CN102268287B - Delayed coking method of advanced deacidification of high acid raw oil - Google Patents

Delayed coking method of advanced deacidification of high acid raw oil Download PDF

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CN102268287B
CN102268287B CN 201010188878 CN201010188878A CN102268287B CN 102268287 B CN102268287 B CN 102268287B CN 201010188878 CN201010188878 CN 201010188878 CN 201010188878 A CN201010188878 A CN 201010188878A CN 102268287 B CN102268287 B CN 102268287B
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oil
coke drum
peracid
coke
tower
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CN102268287A (en
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黄新龙
李和杰
王龙延
王辰涯
秦如意
顾月章
袁强
胡艳芳
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China Petrochemical Corp
Sinopec Luoyang Guangzhou Engineering Co Ltd
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Sinopec Luoyang Petrochemical Engineering Corp
China Petrochemical Corp
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Abstract

The invention provides a delayed coking method of advanced deacidification of high acid raw oil. The method comprises the following steps: a routine coking feedstock from a radiant section of a heating furnace enters a coke tower from the bottom of the coke tower; the high acid raw oil which is from the same radiant section of the heating furnace and is heated to 380-520DEG C has a countercurrentcontact with a high temperature oil gas from a lower part of the coke tower by a distributor from the top of the coke tower or a lower part of the side surface of the coke tower and enters the coke tower; the high acid raw oil is gasified and pyrolyzed, generated lightweight hydrocarbon oil, and CO2, CO and H2O and the high temperature oil gas from the lower part of the coke tower escape the coketower from the top of the coke tower; and ungasified parts are continuously pyrolyzed in the coke tower. According to the delayed coking method of the present invention, the high acid raw oil is pyrolyzed after entering the coke tower, so petroleum acid is converted into components of CO2, CO, H2O and the like, the purpose of advanced deacidification is reached, and the deacidification rate is generally more than 98%, thereby the subsequent processing equipment corrosion can be effectively avoided.

Description

The delayed coking method of a kind of peracid stock oil degree of depth depickling
Technical field
The present invention relates to a kind of delayed coking method, particularly a kind of peracid stock oil is carried out degree of depth depickling and improves the delayed coking method that liquid is received.
Technical background
Petroleum acid refers to the acid oxygenatedchemicals in the oil, comprises naphthenic acid, aromatic acid, lipid acid and phenols etc., and wherein naphthenic acid content is the highest, accounts for about 90%.The content of naphthenic acid is different because of classification and the place of production of crude oil, and the naphthenic acid content of paraffinic crude is less, and the naphthenic acid content of intermediate base and naphthenic base crude is higher.
The acid content of oil generally uses acid number (TAN) to represent, namely in and the milligram number of the required potassium hydroxide (KOH) of the petroleum acid of 1 gram in the oil sample.Crude oil is divided three classes by the big I of acid number, and namely acid number is called low sour crude oil less than the crude oil of 0.5mgKOH/g, and the crude oil of 0.5mgKOH/g~1.0mgKOH/g is called acid-containing raw oil, and is called high-acid crude oil greater than the crude oil of 1.0mgKOH/g.It is generally acknowledged that low sour crude oil is lighter to the corrosion of refining equipment in petroleum refining process, thus less demanding to the material of equipment, invest also low; And the refining high-acid crude oil brings heavy corrosion to refining equipment, so the material of equipment is required very high, makes investment increase considerably, so processing highly acid crude oil is reluctant by the refinery.But the low price of high-acid crude oil is one of effective way that improves the oil refining enterprise economic benefit, thereby impels oil refining enterprise to pay attention to the processing of high-acid crude oil.
When temperature was lower than 220 ℃, naphthenic acid did not corrode; When temperature was 270 ℃~280 ℃, corrodibility was the strongest, and along with the rising of temperature, corrodibility begins to weaken; When being warmed up to 350 ℃~400 ℃, corrodibility is further aggravation again; After surpassing 400 ℃, naphthenic acid is easy to decompose, and corrodibility begins again to descend.Therefore not only the naphthenic acid in the oil can not be removed by atmospheric and vacuum distillation unit, and can cause heavy corrosion to atmospheric and vacuum distillation unit; The distillate of producing simultaneously and normal, vacuum residuum also can cause heavy corrosion to follow-up processing unit (plant).Carry out depickling earlier in the high-acid crude oil first being processed handles very necessary for this reason.
