CN1003601B - Catalytic cracking-catalytic heavy oil aromatic extraction combined process - Google Patents
Catalytic cracking-catalytic heavy oil aromatic extraction combined process Download PDFInfo
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- CN1003601B CN1003601B CN87107146.0A CN87107146A CN1003601B CN 1003601 B CN1003601 B CN 1003601B CN 87107146 A CN87107146 A CN 87107146A CN 1003601 B CN1003601 B CN 1003601B
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- 238000000605 extraction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000295 fuel oil Substances 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 title 1
- 239000002904 solvent Substances 0.000 claims abstract description 74
- 239000003921 oil Substances 0.000 claims abstract description 43
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 31
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 claims description 23
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 22
- 230000010354 integration Effects 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 241000282326 Felis catus Species 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007701 flash-distillation Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000003502 gasoline Substances 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The catalytic cracking-catalytic heavy oil aromatic hydrocarbon extraction combined process combines a catalytic cracking process and a double-solvent aromatic hydrocarbon extraction process, and can reduce the coke yield, improve the processing capacity of a catalytic cracking device and obtain high-purity heavy petroleum aromatic hydrocarbon in order to adapt to the process of the heavy conversion of catalytic cracking raw oil.
Description
The present invention relates to the improvement of petroleum refining process method, it comprises catalytic cracking process and combines with the aromatic hydrocarbons technology in the solvent pairs extracting catalysis heavy oil, be characterized in to adapt to the heaviness (its boiling range scope is 300-530 ℃) of catalytically cracked stock, reduce coke yield, improve the catalytic cracking unit processing power.
At present a large amount of research and design effort are improvement or the development of new catalyzer round catalytic cracking process.The general treatment process that catalysis heavy oil is adopted has two kinds: first method is full freshening and part freshening, and its recycle ratio is 0.3～0.7.Second method is that catalysis heavy oil is thrown away device, promptly gets rid of slurry oil, and the amount of throwing away is the 5-12% of stock oil.Above-mentioned two kinds of methods all have its weak point; The shortcoming of first method is heavy arene circulation constantly in catalytic cracking unit, thereby produce a large amount of coke and dry gas, only generate a spot of gasoline and diesel oil, constantly increase new heavy arene again simultaneously, so just reduced the throughput of catalytic cracking unit.Whole slurry oils that throw away that alternative plan is used have lost the fine quality catalytic cracking raw material oil that accounts for the whole amount of throwing away 40-60% again.At United States Patent (USP) (3239456,3317423,4304660) disclose catalytic lightweight oil of employing solvent pairs extracting and mink cell focus in, its objective is in order to obtain certain Chemicals and raw material thereof, for example make the raw material of naphthalene, make the sooty raw material and produce ice machine oil etc.
The objective of the invention is to solve weak point in the above-mentioned prior art, set about from the chemical composition analysis of catalysis heavy oil, wherein aromaticity content is a 30-60%(weight), this is the undesirable components in the catalytic cracking unit stock oil, also has 40-70%(weight) alkane and naphthenic hydrocarbon be desirable component.The present invention adopts the solvent pairs extraction process, the used solvent of extraction process has phenol, sulfoxide, dimethyl pyrrolidone, dried furfural, the wet furfural of 5-8% moisture, and aromaticity content≤5%(weight) lightweight oil, its boiling range scope is between 80-200 ℃, and best fraction is 90-120 ℃.It is first solvent that the present invention selects furfural for use, and lightweight oil is as second solvent, and highly selective is extracted the heavy arene in the catalysis heavy oil out, can improve the processing power of catalytic cracking unit, reduce the productive rate of coke and dry gas, improve gasoline yield, and can obtain high purity heavy crude aromatic hydrocarbons.For this reason, the present invention proposes combining technique of catalytic cracking and extraction of heavy oil aroma.
