CN101280213A - Coking method for processing highly acid crude oil - Google Patents
Coking method for processing highly acid crude oil Download PDFInfo
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- CN101280213A CN101280213A CNA2007101484308A CN200710148430A CN101280213A CN 101280213 A CN101280213 A CN 101280213A CN A2007101484308 A CNA2007101484308 A CN A2007101484308A CN 200710148430 A CN200710148430 A CN 200710148430A CN 101280213 A CN101280213 A CN 101280213A
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Abstract
The invention discloses a method of processing highly-acidic crude oil through the delayed coking process; the method includes that the low temperature highly-acidic crude oil is fed from the middle-lower part and the high temperature low-acidic coking raw material is fed from the bottom; the high temperature oil gas generated by the high temperature cracking of the low-acidic coking raw material is mixed with the low temperature highly-acidic crude oil so that the highly-acidic crude oil is enabled to realize the purpose of the deacidification through the pyrolysis deacidification under high temperature; meanwhile, the cracking temperature of the low-acidic coking raw material is lowered; the high temperature cracking time of the conventional raw materials; thereby, the coking yield is reduced and the stable operation period of the single tower is prolonged; besides, the preheating temperature of the highly-acidic crude oil can avoid the strong corrosion stage of the acid; the corrosion on the heating device caused by the acid can be reduced or avoided when the temperature is even lower than the corrosion temperature.
Description
Technical field
The invention belongs to a kind of thermo-cracking deacidifying process, specifically, is a kind of method that removes acidic cpd in the high-acid crude oil in the delayed coking operation process.
Background technology
In recent years, world's high-acid crude oil produced quantity increases year by year, and acid value for crude oil high price more is low more.Therefore, refinery's processing highly acid crude oil will have favorable economic benefit.But because the acid compounds that contains in the high-acid crude oil, mainly be that form with naphthenic acid exists, naphthenic acid easy and iron or iron sulphide reaction cause the heavy corrosion to refining equipment, so the problem that refinery's processing highly acid crude oil is faced is how depickling can reduce equipment corrosion.
Naphthenic acid in the high-acid crude oil is subjected to Temperature Influence bigger to the corrosive nature of equipment, almost do not having corrosive nature below 220 ℃, along with the rising of temperature, corrosive nature is strengthened gradually, corrodibility in the time of 270 ℃～280 ℃ is the strongest, raise with temperature then, corrosion begins to descend, when temperature reaches 350～400 ℃ again, corrosion is aggravation again, when temperature surpasses more than 400 ℃, naphthenic acid is easy to decompose, and corrodibility reduces.
The concentration of acid or content use total acid value to represent in the oil.During total acid value (TAN) is meant and the milligram number of 1 gram crude oil or the needed potassium hydroxide of all acidic components of petroleum fractions (KOH), unit is mg KOH/g.
At present, the acid stripping method of high-acid crude oil mainly contains shortening depickling and pyrolysis depickling.
The principle of shortening deacidifying process is that the petroleum acid and the hydrogen reaction of crude oil generates hydrocarbon and water.USP5897769 has reported that (aperture 5～8.5nm) hydrogenation selectivity remove the method for oil lower molecular weight naphthenic acid to use aperture hydrogenation catalyst.US5910242 discloses in the hydrogenation deacidification process and to have added a certain amount of hydrogen sulfide and help depickling.The disclosed hydrogenation crude method of US6063266 is that the condition (1～50bar, 100～300 ℃) in gentleness is carried out shortening to remove naphthenic acid.
Petroleum acid generally in that the heat scission reaction depickling takes place more than 300 ℃, changes into hydrocarbons.The pyrolysis deacidifying process is exactly the principle depickling that utilizes the petroleum acid Pintsch process, all is at first high-acid crude oil to be heated to enter after 345 ℃-400 ℃ to carry out the depickling reaction in the reactor as the method for the processing high-acid crude oil introduced among US5976360, the US6086751.In addition, the pyrolysis deacidifying process also can add catalyzer and be beneficial to the depickling reaction, as US5928502, US5871636.The catalyse pyrolysis deacidifying process is not owing to there is good catalyzer to make acid removal rate lower at present, and deacidification effect is poor.