Crude oil deacidification technology has: hydrogenation deacidification method, catalytic cracking method, extraction separation method, absorption extraction method, ionization partition method and thermal decomposition method etc.And being exactly the principle of utilizing petroleum acid at high temperature to carry out cracking, thermal decomposition method technology carries out depickling.
Delay coking process is one of important heat processing technique, at high temperature heavy oil or residual oil drastic cracking can be converted into gas, gasoline fraction, diesel oil distillate, wax oil cut and coke.Conventional delay coking process is that stock oil is entered coking fractional distillation column after the coking heater convection zone is preheating to 300 ℃~350 ℃, on the one hand with high-temperature oil gas heat exchange from the coke cat head, be warmed up to after 360 ℃~380 ℃ and radiation section that turning oil comes along coking heater further is heated to 480 ℃~515 ℃, the coke powder that high-temperature oil gas is carried secretly carries out drip washing on the other hand; Flexible recycle ratio technology be with stock oil in the preheating of coking heater convection zone, further be heated to 480 ℃~515 ℃ with the radiation section that comes along coking heater from the turning oil at the bottom of the coking fractional distillation column then.Enter from the high-temperature hot oil of the coking heater radiation section bottom from coke drum, in tower, carry out cracking and condensation (coking) reaction, 440 ℃~465 ℃ the high-temperature-coked oil gas that generates is discharged from cat head and is gone coking fractional distillation column to fractionate out gas, gasoline fraction, diesel oil distillate, wax oil cut etc. about 420 ℃ through being quenched to, and the coke that generates then is deposited in the coke drum.
Patent US5976360, US6086751 and US5891325 have introduced and have utilized heat-treating methods to remove petroleum acid in the crude oil.Namely the high-acid crude oil after the dehydration carries out the depickling reaction in 340 ℃~425 ℃ temperature range, because temperature is lower, acid removal rate is not high, is one of high-acid crude oil processing approach and utilize the higher characteristics of delay coking process temperature of reaction to come processing highly acid crude oil.
CN1814704A discloses the method for a kind of deep removal acid-containing raw oil PetroChina Company Limited. acid.Petroleum acid is to the corrosion of separation column under the high temperature, high-acid crude oil does not advance separation column and high-temperature oil gas contact heat-exchanging and washing, goes coke drum to carry out pyrogenic reaction after the convection zone of process furnace and radiation section are heated to 480 ℃~510 ℃ to remove petroleum acid but directly enter.This method depickling is thorough, but technical process and CN1189540C (but delay coking process of flexible recycle ratio operation) basically identical, just stock oil has changed high-acid crude oil into; Because not having the high-temperature oil gas washing function in the coking fractional distillation column bottom of this flow process, so that the distillate that distills out carries coke powder is comparatively serious.
CN1580193A discloses a kind of delayed coking method of high acid value hydrocarbon ils.Enter the mitigation thermal cracking reactor after this method is heated to 350 ℃~450 ℃ to high-acid crude oil by process furnace and carry out the depickling reaction, then the low sour heavy cracking thing that generates is delivered to the process furnace heating again, go coke drum to carry out pyrogenic reaction after being heated to 480 ℃~510 ℃.This method not only work flow is longer, and the distillate that exists coking fractional distillation column to distill out equally carries comparatively serious problems of coke powder.
CN101280212A discloses the method for utilizing delay coking process to handle high-acid crude oil.This method heats high acid starting material respectively with low acid starting material in different process furnace, enter a coke drum after high acid starting material is heated to 450 ℃~510 ℃ and carry out heat scission reaction, and low acid starting material enters another coke drum after being heated to 480 ℃~510 ℃ and carries out heat scission reaction; The high-temperature oil gas that generates enters same separation column and carries out fractionation.This method adopts different reaction conditionss to the raw material of different acid numbers, and depickling is thorough, but the work flow complexity is invested higher.
