stacking area 11-1, and another part coking raw material enters liquid phase material buffering stacking area 11-1 from being positioned at the second coking raw material entrance 3-2 of coking oil gas entrance below 10.
The product of delayed coking comprises coker gasoline, coker gas oil, wax tailings, petroleum coke and rich tail gas of coking plant, wherein after coking gasoline hydrogenation refining, can be used as the raw material of cracking ethylene preparation, coker gas oil can be used as derv fuel oil blend component after hydrofining, and wax tailings can be used as the raw material of catalytic cracking or hydrocracking.For common coking raw material, in the petroleum coke that coking obtains, sulphur and ash oontent are high, purposes is narrower, its price is generally only 15～30% of liquid product price, the liquid yield of therefore wishing to improve delayed coking unit is coker gas oil yield particularly, reduce as far as possible coke and gas recovery ratio, so that maximization of economic benefit.Conventionally adopt low recycle ratio (recycle ratio refers to that the reaction oil gas of coke drum outlet is the ratio of turning oil and coking raw material in the partial material of coking fractional distillation column bottom condensation) and comparatively high temps to improve liquid yield.But too low recycle ratio mainly increases the yield of wax tailings, and make wax tailings quality become bad, too high coking temperature affects the equipment safety operations such as process furnace, therefore recycle ratio reduces and heater outlet temperature raising has all certain limit.Industrial recycle ratio is generally 0.2～1, and coking furnace temperature out is 500 ℃ of left and right.
CN01143254.3 discloses a kind of improvement delay coking process that increases vapour, diesel yield, be characterized in conventional delay coking process, bottom at coking fractional distillation column, at diesel oil draw out line and wax oil, extract out between line, increased a light cycle oil and extracted line out, the light cycle oil of extraction mixes with oil phase at the bottom of fresh feed pump coking fractional distillation column out with the outlet line that light cycle oil pump is made the fresh feed pump of past coking heater.
In the method for the increasing yield of liquid products in delayed coking process that CN97193162.3 provides, by a kind of method that adds noncoking hydrocarbon diluent of heating, improve the temperature of liquid in coke-drum.The noncoking thinner of heating can be added to and enter in coke-drum delay coking device process furnace effluent liquid before, or is directly added in coke-drum, or by these two kinds of modes, adds simultaneously.
CN02139673.6 discloses a kind of method that improves liquid yield in delayed coking process, in coking, add a kind of lower boiling evaporation agent to shorten the residence time of distillate in coking tower, reduce the chance that the further condensation of second pyrolysis and hydrocarbon molecules generates coke.Evaporation agent can be coker gasoline, hydrotreated coker gasoline, Organic Alcohol, carburet hydrogen etc. one or more, can be injected in the front coking charging of coking furnace or in coking furnace after cut oil or directly inject in coking tower, or adopting any two kinds of modes or three kinds of modes to inject simultaneously simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of delayed coking method of new raising coker gas oil yield.
The invention provides a kind of delayed coking method, comprise hydrocarbon ils is carried out to pyrogenic reaction at coke drum, the coking oil gas introducing coking fractional distillation column that reaction generates and first part's coking raw material are at the oil gas heat transfer zone of coking fractional distillation column contact heat-exchanging, the coking oil gas of condensation and first part's coking raw material enter the turning oil stripping zone of coking fractional distillation column, and introduce the liquid phase material buffering stacking area that enters coking fractional distillation column bottom after the water vapor counter current contact of turning oil stripping zone; Uncooled coking oil gas with leave the water vapor of turning oil stripping zone and carry and heat up in a steamer the distillate obtaining and mix, through coking fractional distillation column separation, obtain cooking gas product and coking distillate; Wherein, the weight ratio of water vapor and coking raw material is 0.5～5: 100.
The present invention also provides a kind of delayed coker fractionator, at the bottom of comprising tower body and tower, at the bottom of tower, comprise coking oil gas import, stock oil import, wax tailings backflow import, wherein, under coking oil gas import, also comprise steam entry, between steam entry and coking oil gas import, form turning oil stripping zone.
