CN103131466A - Aromatic hydrocarbon-rich wax oil hydrotreating method - Google Patents
Aromatic hydrocarbon-rich wax oil hydrotreating method Download PDFInfo
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- CN103131466A CN103131466A CN2011103802354A CN201110380235A CN103131466A CN 103131466 A CN103131466 A CN 103131466A CN 2011103802354 A CN2011103802354 A CN 2011103802354A CN 201110380235 A CN201110380235 A CN 201110380235A CN 103131466 A CN103131466 A CN 103131466A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 55
- 239000007792 gaseous phase Substances 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000005504 petroleum refining Methods 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract 4
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 239000010779 crude oil Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- -1 2 compressors Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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Abstract
The invention relates to a hydrotreating method of wax oil rich in aromatic hydrocarbon; raw oil rich in aromatic wax oil and a gas-phase material from the second heat high-pressure separator are mixed and then enter the first reactor, a reaction product of the first reactor enters the first heat high-pressure separator, a liquid-phase material from the first heat high-pressure separator and circulating hydrogen are mixed and then enter the second reactor, the gas-phase material is cooled and then enters the cold high-pressure separator, the gas obtained by desulfurizing the gas-phase material from the cold high-pressure separator through a hydrogen sulfide removal tower is pressurized by a compressor and then mixed with the circulating hydrogen, a reaction product of the second reactor enters the second heat high-pressure separator, the liquid-phase material from the second heat high-pressure separator and the liquid-phase product from the cold high-pressure separator are mixed and decompressed and then enter the heat low-pressure separator, and the gas-phase material from the heat low-pressure separator and the liquid-phase material from the heat low-; the reaction result of the process shows that the aromatic hydrocarbon saturation rate is obviously improved, and the cracking performance of the wax oil rich in aromatic hydrocarbon can be greatly improved.
Description
Technical field
The present invention relates to a kind of aromatic hydrocarbons wax oil hydrogenation treatment process that is rich in, be rich in the aromatic hydrocarbons wax oil and be the wax oil cut of 350～600 ℃.
Background technology
In high position concussion, in the situation that oil property becomes heavy, variation gradually, the price difference of crude oil with poor quality and ordinary crude oils has the trend of increasing to the our times crude oil price always.For obtaining economic benefit preferably, many enterprises target lock-on in the processing of crude oil with poor quality.Crude oil with poor quality particularly high-acid crude oil belongs to naphthenic base crude more, and except sulphur, nitrogen, acid number height, aromaticity content is very high, cracking performance is very poor, show the shortcoming that the petrol and diesel oil yield is low, coking yield is high when catalyzed cracking processing, affect the economic benefit of device, be necessary to carry out upgrading and processing.
Hydrotreatment has the cracking performance that improves the FCC charging, reduce the catalysis green coke, increase the light-end products productive rate, reduce the product sulphur content, reduce SOX and the NOX content in the FCC flue gas and improve the advantages such as FCC apparatus processing inferior raw material ability, therefore can for the user creates good economic benefit, obtain using more and more widely.Under the prevailing general layout of China's oil refining industry catalytic cracking process, the hydrotreatment technology that development FCC raw material particularly is rich in the faulty wax oil of aromatic hydrocarbons has the meaning that is even more important.
Summary of the invention
The purpose of this invention is to provide a kind of aromatic hydrocarbons wax oil wax oil cut of 350～600 ℃ (be rich in the aromatic hydrocarbons wax oil be) Deep Hydrotreating method that is rich in, can effectively improve desulfurization and aromatic saturation rate under the reaction conditions of routine, have the partition zone optimizing reaction conditions, improve the characteristics of hydrogenation wax oil cracking performance, need in the impurity such as desulfurization nitrogen, increase substantially the requirement of aromatic saturation rate for being rich in the aromatic hydrocarbons wax oil.
The present invention is rich in aromatic hydrocarbons wax oil hydrogenation treatment process and is comprised following content:
at first enter the first reactor after being rich in aromatic hydrocarbons wax oil stock oil and the second high pressure hot separator gaseous phase materials that is rich in hydrogen out mixing of pressurizeing of heating, the first reactor reaction product enters the first high pressure hot separator, the liquid phase material of the first high pressure hot separator with enter the second reactor after circulating hydrogen mixes, the gaseous phase materials of the first high pressure hot separator enters cold high pressure separator after cooling, the cold high pressure separator gaseous phase materials mixes with circulating hydrogen after the compressed machine of the gas after the de-hydrogen sulfide column desulfurization boosts, hydrogen source for system, the second reactor reaction product enters the second high pressure hot separator, the second high pressure hot separator liquid phase material enters thermal low-pressure separators mix decompression with the liquid product of cold high pressure separator after, isolate the thermal low-pressure separators gaseous phase materials and the thermal low-pressure separators liquid phase material is processed into respectively various product,
Described the first reactor operating condition is reaction pressure 4～20MPa, hydrogen to oil volume ratio 100: 1～1500: 1, volume space velocity 0.1～8.0h
-1, 270～450 ℃ of temperature of reaction;
The optimum operation condition of described the first reactor is reaction pressure 6～12MPa, hydrogen to oil volume ratio 300: 1～1000: 1, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
Described the second reactor operating condition is reaction pressure 4～20MPa, hydrogen to oil volume ratio 100: 1～1500: 1, volume space velocity 0.1～8.0h
-1, 240～450 ℃ of temperature of reaction.