CN101280213A discloses a kind of coking method of processing highly acid crude oil.This method enters low temperature (180 ℃~270 ℃) high-acid crude oil in the middle and lower part of coke drum, and the bottom of coke drum enters the low sour coking raw material of high temperature (450 ℃~550 ℃), low sour coking raw material mixes with the low temperature high-acid crude oil through the high-temperature oil gas that Pintsch process produces, thereby makes high-acid crude oil carry out the depickling reaction under suitable high temperature.This method work flow is simple, but enters from the middle and lower part of coke drum, makes that the high-acid crude oil lighter fraction residence time is longer, and secondary reaction is accelerated, thereby has reduced the yield of liquid product, has increased the yield of dry gas and coke; High-acid crude oil contains higher lighting end simultaneously, can aggravate the amount of carrying of coke powder after the gasification.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of delayed coking method of processing highly acidic stock oil, and namely delayed coking unit carries out the method that the liquid receipts were handled and improved in degree of depth depickling to peracid stock oil in the conventional coking raw material of processing.This method is processing highly acidic stock oil economically not only, and invest little, also little to the corrosion of equipment simultaneously.
The delayed coking method of a kind of peracid stock oil degree of depth provided by the invention depickling may further comprise the steps:
1) enters coke drum from the conventional coking charging of 450 ℃~530 ℃ of process furnace radiation sections from the bottom of coke drum and carry out pyrogenic reaction;
2) be heated to 380 ℃~520 ℃ peracid stock oil from the top of coke drum from same process furnace radiation section or top, side enters coke drum by divider and high-temperature oil gas counter current contact from the coke drum bottom, or directly enter coke drum; The gasification of peracid stock oil, and carry out pyrolytic reaction, light hydrocarbon oil, CO that reaction generates 2, CO and H 2O goes out coke drum with the high-temperature oil gas of coming from the tower bottom from cat head; Not gasification part is proceeded pyrolytic reaction in coke drum;
3) sedimentation of coke that generates through coking or pyrolytic reaction is in coke drum, when coke drum be full of defocused, step 1) and 2) two bursts of chargings switch in another coke drum; The tower that is full of coke then through steam out, standby after the process such as cold Jiao, decoking.
It is 400 ℃~470 ℃ that the present invention controls the temperature that high-temperature oil gas goes out the coke cat head, and preferred 400 ℃~450 ℃, best 410 ℃~420 ℃, the high-temperature oil gas that goes out the coke cat head goes coking fractional distillation column to carry out fractionation; Temperature from the conventional coking charging of process furnace radiation section is preferably 485 ℃~515 ℃, is preferably 400 ℃~490 ℃ from the temperature of the peracid stock oil of process furnace radiation section; The pressure of coke drum cat head is advisable with the pressure that can overcome system, is generally 0.1MPa~1.0MPa (gauge pressure, down together), preferred 0.1MPa~0.25MPa.
Peracid stock oil after the heating of the present invention enters coke drum from top or the top, side of coke drum, be that peracid stock oil is gone into tower through divider, divider is installed in more than the foam layer, is preferably mounted at the above place of foam layer 1m, preferably is installed near the tangent line highest point ± 1m place of coke drum; Peracid stock oil is gone at least 1 of the pipeline of tower.
Peracid stock oil after the heating of the present invention has spray and tangent line dual mode to go into tower.In the mode (generation drop) when going into tower of spray, divider have at least 3 at nozzle and more than, the droplet dia after the dispersion is 500 μ m~3000 μ m, preferred 1000 μ m~1500 μ m.When going into tower with tangential way, more than at least 2 in the shower nozzle of export distributor reached, shower nozzle was preferably rectangle, and the downward inclination angle of shower nozzle is 1 °~30 °, best 5 °~15 °.Nozzle and shower nozzle are refining of petroleum field common equipment.
Process furnace radiation section of the present invention generally has 3~5 stroke radiation furnace tubes, and wherein minimum 1 journey is used for heating peracid stock oil; From the coke drum top or the peracid raw material oil mass of top, side charging be 20~80: 80~20 by weight with ratio from the inlet amount of coke drum bottom, be preferably 25~75: 75~25.
Peracid stock oil of the present invention is acid number greater than one or more the mixture in distillate between 150 ℃~560 ℃ of the crude oil of 1.0mgKOH/g, topped crude, boiling range, long residuum, the vacuum residuum; The mixture of one or more in extraction oil, catalytic cracking recycle oil, clarified oil, cracking of ethylene residual oil, coal tar, tar-bitumen, shale oil and the coking recycle oil that described conventional coking charging is heavy crude, atmospheric residue, vacuum residuum, decompressed wax oil, de-oiled asphalt, residual hydrogenation heavy oil, thermal cracking residue, lube oil finishing.
