CN102220166A - Delayed coking method - Google Patents
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- CN102220166A CN102220166A CN2010101449096A CN201010144909A CN102220166A CN 102220166 A CN102220166 A CN 102220166A CN 2010101449096 A CN2010101449096 A CN 2010101449096A CN 201010144909 A CN201010144909 A CN 201010144909A CN 102220166 A CN102220166 A CN 102220166A
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Abstract
The invention provides a delayed coking method which comprises the following steps of: enabling a delayed coked raw material to enter a coke tower from the top or the side surface of the coke tower after discharging the delayed coking raw material from a radiation section of a heating furnace, installing a raw material distributor at a crude oil inlet of the coke tower to ensure that the raw material entering the coke tower passes through the distributor and turns into small liquid drops, and meanwhile, blowing a certain amount of gaseous phase into the bottom of the coke tower. The delayed coking method has the advantages of increasing the evaporating area and the vapor pressure of raw oil, being beneficial to the gasification of raw oil and generated oil and reducing the generation of secondary reaction; and therefore, the liquid yield of the delayed coking process is increased.
Description
Technical field
The invention belongs to the Petroleum Processing Technology field, relate to a kind of delayed coking method that improves liquid yield.Specifically, relate to a kind of delayed coking method that improves liquid yield by the feeding manner that improves coking tower.
Background technology
The delayed coking technology is heavy oil lighting means important in the petroleum refining process.Its outstanding feature is that adaptability to raw material is strong, can process the inferior heavy oil that other heavy oil upgrading technology can't be processed, even can process sump oil, greasy filth.Along with the lasting exploitation of crude oil, the trend of the poor qualityization of crude oil and heaviness is more and more obvious, and the amount of heavy oil and inferior heavy oil can be more and more many, and delayed coking method is just more and more important.
The raw material of delayed coking generally is the residual oil behind the crude oil process atmospheric and vacuum distillation, and its boiling range scope is usually greater than 500 ℃.Residual oil usually and delayed coking turning oil pass through process furnace together and be heated to the coking tower that enters delayed coking about 500 ℃, under 450～480 ℃ temperature, carry out thermally splitting and condensation reaction.Crackate is dry gas, liquefied gas, petroleum naphtha, intermediate oil and wax tailings normally.Condensation product is a coke.Usually petroleum naphtha, intermediate oil and wax tailings yield and, be called the liquid yield of delayed coking method.Liquid yield is the most important technico-economical comparison of delayed coking method.
In addition, in delayed coking process, in the coking tower because oil gas generation foam layer.Foam layer has influenced the utilization ratio of coking tower, can cause when serious and confusingly bring Jiao into coking fractional distillation column towards the tower accident, causes pipeline and coking fractional distillation column coking, obstruction, makes the improper shut-down of device.The method of generally using is to inject defoamer in coking tower now.
Patent CN101638585A discloses a kind of delayed coking method that relates to charging, and its main purpose is to improve the green coke cycle that decoking shortens coking tower simultaneously.The core of this technology is, when the temperature of coke was also quite high, coke was can mobile, by inject a kind of rare gas element in tower coke is extruded.This patent does not relate to liquid yield.
Patent CN200610106994.0 discloses a kind of method that improves the delayed coking liquid yield.This method is to add the liquid yield that a kind of auxiliary agent improves delayed coking method in delayed coking process.This auxiliary agent is made up of the alkyl nitric ether of 20～40 weight %, the Fatty Alcohol(C12-C14 and C12-C18) of 10～30 weight %, dimethyl polysiloxane and the balance solvent of 10～20 weight %.Use this invention can obviously improve the yield of delayed coking liquid, reduce coke yield.This method will make used additives, and the raw material of production auxiliary agent is all somewhat expensive, also injecting equipment will be arranged, and can improve the tooling cost of delayed coking, also can increase the complicacy of operation.
Patent CN03133538.1 discloses a kind of method that the delayed coking light oil yield reduces coke yield that improves.This method uses coal tar fraction as anticoking agent, and add-on ranges up to 10%, has improved yield of light oil, has reduced coke yield.This method need be used coal tar as anticoking agent, and is the benzoline of coal tar, and cutting coal tar certainly will increase energy consumption.And the treatment capacity of meeting reduction delayed coking behind the adding coal tar.
The disclosed technology of patent CN02139673.6 is that a kind of lower boiling hydro carbons of adding can improve the liquid yield of delayed coking in coking.But this method can cause the flow process complexity, and increases the load of separation column, causes energy consumption to increase.
