CN103421538A - Method for adding coking distillate oil into residual oil for hydrogen supply coking - Google Patents
Method for adding coking distillate oil into residual oil for hydrogen supply coking Download PDFInfo
- Publication number
- CN103421538A CN103421538A CN201210152634XA CN201210152634A CN103421538A CN 103421538 A CN103421538 A CN 103421538A CN 201210152634X A CN201210152634X A CN 201210152634XA CN 201210152634 A CN201210152634 A CN 201210152634A CN 103421538 A CN103421538 A CN 103421538A
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- CN
- China
- Prior art keywords
- coking
- oil
- distillate
- hydrogen supply
- residual oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004939 coking Methods 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000005855 radiation Effects 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- 239000002283 diesel fuel Substances 0.000 abstract 1
- 239000000852 hydrogen donor Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 17
- 239000002010 green coke Substances 0.000 description 8
- -1 cycloalkyl aromatic hydrocarbons Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
Landscapes
- Coke Industry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for adding coking distillate oil into residual oil for hydrogen supply and coking; mixing coking distillate oil and coking raw material residual oil according to the weight ratio of 0.2-0.4, preheating in a convection section of a heating furnace, entering a buffer tank, entering a radiation section of the heating furnace, heating to coking temperature, and entering a coking tower for coking; the inlet temperature of the reaction tower is 480-520 ℃, and the pressure is 0.1-1.0 MPa; the coking distillate oil is selected from coking diesel oil, coking middle distillate, coking light wax oil, coking heavy wax oil or their mixture; the method can be used as a hydrogen donor to inhibit the generation of furnace tube coking and shot coke, reduce the coke yield and improve the yield of liquid distillate oil products because the coking distillate oil is rich in benzocycloalkane rings.
Description
Technical field
The present invention relates to add in a kind of residual oil the method for coking distillate hydrogen supply coking.
Background technology
The advantages such as delayed coking is as a kind of important heavy oil lighting means, and pair adaptability to raw material is strong owing to having, technology maturation, investment are lower are the complete processings that each large refinery extensively adopts both at home and abroad always.Select suitable recycle ratio and definite optimum cycle logistics, not only very large on the impact of delayed coking products distribution, and affect the green coke trend of the logistics in process furnace, cause thus many problems: as shot coke appears, the distillation tower overload, distilling effect is not good, sometimes also causes the furnace tubing coke-burning cycle to shorten etc.
The additive that interpolation free radical inhibitors, hydrogen supply agent or interpolation have the good distribution ability to the bituminous matter free radical is all the effective way of coke inhibiting.The high aromatic hydrocarbons petroleum fractions generated in thermally splitting, because its aromaticity content is high, cracking performance is poor, bad processing treatment, but, because itself containing a large amount of cycloalkyl aromatic hydrocarbons and polycyclic aromatic hydrocarbons, can provide reactive hydrogen, we can be used to this.Therefore add recycle fraction, can improve liquid and receive and reduce green coke, optimize coking process.
Originally hydrogen supply agent is used in direct coal liquefaction process, and afterwards, people start exploration and adopt hydrogen supply agent in residual oil processing, and propose the series of process process.
The cycloalkyl aromatic hydroxy compound is to introduce more a kind of hydrogen supply agent in document as naphthane, but its price needs recovery and manipulation of regeneration could continue to use; And boiling point is lower, need under high pressure carry out, be unsuitable for the heavy industrialization application.Therefore, develop afterwards other materials and replaced naphthane.
Directly adopt the thermally splitting distillate to do hydrogen supply agent, also can reach effect preferably, abroad do a lot this side.U.S. Ai Kesen company just utilizes the FCC heavy distillate to carry out the residual oil viscosity breaking as hydrogen supply agent, produces gasoline and oil fuel; LURGI utilizes the distillate of 200~500 ℃ to carry out Hydro-visbreaking as hydrogen supply agent, produces gasoline and distillate; Canada bay company utilizes the FCC benzoline to carry out refined asphaltic bitumen as hydrogen supply agent.Conoco Inc utilizes the distillate of 315~537 ℃ to carry out viscosity breaking as hydrogen supply agent, Japan National Oil Corporation utilizes FCC turning oil to carry out the residual oil viscosity breaking as hydrogen supply agent, and U.S. DM international corporation also once carries out viscosity breaking with coker gas oil as hydrogen supply agent and produces coking raw material.Domestic also have a correlative study, and Luoyang petroleum chemical engineering company utilizes the petroleum fractions of 350~550 ℃ to suppress furnace coking as hydrogen supply agent and also obtained good effect.Adopt the petroleum fractions (refinery's byproduct) of the fragrant compounds of many cyclophanes to make hydrogen supply agent, the Liaohe River is subtracted to slag hydrogen supply viscosity breaking research, can obtain economic benefit preferably.
Summary of the invention
The purpose of this invention is to provide in a kind of residual oil the method for adding the coking of coking distillate circulation hydrogen supply, filter out suitable industrial hydrogen supply agent cut and carry out hydrogen supply coking cut, determine best hydrogen supply ratio, to improve, liquid is received and reduction green coke amount, the problems such as the common coke-burning cycle of furnace tube of delayed coking is shorter, Petroleum Coke is not high (shot coke, sticky burnt, coke breeze) thereby improve, and liquid product yield is on the low side.Wax tailings to the processing characteristics extreme difference has had good utilization.
The method of adding the coking of coking distillate circulation hydrogen supply in residual oil of the present invention comprises the following steps:
After coking distillate is mixed by the weight ratio of 0.2-0.4 with residual oil raw material, be introduced into the preheating of process furnace convection zone, then enter surge tank, after then entering the process furnace radiation section and being heated to coking temperature, enter the coking tower coking; 480~520 ℃ of reaction tower temperature ins, pressure is 0.1~1.0MPa.