Purpose of the present invention reaches by following measure; Catalytically cracked stock 1 enters catalytic cracking unit 2, gained catalysis heavy oil 3 enters flashing tower (A) 4, the flashing tower cat head must do≤and 330 ℃ fraction 5 incorporates catalytic diesel oil 28 into and goes out device as product together, is that initial boiling point is that 〉=330 ℃ the catalysis heavy oil 6 that pulls out enters solvent pairs extraction tower 7 at the bottom of the flash distillation Tata.Solvent cycle jar 22, it is divided into furfural, three layers of water and lightweight oils.Moisture furfural 24 enters solvent pairs extraction tower top, and lightweight oil 23 enters solvent pairs extraction tower bottom, carries out the solvent pairs extracting in tower, and extraction temperature is that cat head is 60-100 ℃, and tower middle part is 50-75 ℃, at the bottom of the tower about 40 ℃.Solvent ratio is a raw material: furfural: lightweight oil (weight ratio) is 1: 0.5～2.5: 0.2～1.0, and the optimum solvent ratio is 1: 0.5～1.0: 0.3～0.6.By the change of solvent ratio, can control of the variation of the aromatic hydrocarbons sucrose extraction of catalysis heavy oil in 50～95% scopes.Solvent pairs extraction tower 7 top distilled raffinates 8 enter raffinate stripping tower 10, and solvent 11 enters solvent tank 22, the gained 12 Returning catalyticing cracking device circulation crackings of raffinating oil at the bottom of the raffinate stripping tower.Gained Extract 9 enters flashing tower (B) 13 at the bottom of the solvent pairs extraction tower, the flash distillation cat head distillates solvent 14 and enters solvent tank 22, Extract 15 enters extract stripper 16 at the bottom of the flashing tower, the stripping cat head distillates solvent 17 and enters solvent tank 22, can obtain purity 〉=95%(weight at the bottom of the stripping tower) heavy crude aromatic hydrocarbons 18 go out device as product.
Adopted the combining technique of catalytic cracking and extraction of heavy oil aroma coke yield to descend 0.4～1.0%, the catalytic cracking unit processing power has improved 5-25%; Total liquid is received and has been increased by 3.2%; Obtained purity 〉=95%(weight) heavy crude aromatic hydrocarbons; Can reduce reacted gas productive rate 1～2%, improve yield of gasoline 2.5～3.0%, the diesel yield 2-6% that descended.
Description of drawings:
Figure one is the combining technique of catalytic cracking and extraction of heavy oil aroma schema.Among the figure:
1. catalytically cracked stock
2. catalytic cracking unit
3. catalysis heavy oil
4. flashing tower (A)
5. diesel oil
6. pull out a catalysis heavy oil
7. solvent pairs extraction tower
8. raffinate
9. Extract
10. raffinate stripping tower
11. solvent
12. raffinate oil
13. flashing tower (B)
14. solvent
15. Extract
16. extract stripper
17. solvent
18. heavy crude aromatic hydrocarbons
19. dehydration tower
20. solvent
21. waste water
22. solvent tank
23. second solvent (lightweight oil)
24. first solvent (moisture furfural)
25. contain aldehyde water
26. reacted gas
27. gasoline
28. diesel oil
29. coke
30. steam
31. steam
Embodiment 1
Year treatment capacity be on 1,000,000 tons the catalytic cracking unit, mix year treatment capacity and be 25～350,000 tons solvent extraction device, to remove the heavy arene component in the catalysis heavy oil, with rich alkane component again Returning catalyticing cracking device carry out cracking, constitute combining technique of catalytic cracking and extraction of heavy oil aroma provided by the present invention.
The raw materials used oil of catalytic unit, it is intermediate base crude oil gained decompressed wax oil, or mix the refining some amount the available domestic Shandong crude oil of vacuum residuum (5～25%), with Shandong crude oil and central plain oil commingled crude (the domestic pipeline oil that is called), the decompressed wax oil of gained is made the stock oil of catalytic cracking.Also available pipeline oil gained decompressed wax oil is mixed the raw material that the vacuum residuum that refines same stock oil gained is done catalytic cracking jointly, behind the employing process integration, all obtains good result.
The general flow chart of process integration is seen Fig. 1.
Catalytic cracking gained catalysis heavy oil enters flashing tower (A) 4 through 3.Go into 360～375 ℃ of tower temperature, flash off the heavy gas oil component, can be used as catalytic diesel oil and go out device, also can be used as the light cycle oil of catalytic cracking with tower 4 tops.Obtain the catalysis heavy oil of initial boiling point 〉=330 ℃ at the bottom of the tower, as extracting raw material 6.
6 enter solvent pairs extraction tower 7, and stock oil enters from tower 7 middle parts, and first solvent 24 is gone in tower 7 jackings, and in the upper semisection of tower 7, stock oil 6 and first solvent, 24 counter current contact are to extract the heavy arene in fuel-displaced 6.Extract that flows downward from tower 7 middle parts and second solvent, 23 counter current contact that enter from tower 7 bottoms go out alkane component in the Extract with second solvent exchange, reach the purpose of purification heavy arene.
Tower 7 extraction temperatures, cat head is 60～100 ℃, is 50～75 ℃ in the tower, at the bottom of the tower about 40 ℃; Solvent ratio is a catalysis heavy oil: first solvent: second solvent=1: 0.5～1.0: 0.3～0.6.Full tower number of theoretical plate is 7～10.
Raffinate 8 enters stripping tower 10, and to reclaim solvent, going into the tower temperature is 210～225 ℃, and tower 10 top temperature are 100～135 ℃, and 10 end of tower temperature is 210～225 ℃, and the stripped vapor amount is into 3～6% of tower amount.
