CN102268292A - Combined hydrogenation method - Google Patents
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- CN102268292A CN102268292A CN2010101960147A CN201010196014A CN102268292A CN 102268292 A CN102268292 A CN 102268292A CN 2010101960147 A CN2010101960147 A CN 2010101960147A CN 201010196014 A CN201010196014 A CN 201010196014A CN 102268292 A CN102268292 A CN 102268292A
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Abstract
The invention discloses a combined hydrogenation method. Reaction effluent of a medium and high pressure hydrogenation device is separated in a high pressure separator of the medium and high pressure hydrogenation device, high fraction oil enters a low pressure separator, one part of the separated high fraction gas enters a recycle hydrogen compressor to serve as recycle hydrogen to return to a reactor of the medium and high pressure hydrogenation device, and the other part of the separated high fraction gas is dissolved in a liquid-solid two-phase hydrogenation material, so that a liquid-solid two-phase hydrogenation device is not provided with a new hydrogen compressor, and investment is saved.
Description
Technical field
The present invention relates to the hydrocarbon oil hydrogenation technology, particularly the combined hydrogenation Technology.
Background technology
The sustainable development of world economy and the increasingly stringent of environmental regulation need to produce a large amount of light clean fuels at present, and these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.Along with the worsening shortages of crude resources and heaviness, poor qualityization development, distillate hydrogenation technology has obtained widespread use in Clean Fuel Production.
Tradition hydrocarbon oil hydrogenation process reaction system needs a large amount of hydrogen to guarantee certain hydrogen dividing potential drop, and wherein sub-fraction hydrogen falls by the hydrogenation consumption of chemical reaction, and major part recycles after being boosted by circulating hydrogen compressor.
Conventional hydrogenation technique is (as residual hydrogenation, the wax oil hydrogenation cracking, wax oil hydrogenation is handled, diesel oil hydrofining, diesel oil hydrogenation modification, devices such as hydrodewaxing, hereinafter to be referred as " mesohigh hydrogenation unit ") employing hydrogen recycle flow process, coming the reaction product of autoreactor to carry out gas-liquid after cooling off under high-pressure separator specified temp and pressure is separated, the high score aerial root can be selected whether carry out amine through the desulphurization of recycle hydrogen tower according to arts demand and wash, hydrogen purity about 80～95% (v), after circulating hydrogen compressor boosts, mix and heat up with the new hydrogen that boosts through make-up hydrogen compressor, enter reactor and stock oil again and hydrogenation reaction takes place under catalyst action (referring to the publication of in July, 2000 oil industry press, the woods generation ruler of great talent and bold vision compiles the petroleum refining engineering third edition, the 422nd～423 page).Because the processing condition of different fractions oil hydrogenation unit are different, the high-pressure separator pressure range is between 5.0～18.0MPa (G).
Hydrogen such as part mesohigh hydrogenation unit employing membrane sepn are put forward dense facility raising recycle hydrogen purity and are guaranteed the reactive hydrogen dividing potential drop, be that recycle hydrogen enters unit such as membrane sepn after a part of desulfurization, carry dense back hydrogen through carrying the dense hydrogen compressor Returning reacting system that boosts, tail gas send the fuel gas pipe network or (China petrochemical industry press publishes referring in January, 2008 as the device for producing hydrogen raw material, direction is edited oil refining process technical knowledge book series morning, hydrofining, the 349th～350 page).
CN101338219 discloses a kind of two-phase hydrogenation method, hydrogen is dissolved in fresh feed oil and the turning oil, form mixture flow and enter reactor, liquid contacts with catalyzer and reacts, residual gas is discharged from reactor head, a reaction effluent part is as turning oil, and another part enters light pressure separator and carries out gas-liquid separation after the dropping valve step-down.Compare with conventional hydrogenation technique, high pressure equipment such as circulating hydrogen compressor, high pressure heat exchanger, high-pressure air cooler and high-pressure separator have been cancelled, strengthen the touch opportunity of fresh feed oil and hydrogen and catalyzer, improve mass transfer and speed of response, reduced reactor volume, the reaction pressure that has reduced investment and process cost liquid-solid two-phase hydrogenation technology is between 4.0～12.0MPa.Because and therefore the reaction raw materials of hydrogenation need to sneak into the hydrogen supercharging in fresh feed oil and the turning oil between 4.0～12.0MPa, i.e. make-up hydrogen compressor, though liquid-solid two-phase hydrogenation without circulating hydrogen compressor, make-up hydrogen compressor is must setting.As everyone knows, the output investment ratio of the compressor of hydrogen is higher, occupies bigger ratio in the investment of whole hydrogenation unit.