Coking distillate is selected from coker gas oil, coking stage casing cut, coking light wax oil, coking wax slop or their mixing.
Owing to being rich in the benzo naphthenic ring in coking distillate, therefore, as hydrogen supply agent, and subtract the slag raw material and evenly mixed before advancing furnace tubing, advance coke drum after mixing and carry out pyrogenic reaction.
Embodiment
Embodiment 1:
A kind of typical hydrogen supply agent cut character is in Table 1.
Table 1 hydrogen supply agent wax tailings structural parameter
What can see is, the cycloalkanes carbon of this part coking distillate divides rate higher, therefore the reactive hydrogen atom concentration passed out at the large aromaticity free radical of Shi Suoneng to other easy condensation green coke that be heated is higher, therefore in delay coking process, with this part cut, circulated, certainly will be able to suppress tube coking and shot coke generation, reduce coke yield, improve the yield of the oily product of liquid distillate.The alkyl carbon of this hydrogen supply wax oil component divides rate lower, the quantity minimum that is generated free radical while being heated by this part alkyl carbon is described, thereby the probability that consumes self potential hydrogen supply capacity is minimum, so, the relative hydrogen supply capacity of this hydrogen supply cut wax oil may be the strongest (supplying the hydrogen index (HI) maximum).From table 2, see, after adding the hydrogen supply agent wax tailings, liquid yield and green coke amount have had improvement.
The variation of table 2 liquid receipts and green coke amount
Embodiment 2:
A kind of typical hydrogen supply agent cut character is in Table 1.
Table 3 hydrogen supply agent wax tailings structural parameter
The variation of table 4 liquid receipts and green coke amount
Can see, the cycloalkanes carbon of this part coking distillate divides rate lower, and the alkyl carbon of this hydrogen supply wax oil component divides rate higher, so its effect after adding does not have distillate D good, green coke amount and liquid are received poor effect.
Claims (2)
1. add the method for coking distillate hydrogen supply coking in a residual oil, it is characterized in that: after coking distillate is mixed by the weight ratio of 0.2-0.4 with coking raw material residual oil, be introduced into the preheating of process furnace convection zone, enter again surge tank, then, after entering the process furnace radiation section and being heated to coking temperature, enter the coking tower coking; 480~520 ℃ of reaction tower temperature ins, pressure is 0.1~1.0MPa.
2. according to adding the method for coking distillate hydrogen supply coking in residual oil claimed in claim 1, it is characterized in that: described coking distillate is coker gas oil, coking stage casing cut, coking light wax oil, coking wax slop.
Priority Applications (1)
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CN201210152634XA CN103421538A (en) | 2012-05-15 | 2012-05-15 | Method for adding coking distillate oil into residual oil for hydrogen supply coking |
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CN201210152634XA CN103421538A (en) | 2012-05-15 | 2012-05-15 | Method for adding coking distillate oil into residual oil for hydrogen supply coking |
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CN201210152634XA Pending CN103421538A (en) | 2012-05-15 | 2012-05-15 | Method for adding coking distillate oil into residual oil for hydrogen supply coking |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105331390A (en) * | 2015-11-27 | 2016-02-17 | 中国海洋石油总公司 | Method for delaying coking by supplying hydrogen |
CN105505449A (en) * | 2015-11-27 | 2016-04-20 | 中国海洋石油总公司 | Hydrogen-donor coking method |
CN105885939A (en) * | 2014-12-15 | 2016-08-24 | 中石化洛阳工程有限公司 | Method for processing deoiled asphalt |
CN105885933A (en) * | 2014-12-15 | 2016-08-24 | 中石化洛阳工程有限公司 | Deoiled asphalt processing method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA845721B (en) * | 1983-08-01 | 1986-03-26 | Mobil Oil Corp | Process for visbreaking resids in the presence of hydrogen-donor materials |
US5711870A (en) * | 1996-05-28 | 1998-01-27 | Texaco Inc. | Delayed coking process with water and hydrogen donors |
CN1297979A (en) * | 1999-12-01 | 2001-06-06 | 中国石油化工集团公司 | Method of producing acicular petroleum coke from residual oil |
CN1580194A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | High-yield chemical light oil delayed coking method |
CN101302435A (en) * | 2008-06-20 | 2008-11-12 | 中国石油大学(华东) | Improved method of delay coking process |
-
2012
- 2012-05-15 CN CN201210152634XA patent/CN103421538A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA845721B (en) * | 1983-08-01 | 1986-03-26 | Mobil Oil Corp | Process for visbreaking resids in the presence of hydrogen-donor materials |
US5711870A (en) * | 1996-05-28 | 1998-01-27 | Texaco Inc. | Delayed coking process with water and hydrogen donors |
CN1297979A (en) * | 1999-12-01 | 2001-06-06 | 中国石油化工集团公司 | Method of producing acicular petroleum coke from residual oil |
CN1580194A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | High-yield chemical light oil delayed coking method |
CN101302435A (en) * | 2008-06-20 | 2008-11-12 | 中国石油大学(华东) | Improved method of delay coking process |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105885939A (en) * | 2014-12-15 | 2016-08-24 | 中石化洛阳工程有限公司 | Method for processing deoiled asphalt |
CN105885933A (en) * | 2014-12-15 | 2016-08-24 | 中石化洛阳工程有限公司 | Deoiled asphalt processing method |
CN105331390A (en) * | 2015-11-27 | 2016-02-17 | 中国海洋石油总公司 | Method for delaying coking by supplying hydrogen |
CN105505449A (en) * | 2015-11-27 | 2016-04-20 | 中国海洋石油总公司 | Hydrogen-donor coking method |
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Application publication date: 20131204 |