CN1068623C - Method for inhibiting coke generation of heating-furnace - Google Patents
Method for inhibiting coke generation of heating-furnace Download PDFInfo
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- CN1068623C CN1068623C CN97121634A CN97121634A CN1068623C CN 1068623 C CN1068623 C CN 1068623C CN 97121634 A CN97121634 A CN 97121634A CN 97121634 A CN97121634 A CN 97121634A CN 1068623 C CN1068623 C CN 1068623C
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- oil
- inhibitor
- coking
- green coke
- residual oil
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000571 coke Substances 0.000 title description 21
- 230000002401 inhibitory effect Effects 0.000 title 1
- 239000003921 oil Substances 0.000 claims abstract description 53
- 239000003112 inhibitor Substances 0.000 claims abstract description 33
- 238000004939 coking Methods 0.000 claims abstract description 27
- 239000000295 fuel oil Substances 0.000 claims abstract description 17
- 230000003111 delayed effect Effects 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 239000002010 green coke Substances 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004230 steam cracking Methods 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract 4
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a method for restraining from coking in heating furnaces of heavy oil and residual oil. The present invention adopts a coking inhibitor to add in the heavy oil or the residual oil, the boiling range of the inhibitor is from 350 to 550 DEG C, the aromatic content is larger than 60m%, and the content of double rings and three-rings is more than 30m%. The added quantity of the coking inhibitor is from 1 to 30m% of heavy oil or residual oil. The method can be applied to the heating furnaces of processing devices of the heavy oil or the residual oil, such as reduced pressure distillation, delayed coking, fluid coking, thermal cracking, visbreaking, etc. The method can effectively restrain from coking in the heating furnaces, and can enhance the processing capacity of the heating furnaces.
Description
The invention belongs to the heavy oil and the residual oil deep processing technology in oil refining field, relate generally to the technology that suppresses heavy oil and residual oil green coke in process furnace.
Heavy oil and residual oil generate the coke of different quantities because of being heated in furnace tubing, cause coking, influence heat-transfer effect, even form local superheating and obstruction accident.Improve the processing power of process furnace, then need improve the cold oil linear speed in the boiler tube, correspondingly will increase hot strength, under higher hot strength, the life/coking in the boiler tube will more become seriously, become the further important factor of raising process furnace processing power of restriction.Feedstock property variation in boiler tube, when adopting once by technology as delayed coking, the coking of raw material tendency is bigger in the boiler tube, prevents or reduces life/coking in the boiler tube, is the key problem in technology of realizing once by technology.
Heavy oil and residual oil are heated when reacting, and saturated branch and light fragrance divide the main scission reaction that takes place, and contract and react seldom.Colloid is except that having small part generation scission reaction, and quite a large amount of colloids contracts and becomes secondary bituminous matter and toluene insolubles.Bituminous matter just can spontaneous generation free radical when being lower than 400 ℃, except that dealkylation seldom, the auto-polymerization reaction mainly takes place generate more macromolecular polycondensation asphalt matter, and deposition further forms coke.Along with the further raising of temperature of reaction, cause the increase of the free radical that produces, thereby cause more serious polycondensation, generate coke.Therefore, the polycondensation asphalt matter that bitum autohemagglutination produces is the major cause of green coke, and suppresses the generation or the termination of free radical, just becomes to prevent or reduce one of green coke method.China is heavy, the asphalt content of residual oil is generally less than 1%, and colloid is up to 30～50%, so the characteristics of the weight of China, residual oil green coke mainly are the results of the further polycondensation of secondary bituminous matter that generates of colloid condensation.
According to colloid property heavy, residual oil, the colloid and the heavy arene of bituminous matter and or inner absorption surperficial at its constitute colloidal disperse phase (micella), and saturated branch and fragrance branch constitute dispersion medium.This is the thermodynamic instability system.Any factor that causes that the adsorption equilibrium between disperse phase and the medium moves all will be destroyed the type of system.Therefore, keep the good peptization of system, the micella that bituminous matter is formed does not deposit, and is the another kind of method that prevents or reduce green coke.
Patent WO94/06889 has proposed a kind of method that reduces coking in the steam cracking furnace, and its principle is to introduce metal ion to carry out catalysis and impel the coke vaporization to generate CO
2Or CO, reaching the purpose that reduces coking, its suitable raw material is C2～C4 alkane, light, heavy naphtha and fraction of diesel oil.
