CN102485845B - Denitrogenation hydrogenation method for secondary processing diesel oil - Google Patents
Denitrogenation hydrogenation method for secondary processing diesel oil Download PDFInfo
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- CN102485845B CN102485845B CN201010580667.5A CN201010580667A CN102485845B CN 102485845 B CN102485845 B CN 102485845B CN 201010580667 A CN201010580667 A CN 201010580667A CN 102485845 B CN102485845 B CN 102485845B
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Abstract
The invention relates to a denitrogenation hydrogenation method for secondary processing diesel oil, which is characterized in that coker diesel oil or catalyzed diesel oil raw materials can be performed heat exchange in a heat exchanger to the temperature of 25-150 DEG C, mixed with a nitrogen removal agent in a static state mixer and then enters in a settlement pot for depositing and separating slag, sediment is discharged from the bottom of the settlement pot, nitrogen removal oil is passed through an electric settlement pot, the sediment is discharged from the bottom, upper layer refining oil is refined through an adsorption filter, the refined oil is performed heat exchange in the heat exchanger to the temperature of 200-350 DEG C and enters in a hydrogenation system for hydrofinishing treatment, wherein the hydrogenation partial pressure is 5.0-9.0 MPa, space velocity is 0.5-2h<-1>, the addition weight of the nitrogen removal agent accounts for 0.2%-5% of coker diesel oil weight, the adsorption filtering medium is active carbon, white clay or diatomite. The denitrogenation hydrogenation method of the invention has the advantages of less denitrogenation residue, high refined oil yield and obvious economic benefit.
Description
Technical field
The present invention relates to a kind of denitrogenation hydrogenation method for secondary processing diesel oil.
Background technology
The nitride that contains a great deal of in the secondary processing diesel oil such as catalytic cracking and delayed coking, sulfide and unsaturated olefin, these components are destabilization very all, is very easy to oxidation, and diesel colour is deepened, and colloid raises, and oxidation sediment is high.If this diesel oil is directly used on oil engine, be easy to cause incomplete combustion, carbon deposit is high, and cylinder of internal-combustion engine damage intensity is accelerated.Therefore, the up-to-date diesel oil new standard that dispatches from the factory of having formulated of country.New standard has strictly been controlled the quality standards such as the sulphur in diesel oil, colloid, oxidation sediment.New standard is revised sulphur content in derv fuel oil, and sulphur content is down to 0.05% (w) from 0.3% original (w), and this is equivalent to the standard of Europe (II) derv fuel oil.At present, developed country generally adopts Europe (III) standard, and wherein sulphur content requires≤0.015%, and Europe, Europe (IV) (V) standard also puts into effect, and finally requires sulphur content≤0.001%, aromaticity content≤11%.Along with economic globalization, derv fuel oil standard will inevitably improve in China, and sulphur content in diesel oil and aromaticity content are required to improve constantly, and the ultra-low-sulphur diesel of producing clean≤0.001% is the inexorable trend of oil refining enterprise from now on.
Hydrogenation is desulfurization, denitrogenation, the effective means of the matter of coming unstuck, but in conventional hydrogenation unit charging, the basic nitrogen compound content of catalysis solar oil and coker gas oil is high, these basic nitrogen compound severe inhibition the hydrodesulfurization reaction of steric hindrance dibenzothiophene, be the maximum inhibition of hydrodesulfurization reaction.Carbazole also can largely hinder hydrodesulfurization reaction, the desulfurization of steric hindrance sulfide and carbazole denitrogenation are vied each other by hydrogenation approach in catalyst active center, denitrification reaction is slower than desulphurization reaction, it is longer than sulfide that nitride is trapped in time in active centre, therefore can reduce desulfurization rate, and greatly shorten the work-ing life of hydrogenation catalyst.As can be seen here, the basic nitrogen compound that pre-treatment removes in hydrogenating materials is very necessary.It is raw material that CN200610104371.X has proposed a kind of diesel oil or catalytic cracking unit diesel oil of take refinery delayed coking unit, by denitrification refining, carry out again the combination process of hydrofining processing, this technique by coker gas oil or catalytic diesel oil raw material in interchanger heat exchange to 25-150 ℃, in static mixer, carry out after hybrid reaction with denitrfying agent, enter sedimentation in electrofining slurry tank and divide slag, sediment is discharged from slurry tank bottom, denitrogenation oil mixes by electric slurry tank further refining with cleaning water, upper strata treated oil enters hydrogenation system and carries out hydrofining processing after interchanger heat exchange.The method is owing to adding cleaning water to mix with treated oil, can cause treated oil emulsification, profit is difficult to separation, cause on the one hand oil yield to decline, on the other hand, diesel oil water content is high, also contain some denitrogenation residual components simultaneously, the existence of denitrogenation residual component can be adsorbed on catalyzer, causes poisoning of catalyst, beds pressure drop to rise, and affects hydrogenation effect.