Delayed coking method provided by the invention, in the turning oil stripping zone of coking fractional distillation column, introduce water vapor, the lighting end strippings such as coker gas oil in turning oil and coking raw material mixture can be gone out, improve the yield of diesel oil, reduce the load of process furnace, coke tower, improve the efficiency of process furnace, improve the treatment capacity of coker feedstocks, promote the economic benefit of delayed coking; And the tower body part at separation column after water vapor mixes with uncooled coking oil gas is further separated, and not needing increases extra fractionation apparatus, simple.Compare with conventional delayed coking method, the inventive method can make coker gas oil yield improve 1～5 percentage point.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of existing delayed coking method.
Fig. 2 is the tower bottom structure schematic diagram of existing delayed coking coking fractional distillation column used, and in figure, dotted line represents the liquid level of materials at bottom of tower buffering stacking area.
Fig. 3 is the tower bottom structure schematic diagram of a kind of delayed coker fractionator provided by the invention.In figure, omitted tower body part, dotted line represents the liquid level of materials at bottom of tower buffering stacking area.
Embodiment
Originally in the delayed coking method providing, preferably coking raw material divides two portions to introduce in coking system, first part's coking raw material enters coking fractional distillation column bottom, after the reaction oil gas contact heat-exchanging exporting from coke drum, together with being coking recycle oil with the oil gas being condensed, enter turning oil stripping zone, then enter the material buffer stacking area of coking fractional distillation column bottom; Second section coking raw material, directly introduces the material buffer stacking area ，Yu first part coking raw material of coking fractional distillation column and turning oil and mixes in material buffer stacking area, then through radiation fresh feed pump, coking heater, is heated to coking temperature and enters coke drum.In coke drum, coking raw material and coking recycle oil rely on the self-contained heat of absorption to carry out pyrogenic reaction, and the coke of generation is stayed in coke drum, and the cooking gas of generation and coking distillate go out top of coke tower and enter coking fractional distillation column.The oil gas not being condensed at the bottom of separation column tower enters the tower body part of separation column, and separation obtains cooking gas, coker gasoline, coker gas oil, wax tailings.Wherein in the bottom of turning oil stripping zone, pass into water vapor, steam rates is 0.5～5 % by weight of coking raw material total amount, is preferably 1.5～2.5 % by weight.Preferably 200～350 ℃ of the temperature of water vapor.Second section coking raw material is directly introduced the liquid phase material buffering stacking area at the bottom of coking fractional distillation column tower, the source line of this part coking raw material liquid phase material buffering stacking area at the bottom of inserting tower can be introduced.The coking raw material of first part accounts for 5～80 % by weight of coking raw material total amount (first part's coking raw material and second section coking raw material sum), preferably accounts for 10～50 % by weight.Coking raw material is preferably 5～20 minutes in the residence time of liquid phase material buffering stacking area.
In delayed coking method provided by the invention, at the bottom of described coking fractional distillation column comprises tower body and tower, wherein, tower body is mainly used in coking product separation to become cooking gas and coking distillate, partly compares and there is no particular requirement with the tower body of existing coking fractional distillation column.A kind of embodiment that tower bottom of the present invention divides as shown in Figure 3, comprise the liquid phase material buffering stacking area 11-1 being arranged in order from top to bottom, turning oil stripping zone 11-4, oil gas heat transfer zone 11-2 and backflow rectification zone 11-3, first part's coking raw material is introduced separation column from the first coking raw material import 3-1 between backflow rectification zone 11-3 and oil gas heat transfer zone 11-2, coking oil gas is introduced separation column from the coking oil gas import 10 between turning oil stripping zone 11-4 and oil gas heat transfer zone 11-2, water vapor is introduced separation column from the water vapor import 16 between liquid phase material buffering stacking area 11-1 and turning oil stripping zone 11-4.Coking fractional distillation column provided by the invention, under its water vapor import 16, also comprise second section coking raw material import 3-2, for second section coking raw material is introduced to coking fractional distillation column, this second section coking raw material import 3-2 is preferably placed at below the 11-4 liquid level of turning oil stripping zone.
