CN1487056A - Method of raising liquid yield during delayed coking - Google Patents
Method of raising liquid yield during delayed coking Download PDFInfo
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- CN1487056A CN1487056A CNA021396736A CN02139673A CN1487056A CN 1487056 A CN1487056 A CN 1487056A CN A021396736 A CNA021396736 A CN A021396736A CN 02139673 A CN02139673 A CN 02139673A CN 1487056 A CN1487056 A CN 1487056A
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- coking
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- coke
- gasoline
- evaporation agent
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Abstract
The method of raising liquid yield during delayed coking is to add one kind of low-boiling point evaporant capable of shortening the setting period of distillate oil in coking tower, and reducing the possibility of secondary cracking and re-condensation of hydrocarbon to form coke. The evaporatn may be gasoline, hydrogenated coked gasoline, organic alcohol, gaseous hydrocatbon or their mixture; and may be added into the fed material before coking tower, into the distillate oil in the back of coking tower and/or into the coking tower. The present invention can raise liquid yield by 2-8% and lower coke yield by over 2%.
Description
1, technical field:
The present invention relates to delayed coking, more particularly, relate to a kind of method that improves liquid yield in the delayed coking process and reduce coke yield, said yield is based on coker feed.
2, background technology:
Delayed coking is a kind of heat processing technique that residual oil is converted into gas, light, middle matter distillate and coke through drastic cracking.Conventional delay coking process is: stock oil enters separation column and the next coking oil gas heat exchange of coke drum after the process furnace preheating, entering the process furnace radiation section again is heated to coking temperature and enters the coke drum coking, coking oil gas distillates from the coke cat head and enters separation column, fractionate out gas, gasoline, diesel oil and wax tailings, wax oil at the bottom of the separation column can be circulated to surge tank by pump to be mixed with the stock oil of process furnace convection zone preheating, recycle ratio is adjustable arbitrarily in 0～0.65 scope, and coke is flocked in the coke drum.
The delay coking process technology maturation is once invested lowly, is a kind of widely used Heavy Oil Processing Technology.The working ability of existing delayed coking unit surpasses 60% of residual oil processing total capacity, and in China, the most especially refinerys of delayed coking are handled the most common means of residual oil.The problem that delayed coking exists is that the low and coke of liquid product yield is worth not high and slack market sometimes, liquid product yield generally can reach about 70%, particularly when handling poor residuum, the massfraction that its liquid is received has only 50%～60%, and coke yield might surpass 30%.Therefore each major oil companies of the world never stop delayed coking Study on Technology and improvement.The liquid product yield that wherein improves delay coking process is the major objective of research always, because the tonnage of delayed coking unit is bigger, liquid yield improves 1% just can bring huge economic interests to the refinery, so each company has proposed the technical measures that many raising liquid are received.For example: US4,455,219 disclose a kind of delayed coking method, replace a part common and the heavy recycle that fresh feed merges with a kind of boiling range thinner lower than heavy recycle, improve the coking liquid yield, and correspondingly coke output descends.USP4,518,487 disclose a kind of low boiling range thinner replaces all heavy recycle, to improve the coking liquid yield and to reduce coke output.Coking furnace overhead product or add in the coke drum.Application number 97193162.3 patent applications have proposed to add a kind of hydrocarbon attenuant of better heat stability in coking tower, thereby improve the total liquid receiving method of reaction to coking tower input additional heat with the temperature that increases liquid in the tower simultaneously.USP4,455,219, USP4,518,478, USP4,661,241 and application number be 97193162.3 patent applications, the thinner boiling range that is adopted is all between about 335 °F～850 °F.
3, summary of the invention:
The invention provides a kind of improve liquid yield and the method that reduces coke yield in the delayed coking process.
Method of the present invention is to realize like this, stock oil is introduced into the preheating of process furnace convection zone, enter surge tank again, entering the process furnace radiation section through pump then is heated to coking temperature and enters coke drum, high-temperature oil gas after the pyrogenic reaction enters the separation column separation and obtains gas, distillate, coke is flocked in the coke drum, it is characterized in that in coking adding a kind of boiling point less than organic class evaporation agent of 165 ℃.