Characteristics of the present invention are on the basis of mature delay coking process, and peracid stock oil is gone into tower more than the foam layer of coke drum, and peracid stock oil gasifies after going into tower fast, and heat scission reaction takes place, and makes petroleum acid be converted into CO 2, CO and H 2Components such as O reach degree of depth depickling purpose; Simultaneously the mink cell focus of gasification does not contact with high-temperature oil gas from the coke drum bottom, make high-temperature oil gas be able to drip washing, the coke powder amount that can bring high-temperature oil gas to carry is few, namely reduced the coking in the separation column, also the coke powder content reduction because of heavy wax tailings (or claiming turning oil) has prolonged the operation of process furnace, thereby has prolonged the benefits such as the cycle of operation of coker.
The present invention compared with prior art also has following advantage:
1. peracid stock oil gasifies in tower and pyrolytic reaction takes place, the a large amount of oil gas that generate with mix from the high-temperature oil gas of coke drum bottom, shortened the residence time of oil gas, the secondary reaction of having drawn up, thereby reduced the productive rate of dry gas and coke, namely improved the liquid of coking and received.When peracid stock oil was crude oil, effect can be better.
2. the part high-temperature material that enters in the coke drum is gone into tower from top or the top, side of coke drum, the high-temperature oil gas that gasification and pyrolysis produce etc. directly go out tower without soft burnt layer and foam layer, thereby reduced the oil gas linear speed of coke drum bottom, namely reduced the amount of carrying of coke powder again.
3. the present invention heats two media with a process furnace, and flow process is simple, invests lower.
4. acid removal rate height of the present invention generally greater than 98%, can effectively be avoided the corrosion of following process equipment.
5. the inventive method is simple to operate, is easy to grasp; Not only be used for the processing of peracid stock oil, also can be used for the processing of other stock oil.
With the drawings and specific embodiments the present invention is described in further detail below, but do not limit the scope of the invention, those skilled in the art can be according to raw material properties, be easy to select appropriate operational parameters to reach the depickling purpose of peracid stock oil within the scope of the present invention, reduce dry gas and coke yield simultaneously, namely increased the liquid receipts.
Description of drawings
Fig. 1 is a kind of simple process flow diagram of the present invention.
Fig. 2 is another kind of simple process flow diagram of the present invention.
Among the figure: 1-process furnace, the conventional coking charging of 2-radiation section feed oil, 3-high-temperature oil gas transfer line, 4, the 11-coke drum, 5-reaction oil gas transfer line, 6-reaction oil gas, 7-peracid stock oil, 8,12-peracid stock oil goes out the transfer line of process furnace, 9, the 10-coke.
Embodiment
As shown in Figure 1, conventional coking charging radiation section feed oil 2 is heated to after 450 ℃~530 ℃ through the radiation section of process furnace 1 and enters through the bottom of high-temperature oil gas transfer line 3 from coke drum 4 (11 are carrying out decoking process), be to carry out conventional pyrogenic reaction under the condition of 0.1MPa~1.0MPa at the coke drum tower top pressure, the coke of generation is stayed the bottom of coke drum.Peracid stock oil 7 also is heated to 380 ℃~520 ℃ through the radiation section of process furnace 1 and enters coke drum from the top of coke drum through divider by transfer line 8 and gasify fast and pyrolytic reaction.When high temperature peracid stock oil was gone into tower with drop, divider had 3 and with nozzle at least, was dispersed into behind the particle of 500 μ m~3000 μ m and split product-high-temperature oil gas counter current contact from the coke drum bottom, to the high-temperature oil gas drip washing from the tower bottom; When with the feeding manner of tangent line, high temperature peracid stock oil is through 2 and goes into tower with upper nozzle.The heavy oil that high temperature peracid stock oil does not gasify is fallen and is proceeded pyrolysis and depickling reaction under the tower.The high-temperature oil gas temperature of controlling out the coke cat head is 400 ℃~470 ℃, preferred 400 ℃~450 ℃, and best 410 ℃~420 ℃; The high-temperature oil gas 6 that goes out the coke cat head goes coking fractional distillation column to carry out fractionation through transfer line.When coke drum 4 be full of defocused, at the bottom of the tower and the charging of top of tower switch among the coke drum 4B.Coke 9 and coke 10 are discharged by coke drum 4 and coke drum 11 bottoms respectively.