In delayed coking method provided by the invention, water vapor import at the bottom of coking fractional distillation column tower is positioned at the below of coking oil gas product inlet, the turning oil stripping zone of described coking fractional distillation column is between the water vapor import and coking oil gas product inlet at the bottom of coking fractional distillation column tower, this district is preferably provided with 2～8 floor column plate or is provided with the packing layer of 0.5～6 meter, described column plate can be one or more in existing column plate, for example consolidate jet tray, screen hole type column plate, float valve type column plate, described filler can be filler conventional in packing tower, for example draw uncommon ring, Pall ring, Mellapak packing, the filler heap that can whole block also can fall apart.
In delayed coking method provided by the invention, the first coking raw material import of coking fractional distillation column and the region between coking oil gas product inlet are oil gas heat transfer zone, this oil gas heat transfer zone is preferably provided with 2～6 layers of column plate or establishes 0.5～4m packing layer, column plate form can be solid tongue, sieve aperture or float valve, and form of bio-carrier is random packing, structured packing.
In delayed coking method provided by the invention, the first coking raw material import of coking fractional distillation column is positioned at wax tailings backflow import below, between the first coking raw material import of coking fractional distillation column and wax tailings backflow import, it is wax tailings backflow rectification zone, this district is preferably provided with 2～10 floor column plate, and column plate is solid tongue, sieve aperture or float valve type column plate.A part for the wax tailings that fractionation obtains, is back to the top, backflow rectification zone at the bottom of coking fractional distillation column tower by wax tailings reflux inlet, and the wax tailings flow of this backflow accounts for 10～60 % by weight of coking raw material.
Originally the delayed coking method providing, described coking raw material is one or more in long residuum, vacuum residuum, petroleum pitch, heavy distillate, catalytically cracked oil or clarified oil, cracking of ethylene residual oil and thermal cracking residue.
The present invention is further described as example to take stove two towers below, but and should not be understood as limitation of the present invention, for example two stove four towers or three stove six towers can be implemented with reference to the inventive method.In comparative example and embodiment, unit scale is 500,000 tons/year, the coking raw material hour inlet amount of device is 62.5 tons/hour, coking raw material character is in Table 1, flow process as shown in Figure 1, coking raw material is introduced surge tank 2 by pipeline 1, through the pipeline 3 at 2 ends of surge tank, introduce coking fractional distillation column 11 bottoms and coking oil gas heat exchange again, materials at bottom of tower by pipeline 4 through the radiation fresh feed pump 17 laggard coking heater 5 that boosts, in radiating furnace tube 18, be heated to 500 ℃, the water that injects 2 % by weight (take coking raw material gross weight as benchmark) by pipeline 15 to the coking material in boiler tube before process furnace entrance is to slow down tube coking, the coking material that goes out process furnace is introduced coke drum 7 (or coke drum 9) by pipeline 6 (or pipeline 8), in coke drum, there is pyrogenic reaction in coking raw material, the coke generating is stayed in coke drum, coking oil gas goes out top of coke tower and enters coking fractional distillation column 11 by import 10, be isolated to cooking gas, coker gasoline, coker gas oil, wax tailings, cooking gas and coker gasoline are derived by pipeline 12, coker gas oil is derived by pipeline 13, wax tailings is derived by pipeline 14, coking recycle oil returns coking system.Coke drum 7,9 is with 48 hours coking cycle interval blocked operation, and in a coking cycle, coke drum 7 is full of coke, and furnace outlet material is switched to the burnt process of filling that coke drum 9 repeats coke drum 7, and coke drum 7 carries out cold Jiao, decoking operation.