Extract 9 enters flashing tower (B) 13, and the recovery part solvent is gone into 180～200 ℃ of tower temperature, 100～160 ℃ of cats head.At the bottom of the tower about 200 ℃.
Enter stripping tower 16 from 13 end of tower gained Extract 15, with in 15 all solvents drive out of.Operational condition and tower 10 are basic identical.16 ends of tower, obtain the high purity heavy arene.
From tower 10, tower 13, first, second solvent of tower 16 top gained enters circulation tank 22 after condensation, in jar 22, be divided into three layers; First solvent layer, contain aldehyde water layer and moisture aldehyde layer.
First solvent layer, returns into tower 7 and recycles through 24 through 23, the second solvent layers.Jar 22 temperature are at 30～40 ℃, in order to layering.
Contain aldehyde water and enter dehydration tower 19 through 25, tower 19 pushes up to such an extent that aldehyde water azeotrope returns jar 22, and the sewage that 19 ends of tower must remove aldehyde goes out device.
After process integration, can reduce reacted gas productive rate 1～2%, improve yield of gasoline 2.5～3.0%; Diesel yield has descended 2～6%; Coke yield descends 0.5～1.0%; Treatment capacity can improve 5～25%.
Embodiment 2
Result and this process integration of catalytic cracking being mixed refining residual oil and externally extracting oil contrast.
Mix in the fcc raw material and refined 25.4% vacuum residuum.The fcc raw material carboloy residue is 4.5%.
Per hour 100 tons/hour of the chargings of former catalytic unit, (800,000 tons of year treatment capacities), adopt process integration after charging bring up to 107.5 tons/hour, 36 tons/hour of the extraction plant chargings supporting with it.(300,000 tons of year treatment capacities) solvent ratio is 1: 0.6: 0.3; Promptly first solvent and the second solvent feed amount are 21.6 tons/hour and 10.8 tons/hour.The gained amount of raffinating oil is 30 tons/hour, and the Returning catalyticing cracking device cracking in addition, obtains 6 tons/hour heavy arene, and its aromatic hydrocarbons+gum level is that 96.8%(is heavy).Aromatic hydrocarbon oil sucrose extraction 20%(is heavy).
Now with former catalytic unit and combining technique of catalytic cracking and extraction of heavy oil aroma, product yield of both gained and output are listed in the table below.
Both catalytic cracking conditions are identical, temperature of reaction: 482 ℃, and agent-oil ratio: 5.0, the reaction times: 2.79 seconds.
Process integration and externally extracting oil contrast, yield of gasoline increases by 2.9%, and reacted gas has reduced by 1.1%; Coke has reduced by 0.4%; Diesel yield is low 2.1%; Get rid of 4.9% slurry oil outside former, become the outer heavy arene 5.6% that gets rid of.
The actual output of vapour, diesel oil (light oil output) has increased by 6.6 tons/hour.Treatment capacity has improved 7.5%.
Former catalytic cracking
Process integration
Process integration output
% ton/hour ton/hour
Treatment capacity ton/hours 100-107.5-
Catalysis gas 8.9 8.9 7.8 8.4
Gasoline 46.7 46.7 49.6 53.3
Diesel oil 30.1 30.1 28.0 30.1
Externally extracting oil 4.9 4.9 00
Heavy arene 00 5.6 6.0
Coke 9.4 9.4 9.0 9.7
Claims (6)
1, the aromatic hydrocarbons extracting process integration of catalytic cracking-catalysis heavy oil is that the heavy oil with catalytic cracking unit carries out the solvent pairs extracting, it is characterized in that catalytic cracking unit stock oil 1 enters catalytic cracking unit 2, gained catalysis heavy oil 3 enters flashing tower (A) 4, the flash distillation cat head distillates and does≤and 330 ℃ fraction 5 incorporates catalytic diesel oil 28 into and goes out device as product together, distillate initial boiling point at the bottom of the flashing tower and enter solvent pairs extraction tower 7 for 〉=330 ℃ the catalysis heavy oil 6 that pulls out, solvent cycle jar 22, it is divided into first solvent, three layers of the water and second solvents, first solvent 24 enters solvent pairs extraction tower top, second solvent 23 enters solvent pairs extraction tower bottom, solvent-laden water 25 enters dehydration tower 19 and reclaims solvent, and solvent cycle is used; Solvent pairs extraction tower 7 top distilled raffinates 8 enter the surplus liquid stripping tower 10 of suction, and solvent 11 enters solvent tank 22, the gained 12 Returning catalyticing cracking device circulation crackings of raffinating oil at the bottom of the raffinate stripping tower; Gained Extract 9 enters flashing tower (B) 13 at the bottom of the solvent pairs extraction tower, the flash distillation cat head distillates solvent 14 and enters solvent tank 22, distilled Extract 15 enters Extract extraction tower 16 at the bottom of the flashing tower, the stripping cat head distillates solvent 17 and enters solvent tank 22, gets heavy crude aromatic hydrocarbons 18 at the bottom of the stripping tower and goes out device as product.