The difference of Fig. 2 and Fig. 1 is to go into tower through transfer line 8 (or 12) from the top, side of coke drum from the high temperature peracid stock oil 7 of coking heater 1.
The following examples will further specify method afford provided by the invention, but not limit the present invention because of embodiment.
Among the embodiment used peracid stock oil be acid number greater than the high-acid crude oil of 1.0mgKOH/g, the character of high-acid crude oil and conventional coking charging sees Table 1.The operational condition of embodiment and Comparative Examples and product distribute and character sees Table 2.
The method of calculation of acid removal rate are defined as:
Acid removal rate=(acid number of peracid stock oil acid number-peracid charging gained liquid product)/peracid is former
Material oleic acid value * 100%
Embodiment 1
120 ℃ conventional coking raw material enters three tunnel heating of process furnace convection chamber after heat exchange, be heated to after 370 ℃ with from the turning oil at the bottom of the fractionation Tata and mix, and then three tunnel heating that enter the process furnace radiation chamber, radiation chamber population injects the water vapor that accounts for conventional coking raw material 1.55%, the outlet oil temperature of control process furnace is 498 ℃, and the bottom from coke drum enters then, in tower top pressure 0.17MPa (gauge pressure, under the condition down together), conventional coking raw material carries out cracking and condensation reaction in tower.
80 ℃ peracid stock oil I is heated to through another road furnace tubing of same process furnace convection chamber and radiation chamber that the cat head from coke drum enters through the drop that nozzle becomes to be dispersed into 1000 μ m~1500 μ m after 450 ℃, the high-acid crude oil gasification is also carried out pyrolytic reaction, simultaneously to carrying out drip washing from the high-temperature oil gas under the tower.The coke that generates is stayed in the coke drum, and the high-temperature oil gas that goes out coke drum goes separation column to separate.The notes vapour amount of this furnace tubing accounts for 0.6% of peracid stock oil I inlet amount.
Conventional coking inlet amount is 75: 25 with the ratio of the inlet amount of high-acid crude oil I by weight.
Embodiment 2
Method is with embodiment 1, and conventional coking inlet amount that different is is 50: 50 with the ratio of the inlet amount of high-acid crude oil I by weight; The temperature of the high-acid crude oil I that enters from cat head is 485 ℃; High temperature high-acid crude oil I sprays along the tower wall through the rectangle shower nozzle with tangential direction after cat head is gone into tower.
Embodiment 3
Method is with embodiment 1, and conventional coking charging that different is is 60: 40 with the ratio of the inlet amount of high-acid crude oil II by weight; The temperature of the high-acid crude oil II that enters from cat head is 465 ℃, and the gauge pressure of coke drum cat head is 0.15MPa.
Embodiment 4
Method is with embodiment 1, and conventional coking charging that different is is 15: 85 with the ratio of the inlet amount of high-acid crude oil II by weight; The temperature of the high-acid crude oil II that enters from cat head is 493 ℃; The high temperature high-acid crude oil sprays along the tower wall through the rectangle shower nozzle with tangential direction after cat head is gone into tower; The gauge pressure of coke drum cat head is 0.15MPa.
Comparative Examples 1
The same EXAMPLE l of method, its difference are that the cat head of coke drum does not have high-acid crude oil to enter.
As seen from Table 2, adopt the acid removal rate of this patent method processing highly acid crude oil all more than 98%.
The main character of table 1 embodiment 1 and Comparative Examples 1 charging heavy oil I
The operational condition of table 2 patent of the present invention and existing technology and product distribute and contrast
Figure BSA00000140828200062

Claims (10)

1. the delayed coking method of peracid stock oil degree of depth depickling is characterized in that may further comprise the steps:
1) enters coke drum from the conventional coking charging of 450 ℃~530 ℃ of process furnace radiation sections from the bottom of coke drum and carry out pyrogenic reaction;
2) be heated to 380 ℃~520 ℃ peracid stock oil from the top of coke drum from same process furnace radiation section or top, side enters coke drum by divider and high-temperature oil gas counter current contact from the coke drum bottom, or directly enter coke drum; The gasification of peracid stock oil, and carry out pyrolytic reaction, light hydrocarbon oil, CO that reaction generates 2, CO and H 2O goes out coke drum with the high-temperature oil gas of coming from the tower bottom from cat head; Not gasification part is proceeded pyrolytic reaction in coke drum;
3) sedimentation of coke that generates through coking or pyrolytic reaction is in coke drum, when coke drum be full of defocused, step 1) and 2) two bursts of chargings switch in another coke drum; The tower that is full of coke then through steam out, standby behind cold Jiao and the decoking process.