Comparative example
The tower bottom flow journey of this comparative example coking fractional distillation column, as shown in Figure 2, comprises liquid phase material buffering stacking area 11-1, oil gas heat transfer zone 11-2, backflow rectification zone 11-3.Wax oil refluxes by the entrance 14-1 11-3 top, rectification zone of entering to reflux, coking raw material is introduced coking fractional distillation column by pipeline 3 by coking raw material import 3-1 and 3-2, the top of the coking raw material oil-feed gas heat transfer zone 11-2 of first part introducing by import 3-1, with the pyrogenic reaction oil gas contact heat-exchanging of being introduced by the pyrogenic reaction oil and gas import 10 that is positioned at oil gas heat transfer zone 11-2 below, the second section coking raw material of introducing by import 3-2 is introduced by the pipeline that directly inserts liquid phase material buffering stacking area 11-1.In this comparative example, first part's coking raw material of being introduced by opening for feed 3-1 accounts for 25 % by weight of coking raw material total amount, and the second section coking raw material of being introduced by opening for feed 3-2 accounts for 75 % by weight of total coking raw material; Wax oil (14-1) amount that refluxes is 26 % by weight of coking raw material total amount.The operational condition of this comparative example and material balance related data are in Table 2.
Embodiment
The tower bottom flow journey of the coking fractional distillation column of the present embodiment, as shown in Figure 3.Compare with the tower bottom flow journey of comparative example, below the oil gas heat transfer zone 11-2 at the bottom of coking fractional distillation column tower liquid phase material buffering stacking area 11-1 above, increased turning oil stripping zone 11-4, by the water vapor import 16 that is positioned at this turning oil stripping zone 11-4 below, introduce water vapor, in this turning oil stripping zone, contact with coking raw material with the turning oil coming from this top, turning oil stripping zone, stripping zone is provided with 6 layers of solid tongue type column plate.The quantity of steam of being introduced by import 16 accounts for 2 % by weight of coking raw material total amount, and the temperature of water vapor is 300 ℃.First part's coking raw material accounts for 25 % by weight of coking raw material total amount, and second section coking raw material accounts for 75 % by weight of coking raw material total amount, and the quantity of reflux of wax oil backflow 14-1 is 26 % by weight of coking raw material total amount.The operational condition of the present embodiment and material balance related data are in Table 2.
From table 2, to compare with existing coking method, the inventive method can improve the yield of coker gas oil, improves the treatment capacity of coking raw material.
Table 1
| Material name | Residual oil |
| Density (20 ℃), g/cm 3 | 0.9622 |
| Sulphur content, % by weight | 1.51 |
| Bituminous matter, % by weight | 3.2 |
| Carbon residue, % by weight | 18.9 |
| Ash content, % by weight | 0.06 |
| 100 ℃ of kinematic viscosity, mm 2/s | 678 |
Table 2
Claims (9)
1. a delayed coking method, comprise hydrocarbon ils is carried out to pyrogenic reaction at coke drum, the coking oil gas introducing coking fractional distillation column that reaction generates and first part's coking raw material are at oil gas heat transfer zone contact heat-exchanging, the coking oil gas of condensation and first part's coking raw material enter the turning oil stripping zone of coking fractional distillation column, with the water vapor counter current contact of introducing turning oil stripping zone, then enter the liquid phase material buffering stacking area of coking fractional distillation column bottom; Uncooled coking oil gas with leave the water vapor of turning oil stripping zone and carry and heat up in a steamer the distillate obtaining and mix, through coking fractional distillation column separation, obtain cooking gas product and coking distillate; Wherein, the weight ratio of water vapor and coking raw material total amount is 0.5～5: 100; The turning oil stripping zone of described coking fractional distillation column is between the water vapor import and coking oil gas product inlet at the bottom of coking fractional distillation column tower; First part's coking raw material accounts for 5～80 % by weight of coking raw material gross weight.
2. in accordance with the method for claim 1, it is characterized in that, described coking raw material divides two portions to introduce in coking fractional distillation column, and second section coking raw material is introduced by coking oil gas import below.