CN1814704A introduces a kind of method of utilizing delay coking process to handle high-acid crude oil.This method is at first high-acid crude oil directly to be entered to enter after process furnace is heated to 480 ℃-510 ℃ to carry out pyrolytic reaction in the coking tower, generates gas, middle runnings and coke, removes acid constituents simultaneously.CN1580193A introduces a kind of delayed coking method of high acid value hydrocarbon ils.This method is that at first high-acid crude oil directly enters to enter after process furnace is heated to 350 ℃-450 ℃ and relaxes the cracking case internal reaction, remove acidic components, the low sour heavy cracking thing that will generate then enters to enter after the process furnace radiation section is heated to 480 ℃-510 ℃ and carries out pyrolytic reaction in the coking tower, generate gas, middle runnings and coke, reduce the corrosion of high-acid-value material delayed coking unit.Above-mentioned two kinds of methods all need high-acid crude oil is heated in process furnace, and have experienced the stronger stage of corrodibility, and therefore, these two kinds of methods can not avoid naphthenic acid in the high-acid crude oil to the heavy corrosion of heating installation.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of delayed coking method that heating installation is corroded the processing high-acid crude oil little, that acid removal rate is high.
Coking delay process of the present invention comprises the steps:
(1) the low sour coking raw material of routine through preheating enters the separation column bottom, with high-temperature-coked oil gas countercurrent flow from the coking cat head, and the coke powder that carries in the coking oil gas of drip washing simultaneously;
(2) the low sour coking raw material of the routine after heat exchange is extracted out from the separation column bottom, after entering the process furnace radiation section and being heated to 450 ℃-570 ℃, enters in the coking tower from the coking tower bottom, under the delay coking process operational condition, carries out cracking reaction;
(3) high-acid crude oil is after being preheated to 180 ℃-270 ℃, and directly the middle and lower part by coking tower enters coking tower, and contact by the high-temperature oil gas of step (2) cracking reaction gained in the coking tower, through gasification, reaction, mild cracking of macromole hydrocarbon and decarboxylation reacted;
(4) sedimentation of coke of step (3) reaction generation is at the bottom of coking tower, the high-temperature-coked oil gas that is generated is discharged by the coking cat head, then by entering separation column at the bottom of the separation column, after the low sour coking raw material heat exchange of routine, carry out fractionation and obtain gas, gasoline, diesel oil, light wax oil and wax slop.
In the inventive method, described delayed coker operation condition is as follows: reaction pressure (absolute pressure) 0.05MPa-0.80MPa is preferably in 0.10MPa-0.20MPa; Adopt the one way pass-through mode; Residence time 5min-60min, preferably 10min-40min.
The low sour coking raw material of the routine that the present invention uses can be weight, the residual oil raw material of initial boiling point＞350 ℃, its total acid value is less than 1.0mgKOH/g, preferably less than 0.5mgKOH/g, generally can be selected from heavy deasphalted oil, catalytically cracked oil, viscous crude and the topped crude of residual oil, visbroken resids, deasphalting unit of atmospheric and vacuum distillation unit one or more, also can be selected from other certainly as liquefied coal coil, shale wet goods.
Described high-acid crude oil is crude oil or the topped crude of total acid value greater than 1.0mgKOH/g.High-acid crude oil preferably is preheated to 200 ℃-220 ℃ through being preheated to 180 ℃-270 ℃, enters coking tower in the coking tower middle and lower part then and reacts.Described coking tower middle and lower part preferably accounts for the 1/5-2/5 place of the whole height of coking tower apart from the distance of coking tower bottom.Described high-acid crude oil preferably passes through pre-treatment, and described preprocessing process is processes such as conventional crude oil desalting, dehydration, decalcification, removes most of salts substances, water and calcium etc. in the crude oil.
The percentage ratio that high-acid crude oil inlet amount of the present invention accounts for conventional low sour coking raw material inlet amount is 10wt%-60wt%, preferably 20-40wt%.
The inventive method is particularly suitable for the low sour coking raw material of described routine and high-acid crude oil by the total acid value of the mixture of the charge proportion situation greater than 1.0mgKOH/g.