Patent CN99119740.2 discloses a kind of method that reduces the coking tower foam layer height.When foam layer is low, do not annotate defoamer, when foam layer height is higher, inject defoamer, can reduce the silicone content that generates in the oil.This can make operation become complicated.
Summary of the invention
The invention provides a kind of delayed coking method, overcome the deficiencies in the prior art, under investment and process cost situation about not increasing substantially, improve the liquid yield of delayed coking, do not increase energy consumption, can also reduce the interior foam layer height of coking tower.
In addition, use the present invention not influence the use of other patented technology.That is to say,, can also continue to use technology of the present invention even used other increase liquid receipts technology.The present invention can receive on the basis of technology at the existing liquid that increases, and increases the liquid yield of delayed coking again.
Delayed coking method provided by the invention comprises the steps:
(a) stock oil mixes after process furnace is heated to coking temperature separately or with turning oil;
(b) stock oil from step (a) enters coking tower from the top or the side of coking tower (other coking tower is in other as processes such as decoking, warm towers);
(c) drop of step (b) generation carries out thermally splitting and condensation reaction in coking tower;
(d) from step (b) and the coking that (c) produces generate oil gas and flow out from the coking tower top or near the side at top, enter coking fractional distillation column and be divided into gas, petroleum naphtha, intermediate oil and wax tailings;
(e) from step (b) and the coke that (c) generates then stay in the coking tower;
(f) when carrying out, above step is blown into a certain amount of gas phase media to the coking tower bottom;
(g) behind the green coke certain hour, charging is switched to the coking tower that has been ready to charging in addition, carry out decoking with conventional decoking and filled burnt coking tower; Decoking finish after seal, standby behind the conventional steps such as warm tower; Circulation is switched between the coking tower, and process is able to continuously.
The gas phase media that the coking tower bottom blowing is gone into is the gas of discord hydro carbons generation chemical reaction, and for example water vapor, nitrogen, carbonic acid gas, dry gas, lighter hydrocarbons etc. can be one or more mixtures wherein, and described lighter hydrocarbons are the hydro carbons of carbonatoms 1～4.
As the technical scheme of further optimization, also can be in coking tower stock oil ingress install at least one feed distributor to from the coking tower top or the side stock oil that enters coking tower disperse to reach better dispersion effect.
But the present invention also can adopt the delayed coking technology of the disclosed flexible recycle ratio of patent CN02139312.5, just to change the charging of coking tower into feeding manner of the present invention, promptly the raw material that the process furnace radiation section is come out is entered from the top of coking tower, and raw material is disperseed, and at the bottom of coking tower, feed a certain amount of gas phase media and get final product by a cover divider.
Core of the present invention is the feeding manner of coking tower.With regard to existing delayed coking technology, the charging of coking tower all is the bottom feed from coking tower, and does not adopt any special measure; Feeding manner of the present invention then is to tell top or the side-fed of a part of raw material from coking tower, before raw material advances coking tower and generate the technical process that oil gas advances behind the separation column and can adopt existing known technology or existing patented technology.
The principle that employing the present invention increases liquid yield is as follows: stock oil forms in coking tower in the process of dispersive drop and whereabouts through the raw material decollator, because raw material is disperseed, increased the evaporation of liquid area, simultaneously because the increase of the drip gauge curvature of face, vapour pressure also increases, and certainly will make the amount of vaporization of stock oil in the decline process increase greatly.Simultaneously be blown into a certain amount of gas phase media, make generation oil gas after the gasification leave coking tower and enter separation column in the bottom of coking tower.Be blown into a certain amount of gas phase media in the bottom of coking tower and also help to keep cold burnt passage, and can use existing decoking.There is not the liquid of gasification to continue cracking and condensation in coking tower.So not only can reduce the secondary reaction that generates oil gas, reduce the productive rate of dry gas, reduce owing to entering the raw material that participates in condensation reaction in the tower simultaneously, will reduce the productive rate of coke, increase the yield of liquid.Also owing to generate oil gas and in the decline process of drop, gasify and fallen a part, make that the escaping gas amount reduces in the liquid level, flow velocity reduces, and will make foam layer height decline in the coking tower.
Compared with prior art, under the situation that needn't change coking tower fractionating system and reheat furnace system, just feed entrance point is changed and the increase feed distributor, just can be improved liquid yield and reduce the coking tower foam layer height, will produce bigger economic benefit.
Description of drawings
The present invention will be further described below in conjunction with accompanying drawing:
Fig. 1 is the process flow diagram of delayed coking method of the present invention;
Fig. 2 is medium-sized delayed coking testing apparatus schema;
Fig. 3 is the medium-sized delayed coking unit schema that has adopted delayed coking method of the present invention.