Principle of the present invention is: in delayed coking process, the coking of residues reaction mainly is that heat cracking reaction is with Shrink closes reaction.Thermally splitting is a kind of parallel consecutive reaction of complexity, and residual oil is heated to certain temperature, and alkane that thermostability is little and the at first cracking of the long side chain of the alkyl of cyclic hydrocarbon generate the low molecular hydrocarbon class, i.e. distillate.Along with the lengthening in reaction times, distillate generation second pyrolysis generates the littler molecule of molecular weight.On the other hand, the unsaturated hydrocarbons that thermo-cracking produces or contain heteroatomic hydro carbons and exist with the radical form, extremely unstable, they will continue to take place cracking again and condensation reaction, until generating coke.Alkene and aromatic hydrocarbons or aromatic hydrocarbons and Fang Ting Shrink close and also generate macromole simultaneously, and Gao Du Shrink symphysis becomes the colloid and the bituminous matter of poor hydrogen, also generates coke at last.
A kind of evaporation agent of adding can increase the short residence time of distillate in coking tower of gas flow rate Shrink in the coking tower in coking, reduce the chance of second pyrolysis and hydrocarbon molecules Jin Yi Bu Shrink symphysis coke, control coking tower gas phase temperature and reduction distillate dividing potential drop are also had certain effect.Can improve the distillate yield thus, and reduce coke yield.
Above-mentioned evaporation agent is meant gasoline, organic alcohol, any one among the carburet hydrogen three or two or more.
Above-mentioned gasoline is meant straight-run spirit, catalytic gasoline, coker gasoline etc., preferred hydrogenation coker gasoline.
Above-mentioned organic alcohol is meant methyl alcohol, ethanol, propyl alcohol, butanols etc., preferred alcohol.
Above-mentioned carburet hydrogen is meant the carburet hydrogen that oil refining apparatus produces, such as C2 hydrocarbon, carbon three hydrocarbon, carbon four hydrocarbon, carbon five hydrocarbon etc. and hydrocarbon mixture thereof, preferred alkane.
Described evaporation agent injection rate is 0.01～29% of a coking inlet amount, and preferred injection rate is 2～10% of a coking inlet amount.
Described evaporation agent can be injected into before the coking furnace in the charging or in the coking furnace after cut oil or directly inject in the coking tower, or adopts any dual mode or three kinds of modes to inject simultaneously simultaneously.
Described coking raw material comprises that the long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil of any crude oil extract oil and two or more out.
Adopt method of the present invention, can improve coking liquid yield 2～8%, reduce coke yield simultaneously more than 2%.
4, description of drawings:
Fig. 1 implements a kind of delay coking process schema of the present invention.
5, embodiment:
Further describe the present invention below in conjunction with embodiment and accompanying drawing, but therefore do not limit the present invention.The employed raw material of embodiment and Comparative Examples is a vacuum residuum; The employed testing apparatus of embodiment and Comparative Examples is the delayed coking simulator.
As shown in Figure 1, adopt pipe oil transportation vacuum residuum, coking raw material I enters surge tank 2 after process furnace 1 convection zone preheating, enter process furnace 1 radiation section by pump 3 again and be heated to coking temperature, advances coke drum 4/5 coking again.The coker gasoline that separation column 6 fractionation obtain is as evaporation agent II, before entering coking tower, injects process furnace 1 overhead product, coking oil gas enters separation column 6 by coke drum 4/5 overhead line, fractionation obtains gas III and distillate (gasoline IV, diesel oil V, light wax oil VI and wax slop VII), separation column 6 wax oils can enter surge tank 2 by pump 7 and circulate, and recycle ratio is adjustable arbitrarily in 0～0.65 scope.Coke is flocked in the coke drum.Test-results sees Table 1.
Compare with embodiment 1, difference is that present embodiment injects the hydrogenation coker gasoline and makes evaporation agent in coking.Test-results sees Table 1.
Compare with embodiment 1, difference is that present embodiment injects ethanol and makes evaporation agent in coking.Test-results sees Table 1.
Embodiment 4
Compare with embodiment 1, difference is that present embodiment injects mixed c 4 and makes evaporation agent in coking.Test-results sees Table 1.
Comparative Examples 1
Compare with embodiment 1, difference is that this Comparative Examples do not inject any evaporation agent in coking.Test-results sees Table 1.