Patent USP5221462 utilizes hydrogenated quinoline to be that inhibitor suppresses coking in the steam cracking furnace, and its suitable raw material is C2～C4 alkane, light, heavy naphtha and fraction of diesel oil.
The way that utilize to improve heavy, residual oil peptization and suppress free radical reaction suppresses the research of coke generation of heating-furnace and is applied in all to find report in the domestic and foreign literature.
The object of the present invention is to provide a kind of method of utilizing the way that improves weight, residual oil peptization and suppress free radical reaction to suppress coke generation of heating-furnace.
Method of the present invention is: add the green coke inhibitor in heavy oil that passes through process furnace or residual oil raw material, described green coke inhibitor is a kind of refinery products, its boiling range is 350～550 ℃, best boiling range is 350～500 ℃, aromaticity content is greater than 60m%, the best is more than the 70m%, and wherein dicyclo+three ring content is more than the 30m%, and the best is more than the 40m%; The add-on of green coke inhibitor accounts for the 1m%～30m% of heavy oil or residual oil, and the best is 3～20m%.
Above-mentioned green coke inhibitor is rich in aromatic hydrocarbons and some amount colloid, and it is added in heavy oil or the residual oil, can improve the peptization of heavy oil or residual oil, and in being subjected to thermal process, it all has peptization preferably to primary or secondary bituminous matter, suppresses their deposition.Polycyclic aromatic hydrocarbons is rich in α hydrogen again simultaneously, has good hydrogen supply performance, and the Hydrogen Energy of nascent state is ended free radical reaction rapidly.In addition, this inhibitor viscosity is lower, and the viscosity of mixing raw material is reduced, and reduces near the retention layer thickness of tube wall, and this also helps reducing green coke.
Green coke inhibitor of the present invention can derive from refinery and petroleum chemical enterprise, as the wax oil and the turning oil of hot-work such as delayed coking, fluid coking, thermally splitting and eureka production; The solvent-extracted oil of catalytic cracking recycle oil and slurry oil etc.; Lubex, the tar of preparing ethylene by steam cracking etc.
The present invention can be used for: the process furnace of underpressure distillation, delayed coking, fluid coking, thermally splitting, viscosity breaking etc. and visbreaking reactor etc., suppress the life/coking of heat-processed.Can inject the green coke inhibitor at the process furnace inlet, also can inject before the stock oil heat exchange, the latter can also reduce the life/coking problem of heat-exchange system.Inhibitor once uses, and need not circulate specially, and it does not have disadvantageous effect to the product of above-mentioned each technology.When using in delayed coking process, it can also produce the part lighting end and improve the quality of coke.
The pyrogenic coke generation of heating-furnace experiment of analogue delay shows that it is obvious that the present invention suppresses the green coke effect.When green coke inhibitor add-on is 3～8m%, under the same conditions, compare with not adding the green coke inhibitor, in the time of reaching identical predetermined boiler tube pressure and fall, boiler tube is handled oil mass can increase by 1.3～1.7 times.If be defined as 1.0, add coke forming property behind the green coke inhibitor (do not add the oil inlet quantity of agent/add agent oil inlet quantity) so and can drop to 0.6～0.8 with the coke forming property that does not add the green coke inhibitor.
Be embodiments of the invention below:
Embodiment 1
Certain wax tailings (CGO) and catalytic cracking recycle oil (RCO), after furfural and the extracting of back suction agent solvent pairs, it is extracted oil out and makes the green coke inhibitor.Their saturated hydrocarbon content is less than 2m%, and aromaticity content is greater than more than the 70m%, and dicyclo and thrcylic aromatic hydrocarbon content are respectively 44.9m% and 46.7m%.Its main character such as table 1.Be analogue delay coking or viscosity breaking coke generation of heating-furnace situation, designed a cover simulation testing apparatus, the furnace tubing of this device is of a size of, 10 millimeters of external diameters, and 2 millimeters of wall thickness, are heated by the electric furnace automatic control by long 1.5 meters.When under a certain steady temperature and cold oil linear speed, pump into vacuum residuum and test.Along with the increase of green coke amount, the boiler tube inlet outlet pressure differential increases gradually, stops test when reaching predetermined 0.5Mpa.The coke forming property of how much passing judgment on oil inlet quantity.Suppose that under the same conditions the coke forming property when not adding the green coke inhibitor is 1.0, the coke forming property that adds the green coke inhibitor is defined as:
The oil inlet quantity of coke forming property=do not add green coke inhibitor/the add oil inlet quantity of green coke inhibitor
This value is less than 1, and numerical value is more little, and the expression coke forming property is low more.