Embodiment
As shown in Figure 1, coking raw material oil 1 enters the convection zone and the radiation section of process furnace 2.After radiation section is heated to 480～550 ℃, enter the top of coking tower 6 through transfer line 3, divider 4 through installing on the top of coking tower enters coking tower, the coking raw material that enters coking tower disperses coking raw material through divider 4, the liquid that does not gasify in the stock oil is dispersed into drop even droplet, fall into the bottom of coking tower, carry out thermally splitting and condensation reaction.Simultaneously, be blown into a certain amount of gas phase media 8 in the bottom of coking tower 6, one of its effect is to take the oil gas that generates out of coking tower as early as possible, reduces the generation of secondary reaction; Two of its effect is that the oil gas to thermally splitting carries out stripping; Three of its effect is to keep the passage that steams out with cold Jiao, so that use conventional decoking technology to carry out decoking.The oil-feed time of coking tower 6 is 6～36 hours, switches to coking tower 7 oil-feeds then, by divider 5 coking raw material is disperseed, and repeats said process.Carry out decoking with conventional method behind the conventional process such as 6 processes of coking tower steam out, cold Jiao.Prepare oil-feed again after decoking finishes, so circulate.
The oil gas 9 that generates is the same with conventional delayed coking, enters follow-up coking fractionating system fractionating method routinely and separates.
The present invention will be further described for the following examples, but do not limit the present invention.
The comparative example 1
As shown in Figure 2, on medium-sized delayed coking testing apparatus, certain vacuum residuum has been carried out the conventional delayed coking experiment of one way.Stock oil pumps in the process furnace 5 after the water vapor that pump 3 is extracted out and water vapor producer 6 produces mixes from material tank 1, and through pump 4 extractor pump entry Steam generating furnaces 6, the stock oil that the steam of generation and pump 3 come out mixes deionized water from water pot 2 simultaneously.The mixture of stock oil and water vapor enters coking tower from the bottom of coking tower 7 and carries out cracking and condensation reaction after process furnace 5 is heated to coking temperature.Coking generates oil gas and flows out from the top of coking tower 7, after condenser 8 condensations, enter and generate oily receiving tank 9, uncooled gas through cold well 10 further condensation coolings after wet test meter measures post-sampling emptying.The coking that receiving tank 9 and cold well 10 are collected generates oil and obtain petroleum naphtha, intermediate oil, wax tailings after the distillation of FY-III type true boiling point device.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
The comparative example 2
As shown in Figure 2, on medium-sized delayed coking testing apparatus, certain vacuum residuum has been carried out conventional belt circulation delay coking experiment.Stock oil and turning oil prepare in the charging feedstock oil tank 1 by a certain percentage in advance.Thereafter process is with comparative example 1.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
As shown in Figure 3, on the medium-sized delayed coking unit that adopts delayed coking method of the present invention, certain vacuum residuum has been carried out one way delayed coking experiment.Stock oil pumps in the process furnace 5 after the part mixing of the water vapor that pump 3 is extracted out and water vapor producer 6 produces from material tank 1, simultaneously deionized water from water pot 2 through pump 4 extractor pump entry Steam generating furnaces 6, the steam separated into two parts that produces, the stock oil that a part and pump 3 come out mixes; Another part enters the bottom of coking tower 7.The mixture of stock oil and water vapor is heated to coking temperature through process furnace 5 and enters coking tower from the top from coking tower 7 after divider disperses, and carries out cracking and condensation reaction in coking tower 7.Coking generates oil gas and flows out from the top of coking tower 7, after condenser 8 condensations, enter and generate oily receiving tank 9, uncooled gas through cold well 10 further condensation coolings after wet test meter measures post-sampling emptying.The coking that receiving tank 9 and cold well 10 are collected generates oil and obtain petroleum naphtha, intermediate oil, wax tailings after the distillation of FY-III type true boiling point device.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
As shown in Figure 3, on the medium-sized delayed coking unit that adopts delayed coking method of the present invention, certain vacuum residuum has been carried out circulation delay coking experiment.Stock oil and turning oil prepare in the charging feedstock oil tank 1 by a certain percentage in advance.Thereafter process only cuts out turning oil when distillation with embodiment 1.The raw material oil properties sees Table 1, and operational condition sees Table 2, and material balance sees Table 3.