Table 1
| Sequence number | The evaporation agent kind | Evaporation agent add-on (accounting for raw material %) | Liquid yield (accounting for raw material %) | Coke yield (accounting for raw material %) |
| | Coker gasoline | ????0 | ????69.10 | ????19.58 |
| ????5 | ????71.29 | ????17.93 | ||
| ????10 | ????73.21 | ????17.53 | ||
| ????20 | ????73.61 | ????16.49 | ||
| ????29 | ????71.26 | ????16.89 | ||
| | The hydrogenation coker gasoline | ????0 | ????69.10 | ????19.58 |
| ????5 | ????70.63 | ????17.46 | ||
| ????10 | ????73.06 | ????17.33 | ||
| ????20 | ????74.62 | ????16.58 | ||
| ????29 | ????73.80 | ????16.38 | ||
| | Ethanol | ????0 | ????68.32 | ????19.18 |
| ????5 | ????71.87 | ????16.93 | ||
| Embodiment 4 | Carbon four hydrocarbon | ????0 | ????68.26 | ????19.63 |
| ????5 | ????71.53 | ????17.79 | ||
| ????10 | ????72.90 | ????17.33 |
Claims (10)
1, a kind of method that improves the delayed coking process liquid yield, stock oil is introduced into the preheating of process furnace convection zone, enter surge tank again, entering the process furnace radiation section through pump then is heated to coking temperature and enters coke drum, high-temperature oil gas after the pyrogenic reaction enters the separation column separation and obtains gas, distillate, coke is flocked in the coke drum, it is characterized in that in coking injecting a kind of boiling point less than organic class evaporation agent of 165 ℃.
2, method according to claim 1, it is characterized in that described evaporation agent be meant among gasoline, organic alcohol, the carburet hydrogen three any one or two or more.
3, method according to claim 2 is characterized in that described gasoline is meant the hydrogenation coker gasoline.
4, method according to claim 2 is characterized in that described organic alcohol is meant ethanol.
5, method according to claim 2 is characterized in that described carburet hydrogen is the carburet hydrogen that oil refining apparatus produces.
6, method according to claim 5 is characterized in that described carburet hydrogen is meant butane.
7, method according to claim 1 is characterized in that described evaporation agent injection rate is 0.01～29% of a coking inlet amount.
8, method according to claim 7 is characterized in that described evaporation agent injection rate is 2～10% of a coking inlet amount.
9, method according to claim 1 is characterized in that described evaporation agent is to be injected into before the coking furnace in the charging or in the coking furnace after cut oil or directly inject in the coking tower, or adopts any dual mode or three kinds of modes to inject simultaneously simultaneously.
10, method according to claim 1 is characterized in that described stock oil comprises that the long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil of any crude oil extract oil and two or more out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021396736A CN1487056A (en) | 2002-10-01 | 2002-10-01 | Method of raising liquid yield during delayed coking |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021396736A CN1487056A (en) | 2002-10-01 | 2002-10-01 | Method of raising liquid yield during delayed coking |
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| CN1487056A true CN1487056A (en) | 2004-04-07 |
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| CNA021396736A Pending CN1487056A (en) | 2002-10-01 | 2002-10-01 | Method of raising liquid yield during delayed coking |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987961A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Coking delaying method |
| CN102311757A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311755A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Auxiliary agent used for increasing yield of delayed-coked liquid products |
| CN102311756A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN101619238B (en) * | 2008-07-04 | 2012-08-29 | 中国石油化工股份有限公司 | Delayed coking and reduced pressure distillation combined processing method |
| CN104711009A (en) * | 2015-02-26 | 2015-06-17 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Method for rapidly predicting coking furnace in-pipe standing time |
| WO2017096556A1 (en) * | 2015-12-09 | 2017-06-15 | 季国平 | Method for producing petrochemical products by thermal cracking reaction |
-
2002
- 2002-10-01 CN CNA021396736A patent/CN1487056A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619238B (en) * | 2008-07-04 | 2012-08-29 | 中国石油化工股份有限公司 | Delayed coking and reduced pressure distillation combined processing method |
| CN101987961A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Coking delaying method |
| CN101987961B (en) * | 2009-07-30 | 2014-01-15 | 中国石油化工股份有限公司 | Coking delaying method |
| CN102311757A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311755A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Auxiliary agent used for increasing yield of delayed-coked liquid products |
| CN102311756A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN102311757B (en) * | 2010-06-29 | 2013-11-06 | 中国石油化工股份有限公司 | Method for improving yield of delayed coking liquid product |
| CN102311756B (en) * | 2010-06-29 | 2013-11-27 | 中国石油化工股份有限公司 | Addition agent for thermal inversion process of heavy oil and preparation method of addition agent |
| CN102311755B (en) * | 2010-06-29 | 2013-12-25 | 中国石油化工股份有限公司 | Auxiliary agent used for increasing yield of delayed-coked liquid products |
| CN104711009A (en) * | 2015-02-26 | 2015-06-17 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Method for rapidly predicting coking furnace in-pipe standing time |
| WO2017096556A1 (en) * | 2015-12-09 | 2017-06-15 | 季国平 | Method for producing petrochemical products by thermal cracking reaction |
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