CN101979469A - Method for removing free oxygen from inferior hydrogenation raw oil - Google Patents

Method for removing free oxygen from inferior hydrogenation raw oil Download PDF

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Publication number
CN101979469A
CN101979469A CN2010105469347A CN201010546934A CN101979469A CN 101979469 A CN101979469 A CN 101979469A CN 2010105469347 A CN2010105469347 A CN 2010105469347A CN 201010546934 A CN201010546934 A CN 201010546934A CN 101979469 A CN101979469 A CN 101979469A
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inferior
oil
hydrogenation
free oxygen
hydrogenating materials
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CN101979469B (en
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佘喜春
李庆华
朱方明
刘呈立
郭朝晖
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Anhui molifu renewable resources Co.,Ltd.
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Hunan Changling Petrochemical Technology Development Co Ltd
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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

Hydrogenating materials oil inferior removes the method for free oxygen
Technical field
The present invention relates to the deep processing of hydrogenating materials oil inferior, particularly relate to the method that a kind of hydrogenating materials oil inferior removes free oxygen.
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, 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 facilitation to coking.Free oxygen can make the aromatic thiol oxidation in the hydrogenating materials oil inferior produce sulfonic acid, and sulfonic acid and pyrroles condensation reaction are taken place produced 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 free oxygen level is higher in the hydrogenating materials oil inferior, be easy to cause its bad stability, and form coking easily at high temperature equipment such as raw materials furnace and heating, interchanger and hydrogenator tops, and cause the device unplanned shutdown, influence 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 the 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, promptly at first easily carries out main hydrogenation again behind the organic compound of coking removing heteroato mic organic compounds such as part sulphur, nitrogen, oxygen, saturated diolefine, vinylbenzene etc. under the effect of 150~300 ℃ temperature and catalyzer.But it is because temperature required higher, hydrogenating materials oil inferior might coking in 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 the oil was higher, this coking situation just more likely took place.
Therefore, for preventing the coking and blocking problem in the pre-hydrogenation process, generally before the pre-hydrogenation of hydrogenating materials oil inferior, it is carried out pre-treatment.Remove heavy constituent in the coal tar as employing distillatory technologies such as CN200610028263, CN200610018476, CN200400123146.4, promptly remove coking precursorses such as colloid, bituminous matter, also can play the effect that removes free oxygen simultaneously.But this method has been removed heavy component, has wasted valuable tar resource, and the cutting temperature height, and investment is big, the energy consumption height.300~360 ℃ service temperature also causes the distillation tower coking easily in addition.
Adopt methods such as thinning oil technology, technology of electric de-salting, adding coke inhibitor to come the restraining device coking in addition in addition, but all can not remove the free oxygen in the hydrogenating materials oil inferior.
Summary of the invention
The purpose of this invention is to provide a kind of be applicable to full cut hydrogenating materials oil inferior hydrogenation technique, simple, energy consumption is low, the method that removes free oxygen in the hydrogenating materials oil inferior of no coking.
Content of the present invention is achieved through the following technical solutions: a kind of hydrogenating materials oil inferior removes the method for free oxygen, it is characterized in that: will be transported in the flashing tower after the hydrogenating materials oil inferior heating, by the light constituent evaporation free oxygen in the hydrogenating materials oil inferior is carried out, light constituent reclaims light oil by condensation, light oil is back in the flashing tower, non-condensable gas carries out emptying, and the hydrogenating materials oil inferior in the 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, the 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 the accumulating and the course of processing, will make the character rapid deterioration of low grade oils, 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, relatively more responsive to temperature.Too high flash vaporization point though help reducing the meltage of free oxygen, causes hydrogenating materials oil inferior coking easily; Cross low flash vaporization point, it is bad to cause light oil to carry the effect of free oxygen in the hydrogenating materials oil inferior.Therefore, it is comparatively suitable at 70-150 ℃ to take all factors into consideration temperature.
It is relatively poor that the inventive method is equally applicable to character, can be used as the 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 control, 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 obvious to the coking effect that delays hydrogenation process, the hydrogenation unit cycle of operation obviously prolongs.
(4) be applicable to the hydrogenating materials inferior oil hydrogenation technique of full cut.
(5) be applicable to that the high hydrogenating materials oil inferior of free oxygen content carries 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 the flashing tower, the cat head light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas then enters blowdown system, and coal tar is as the hydrogenation unit charging in the tower, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the 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 the flash distillation 1860
After the coal tar hydrogenating feeding gas was carried as can be seen from Table 1, device prolonged runtime greatly.
Embodiment 2
Coker gasoline is heated to 120 ℃, and with being pumped in the flashing tower, the cat head light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas then enters blowdown system, and coker gasoline is as the hydrogenation unit charging in the tower, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the coker gasoline hydrogenation 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 charging of coker gasoline hydrogenation Install runtime, h
Be untreated 256
After the flash distillation 1782
After the coal tar hydrogenating feeding gas was carried as can be seen from Table 2, device prolonged runtime greatly.
Embodiment 3
Crude benzol is heated to 70 ℃, and with being pumped in the flashing tower, the cat head light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas then enters blowdown system, and crude benzol is as the hydrogenation unit charging in the tower, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the 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 the flash distillation 2006
After the coal tar hydrogenating feeding gas was carried as can be seen from Table 3, device prolonged runtime greatly.
Embodiment 4
Biomass thermal cracking oil is heated to 150 ℃, with being pumped in the flashing tower, the cat head light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas then 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 the flash distillation 2268
After the coal tar hydrogenating feeding gas was carried as can be seen from Table 4, device prolonged runtime greatly.
Embodiment 5
Tire oil is heated to 120 ℃, and with being pumped in the flashing tower, the cat head light constituent reclaims light oil by condensation, light oil is back to flashing tower, noncondensable gas then enters blowdown system, and tire oil is as the hydrogenation unit charging in the tower, and hydrogenation process adopts pre-hydrogenation and main hydrogenation two-stage process.The cycle of operation after the flash distillation of tire oil 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 the flash distillation 1956
After the coal tar hydrogenating feeding gas was carried as can be seen from Table 5, device prolonged runtime greatly.

Claims (3)

1. a hydrogenating materials oil inferior removes the method for free oxygen, it is characterized in that: will be transported in the flashing tower after the hydrogenating materials oil inferior heating, by the light constituent evaporation free oxygen in the 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 the flashing tower is as the hydrogenation unit charging.
2. method according to claim 1 is characterized in that: described hydrogenating materials oil inferior is one or more in coal tar, crude benzol, coker gasoline, biomass pyrolysis oil, the tire oil.
3. method according to claim 1 is characterized in that: described hydrogenating materials oil Heating temperature scope inferior is 70 ~ 150 ℃.
CN 201010546934 2010-11-17 2010-11-17 Method for removing free oxygen from inferior hydrogenation raw oil Active CN101979469B (en)

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CN101979469B CN101979469B (en) 2013-05-15

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Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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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Address before: 243000 Ma'anshan Economic and Technological Development Zone, Anhui Province, No. 398 Yanghu Road, No. 14 Fuma Zhisheng Ninth Floor

Patentee before: Molifu Environmental Protection Technology Co.,Ltd.

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