By table 1, table 2 and table 3 as seen, the density of stock oil is 990.9kg/m
3, carbon residue is 16.6%.Comparative example 1 is identical with the operational condition of embodiment 1, and comparative example 2 is identical with the operational condition of embodiment 2.After adopting technology of the present invention, pass through (recycle ratio is 0, embodiment 1 and comparative example 1) for one way, liquid yield has increased by 1.98 percentage points, and foam layer height has reduced by 25%; After adopting technology of the present invention, for circulation coking (recycle ratio is 0.3, embodiment 2 and comparative example 2), liquid yield has increased by 2.56 percentage points, and foam layer height has reduced by 22.3%.Table 4～8 have been listed the composition and the character of cooking gas, coking naphtha, coking intermediate oil, wax tailings and coke among each embodiment respectively.
Table 1 stock oil character
| Density (20 ℃), kg/m 3 | 991.1 |
| Carbon residue, % | 16.8 |
| Sulphur content, % | 2.25 |
| Stable hydrocarbon, % | 17.1 |
| Aromatic hydrocarbons, % | 56.1 |
| Colloid+bituminous matter | 26.8 |
Table 2 operational condition
| The pyrogenic | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| The furnace outlet temperature, ℃ | 497 | ?497 | 497 | ?497 |
| The coking column bottom temperature, ℃ | 490 | ?490 | 490 | ?490 |
| The coking tower top pressure, MPa | 0.17 | ?0.17 | 0.17 | ?0.17 |
| Water injection rate, % | 2.1 | ?2.1 | 2.1 | ?2.1 |
| Recycle ratio | 0 | ?0 | 0.32 | ?0.31 |
Table 3 product distributes
| | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| Gas | 6.37 | ?6.92 | 7.59 | ?8.37 | |
| Petroleum naphtha (C5～180 ℃) | 7.75 | ?8.18 | 12.67 | ?13.23 | |
| Intermediate oil (180～360 ℃) | 24.77 | ?26.41 | 30.51 | ?31.09 | |
| Wax tailings | 39.28 | ?35.23 | 24.47 | ?20.77 | |
| Coke | 21.30 | ?22.67 | 24.14 | ?25.98 | |
| Loss | 0.51 | ?0.59 | 0.62 | ?0.56 | |
| Liquid yield, % | 71.80 | ?69.82 | 67.65 | ?65.09 | |
| Liquid is received to be increased, percentage point | 1.98 | 2.56 | |||
| Foam layer height, relatively | 75 | ?100 | 70 | ?90 |
The composition of table 4 cooking gas
| Component, m% | |
The comparative example 1 | |
The comparative example 2 |
| H 2S H 2 C 1 0 C 2 0 C 2 ＝ C 3 0 C 3 ＝ i-C 4 0 n-C 4 0 n-C 4 ＝ i-C 4 ＝ t-C 4 ＝ c-C 4 ＝ C 4 ＝＝ ∑ | 8.57 0.59 24.83 18.44 3.27 18.23 8.61 1.70 8.69 1.05 3.14 1.59 1.16 0.13 100.00 | ?8.90?0.70?25.91?18.48?3.15?17.58?8.42?1.70?8.54?0.78?3.02?1.61?1.06?0.15?100.00 | 8.84 0.69 26.52 19.31 3.15 17.24 8.10 1.68 8.25 0.68 2.97 1.52 0.95 0.10 100.00 | ?9.01?0.72?28.93?20.18?3.32?15.46?7.71?1.65?7.86?0.62?2.39?1.26?0.85?0.04?100.00 |
Table 5 coking naphtha character
| | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| Density (20 ℃), kg/m 3Acidity, the mgKOH/100ml sulphur content, μ g/g nitrogen content, μ g/g hydrocarbon system forms, m% stable hydrocarbon alkene aromatic hydrocarbons | 737.5 3.62 4864 96 47.67 44.61 7.72 | ?738.7?4.15?4900?85 46.53?45.20?8.27 | 739.2 3.99 4803 95 45.14 46.09 8.77 | ?740.1?3.71?5211?77 42.02?48.16?9.82 |
Table 6 coking middle runnings oil nature
| | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| Density (20 ℃), kg/m 3Acidity, mgKOH/100ml sulphur content, m% nitrogen content, μ g/g cetane index | 854.1 3.73 1.25 997 48 | ?854.7?4.13?1.19?953?47 | 855.0 3.92 1.34 1029 47 | ?855.1?3.78?1.26?987?46 |
Table 7 wax tailings character
| | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| Density (20 ℃), kg/m 3Condensation point, ℃ acid number, mgKOH/g sulphur content, m% nitrogen content, μ g/g | 934.3 30 0.04 1.85 4450 | ?934.5?30?0.06?1.82?4364 | 934.8 30 0.05 1.75 4876 | ?934.6?29?0.05?1.73?4390 |
Table 8 coke property
| | Embodiment | 1 | The comparative example 1 | |
The comparative example 2 |
| Sulphur content, m% volatile matter, m% ash content, m% | 2.79 8.64 0.80 | ?2.79?8.88?0.78 | 2.79 9.02 0.72 | 2.79 9.26 0.69 |
Claims (4)
1. a delayed coking method is characterized in that comprising the steps:
(a) stock oil mixes after process furnace is heated to coking temperature separately or with turning oil;
(b) stock oil from step (a) enters coking tower from the top or the side of coking tower;