The quantity of hydrogenation unit is more and more in the modernization factory, the reaction conditions difference of different device is also very big, if can keep the hydrogen of traditional hydrogenation process to divide pressure request, can rationally utilize the hydrogen of each hydrogenation unit again, to reduce investment outlay greatly and cut down the consumption of energy, safe, efficient, the economical operation of enterprise brought benefit.
Summary of the invention
The present invention proposes a kind of combined hydrogenation method,, effectively utilize the purity and the pressure of this part hydrogen the recycle hydrogen of part mesohigh hydrogenation unit new hydrogen as liquid-solid two-phase hydrogenation.
A kind of combined hydrogenation method of the present invention, its step is as follows:
1) parallel feeding of mesohigh hydrogenation unit enters into the High-pressure Hydrogenation Unit reactor and reacts, mesohigh hydrogenation unit reaction effluent carries out in mesohigh hydrogenation unit high-pressure separator, isolated mesohigh hydrogenation unit high score oil enters mesohigh hydrogenation unit light pressure separator, an isolated mesohigh hydrogenation unit separator hydrogen part enters circulating hydrogen compressor and returns mesohigh hydrogenation unit reactor as recycle hydrogen, and isolated mesohigh hydrogenation unit separator hydrogen another part enters into step 2);
2) isolate mesohigh hydrogenation unit separator hydrogen another part hydrogen from step 1), and enter the liquid-solid two-phase hydrogenation reactor after the liquid-solid two-phase hydrogenation raw material mixes.Described a kind of combined hydrogenation method is characterized in that: isolate mesohigh hydrogenation unit separator hydrogen another part hydrogen, and enter the liquid-solid two-phase hydrogenation reactor after the liquid-solid two-phase hydrogenation raw material mixes in mixing tank.
Described a kind of combined hydrogenation method is characterized in that: it is that the pressure of the high-pressure separator of described mesohigh hydrogenation unit is greater than 4.5MPa greater than 4.5MPa that the mesohigh hydrogenation unit has a hydrogenation unit working pressure at least.
Described a kind of combined hydrogenation method is characterized in that: it is characterized in that: the pressure of the high-pressure separator of mesohigh hydrogenation unit is at least than the high 0.5MPa of pressure of liquid-solid two-phase hydrogenation device mixing dissolver.
Mesohigh hydrogenation unit of the present invention is the hydrogenation unit of various hydrocarbon ils, as: hydrogenation units such as hydrotreatment, hydrocracking and hydrofining, particularly residual hydrocracking, wax oil hydrogenation cracking, wax oil hydrogenation processing, gasoline and diesel oil hydrofining, diesel oil hydrogenation modification, diesel hydro-pour-reducing, lube hydrotreating, mineral spirit platreating.
Mesohigh hydrogenation unit catalyst system therefor of the present invention is conventional hydrogenation catalyst, and operational condition is the operational condition of the mesohigh hydrogenation unit of routine.
Liquid-solid two-phase hydrogenation device of the present invention is the hydrogenation unit of hydrocarbon oil refining, as the liquid-solid two-phase hydrogenation device of petroleum naphtha, kerosene, diesel oil, wax oil.
The catalyzer that liquid-solid two-phase hydrogenation device of the present invention uses is the hydrogenation catalyst of routine, and operational condition is the operational condition of the liquid-solid two-phase hydrogenation device of routine.
Combined hydrogenation method of the present invention is meant the combination of two or more devices under the prerequisite that hydrogen pressure can utilize step by step.
The present invention in mesohigh hydrogenation unit high-pressure separator cutting out partial hydrogen as the sources of hydrogen of liquid-solid two-phase hydrogenation device, the make-up hydrogen compressor of liquid-solid two-phase hydrogenation device can be set on the one hand, reduce investment, on the other hand, for the mesohigh hydrogenation unit, use new hydrogen replenishment cycles hydrogen amount, so promptly improved the hydrogen dividing potential drop in the mesohigh hydrogenation unit, the carrying out that helps hydrogenation reaction, reduced again that hydrogen sulfide has also lowered the stagnation pressure of mesohigh hydrogenation unit to the influence of hydrogenation reaction in the recycle hydrogen.