Test vacuum residuum of usefulness and test-results see Table 2 and table 3 respectively.The I agent of green coke inhibitor in the table 1.As can be seen, use the green coke inhibitor after, coke forming property obviously reduces, only be unconstrained dose 58～59%; When reaching identical coking degree, can multiprocessing about 1.7 times stock oil.Table 1 green coke inhibitor
Table-2 stock oil character
Table-3 analog reslts
| The green coke inhibitor | CGO extracts oil (I) out | RCO extracts oil (II) out |
| Density d 20 4g/cm 3 | 1.0134 | 1.0283 |
| Condensation point ℃ | 22 | 14 |
| Carbon residue m% | 3.58 | 2.14 |
| Viscosity 100℃mm 2/s | 32.82 | 13.62 |
| Molecular weight | 294 | 275 |
| 10～95% ℃ of boiling ranges | 370～507 | 380～500 |
| Group composition: stable hydrocarbon m% | 1.5 | 0.4 |
| Aromatic hydrocarbons m% | 73.1 | 97.8 |
| Monocycle | 19.1 | 25.0 |
| Dicyclo | 20.5 | 17.4 |
| Three rings | 24.4 | 29.3 |
| More than the Fourth Ring reaches | 9.1 | 26.1 |
| Colloid+bituminous matter m% | 25.4 | 1.8 |
| Density d 20 4g/cm 3 | 0.9845 | Stable hydrocarbon m% | 19.8 |
| Condensation point ℃ | 45 | Aromatic hydrocarbons m% | 35.9 |
| Viscosity 100℃ mm 2/s | 2045 | Colloid m% | 43.1 |
| Bituminous matter m% | 1.2 |
| Temperature ℃ in the process furnace | 450 | 500 | ||
| Cold oil linear speed m/s | 1.0 | 1.0 | ||
| Initial boiler tube inlet outlet pressure differential MPa | 0.01 | 0.01 | ||
| Stop boiler tube inlet outlet pressure differential MPa | 0.5 | 0.5 | ||
| Green coke inhibitor add-on m% | / | 5 | / | 5 |
| Handle oil mass L | 459 | 796 | 408 | 694 |
| Coke forming property | 1 | 0.58 | 1 | 0.59 |
Embodiment 2
With testing apparatus among the embodiment 1 and stock oil, estimated the II green coke inhibitor in the table 1, to the influence of different add-ons.It the results are shown in table-4, and as can be seen, the II agent has good green coke to suppress effect equally, and with the increase of add-on, it is more obvious to suppress effect.Table-4 analog reslts
| Temperature ℃ in the process furnace | 500 | |||
| Cold oil linear speed m/s | 1.0 | |||
| Initial inlet outlet pressure differential MPa | 0.01 | |||
| Stop inlet outlet pressure differential MPa | 0.5 | |||
| Add dosage m% | / | 2 | 4 | 6 |
| Handle oil mass L | 408 | 523 | 600 | 668 |
| Coke forming property | 1 | 0.78 | 0.68 | 0.61 |
Claims (4)
1, a kind of method that suppresses heavy oil and residual oil green coke in process furnace, it is characterized in that: in heavy oil that passes through process furnace or residual oil raw material, add the green coke inhibitor, this green coke inhibitor is a kind of refinery products, its boiling range is 350～550 ℃, aromaticity content is 60m%～98m%, wherein dicyclo+three ring content is 30m%～47m%, and the add-on of green coke inhibitor accounts for the 1m%～30m% of heavy oil or residual oil.
2, method according to claim 1 is characterized in that: the boiling range of employed inhibitor is 350～500 ℃, and aromaticity content is 70m%～98m%, and wherein dicyclo+three ring content is 40m%～47m%; The add-on of green coke inhibitor accounts for the 3m%～20m% of heavy oil or residual oil total amount.