(c) drop of step (b) generation carries out thermally splitting and condensation reaction in coking tower;
(d) from step (b) and the coking that (c) produces generate oil gas and flow out from the coking tower top or near the side at top, enter coking fractional distillation column and be divided into gas, petroleum naphtha, intermediate oil and wax tailings;
(e) from step (b) and the coke that (c) generates then stay in the coking tower;
(f) when carrying out, above step is blown into a certain amount of gas phase media to the coking tower bottom;
(g) behind the green coke certain hour, charging is switched to the coking tower that has been ready to charging in addition, carry out decoking with conventional decoking and filled burnt coking tower; Decoking finish after seal, standby behind the conventional steps such as warm tower; Circulation is switched between the coking tower, and process is able to continuously.
2. delayed coking method according to claim 1, it is characterized in that in coking tower stock oil ingress install at least one feed distributor to from the coking tower top or the side stock oil that enters coking tower disperse.
3. delayed coking method according to claim 1 and 2 is characterized in that described gas phase media of going into to the coking tower bottom blowing is one or more the mixture in water vapor, nitrogen, carbonic acid gas, dry gas and the lighter hydrocarbons.
4. delayed coking method according to claim 3 is characterized in that described lighter hydrocarbons are the hydro carbons of carbonatoms 1～4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899079A (en) * | 2011-07-27 | 2013-01-30 | 中国石油化工股份有限公司 | Delayed coking method |
| CN103805226A (en) * | 2012-11-02 | 2014-05-21 | 中国石油化工集团公司 | Delayed coking method |
| CN104099124A (en) * | 2013-04-15 | 2014-10-15 | 中石化洛阳工程有限公司 | Test method for on-line circulation of delayed coking cycle oil |
| CN105586079A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Heavy oil coking method |
| CN105586078A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Heavy oil coking method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501654A (en) * | 1983-11-17 | 1985-02-26 | Exxon Research & Engineering Co. | Delayed coking process with split fresh feed and top feeding |
| CN86102643A (en) * | 1985-05-13 | 1986-11-12 | 东洋工程株式会社 | The treating processes of heavy oil residue |
| CN101638585A (en) * | 2009-06-25 | 2010-02-03 | 中国石油化工集团公司 | Delayed coking method |
-
2010
- 2010-04-13 CN CN2010101449096A patent/CN102220166A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501654A (en) * | 1983-11-17 | 1985-02-26 | Exxon Research & Engineering Co. | Delayed coking process with split fresh feed and top feeding |
| CN86102643A (en) * | 1985-05-13 | 1986-11-12 | 东洋工程株式会社 | The treating processes of heavy oil residue |
| CN101638585A (en) * | 2009-06-25 | 2010-02-03 | 中国石油化工集团公司 | Delayed coking method |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899079A (en) * | 2011-07-27 | 2013-01-30 | 中国石油化工股份有限公司 | Delayed coking method |
| CN102899079B (en) * | 2011-07-27 | 2014-09-10 | 中国石油化工股份有限公司 | Delayed coking method |
| CN103805226A (en) * | 2012-11-02 | 2014-05-21 | 中国石油化工集团公司 | Delayed coking method |
| CN103805226B (en) * | 2012-11-02 | 2016-05-11 | 中国石油化工集团公司 | A kind of delayed coking method |
| CN104099124A (en) * | 2013-04-15 | 2014-10-15 | 中石化洛阳工程有限公司 | Test method for on-line circulation of delayed coking cycle oil |
| CN105586079A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Heavy oil coking method |
| CN105586078A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Heavy oil coking method |
| CN105586078B (en) * | 2014-10-21 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of heavy oil coking method |
| CN105586079B (en) * | 2014-10-21 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of heavy oil coking method |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: China Petrochemical Group Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant before: China Petrochemical Group Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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