In the inventive method, the temperature of reaction in the coking tower can be regulated by the ratio of furnace outlet temperature and high-acid crude oil preheating temperature and two kinds of stock oils, generally is controlled at 400 ℃-460 ℃, is preferably in 420 ℃-440 ℃.
The preheating of high-acid crude oil can be adopted conventional type of heating, and preferably employing and high-temperature medium heat exchange are to reach preheating temperature.
In the step (1), anticoking agent can be sneaked in the conventional low acid number coking raw material, described anticoking agent add-on accounts for the 1wt%-20wt% of conventional low sour coking raw material inlet amount, preferably 5wt%-15wt%.
Described anticoking agent can be selected the hydro carbons of Heat stability is good, is preferably that the following cyclic hydrocarbon in Fourth Ring and Fourth Ring accounts for that 60wt% is above, boiling point is 350 ℃-450 ℃ hydrocarbon ils, is preferably in catalytic cracking recycle oil, wax tailings and the ring-type hydro carbons one or more.
The inventive method preferably adds anticoking agent, and the low acid starting material of the routine of described adding anticoking agent is at be heated to 470 ℃-550 ℃ of process furnace radiation section; Described delayed coker operation condition optimization is as follows: temperature of reaction is 420 ℃-440 ℃, reaction absolute pressure 0.10MPa-0.17MPa; Adopt one way to pass through operating method; Residence time 10min-40min.
In the inventive method, can add lighter hydrocarbons heat supply agent in coking tower, its inlet amount accounts for the 1wt%-20wt% of conventional low sour coking raw material inlet amount, preferably 5w%-10w%.The temperature of described lighter hydrocarbons heat supply agent is 500 ℃-580 ℃, and preferred 530 ℃-550 ℃, the heating of lighter hydrocarbons heat supply agent is preferably in the process furnace radiation section and carries out.Described lighter hydrocarbons heat supply agent can add separately from coking tower bottom and add the coking tower, also can be earlier with heat after routine hang down sour coking raw material and mix at the transfer line place and enter coking tower again.The adding of lighter hydrocarbons heat supply agent can make the coking tower interior reaction temperature improve 2 ℃-5 ℃.
Described lighter hydrocarbons heat supply agent mainly is meant the detailed hydrocarbon of boiling point＜180 ℃ or do＜180 ℃ hydrocarbon mixture generally can be C
3-C
12Detailed hydrocarbon or hydrocarbon mixture in the scope for example can be isolating C after the pyrogenic reaction
3, C
4Cut and/or C
5Above coker gasoline partly or entirely, the cut that can certainly use other device is as lighter hydrocarbons heat supply agent of the present invention, as the catalytic cracking petroleum naphtha etc.
Preferred adding lighter hydrocarbons heat supply agent in the inventive method, described delayed coker operation condition is as follows: temperature of reaction is 420 ℃-440 ℃, reaction absolute pressure 0.10MPa-0.15MPa; Residence time 10min-30min; One way is by operation.
The heat-processed of the low sour coking raw material of described routine is as follows: the low sour coking raw material of described routine is after heat exchange, can optionally add anticoking agent, the convection zone that enters process furnace then is heated to 300～350 ℃, be preferably 330 ℃-340 ℃, enter then separation column bottom further with high-temperature-coked oil gas heat exchange from the coking tower top, so not only heated raw material, simultaneously also drip washing the coke powder that carries in the coking oil gas.Stock oil after heat exchange is extracted out from separation column bottom, and then the radiation section that enters process furnace is heated to 450 ℃-550 ℃, is preferably in 495 ℃-505 ℃, enters coking tower from the coking tower bottom then.
Characteristics of the present invention are on the basis of conventional delay coking process, increase the opening for feed of a high-acid crude oil in the middle and lower part of coking tower, because high-acid crude oil temperature after heat exchange is lower, not only can reduce the corrosion of acid to preliminary heating device, and enter coking tower in the coke drum middle and lower part and contact gasification rapidly, reaction with high-temperature oil gas, make the naphthenic acid carboxyl in the high-acid crude oil be transformed into CO, CO
2And H
2O, alkyl is transformed into hydrocarbons, thereby reaches the purpose of depickling, can effectively avoid the corrosion of following process equipment.
