CN101979469B - Method for removing free oxygen from inferior hydrogenation raw oil - Google Patents
Method for removing free oxygen from inferior hydrogenation raw oil Download PDFInfo
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- CN101979469B CN101979469B CN 201010546934 CN201010546934A CN101979469B CN 101979469 B CN101979469 B CN 101979469B CN 201010546934 CN201010546934 CN 201010546934 CN 201010546934 A CN201010546934 A CN 201010546934A CN 101979469 B CN101979469 B CN 101979469B
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Abstract
The invention discloses a method for removing free oxygen from inferior hydrogenation raw oil. In the method, the inferior hydrogenation raw oil is heated and then conveyed to a flash tower, the free oxygen in the inferior hydrogenation raw oil is carried away by evaporated light components, the light components are condensed to recover light oil which is to be returned to the flash tower, non-condensable gas is exhausted, and the inferior hydrogenation raw oil in the flash tower is used as the feedstock of a hydrogenation device. Compared with the prior art, the method in the invention is simple, feasible and low in investment, prolongs the operation period of the hydrogenation device considerably and is suitable for the hydrogenation process of inferior raw oil, particularly the hydrogenation process of high free oxygen-concentration inferior raw oil.
Description
Technical field
The present invention relates to the deep processing of hydrogenating materials oil inferior, particularly relate to a kind of method of removing free oxygen from inferior hydrogenation raw oil.
Background technology
Crude benzol, coal tar, coker gasoline, biomass pyrolysis oil, tire wet goods inferior feedstock oil pass through hydro-upgrading, remove wherein sulphur, nitrogen, oxygen, metallic impurity, the compound such as saturation of olefins, aromatic hydrocarbons improves its stability, can obtain high-quality clean fuel oil and industrial chemicals.This not only meets national energy strategy and Environment Protection Policy, and can bring good economic benefit for enterprise.
But the free oxygen that exists in these hydrogenating materials oil inferior has obvious promoter action to coking.Free oxygen can make the aromatic thiol oxidation in hydrogenating materials oil inferior produce sulfonic acid, and sulfonic acid and pyrroles condensation reaction occur produce sediment; In addition, alkene and the oxygen formation oxidation products that can react, oxidation products forms sediment with the active heteroatomic compound polymerization reaction take place of sulfur-bearing, nitrogen, oxygen again.And sediment is the precursor of coking, and they are easily in the further condensation coking of equipment high temperature position.If in hydrogenating materials oil inferior, free oxygen level is higher, be easy to cause its bad stability, and easily form coking at high temperature equipment such as raw materials furnace and heating, interchanger and hydrogenator tops, and cause the device unplanned shutdown, affect the long-term operation of hydrogenation unit.Therefore, suppress hydrogenating materials oil inferior coking and realize that the key of hydrogenation unit long-period stable operation is the free oxygen content that reduces in hydrogenating materials oil inferior, generally should be lower than 5 μ L/L.
At present, delaying hydrogenating materials oil inferior is the method that adopts the pre-hydrogenation of catalyzer at the conventional treatment method of beds coking, namely at first easily carries out main hydrogenation after the organic compound of coking removing the heteroato mic organic compounds such as part sulphur, nitrogen, oxygen, saturated diolefine, vinylbenzene etc. under the effect of the temperature of 150～300 ℃ and catalyzer again.But due to temperature required higher, hydrogenating materials oil inferior might coking in the high temperature heat-exchange equipments such as interchanger, process furnace before entering pre-hydrogenator, also coking may appear when entering pre-hydrogenator top bed, when particularly the free oxygen concentration in oil was higher, this coking situation just more likely occured.
Therefore, for preventing the coking and blocking problem in pre-hydrogenation process, generally before the pre-hydrogenation of hydrogenating materials oil inferior, it is carried out pre-treatment.Technique as the employings such as CN200610028263, CN200610018476, CN200400123146.4 distillation removes heavy constituent in coal tar, namely removes the coking precursorses such as colloid, bituminous matter, also can play the effect that removes free oxygen simultaneously.But the method has been removed heavy component, has wasted valuable tar resource, and cutting temperature is high, and investment is large, and energy consumption is high.The service temperature of 300～360 ℃ also easily causes the distillation tower coking in addition.