3, method according to claim 1, it is characterized in that: employed inhibitor derives from wax oil and the turning oil that delayed coking, fluid coking, thermally splitting and eureka hot-work are produced, the solvent-extracted oil of catalytic cracking recycle oil and slurry oil, lubex, the tar of preparing ethylene by steam cracking.
4, method according to claim 1 is characterized in that: this method can be used for the heavy oil or the residual oil processing unit (plant) of underpressure distillation, delayed coking, fluid coking, thermally splitting, viscosity breaking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121634A CN1068623C (en) | 1997-11-19 | 1997-11-19 | Method for inhibiting coke generation of heating-furnace |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121634A CN1068623C (en) | 1997-11-19 | 1997-11-19 | Method for inhibiting coke generation of heating-furnace |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1217372A CN1217372A (en) | 1999-05-26 |
| CN1068623C true CN1068623C (en) | 2001-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97121634A Expired - Fee Related CN1068623C (en) | 1997-11-19 | 1997-11-19 | Method for inhibiting coke generation of heating-furnace |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1751257A2 (en) * | 2004-05-14 | 2007-02-14 | Exxonmobil Research And Engineering Company | Inhibitor enhanced thermal upgrading of heavy oils |
| CN100338191C (en) * | 2005-07-21 | 2007-09-19 | 中国石油化工集团公司 | Anti-coking agent, and its preparation and use method |
| CN100503789C (en) * | 2007-04-24 | 2009-06-24 | 中国石油化工集团公司 | Coking inhibitor and preparation method and application thereof |
| CN103160308B (en) * | 2011-12-15 | 2015-02-25 | 中国石油天然气股份有限公司 | A Method for Preventing Coking of Inferior Heavy Oil Visbreaking Heating Furnace |
| CN102559237A (en) * | 2012-01-29 | 2012-07-11 | 何巨堂 | Coal-based oil distillation method using thermal condensation inhibited oil |
| CN103555363B (en) * | 2013-11-01 | 2015-08-19 | 中国海洋石油总公司 | A kind of high containing acid starting material oil hydrogen supply delayed coking method |
| CN106609145B (en) * | 2017-01-02 | 2019-02-15 | 深圳市科拉达精细化工有限公司 | Ethylene cracking tar makees the pretreating process of delayed coking raw material |
| CN109705897B (en) * | 2017-10-26 | 2021-06-11 | 中国石油化工股份有限公司 | Residual oil hydrogenation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246991A (en) * | 1985-12-20 | 1987-10-28 | Res Assoc Residual Oil Process<Rarop> | Thermal cracking treatment for cracked heavy fraction |
| CN1018402B (en) * | 1989-06-10 | 1992-09-23 | 韩商三星电子股份有限公司 | Sense amplifier driver for memory device |
| US5211836A (en) * | 1992-03-12 | 1993-05-18 | Betz Laboratories, Inc. | Reaction products of polyalkenyl succinic anhydrides with aromatic secondary amines and aminoalcohols as process antifoulants |
| CN1140197A (en) * | 1995-03-23 | 1997-01-15 | 菲利浦石油公司 | Method for providing furnace tubes with coke and carbon monoxide formation inhibiting properties for thermal cracking of hydrocarbons |
-
1997
- 1997-11-19 CN CN97121634A patent/CN1068623C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246991A (en) * | 1985-12-20 | 1987-10-28 | Res Assoc Residual Oil Process<Rarop> | Thermal cracking treatment for cracked heavy fraction |
| CN1018402B (en) * | 1989-06-10 | 1992-09-23 | 韩商三星电子股份有限公司 | Sense amplifier driver for memory device |
| US5211836A (en) * | 1992-03-12 | 1993-05-18 | Betz Laboratories, Inc. | Reaction products of polyalkenyl succinic anhydrides with aromatic secondary amines and aminoalcohols as process antifoulants |
| CN1140197A (en) * | 1995-03-23 | 1997-01-15 | 菲利浦石油公司 | Method for providing furnace tubes with coke and carbon monoxide formation inhibiting properties for thermal cracking of hydrocarbons |
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| CN1217372A (en) | 1999-05-26 |
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