Summary of the invention
The object of this invention is to provide a kind of diesel oil or catalytic cracking unit diesel oil of take refinery delayed coking unit is raw material, by denitrification refining, carries out the combination process of hydrofining processing again.
Denitrogenation hydrogenation method for secondary processing diesel oil of the present invention be by coker gas oil or catalytic diesel oil raw material in interchanger A heat exchange to 25-150 ℃, in static mixer, carry out after hybrid reaction with denitrfying agent, enter sedimentation in slurry tank and divide slag, sediment is discharged from slurry tank bottom, denitrogenation oil is after electric slurry tank, sediment is discharged from bottom, and upper strata treated oil is refining through adsorption filter again, and treated oil enters hydrogenation system and carries out hydrofining processing after interchanger F heat exchange.
In the method for the invention, the weight that adds of denitrfying agent is 0.2～5% of diesel oil.
In the method for the invention, the described settling time is 10 minutes～6 hours.
In the method for the invention, the electrofining strength of electric field of electric slurry tank is at 0-2000 volt/cm
2scope.Slurry tank can be electric slurry tank, and slurry tank and electric slurry tank can be an electric slurry tank.
In the method for the invention, the adsorbent filtering medium adopting is
A. the oxide compound of solid alkali metal, alkaline-earth metal and oxyhydroxide thereof, as: Na
+, K
+, NH4
+, Ca
+ 2, Mg
+ 2, Al
+ 3, Zn
+ 2, Fe
+ 2, Fe
+ 3, Ba
+ 2, Pb
+ 2oxide compound and oxyhydroxide etc. thereof
B. the salt that solid alkali weak acid generates, as: Na
2cO
3, Na
3pO
4, K
2cO
3deng.
C. porous mass, comprises gac, coke, coal, cinder, carclazyte, diatomite, silica gel, aluminum oxide, molecular sieve, porous organo polysilica compound, ion exchange resin, chitin etc.
D. adsorb a or b, or inorganic ammonia, organic amine, the c class material of acid amides etc., as: absorption Monomethylamine, ethamine, azanol, urea, triethylamine, quadrol and diethylenetriamine, aniline, ethylaniline, Ortho Toluidine and xylidine, thanomin (has one, two, trolamine), methylamine (second, third, fourth ... stearylamine ...), quadrol (third, fourth, penta, hexanediamine etc.), acid amides (first, second, propionic acid amide, methylformamide, methylacetamide, dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.), dimethyl formamide, dimethylethanolamine, N methyldiethanol amine, α-amino isopropyl alcohol, aryloxy propanol amine, trolamine, phosphorylethanolamine, benzene oxygen Propanolamine, Phenylethanolamine, tri-isopropanolamine, N-aminoethyl ethanolamine, diethylenetriamine, alkanolamine, alkylene amines, ammoniacal liquor, phosphorus ammonium phosphoric acid hydrogen ammonia primary ammonium phosphate etc.
A, b, c, a kind of and mixture in d.
In the method for the invention, the heat-exchange temperature in described interchanger A is 50 ℃～100 ℃.
Accompanying drawing explanation
Fig. 1 is the process for purification schematic flow sheet of secondary processing diesel oil.