For the mesohigh hydrogenation unit, during normal operation since the foreign matter content in the recycle hydrogen improve gradually, must emit a part, could guarantee the purity of recycle hydrogen, satisfy the needs of mesohigh hydrogenation, generally be to send PSA device recover hydrogen, perhaps enter the fuel pipe network and burn, take which kind of method all can waste hydrogen and its pressure.
Compared with prior art, combined hydrogenation method of the present invention has following advantage:
1) reduces plant investment;
2) made full use of the pressure of hydrogen, reduced the consumption of energy, process cost is lower;
3) for the mesohigh hydrogenation unit: because the discharge unit recycle hydrogen, improved hydrogen purity, thus the reaction stagnation pressure that has reduced;
4) for the mesohigh hydrogenation unit: solved mesohigh hydrogenation unit discharge cycle hydrogen problem of outlet;
5) for the liquid-solid two-phase hydrogenation device: because hydrogen itself is exactly high pressure hydrogen, saved make-up hydrogen compressor, simplified flow process;
6) flexibility of operation;
Description of drawings
Fig. 1 is a kind of combined hydrogenation method schematic flow sheet of the present invention.
1. mesohigh hydrogenation unit fresh feed oil, 2. the new hydrogen of mesohigh hydrogenation unit, 3. mesohigh hydrogenation unit mixing hydrogen, 4. mesohigh hydrogenation unit parallel feeding, 5. mesohigh hydrogenation unit reactor, 6. mesohigh hydrogenation unit reaction effluent, 7. mesohigh hydrogenation unit high-pressure separator, 8. mesohigh hydrogenation unit recycle hydrogen, 9. mesohigh hydrogenation unit high score oil, 10. mesohigh hydrogenation unit light pressure separator, 11. mesohigh hydrogenation unit separation column charging, 12. the low gas that divides of mesohigh hydrogenation unit, 13. mesohigh hydrogenation unit separator hydrogen, 14. liquid-solid two-phase hydrogenation device fresh feed oil, 15. liquid-solid two-phase hydrogenation device mixing raw material oil, 16. liquid-solid two-phase hydrogenation device mixing dissolver, 17. liquid-solid two-phase hydrogenation device parallel feeding, 18. liquid-solid two-phase hydrogenation device reaction device, 19. liquid-solid two-phase hydrogenation device waste gas, 20. liquid-solid two-phase hydrogenation device turning oils, 21. liquid-solid two-phase hydrogenation device reaction effluent, 22. liquid-solid two-phase hydrogenation device separator, 23. liquid-solid two-phase hydrogenation device separator gas, 24. liquid-solid two-phase hydrogenation device reaction products.
Embodiment
As shown in Figure 1, a kind of combined hydrogenation method, concrete steps are:
Mesohigh hydrogenation unit fresh feed oil 1 mesohigh hydrogenation unit mixing hydrogen 3 is mixed into mesohigh hydrogenation unit parallel feeding 4, enter in the mesohigh hydrogenation unit reactor 5 and react, mesohigh hydrogenation unit reaction effluent 6 enters into mesohigh hydrogenation unit high-pressure separator 7 and carries out gas-liquid separation, isolated hydrogen partial is mixed into mesohigh hydrogenation unit mixing hydrogen 3 as recycle hydrogen 8 with new hydrogen 2, another part hydrogen is that mesohigh hydrogenation unit separator hydrogen 13 is mixed into liquid-solid two-phase hydrogenation device parallel feeding 17 with liquid-solid two-phase hydrogenation device mixing raw material oil 15 in liquid-solid two-phase hydrogenation device mixing dissolver 16, liquid-solid two-phase hydrogenation device parallel feeding 17 enters liquid-solid two-phase hydrogenation device reaction device 18 and carries out hydrogenation reaction, liquid-solid two-phase hydrogenation device reaction effluent 21 parts are as liquid-solid two-phase hydrogenation device turning oil 20, liquid-solid two-phase hydrogenation device turning oil 20 is mixed into liquid-solid two-phase hydrogenation device mixing raw material oil 15 with liquid-solid two-phase hydrogenation device fresh feed oil 14 and enters liquid-solid two-phase hydrogenation device mixing dissolver 16, another part of liquid-solid two-phase hydrogenation device reaction effluent 21 enters in the liquid-solid two-phase hydrogenation device separator 22 and carries out gas-liquid separation, isolates liquid-solid two-phase hydrogenation device separator gas 23 and liquid-solid two-phase hydrogenation device reaction product 24.