3. in accordance with the method for claim 2, it is characterized in that, at the bottom of the tower of described coking fractional distillation column, comprise the liquid phase material buffering stacking area (11-1) being arranged in order from top to bottom, turning oil stripping zone (11-4), oil gas heat transfer zone (11-2) and backflow rectification zone (11-3), first part's coking raw material is introduced coking fractional distillation column from the first coking raw material import (3-1) being positioned between backflow rectification zone (11-3) and oil gas heat transfer zone (11-2), coking oil gas is introduced coking fractional distillation column from the coking oil gas import (10) between turning oil stripping zone (11-4) and oil gas heat transfer zone (11-2), coking fractional distillation column is introduced in the water vapor import (16) that water vapor cushions between stacking area (11-1) and turning oil stripping zone (11-4) from liquid phase material, second section coking raw material is introduced coking fractional distillation column from the second coking raw material import (3-2) being positioned at below turning oil stripping zone (11-4).
4. in accordance with the method for claim 3, it is characterized in that, described turning oil stripping zone (11-4) is provided with 2～8 layers of column plate or is provided with the packing layer of 0.5～6 meter.
5. in accordance with the method for claim 3, it is characterized in that, described oil gas heat transfer zone (11-2) is provided with 2～6 layers of column plate or establishes 0.5～4m packing layer.
6. in accordance with the method for claim 1, it is characterized in that, the steam temperature of described introducing turning oil stripping zone is 200～350 ℃.
7. in accordance with the method for claim 1, it is characterized in that, first part's coking raw material accounts for 10～50 % by weight of coking raw material gross weight.
8. the delayed coker fractionator for delayed coking method described in claim 1, at the bottom of comprising tower body and tower, at the bottom of tower, comprise coking oil gas import, stock oil import, wax tailings backflow import, wherein, under coking oil gas import, also comprise steam entry, between steam entry and coking oil gas import, form turning oil stripping zone; The turning oil stripping zone of described coking fractional distillation column is between the water vapor import and coking oil gas product inlet at the bottom of coking fractional distillation column tower.
9. according to coking fractional distillation column claimed in claim 8, it is characterized in that, described turning oil stripping zone is provided with 2～8 layers of column plate or is provided with the packing layer of 0.5～6 meter.
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| CN200910157464.2A CN101987961B (en) | 2009-07-30 | 2009-07-30 | Coking delaying method |
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| CN200910157464.2A CN101987961B (en) | 2009-07-30 | 2009-07-30 | Coking delaying method |
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| CN103571515B (en) * | 2012-07-19 | 2015-07-22 | 中国石油天然气股份有限公司 | Method for preventing delayed coking fractionation tower high temperature section oil collection tank coking |
| CN103571526B (en) * | 2012-07-19 | 2015-07-22 | 中国石油天然气股份有限公司 | Delayed coking apparatus non-stop production switching method for processing multiple types of raw materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214074A (en) * | 1996-03-20 | 1999-04-14 | 康诺科有限公司 | Method for increasing yield of liquid products in delayed coking process |
| CN1428399A (en) * | 2001-12-22 | 2003-07-09 | 中国石油乌鲁木齐石油化工总厂 | Improved delayed coking process for raising yield of gasoline and diesel oil |
| CN1487056A (en) * | 2002-10-01 | 2004-04-07 | 曹炳铖 | Method of raising liquid yield during delayed coking |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208427C (en) * | 2002-05-31 | 2005-06-29 | 中国石油化工股份有限公司 | Method of removing fine coke from coking oil gas |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214074A (en) * | 1996-03-20 | 1999-04-14 | 康诺科有限公司 | Method for increasing yield of liquid products in delayed coking process |
| CN1428399A (en) * | 2001-12-22 | 2003-07-09 | 中国石油乌鲁木齐石油化工总厂 | Improved delayed coking process for raising yield of gasoline and diesel oil |
| CN1487056A (en) * | 2002-10-01 | 2004-04-07 | 曹炳铖 | Method of raising liquid yield during delayed coking |
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