Adopt in addition in addition thinning oil technique, technology of electric de-salting, add the methods such as coke inhibitor to come the restraining device coking, but all can not remove the free oxygen in hydrogenating materials oil inferior.
Summary of the invention
The purpose of this invention is to provide a kind ofly be applicable to full cut hydrogenating materials oil inferior hydrogenation technique, simple, energy consumption is low, without the method for free oxygen in removing of coking hydrogenating materials oil inferior.
Content of the present invention is achieved through the following technical solutions: a kind of method of removing free oxygen from inferior hydrogenation raw oil, it is characterized in that: will be transported in flashing tower after hydrogenating materials oil inferior heating, evaporate by light constituent the free oxygen in hydrogenating materials oil inferior is carried out, light constituent reclaims light oil by condensation, light oil is back in flashing tower, non-condensable gas carries out emptying, and the hydrogenating materials oil inferior in flashing tower is as the hydrogenation unit charging.
Described hydrogenating materials oil inferior is coal tar, crude benzol, coker gasoline, biomass pyrolysis oil, tire wet goods hydrogenating materials inferior.Coal tar, crude benzol are the liquid product of by-product in the dry distillation of coal, gasification, can be used as clean fuel oil and the sale of high quality chemical product by hydrogenation; Coker gasoline is the Partial Liquid Phase product that the black petroleum products coking obtains; Biomass thermal cracking oil, tire wet goods are the organic oil product of liquid phase that thermo-cracking obtains.Above-mentioned inferior feedstock oil has produced a large amount of unsaturated olefins in thermal cracking processes, if dissolved a certain amount of free oxygen in accumulating and the course of processing, the character of low grade oils is sharply worsened, and subsequent treatment process is made troubles.
Described hydrogenating materials oil Heating temperature scope inferior is 70 ~ 150 ℃.The poor heat stability of hydrogenating materials oil inferior, more responsive to temperature.Too high flash vaporization point though be conducive to reduce the meltage of free oxygen, easily causes hydrogenating materials oil inferior coking; Too low flash vaporization point causes light oil to carry the effect of free oxygen in hydrogenating materials oil inferior bad.Therefore, consider temperature comparatively suitable at 70-150 ℃.
It is relatively poor that the inventive method is equally applicable to character, can be used as shale oil and the coal-based liquefaction oil of hydrogenating materials oil inferior.
Compare with existing other processing method, the present invention has the following advantages:
(1) automatization is controlled, and is simple to operation.
(2) the present invention only need make and enter flashing tower after the heat exchange of hydrogenating materials inferior oil and can realize, less investment, technical process is simple, energy consumption is low.
(3) deoxidation effect is good, and to delaying the coking successful of hydrogenation process, the hydrogenation unit cycle of operation obviously extends.
(4) be applicable to the hydrogenating materials oil hydrogenation technique inferior of full cut.
(5) be applicable to the high hydrogenating materials oil inferior of free oxygen content and carry out hydro-upgrading.
The inventive method can improve the working time of a whole set of inferior feedstock oil hydrogenation unit greatly, and is specially adapted to the high hydrogenating materials oil inferior of free oxygen concentration.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
Coal tar is heated to 120 ℃, and with being pumped in flashing tower, the tower top light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas enters blowdown system, and in tower, coal tar is as the hydrogenation unit charging, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after coal tar hydrogenating charging flash distillation on the 100ml hydrogenation unit sees Table 1.
The cycle of operation after the flash distillation of table 1 coal tar
| The coal tar hydrogenating charging | Install runtime, h |
| Be untreated | 348 |
| After flash distillation | 1860 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 1.
Embodiment 2
Coker gasoline is heated to 120 ℃, and with being pumped in flashing tower, the tower top light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas enters blowdown system, and in tower, coker gasoline is as the hydrogenation unit charging, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after Hydrogenation of Coker Gasoline charging flash distillation on the 100ml hydrogenation unit sees Table 2.