Claims (6)
1. a combined hydrogenation method is characterised in that, the steps include:
1) parallel feeding of mesohigh hydrogenation unit enters into mesohigh hydrogenation unit reactor and reacts, mesohigh hydrogenation unit reaction effluent separates in mesohigh hydrogenation unit high-pressure separator, isolated mesohigh hydrogenation unit high score oil enters mesohigh hydrogenation unit light pressure separator, an isolated mesohigh hydrogenation unit high score gas part enters circulating hydrogen compressor and returns mesohigh hydrogenation unit reactor as recycle hydrogen, and another part enters into step 2);
2) enter the liquid-solid two-phase hydrogenation reactor after isolating mesohigh hydrogenation unit separator hydrogen another part hydrogen and the liquid-solid two-phase hydrogenation raw material mixes from step 1).
2. according to the described combined hydrogenation method of claim 1, it is characterized in that: enter the liquid-solid two-phase hydrogenation reactor after isolating mesohigh hydrogenation unit separator hydrogen another part hydrogen and the liquid-solid two-phase hydrogenation raw material mixing in mixing tank.
3. according to the described combined hydrogenation method of claim 1, it is characterized in that: it is greater than 4.5MPa that the mesohigh hydrogenation unit has a hydrogenation unit working pressure at least.
4. according to the described combined hydrogenation method of claim 1, it is characterized in that: the pressure of the high-pressure separator of mesohigh hydrogenation unit is greater than 4.5MPa.
5. according to the described combined hydrogenation method of claim 1, it is characterized in that: the pressure of the high-pressure separator of mesohigh hydrogenation unit is at least than the high 0.5MPa of liquid-solid two-phase hydrogenation device mixing dissolver pressure.
6. according to the described combined hydrogenation method of claim 1, it is characterized in that: isolate mesohigh hydrogenation unit separator hydrogen another part hydrogen and mix with the liquid-solid two-phase hydrogenation raw material through after the desulfurization.
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| CN201010196014.7A CN102268292B (en) | 2010-06-07 | 2010-06-07 | Combined hydrogenation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789016A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | Combined distillate oil hydroprocessing method |
| CN103789017A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | A hydrogenation combination process for distillate oil |
| CN108865237A (en) * | 2018-06-01 | 2018-11-23 | 金澳科技（湖北）化工有限公司 | A kind of recycle hydrogen recovery system and method |
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| WO2003086567A1 (en) * | 2002-04-05 | 2003-10-23 | Fluor Corporation | Combined hydrotreating process and configurations for same |
| CN1962829A (en) * | 2006-12-04 | 2007-05-16 | 中国石油化工集团公司 | Hydrogenation method for making clean fuels |
| CN101376836A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Cycloalkyl secondary processing gasoline and diesel hydrogenation method |
| CN101434864A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Coking light distillate hydrogenation modification method |
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2010
- 2010-06-07 CN CN201010196014.7A patent/CN102268292B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003086567A1 (en) * | 2002-04-05 | 2003-10-23 | Fluor Corporation | Combined hydrotreating process and configurations for same |
| CN1962829A (en) * | 2006-12-04 | 2007-05-16 | 中国石油化工集团公司 | Hydrogenation method for making clean fuels |
| CN101376836A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Cycloalkyl secondary processing gasoline and diesel hydrogenation method |
| CN101434864A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Coking light distillate hydrogenation modification method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789016A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | Combined distillate oil hydroprocessing method |
| CN103789017A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | A hydrogenation combination process for distillate oil |
| CN103789016B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Combined distillate oil hydroprocessing method |
| CN103789017B (en) * | 2012-11-03 | 2015-12-02 | 中国石油化工股份有限公司 | A kind of distillate hydrogenation combined technical method |
| CN108865237A (en) * | 2018-06-01 | 2018-11-23 | 金澳科技（湖北）化工有限公司 | A kind of recycle hydrogen recovery system and method |
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| CN102268292B (en) | 2014-02-26 |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: China Petrochemical Group Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant before: China Petrochemical Group Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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