The present invention has compared following advantage with existing depickling technology:
1 with hydrogenation deacidification Technology ratio, do not need hydrogen source and hydrogenation catalyst, cost is low; It is temperature required to need not that raw material is heated to reaction, can avoid the deep-etching stage of acid like this, even at corrosion temperature below 220 ℃, can reduce even avoid the corrosion of acid to heating installation; Deacidification effect is suitable.
2 with US5976360, US6086751 ratio, it is temperature required to need not that raw material is heated to reaction, can avoid the deep-etching stage of acid like this, even at corrosion temperature below 220 ℃, can reduce even avoid the corrosion of acid to heating installation, deacidification effect is good.
3 with the CN1814704A ratio, high-acid crude oil does not need to be heated to temperature of reaction, the heavy corrosion to heating installation of avoiding the raw material temperature-rise period to cause; Conventional coking raw material enters the coking fractional distillation column heat exchange, the one, make full use of the energy, the 2nd, raw material enters the coke powder that oil gas that separation column can the drip washing coking generates carries, prevent the separation column coking, prolong the separation column on-stream time, and can effectively reduce coke powder content in the wax tailings, improve the wax tailings quality.
4 with the CN1580193A ratio, high-acid crude oil does not need to be heated to temperature of reaction, can avoid the deep-etching stage of acid like this, even at corrosion temperature below 220 ℃, can reduce even avoid the corrosion of acid to heating installation; Do not need to establish again a cracking case yet and come first depickling, shorten flow process, reduce cost of investment and process cost.
5 the present invention adopt the middle and lower part to enter the low temperature high-acid crude oil, the bottom enters the method for the low sour coking raw material of high temperature, low sour coking raw material mixes with the low temperature high-acid crude oil through the high-temperature oil gas that Pintsch process produces, not only can make high-acid crude oil pyrolysis depickling under suitable high temperature, reduced the cracking temperature of low sour coking raw material simultaneously, shortened the Pintsch process time of conventional raw material, the further cracking of small molecules and the polycondensation that generate have been stopped, the present invention adopts one way to pass through operating method in addition, cause coking yield to reduce, but each coking tower operate continuously 36 hours-48 hours has been saved warm tower process cost and has been prolonged single tower stable operation cycle.
6 the inventive method technical process adopt one way by operation, and are simple to operate, and equipment does not need to transform, and only need in the coking tower middle and lower part opening for feed to be set and get final product.
7 the present invention preferably adopt and sneak into the anticoking agent technology in conventional coking raw materials, can make raw material be heated to higher temperature and do not make tube coking, prolong boiler tube work-ing life; In addition, improve the Heating temperature of raw material, can improve feed stock conversion, also improved temperature of reaction and the treatment capacity of high-acid crude oil in tower simultaneously, help the depickling reaction and carry out.And do not make tube coking, prolong boiler tube work-ing life.
8 the present invention preferably adopt the lighter hydrocarbons heat supply agent technology of injecting, under the situation that does not improve the raw materials furnace and heating temperature, can improve the cracking temperature of raw material in coking tower, avoid tube coking, prolong boiler tube work-ing life, in addition, also improved temperature of reaction and the treatment capacity of high-acid crude oil in tower, helped the depickling reaction and carry out.
9 the inventive method turndown ratiies are big, flexibly, be easy to grasp, can be extensive use of.
10 acid removal rates of the present invention reach more than 99%.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Fig. 2 is the schematic flow sheet that adds anticoking agent on Fig. 1 basis.
Fig. 3 is the schematic flow sheet that adds lighter hydrocarbons heat supply agent on Fig. 1 basis.
Embodiment
Fig. 1 is employed a kind of schematic flow sheet in following examples 1～5 of the present invention.Be further explained in detail the present invention below in conjunction with accompanying drawing and specific embodiment.