1 catalytic diesel oil or coker gas oil, 2 denitrfying agents,
A: interchanger B: static mixer C: slurry tank D: electrofining slurry tank E: adsorption filter F: interchanger G: hydrogenation system
Embodiment
The present invention implements like this: 1. catalytic diesel oil or or coker gas oil 1 and denitrfying agent 2 in static mixer B, mix after by interchanger A heat exchange.This denitrfying agent can be the denitrfying agent that zL94115105 provides, and can be also the denitrfying agent of other acidic components.Also can be the denitrification refining agent of other prior art.Alkali nitrogen by the diesel oil after denitrogenation processing can be down to 1-20PPm.Agent bavin ratio is 1: 50～1: 1500 (weight), and comparatively preferred ratio is 1: 100～1: 1000, and highly preferred ratio is 1: 500～1: 800; Mixing temperature is 20 ℃～100 ℃.The rear oil of mixing enters slurry tank C and carries out settlement separate; Separating tank denitrogenation oil is out further settlement separate through electrofining slurry tank D, after separated, diesel oil enters hydrogenation system G and carries out hydrotreatment after adsorption filter E and interchanger F heat exchange to 200 ℃～350 ℃, hydrogenation dividing potential drop is 5.0～9.0MPa, preferred dividing potential drop is 5.5～8.5MPa, and air speed is 0.5～2h
-1, after hydrogenation, diesel oil is the qualified product after refining.
2. delayed coking diesel oil 1 and denitrfying agent 2 mix after by interchanger A heat exchange in static mixer B.This denitrfying agent can be the denitrfying agent that ZL94115105 provides, and can be also other denitrification refining agent.Alkali nitrogen by the diesel oil after denitrogenation processing can be down to 50～100PPm.Agent bavin ratio is 1: 20～1: 1000 weight, and comparatively preferred ratio is 1: 50～1: 500, and highly preferred ratio is 1: 50～1: 200; Mixing temperature is 20 ℃～100 ℃.The rear oil of mixing enters slurry tank C and carries out settlement separate.It is further settlement separate that the denitrogenation oil of separating enters electrofining slurry tank D again, and the strength of electric field in electrofining slurry tank C, D is 0 to 2000 volt/cm scope.After separated, diesel oil enters hydrogenation system (G carries out hydrotreatment, and hydrogenation dividing potential drop is 5.0～9.0MPa, and preferred dividing potential drop is 5.5～8.5MPa, and air speed is 0.5～2h after adsorption filter E and interchanger F heat exchange to 200 ℃～350 ℃
-1, after hydrogenation, diesel oil is the qualified product after refining.
The effect that the present invention reaches is to make the basic nitrogen of catalytic diesel oil from 150PPm, and～300PPm is removed to 1～10PPm, can make the basic nitrogen of coker gas oil be removed to 80PPm～120PPm from 800PPm～1200PPm.Denitrogenation diesel oil and not denitrogenation diesel oil are respectively by hydrotreatment, under hydrogenation technique condition same case, denitrogenation diesel oil sulphur content ratio not denitrogenation diesel oil reduces by 200～500PPm, and aromaticity content ratio not denitrogenation diesel oil reduces by 5～20 percentage points, stability in storage is good, has met service requirements; And reach same sweetening effectiveness, and the hydrogenation technique severity of denitrogenation diesel oil obviously reduces, and as temperature can reduce by 20 ℃ of left and right, or air speed can improve 30% left and right.
Embodiment 1
With 10g diatomite, as filler, be packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.032mgKOH/g by 0.82mgKOH/g.
Embodiment 2
With 10g carclazyte, as filler, be packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.024mgKOH/g by 0.79mgKOH/g.
Embodiment 3
With the carclazyte of 10g absorption mineral acid, be that filler is packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.021mgKOH/g by 0.76mgKOH/g.
Embodiment 4
With the carclazyte of 10g absorption mineral alkali, be that filler is packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.034mgKOH/g by 0.86mgKOH/g.
Embodiment 5
With the gac of 10g absorption mineral alkali, be that filler is packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.019mgKOH/g by 0.75mgKOH/g.