The optimum operation condition of described the second reactor is reaction pressure 6～12MPa, hydrogen to oil volume ratio 300: 1～1000: 1, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
Described the second reactor is than the first high 0.1～1.0MPa of reactor reaction pressure, low 5～40 ℃ of temperature of reaction, and hydrogen to oil volume ratio is high 100: 1～and 400: 1.
The described aromatic hydrocarbons wax oil that is rich in is one or more mixing oils in the decompressed wax oil that obtains in petroleum refining process, deasphalted oil, wax tailings, catalytic cycle oil, or from the corresponding cut of coal tar, shale oil or oil sands bitumen.
Described two hydrogenator Hydrobon catalysts are identical or different.
Described the second reactor uses refining and cracking combination catalyst.
Can find out by top embodiment, because the hydrogen hydrogen sulfide content of the second reactor is very low, the hydrogen dividing potential drop is higher, can guarantee sufficiently high desulfurization degree.Simultaneously, owing to adopting lower temperature of reaction, be conducive to the hydrogenation saturated reaction of aromatic hydrocarbons, reaction result shows that the aromatic saturation rate is significantly improved, and can improve by a relatively large margin the cracking performance that is rich in the aromatic hydrocarbons wax oil.
Description of drawings
Fig. 1 is a kind of process flow diagram of the present invention.
wherein: 1 circulating hydrogen, 2 compressors, gas after 3 desulfurization, 4 de-hydrogen sulfide columns, 5 cold high pressure separators, 6 first high pressure hot separator gaseous phase materials, 7 first high pressure hot separators, 8 first reactors, 9 stock oils, 10 first reactor reaction products, 11 first high pressure hot separator liquid phase materials, 12 are rich in the gaseous phase materials of hydrogen, 13 second high pressure hot separators, 14 second reactor reaction products, 15 second reactors, 16 second high pressure hot separator liquid phase materials, 17 thermal low-pressure separators, 18 thermal low-pressure separators gaseous phase materials, 19 thermal low-pressure separators liquid phase materials, the liquid product of 20 cold high pressure separators,
Embodiment
at first enter the first reactor 8 after being rich in aromatic hydrocarbons wax oil stock oil 9 and the second high pressure hot separator 13 gaseous phase materials that is rich in hydrogen 12 out mixing of pressurizeing of heating, the first reactor reaction product 10 enters the first high pressure hot separator 7, the liquid phase material 11 of the first high pressure hot separator with enter the second reactor 15 after circulating hydrogen 1 mixes, the gaseous phase materials 6 of the first high pressure hot separator enters cold high pressure separator 5 after cooling, the cold high pressure separator gaseous phase materials mixes with circulating hydrogen 1 after the compressed machine 2 of the gas 3 after de-hydrogen sulfide column 4 desulfurization boosts, hydrogen source for system, the second reactor reaction product 14 enters the second high pressure hot separator 13, the second high pressure hot separator liquid phase material 16 enters thermal low-pressure separators 17 mix decompression with the liquid product 20 of cold high pressure separator after, isolate thermal low-pressure separators gaseous phase materials 18 and thermal low-pressure separators liquid phase material 19 is processed into respectively various product.
Embodiment
Below by embodiment, the present invention program and effect are described.
Table 1 stock oil main character
| Project | Venezuela's wax oil | Domestic mixed gatch |
| Density (20 ℃)/g/ml | 0.9660 | 0.9310 |
| The boiling range scope, ℃ | 350～520 | 360～600 |
| Sulphur content, wt% | 3.3 | 3.1 |
| Aromaticity content, wt% | 72 | 58 |
Table 2 hydrotreating catalyst main character
| Project | 3936 |
| MoO 3，wt％ | 24.5 |
| NiO，wt％ | 3.8 |
| Specific surface, m2/g | Greater than 160 |
| Pore volume, ml/g | 0.33 |
Table 3 embodiment processing condition and reaction result
Can find out by top embodiment, because the hydrogen hydrogen sulfide content of the second reactor is very low, the hydrogen dividing potential drop is higher, can guarantee sufficiently high desulfurization degree.Simultaneously, owing to adopting lower temperature of reaction, be conducive to the hydrogenation saturated reaction of aromatic hydrocarbons, reaction result shows that the aromatic saturation rate is significantly improved, and can improve by a relatively large margin the cracking performance that is rich in the aromatic hydrocarbons wax oil.