As shown in Figure 1, conventional coking raw material oil 7 enters separation column 13 from separation column 13 bottoms,, enters process furnace 3 by pipeline 1 and is heated to 450～550 ℃ after the high-temperature oil gas of coking tower 4 is carried out heat exchange with next, be preferably 495 ℃-505 ℃, enter coking tower 4 and carry out cracking reaction; High-acid crude oil through being preheating to 200 ℃-220 ℃ enters in the coking tower 4 along pipeline 2 cracking reaction takes place, and the oil gas that pyrogenic reaction produces enters separation column 13 from coking tower 4 tops by pipeline 6 and carries out fractionation, C
4Following cut goes out device by pipeline 8, C
5-180 ℃ of gasoline fractions go out device by pipeline 9, and 180 ℃ of-350 ℃ of diesel oil distillates go out device by pipeline 10, and 350 ℃ of-450 ℃ of light wax oil cuts go out device by pipeline 11, and the wax slop cut goes out device by pipeline 12 more than 450 ℃.The coke that produces in the coking tower then goes out device by pipeline 5.After coking tower 4 is full of, stop charging, switch another coking tower 4a and carry out same operation.
Fig. 2 is the used schematic flow sheet of the embodiment of the invention 6～10, be with the difference of Fig. 1, anticoking agent 14 with enter process furnace 3 after the low sour coking raw material of the routine through preheating from pipeline 1 mixes and heat.
Fig. 3 is the used schematic flow sheet of the embodiment of the invention 11～15, be with the difference of Fig. 1, lighter hydrocarbons heat supply agent 15 mixes with conventional low sour coking raw material at the transfer line place after the radiation section of process furnace 3 is heated to 530 ℃-550 ℃, enters in the coking tower and provides heat for reaction.
The following examples will be elaborated to the inventive method, but the present invention is not subjected to the restriction of embodiment.
Among the embodiment, low acid starting material furnace outlet temperature is 495 ℃-510 ℃, and working pressure is that 0.13-0.18MPa, reaction times 10min-40min, one way are passed through.Total feed is 2kg/h, turns round 10 hours, stops charging, and adustion 2 hours is removed volatile matter.Lighter hydrocarbons heat supply agent is the part light gasoline fraction that coking itself is produced, and enters the process furnace radiation section and be heated to 530 ℃-550 ℃ and be mixed into the coking tower internal reaction at transfer line place and conventional raw material after heat exchange.
Embodiment 1-15:
Embodiment explanation: the deacidification effect of method provided by the present invention.
The method of calculation of acid removal rate are as follows: total acid value * 100% of acid removal rate=(total acid value of the total acid value of high-acid crude oil raw material-gained liquid-phase product)/high-acid crude oil raw material.
All experiments use stock oil identical among the embodiment, are intended to the deacidification effect under the comparison different operating condition.
Testing used high-acid crude oil is Liaohe River viscous crude, and low acid starting material oil is xinjiang viscous crude oil, and its character sees Table 1, and experiment condition and test-results see Table 2.
The stock oil character that table 1 embodiment adopts
| Project | Liaohe River viscous crude | Xinjiang viscous crude oil |
| Density (20 ℃), kg/m 3 | 976.9 | 961.1 |
| Acid number, mgKOH/g | 8.99 | 0.05 |
| Viscosity (80 ℃), mm 2/s | 1410 | 1150 |
| Nitrogen, wt% | 0.71 | 0.53 |
| Sulphur, wt% | 0.45 | 0.18 |
| Colloid, wt% | 28.76 | 22.31 |
| Bituminous matter, wt% | 1.34 | 0.50 |
| Carbon residue, wt% | 14.57 | 10.1 |
| Vanadium, μ g/g | 2.53 | 0.67 |
| Nickel, μ g/g | 132.9 | 21.6 |
| ＜350 ℃ of yields, wt% | 9.1 | 0.0 |
| 350～500 ℃ of yields, wt% | 24.7 | 0.00 |
| ＞500 ℃ of yields, wt% | 65.1 | 100.00 |
Table 2 main technique condition and product distribute and main products character
| |
1 | 2 | 3 | 4 | 5 |
| High-acid crude oil accounts for low sour coking raw material, wt% | 30 | 20 | 25 | 35 | 38 |