2. delayed coking method according to claim 1, it is characterized in that: described process furnace radiation section has 3~5 stroke radiation furnace tubes, wherein minimum 1 journey is used for heating peracid stock oil, from the coke drum top or the peracid raw material oil mass of top, side charging be 20~80: 80~20 by weight with ratio from the inlet amount of coke drum bottom.
3. delayed coking method according to claim 1 and 2 is characterized in that: described peracid stock oil is acid number greater than one or more the mixture in distillate between 150 ℃~560 ℃ of the crude oil of 1.0mgKOH/g, topped crude, boiling range, long residuum, the vacuum residuum.
4. delayed coking method according to claim 3 is characterized in that: the temperature from the peracid stock oil of process furnace radiation section is 400 ℃~490 ℃.
5. delayed coking method according to claim 1 and 2, it is characterized in that: the temperature that described high-temperature oil gas goes out coke drum is 400 ℃~470 ℃, temperature from the conventional coking charging of process furnace radiation section is 485 ℃~515 ℃, and the pressure at coke drum top is 0.1MPa~1.0MPa.
6. delayed coking method according to claim 1 and 2, it is characterized in that: described divider is installed in more than the foam layer, and peracid stock oil is gone at least 1 of the pipeline of tower, and the tower mode of going into of peracid stock oil is spray mode or tangential way.
7. delayed coking method according to claim 6, it is characterized in that: peracid stock oil is gone into tower in the spray mode, divider have at least 3 at nozzle and more than, the droplet dia after the dispersion is 500 μ m~3000 μ m.
8. delayed coking method according to claim 7, it is characterized in that: the droplet dia after the dispersion is 1000 μ m~1500 μ m.
9. delayed coking method according to claim 6, it is characterized in that: peracid stock oil is gone into tower with tangential way, at least 2 in the shower nozzle of export distributor and more than, shower nozzle is rectangle, the downward inclination angle of shower nozzle is 1 °~30 °.
10. delayed coking method according to claim 9, it is characterized in that: the downward inclination angle of described shower nozzle is 5 °~15 °.
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CN105270772A (en) * 2014-07-07 2016-01-27 中石化洛阳工程有限公司 Ethylene spherical tank cooling depressurizing method
CN110747003B (en) * 2019-11-06 2021-04-27 中国石油化工股份有限公司 Coke tower and delayed coking method using same
CN113322098A (en) * 2020-08-19 2021-08-31 中国石油天然气股份有限公司 Method for reducing acid value of high-acid crude oil and marine fuel oil

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Publication number Priority date Publication date Assignee Title
EP0948581B1 (en) * 1995-10-20 2004-05-12 ExxonMobil Research and Engineering Company Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils
CN1580193A (en) * 2003-07-31 2005-02-16 中国石油化工股份有限公司 High acid value hydrocarbon oil delayed coking method
CN101280213A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Coking method for processing highly acid crude oil
CN101280212A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Method for processing highly acid crude oil by using delayed coking process
CN101629093A (en) * 2009-08-03 2010-01-20 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0948581B1 (en) * 1995-10-20 2004-05-12 ExxonMobil Research and Engineering Company Viscosity reduction by heat soak-induced naphthenic acid decomposition in hydrocarbon oils
CN1580193A (en) * 2003-07-31 2005-02-16 中国石油化工股份有限公司 High acid value hydrocarbon oil delayed coking method
CN101280213A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Coking method for processing highly acid crude oil
CN101280212A (en) * 2007-04-04 2008-10-08 中国石油化工股份有限公司 Method for processing highly acid crude oil by using delayed coking process
CN101629093A (en) * 2009-08-03 2010-01-20 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

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