Claims (7)
1. one kind is rich in aromatic hydrocarbons wax oil hydrogenation treatment process, is rich in the aromatic hydrocarbons wax oil and is the wax oil cut of 350～600 ℃, it is characterized in that:
at first enter the first reactor after being rich in aromatic hydrocarbons wax oil stock oil and the second high pressure hot separator gaseous phase materials that is rich in hydrogen out mixing of pressurizeing of heating, the first reactor reaction product enters the first high pressure hot separator, the liquid phase material of the first high pressure hot separator with enter the second reactor after circulating hydrogen mixes, the gaseous phase materials of the first high pressure hot separator enters cold high pressure separator after cooling, the cold high pressure separator gaseous phase materials mixes with circulating hydrogen after the compressed machine of the gas after the de-hydrogen sulfide column desulfurization boosts, hydrogen source for system, the second reactor reaction product enters the second high pressure hot separator, the second high pressure hot separator liquid phase material enters thermal low-pressure separators mix decompression with the liquid product of cold high pressure separator after, isolate the thermal low-pressure separators gaseous phase materials and the thermal low-pressure separators liquid phase material is processed into respectively various product,
Described the first reactor operating condition is reaction pressure 4～20MPa, hydrogen to oil volume ratio 100: 1～1500: 1, volume space velocity 0.1～8.0h
-1, 270～450 ℃ of temperature of reaction;
Described the second reactor operating condition is reaction pressure 4～20MPa, hydrogen to oil volume ratio 100: 1～1500: 1, volume space velocity 0.1～8.0h
-1, 240～450 ℃ of temperature of reaction.
2. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1, it is characterized in that: the described aromatic hydrocarbons wax oil that is rich in is one or more mixing oils in the decompressed wax oil that obtains in petroleum refining process, deasphalted oil, wax tailings, catalytic cycle oil, or from the corresponding cut of coal tar, shale oil or oil sands bitumen.
3. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1, it is characterized in that: the operational condition of described the first reactor is reaction pressure 6～12MPa, hydrogen to oil volume ratio 300: 1～1000: 1, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
4. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1, it is characterized in that: the operational condition of described the second reactor is reaction pressure 6～12MPa, hydrogen to oil volume ratio 300: 1～1000: 1, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
5. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1 is characterized in that: described second reaction zone is than the first high 0.1～1.0MPa of reaction zone pressure, low 5～40 ℃ of temperature of reaction, and hydrogen to oil volume ratio is high 100: 1～and 400: 1.
6. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1, it is characterized in that: described two hydrogenator Hydrobon catalysts are identical or different.
7. the aromatic hydrocarbons wax oil hydrogenation treatment process that is rich according to claim 1 is characterized in that: described the second reactor uses refining and cracking combination catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103802354A CN103131466A (en) | 2011-11-25 | 2011-11-25 | Aromatic hydrocarbon-rich wax oil hydrotreating method |
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| CN2011103802354A CN103131466A (en) | 2011-11-25 | 2011-11-25 | Aromatic hydrocarbon-rich wax oil hydrotreating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239555A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | Processing method of poor quality catalytic cracking raw material |
| CN110013757A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | The Combined type safety processing unit and method of the hydrogeneous periodic off-gases of aromatic hydrogenation system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822476A (en) * | 1986-08-27 | 1989-04-18 | Chevron Research Company | Process for hydrodewaxing hydrocracked lube oil base stocks |
| CN101003748A (en) * | 2007-01-22 | 2007-07-25 | 中国石油天然气华东勘察设计研究院 | Flow for separating outflow from hydrogenation reaction |
| CN101376841A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Heavy fraction oil hydrotreating method |
| CN101987967A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Hydrotreatment method of deep vacuum distillation wax oil |
-
2011
- 2011-11-25 CN CN2011103802354A patent/CN103131466A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822476A (en) * | 1986-08-27 | 1989-04-18 | Chevron Research Company | Process for hydrodewaxing hydrocracked lube oil base stocks |
| CN101003748A (en) * | 2007-01-22 | 2007-07-25 | 中国石油天然气华东勘察设计研究院 | Flow for separating outflow from hydrogenation reaction |
| CN101376841A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Heavy fraction oil hydrotreating method |
| CN101987967A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Hydrotreatment method of deep vacuum distillation wax oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239555A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | Processing method of poor quality catalytic cracking raw material |
| CN108239555B (en) * | 2016-12-23 | 2020-06-09 | 中国石油天然气股份有限公司 | Processing method of poor quality catalytic cracking raw material |
| CN110013757A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | The Combined type safety processing unit and method of the hydrogeneous periodic off-gases of aromatic hydrogenation system |
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Application publication date: 20130605 |