| The high-acid crude oil feed entrance point accounts for tower height apart from the |
1/5 | 2/5 | 2/5 | 2/5 | 1/5 |
| Main operational condition: | |||||
| Low sour coking raw material furnace outlet temperature, ℃ | 500 | 495 | 500 | 500 | 505 |
| The high-acid crude oil preheating temperature, ℃ | 220 | 220 | 200 | 210 | 220 |
| Coking tower pressure, MPa | 0.17 | 0.15 | 0.16 | 0.15 | 0.18 |
| The residence time, min | 30 | 25 | 20 | 10 | 40 |
| Product distributes, wt% | |||||
| Gas | 7.8 | 7.3 | 7.5 | 8.4 | 9.2 |
| C 5 +Liquid | 75.7 | 76.9 | 76.2 | 76.3 | 75.8 |
| Coke | 16.5 | 15.8 | 16.3 | 15.3 | 15.0 |
| The liquid main character: | |||||
| Density (20 ℃), g/cm 3 | 0.8943 | 0.8938 | 0.8940 | 0.8934 | 0.8933 |
| Total acid value, mgKOH/g | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Total acid removal rate, % | ＞99 | ＞99 | ＞99 | ＞99 | ＞99 |
Table 3 main technique condition and product distribute and main products character
| |
6 | 7 | 8 | 9 | 10 |
| High-acid crude oil accounts for low sour coking raw material, wt% | 30 | 25 | 20 | 40 | 50 |
| The high-acid crude oil feed entrance point accounts for tower height apart from the bottom | 1/5 | 2/5 | 2/5 | 2/5 | 1/5 |
| Main operational condition: | |||||
| *The anticoking agent add-on accounts for low sour coking raw material, |
10 | 5 | 8 | 12 | 15 |
| The furnace outlet temperature, ℃ | 510 | 507 | 505 | 510 | 510 |
| The high-acid crude oil preheating temperature, ℃ | 215 | 210 | 200 | 220 | 220 |
| Coking tower pressure, MPa | 0.17 | 0.15 | 0.16 | 0.15 | 0.17 |
| The residence time, min | 20 | 30 | 40 | 20 | 10 |
| Product distributes, wt% | |||||
| Gas | 8.7 | 8.3 | 8.2 | 8.8 | 9.5 |
| C 5 +Liquid | 75.2 | 75.1 | 74.8 | 75.4 | 75.0 |
| Coke | 16.1 | 16.6 | 17.0 | 15.8 | 15.5 |
| The liquid main character: | |||||
| Density (20 ℃), g/cm 3 | 0.8912 | 0.8908 | 0.8915 | 0.8910 | 0.8927 |
| Total acid value, mgKOH/g | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Total acid removal rate, % | ＞99 | ＞99 | ＞99 | ＞99 | ＞99 |
* Embodiment 1 and 2 used anticoking agents are the FCC recycle stock, and boiling range scope: 350-450 ℃, the following cyclic hydrocarbon in Fourth Ring and Fourth Ring accounts for 65wt%;
Table 4 main technique condition and product distribute and main products character
| |
11 | 12 | 13 | 14 | 15 |
| High-acid crude oil accounts for low sour coking raw material, wt% | 40 | 25 | 30 | 20 | 45 |
| Lighter hydrocarbons heat supply agent accounts for low sour coking raw material, |
9 | 7 | 8 | 5 | 10 |
| The high-acid crude oil feed entrance point accounts for tower height apart from the bottom | 1/5 | 2/5 | 2/5 | 2/5 | 1/5 |
| Main operational condition: | |||||
| The furnace outlet temperature, ℃ | 505 | 495 | 503 | 500 | 505 |
| The high-acid crude oil preheating temperature, ℃ | 220 | 220 | 200 | 210 | 220 |
| Lighter hydrocarbons heat supply agent temperature, ℃ | 550 | 530 | 545 | 540 | 550 |
| Coking tower pressure, MPa | 0.14 | 0.15 | 0.13 | 0.14 | 0.15 |
| The residence time, min | 30 | 25 | 20 | 10 | 40 |
| Product distributes, wt% | |||||
| Gas | 8.1 | 7.4 | 7.8 | 8.3 | 8.5 |
| C 5 +Liquid | 76.1 | 76.5 | 75.8 | 76.5 | 77.0 |
| Coke | 15.8 | 16.1 | 16.4 | 15.2 | 14.5 |
| The liquid main character: | |||||
| Density (20 ℃), g/cm 3 | 0.8942 | 0.8912 | 0.8918 | 0.8917 | 0.8957 |
| Total acid value, mgKOH/g | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Total acid removal rate, % | ＞99 | ＞99 | ＞99 | ＞99 | ＞99 |
Claims (21)
1, a kind of method of delayed coking processing highly acid crude oil comprises the steps:
(1) the low sour coking raw material of routine through preheating enters the separation column bottom, with high-temperature-coked oil gas countercurrent flow from the coking cat head, and the coke powder that carries in the coking oil gas of drip washing simultaneously;
(2) the low sour coking raw material of the routine after heat exchange is extracted out from the separation column bottom, after entering the process furnace radiation section and being heated to 450 ℃-550 ℃, enters in the coking tower from the coking tower bottom, under the delay coking process operational condition, carries out cracking reaction;