2, according to the aromatic hydrocarbons extracting process integration of right 1 described catalytic cracking-catalysis heavy oil, it is characterized in that the heavy oil of catalytic unit comprises recycle stock, reprocessed oil slurry or externally extracting oil, its boiling range scope is 300～530 ℃.
3, according to the aromatic hydrocarbons extracting process integration of right 1 described catalytic cracking-catalysis heavy oil, it is characterized in that the first used solvent of extraction plant has furfural, phenol, sulfoxide and dimethyl pyrrolidone, second solvent is a lightweight oil.
4, according to the aromatic hydrocarbons extracting process integration of right 1 or 3 described catalytic cracking-catalysis heavy oil, it is characterized in that extraction plant adopts dried furfural, or the wet furfural that contains 5～8% moisture content is as first solvent; Adopt aromaticity content≤5%(weight), boiling range scope the best at 90-120 ℃ lightweight oil as second solvent.
5,, it is characterized in that to obtain behind the extraction plant gained Extract desolventizing heavy crude aromatic hydrocarbons of purity 〉=95% according to the aromatic hydrocarbons extracting process integration of right 1 described catalytic cracking-catalysis heavy oil.
6, according to the aromatic hydrocarbons extracting process integration of right 1 described catalytic cracking-catalysis heavy oil, it is characterized in that solvent pairs extraction tower extraction temperature, tower top temperature 60-100 ℃, tower middle part temperature is 50-75 ℃, column bottom temperature 20-70 ℃; Solvent ratio is a raw material: furfural: lightweight oil (weight ratio) is 1: 0.5～1.0: 0.3～0.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107146.0A CN1003601B (en) | 1987-10-30 | 1987-10-30 | Catalytic cracking-catalytic heavy oil aromatic extraction combined process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107146.0A CN1003601B (en) | 1987-10-30 | 1987-10-30 | Catalytic cracking-catalytic heavy oil aromatic extraction combined process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87107146A CN87107146A (en) | 1988-04-13 |
| CN1003601B true CN1003601B (en) | 1989-03-15 |
Family
ID=4815992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107146.0A Expired CN1003601B (en) | 1987-10-30 | 1987-10-30 | Catalytic cracking-catalytic heavy oil aromatic extraction combined process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003601B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350020C (en) * | 2005-10-26 | 2007-11-21 | 邓先樑 | Catalyzing and cracking process of inferior oil |
| CN102816594A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Residual oil hydrotreating-catalytic cracking-solvent refining combined process |
Families Citing this family (10)
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|---|---|---|---|---|
| CN1064390C (en) * | 1996-09-06 | 2001-04-11 | 中国石油化工总公司 | Double-solvant extraction for inferior paraffin base oil |
| CN1061366C (en) * | 1997-12-08 | 2001-01-31 | 中国石油化工总公司 | Extraction method for faulty wax oil solvent |
| CN101921623B (en) * | 2009-09-18 | 2013-09-04 | 北京金伟晖工程技术有限公司 | Method with tow double hydrogenation units for preparing high-quality diesel |
| CN102051215A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for producing needle coke by combined process |
| CN101906319B (en) * | 2010-08-10 | 2013-04-17 | 华南理工大学 | Method for pre-processing raw materials for catalytic reforming device and device thereof |
| CN102453503B (en) * | 2010-10-25 | 2014-04-30 | 中国石油化工股份有限公司 | Method for extracting and separating aromatic hydrocarbon and saturated hydrocarbon in catalytic cracking slurry oil |
| CN102863987A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrocarbon oil pretreatment and catalytic cracking combined technology |
| CN104004540A (en) * | 2014-05-29 | 2014-08-27 | 嘉诚(福建)石油化工有限公司 | Method and device for separating heavy aromatics from catalytic cracking oil slurry |
| CN105505463B (en) * | 2015-11-27 | 2017-05-31 | 中国石油大学(北京) | RFCC method and apparatus |
| CN110157404B (en) * | 2019-05-30 | 2020-11-13 | 东北石油大学 | Ecological environment-friendly oil field displacement of reservoir oil system |
-
1987
- 1987-10-30 CN CN87107146.0A patent/CN1003601B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100350020C (en) * | 2005-10-26 | 2007-11-21 | 邓先樑 | Catalyzing and cracking process of inferior oil |
| CN102816594A (en) * | 2011-06-10 | 2012-12-12 | 中国石油天然气股份有限公司 | Residual oil hydrotreating-catalytic cracking-solvent refining combined process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN87107146A (en) | 1988-04-13 |
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