Embodiment 6
With the diatomite of 10g absorption inorganic salt, be that filler is packed into post, the coker gas oil after denitrogenation is divided through fixed bed with 0.5g/, after adsorption filtration is refining, obtain treated oil, by analysis, acid number is by dropping to 0.034mgKOH/g by 0.81mgKOH/g.
Claims (3)
1. a denitrogenation hydrogenation method for secondary processing diesel oil, it is characterized in that: by coker gas oil or catalytic diesel oil raw material in interchanger (A) heat exchange to 25-150 ℃, in static mixer, carry out after hybrid reaction with denitrfying agent, enter sedimentation in slurry tank and divide slag, sediment is discharged from slurry tank bottom, denitrogenation oil is after electric slurry tank, sediment is discharged from bottom, upper strata treated oil is refining through adsorption filter again, treated oil enters hydrogenation system and carries out hydrofining processing after interchanger (F) heat exchange to 200 ℃～350 ℃, hydrogenation dividing potential drop is 5.0～9.0MPa, and air speed is 0.5～2h
-1;
The weight that adds of denitrfying agent is the 0.2%-5% of coker gas oil weight;
Adsorbent filtering medium is: adsorbed mineral acid carclazyte, adsorbed mineral alkali carclazyte, adsorbed the gac of mineral alkali and adsorbed the diatomite of inorganic salt;
The described settling time is 10 minutes～6 hours.
2. denitrogenation hydrogenation method for secondary processing diesel oil according to claim 1, is characterized in that: the electrofining strength of electric field of electric slurry tank is at 0-2000 volt/cm
2scope.
3. according to the denitrogenation hydrogenation method for secondary processing diesel oil described in claim l, be further characterized in that: the heat-exchange temperature in described interchanger (A) is 50 ℃～100 ℃.
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| CN102485845B true CN102485845B (en) | 2014-01-15 |
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| CN104877708B (en) * | 2015-04-30 | 2016-07-20 | 茂名市凯跃特种油剂有限公司 | The method of catalytic cracked oil pulp elimination ash and aluminum, element silicon |
| CN104862006B (en) * | 2015-05-18 | 2016-07-27 | 中国海洋石油总公司 | Anti-evolving-gas additive of transformer oil and preparation method thereof |
| CN114621788B (en) * | 2020-12-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Catalytic diesel denitrification and hydrotreatment method |
| CN114989862B (en) * | 2022-05-25 | 2024-01-19 | 涿州贝尔森生化科技发展有限公司 | Serial denitrification process for vacuum degassing and mixing reaction powered refining separation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251382A (en) * | 1999-11-04 | 2000-04-26 | 中国石化集团武汉石油化工厂 | Improvement of electric refining method for lubricant base-oil denitrification process |
| CN1253165A (en) * | 1999-11-04 | 2000-05-17 | 中国石化集团武汉石油化工厂 | Refining basic oil of lubricating oil by denitrification |
| CN1670129A (en) * | 2005-02-17 | 2005-09-21 | 中国石油化工集团公司 | Pretreating method for diesel-fuel of poor quality |
| CN101121900A (en) * | 2006-08-10 | 2008-02-13 | 中国石化集团武汉石油化工厂 | Denitrogenation hydrogenation combination technique for secondary processing diesel oil |
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|---|---|---|---|---|
| US8246814B2 (en) * | 2006-10-20 | 2012-08-21 | Saudi Arabian Oil Company | Process for upgrading hydrocarbon feedstocks using solid adsorbent and membrane separation of treated product stream |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251382A (en) * | 1999-11-04 | 2000-04-26 | 中国石化集团武汉石油化工厂 | Improvement of electric refining method for lubricant base-oil denitrification process |
| CN1253165A (en) * | 1999-11-04 | 2000-05-17 | 中国石化集团武汉石油化工厂 | Refining basic oil of lubricating oil by denitrification |
| CN1670129A (en) * | 2005-02-17 | 2005-09-21 | 中国石油化工集团公司 | Pretreating method for diesel-fuel of poor quality |
| CN101121900A (en) * | 2006-08-10 | 2008-02-13 | 中国石化集团武汉石油化工厂 | Denitrogenation hydrogenation combination technique for secondary processing diesel oil |
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