(3) high-acid crude oil is after being preheated to 180 ℃-270 ℃, and directly the middle and lower part by coking tower enters coking tower, and contact by the high-temperature oil gas of step (2) cracking reaction gained in the coking tower, through gasification, reaction, mild cracking of macromole hydrocarbon and decarboxylation reacted;
(4) sedimentation of coke of step (3) reaction generation is at the bottom of coking tower, the high-temperature-coked oil gas that is generated is discharged by the coking cat head, by entering separation column at the bottom of the separation column, after low sour coking raw material heat exchange, carry out fractionation and obtain gas, gasoline, diesel oil, light wax oil and wax slop then.
2, in accordance with the method for claim 1, it is characterized in that described delayed coker operation condition is as follows: 400 ℃-460 ℃ of temperature of reaction, reaction absolute pressure 0.05MPa-0.80MPa; Adopt the one way pass-through mode; Residence time 5min-60min.
3, in accordance with the method for claim 1, it is characterized in that the low sour coking raw material of described routine is initial boiling point＞350 ℃, total acid value weight, the residual oil raw material less than 1.0mgKOH/g; Described high-acid crude oil is crude oil or the topped crude of total acid value greater than 1.0mgKOH/g; Described high-acid crude oil is not through pre-treatment or through pre-treatment, and described preprocessing process is conventional crude oil desalting, dehydration, decalcification process.
4, in accordance with the method for claim 3, it is characterized in that the total acid value of the mixture that low sour coking raw material of described routine and high-acid crude oil form by charge proportion is greater than 1.0mgKOH/g.
5, in accordance with the method for claim 3, it is characterized in that the low sour coking raw material of described routine is selected from one or more in heavy deasphalted oil, catalytically cracked oil, viscous crude, topped crude, liquefied coal coil and the shale oil of the residual oil of atmospheric and vacuum distillation unit, visbroken resids, deasphalting unit.
6, in accordance with the method for claim 1, the detailed process that it is characterized in that step (1) is as follows: the low sour coking raw material of described routine enters process furnace after heat exchange convection zone is heated to 300～350 ℃, enter then separation column bottom further with high-temperature oil gas heat exchange from the coking tower top, the coke powder that carries in the coking oil gas of drip washing simultaneously.
7, in accordance with the method for claim 1, it is characterized in that described high-acid crude oil is through being preheated to 200 ℃-220 ℃; Described coking tower middle and lower part accounts for the 1/5-2/5 place of the whole height of coking tower apart from the distance of coking tower bottom.
8, in accordance with the method for claim 1, it is characterized in that it is 10wt%-60wt% that described high-acid crude oil inlet amount accounts for the conventional percentage ratio that hangs down sour coking raw material inlet amount.
9, in accordance with the method for claim 1, it is characterized in that it is 20wt%-40wt% that described high-acid crude oil inlet amount accounts for the conventional percentage ratio that hangs down sour coking raw material inlet amount.
10,, it is characterized in that in the step (1) that anticoking agent is sneaked in the conventional low acid number coking raw material, and described anticoking agent add-on accounts for the 1wt%-20wt% of conventional low sour coking raw material inlet amount according to the arbitrary described method of claim 1～9.
11, in accordance with the method for claim 10, it is characterized in that described anticoking agent add-on accounts for the 5wt%-15wt% of conventional low sour coking raw material inlet amount.