The cycle of operation after the flash distillation of table 2 coker gasoline
| The Hydrogenation of Coker Gasoline charging | Install runtime, h |
| Be untreated | 256 |
| After flash distillation | 1782 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 2.
Embodiment 3
Crude benzol is heated to 70 ℃, and with being pumped in flashing tower, the tower top light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas enters blowdown system, and in tower, crude benzol is as the hydrogenation unit charging, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after crude benzole hydrogenation charging flash distillation on the 100ml hydrogenation unit sees Table 3.
The cycle of operation after the flash distillation of table 3 crude benzol
| The crude benzole hydrogenation charging | Install runtime, h |
| Be untreated | 196 |
| After flash distillation | 2006 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 3.
Embodiment 4
Biomass thermal cracking oil is heated to 150 ℃, with being pumped in flashing tower, the tower top light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas enters blowdown system, tower endogenous substance thermal cracking oil is as the hydrogenation unit charging, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the biomass thermal cracking oil flash distillation on the 100ml hydrogenation unit sees Table 4.
The cycle of operation after the flash distillation of table 4 biomass thermal cracking oil
| Biomass thermal cracking oil | Install runtime, h |
| Be untreated | 315 |
| After flash distillation | 2268 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 4.
Embodiment 5
Tire oil is heated to 120 ℃, and with being pumped in flashing tower, the tower top light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas enters blowdown system, and in tower, tire oil is as the hydrogenation unit charging, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the tire oil flash distillation on the 100ml hydrogenation unit sees Table 5.
The cycle of operation after the flash distillation of table 5 tire oil
| Tire oil | Install runtime, h |
| Be untreated | 206 |
| After flash distillation | 1956 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 5.
Claims (2)
1. the method for a removing free oxygen from inferior hydrogenation raw oil, it is characterized in that: will be transported in flashing tower after hydrogenating materials oil inferior heating, evaporate by light constituent the free oxygen in hydrogenating materials oil inferior is carried out, light constituent reclaims light oil by condensation, light oil is back to flashing tower, non-condensable gas carries out emptying, and the hydrogenating materials oil inferior in flashing tower is as the hydrogenation unit charging; Wherein hydrogenating materials oil Heating temperature scope inferior is 70 ~ 150 ℃.
2. method according to claim 1, it is characterized in that: described hydrogenating materials oil inferior is one or more in coal tar, crude benzol, coker gasoline, biomass pyrolysis oil, tire oil.
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| CN 201010546934 CN101979469B (en) | 2010-11-17 | 2010-11-17 | Method for removing free oxygen from inferior hydrogenation raw oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010546934 CN101979469B (en) | 2010-11-17 | 2010-11-17 | Method for removing free oxygen from inferior hydrogenation raw oil |
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| CN101979469B true CN101979469B (en) | 2013-05-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146475A (en) * | 1977-12-01 | 1979-03-27 | Forsland Audre C | Electrefiner |
| CN1689962A (en) * | 2004-04-29 | 2005-11-02 | 中国石化镇海炼油化工股份有限公司 | Method for producing synthetic gas by gasifying super-heavy inferior oil mixture |
| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
| CN1880411A (en) * | 2006-03-04 | 2006-12-20 | 荆门市金吉化工有限公司 | Process for preparing fuel oil by using coal tar |
-
2010
- 2010-11-17 CN CN 201010546934 patent/CN101979469B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146475A (en) * | 1977-12-01 | 1979-03-27 | Forsland Audre C | Electrefiner |
| CN1689962A (en) * | 2004-04-29 | 2005-11-02 | 中国石化镇海炼油化工股份有限公司 | Method for producing synthetic gas by gasifying super-heavy inferior oil mixture |
| CN1880411A (en) * | 2006-03-04 | 2006-12-20 | 荆门市金吉化工有限公司 | Process for preparing fuel oil by using coal tar |
| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
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