12, in accordance with the method for claim 10, it is characterized in that described anticoking agent is that the following cyclic hydrocarbon in Fourth Ring and Fourth Ring accounts for that 60wt% is above, boiling point is 350 ℃-450 ℃ hydrocarbon ils.
13, in accordance with the method for claim 10, it is characterized in that described anticoking agent is one or more in catalytic cracking recycle oil, wax tailings and the ring-type hydro carbons.
14, in accordance with the method for claim 10, it is characterized in that be heated to 470 ℃-550 ℃ of the low acid starting material of routine of described adding anticoking agent at the process furnace radiation section; Described delayed coker operation condition is as follows: temperature of reaction is 420 ℃-440 ℃, reaction absolute pressure 0.10MPa-0.17MPa; Adopt one way to pass through operating method; Residence time 10min-40min.
15, according to the arbitrary described method of claim 1～9, it is characterized in that in coking tower, adding lighter hydrocarbons heat supply agent, its inlet amount accounts for the 1wt%-20wt% of conventional low sour coking raw material inlet amount; The temperature of described lighter hydrocarbons heat supply agent is 500 ℃-580 ℃.
16, in accordance with the method for claim 15, it is characterized in that the inlet amount of described lighter hydrocarbons heat supply agent accounts for the 5w%-10w% of conventional low sour coking raw material inlet amount; The temperature of described lighter hydrocarbons heat supply agent is 530 ℃-550 ℃.
17, in accordance with the method for claim 15, the heating that it is characterized in that described lighter hydrocarbons heat supply agent is carried out at the process furnace radiation section.
18, in accordance with the method for claim 15, it is characterized in that described lighter hydrocarbons heat supply agent adds the coking tower from coking tower bottom separately, perhaps earlier with heating after routine hang down sour coking raw material and mix at the transfer line place and enter coking tower again.
19, in accordance with the method for claim 15, it is characterized in that described lighter hydrocarbons heat supply agent is meant the detailed hydrocarbon of boiling point＜180 ℃ or do＜180 ℃ hydrocarbon mixture.
20, in accordance with the method for claim 15, it is characterized in that described lighter hydrocarbons heat supply agent is coker gasoline and/or catalytically cracked gasoline.
21, in accordance with the method for claim 15, it is characterized in that described delayed coker operation condition is as follows: temperature of reaction is 420 ℃-440 ℃, reaction absolute pressure 0.10MPa-0.15MPa; Residence time 10min-30min; One way is by operation.
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| CN200710010889 | 2007-04-04 | ||
| CN200710010890.4 | 2007-04-04 | ||
| CN 200710148430 CN101280213B (en) | 2007-04-04 | 2007-08-27 | Coking method for processing highly acid crude oil |
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| CN102268288A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking process for deep deacidification of high-acid raw oil |
| CN102268289A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking method of raw oil containing acid |
| CN102268287A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking method of advanced deacidification of high acid raw oil |
| CN101629093B (en) * | 2009-08-03 | 2012-11-21 | 中海石油炼化有限责任公司 | Delayed coking equipment for high-acid-containing raw oil and delayed coking method using same |
| CN101724429B (en) * | 2008-10-28 | 2012-11-21 | 中国石油化工股份有限公司 | Delayed coking method for processing high-acid crude oil |
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| US4501654A (en) * | 1983-11-17 | 1985-02-26 | Exxon Research & Engineering Co. | Delayed coking process with split fresh feed and top feeding |
| CN1814704A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Method for deeply removing petroleum acids from acid-contained raw oil |
| CN100363467C (en) * | 2005-03-03 | 2008-01-23 | 中国石油化工股份有限公司 | Method for processing crude oil with high acid value |
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| CN102268288A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking process for deep deacidification of high-acid raw oil |
| CN102268289A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking method of raw oil containing acid |
| CN102268287A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Delayed coking method of advanced deacidification of high acid raw oil |
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| CN102268289B (en) * | 2010-06-02 | 2013-10-02 | 中国石油化工集团公司 | Delayed coking method of raw oil containing acid |
| CN103965958A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Method for processing acid-containing oil |
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