CN103102942B - Treating method for in-depth dearomatization of diesel oil fraction - Google Patents
Treating method for in-depth dearomatization of diesel oil fraction Download PDFInfo
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Abstract
The invention discloses a treating method for in-depth dearomatization of a diesel oil fraction. The method is characterized in that raw oil enters into a hypergravity reactor filled with a non-noble metal catalyst for countercurrent contact with hydrogen to realize desulphurization, denitrification and partial aromatic saturation, and then in-depth dearomatization is carried out in a fixed bed reactor filled with a noble metal catalyst. With the treating method provided by the invention, a stripping separation system in a two-stage process can be omitted, and the content of sulfur and aromatic hydrocarbons in a raw material can be greatly reduced.
Description
Technical field
The present invention relates to the treatment process that a kind of diesel oil hydrotreating method, particularly diesel fraction deep hydrogenation take off virtue.
Background technology
Increasingly strict along with environmental regulation, countries in the world have revised diesel oil regulation one after another, require the fuel of oil refining enterprise production environment close friend.In " world's fuel oil specification ", II class diesel oil requires: sulphur content is not more than 300 μ g/g, and total aromaticity content is not higher than 24%, and wherein polycyclic aromatic hydrocarbon content is not higher than 5%, and cetane index is not less than 50; III class diesel oil requires: sulphur content is not more than 30 μ g/g, and total aromaticity content is not higher than 15%, and wherein polycyclic aromatic hydrocarbon content is not higher than 2%, and cetane index is not less than 52.These standards all can produce far-reaching influence to the formulation of various countries' diesel oil standard and diesel production.Meanwhile, because the demand of market to light Fuel constantly increases, the deep conversion degree of heavy resid also improves constantly, and makes secondary processing product as the Quality Down of catalytic diesel oil (LCO) etc., is difficult to find sufficient low-sulfur, low aromatics diesel component is in harmonious proportion with it.
Existing operational means as reduce air speed or improve temperature can make distillate particularly in catalytic diesel oil sulphur content reach requirement, but the aromatic hydrocarbons reduced in product is but a great problem always.Major cause is that aromatic saturation reaction is subject to thermodynamic control, and when improving temperature and removing sulphur more, the saturated of aromatic hydrocarbons will be suppressed.Therefore, the task of taking into account deep desulfuration and Tuo Fang is difficult under common Hydrofinishing conditions.
For realizing the target of low-sulfur, low aromatic hydrocarbons, domestic and international company generally adopts two-stage method to operate.US5114562 describes the two-stage method work flow of a kind of intermediate oil hydrogenating desulfurization and aromatic saturation.The method has two independently reactors, in the first reactor, carry out hydrogenating desulfurization, and the product after desulfurization enters stripping tower, adopts hydrogen adverse current stripping to remove H
2s and NH
3.And then entering second reactor, second reactor adopts noble metal catalyst, and operational condition is high pressure low temperature, mainly carries out the hydrotreated lube base oil reaction of aromatic hydrocarbons.This method is present stage comparatively ripe hydrogenation process, and industrial application is also many.But because it needs a set of stripping system, thus investment and process cost higher.
US5183556 describes the technique of the hydrogenating desulfurization of a kind of diesel oil two-step approach, de-virtue.The first step raw material and hydrogen-rich gas also flow through non-precious metal catalyst, then by the gas in the logistics of the gas-liquid separation device removing the first step, enter second step and fresh hydrogen counter current contact, carry out deep hydrogenation.Second step used catalyst can be non-precious metal catalyst, also can be noble metal catalyst.This technique can be carried out in a reactor, also can carry out in two different reactors.Because second step adopts counter-current operation, hydromechanical restriction being subject to, for preventing the generation of liquid flooding, can only operating under lower hydrogen-oil ratio condition, have adverse influence to deepness hydrogenation dearomatization reaction like this.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind for the treatment of process of in-depth dearomatization of diesel oil fraction, particularly poor ignition quality fuel deepness hydrogenation dearomatization technique.Compared with two-stage hydrogenation treatment process, a set of stripping system can be reduced, have the advantages that technical process is simple, turndown ratio is large.
The treatment process of in-depth dearomatization of diesel oil fraction provided by the invention includes two reaction zones: the first reaction zone and second reaction zone.First reaction zone comprises the hypergravity hydrogenator of a hypergravity hydrogenator or 2 ~ 5 series connection, and second reaction zone comprises conventional fixed bed hydrogenation reactor.
Concrete grammar comprises following content:
A, stock oil enter the hypergravity hydrogenator of the first reaction zone, and in reactor, filling non-precious metal catalyst, adopts gas-liquid counter current operating method, carry out deep hydrodesulfurizationof, denitrogenation and the reaction of part aromatic saturation.The liquid phase material part that first reaction zone is discharged enters second reaction zone, and a part is circulated to the first reaction zone entrance;
Directly enter the fixed bed hydrogenation reactor of second reaction zone after b, step a liquid effluent phase materials mix with hydrogen in the mode also flowed, contact the deep hydrogenation carrying out aromatic hydrocarbons with noble metal catalyst saturated.
The catalyzer that non-precious metal catalyst described in step a is familiar with by those skilled in the art, generally with aluminum oxide, amorphous silicon aluminium and (or) molecular sieve are carrier, with VIB and group VIII metal as W, Mo, Co, the oxide compound of Ni etc. is active ingredient, in the content of oxide weight active metal component for 20% ~ 60%, optionally add other various auxiliary agent as P, Si, F, the elements such as B, non-precious metal catalyst carries out sulfuration before use, by active metal component oxygenate conversion be active higher sulfide, sulfidizing is the ordinary method of this area.
Hypergravity hydrogenator described in step a is the rotary hearth structure of reactor that this area is commonly used, catalyst bed rotates with rotating shaft, rotating shaft is preferably tube-in-tube structure, rotating shaft inner core arranges material distribution hole, rotating shaft urceolus and catalyst bed are fixed as one, urceolus has material stream passed opening, and urceolus top arranges gaseous phase materials exhaust channel.Hydrogen is entered by the outside housing of hyper-gravity gas hydrogenator, flowed out by the urceolus of shaft sleeve, stock oil enters hypergravity hydrogenator by the inner core of shaft sleeve, stock oil is driven by the high speed rotating of beds rotor, form counter current contact with hydrogen, reacted gas phase flows out at the urceolus of shaft sleeve.Form super gravity field because beds rotor rotates, make gas-to-liquid contact place produce the universal gravity constant of 50 ~ 1000 times, thus greatly enhance gas-liquid mass transfer efficiency, promote the saturated reaction of aromatic hydrocarbons.Simultaneously under the effect of super gravity field, liquid phase is better than the fixed-bed reactor under gravity field greatly by the ability of beds, so hypergravity hydrogenator is when adopting higher vapour-liquid ratio operation, also Concerning Flooding Phenomenon can not occur.The processing condition of hypergravity hydrogenator are: reaction pressure 2.0MPa ~ 15.0MPa, preferred 3.0MPa ~ 10.0MPa, and temperature of reaction is 250 DEG C ~ 500 DEG C, preferably 300 DEG C ~ 380 DEG C, and during liquid, volume space velocity (combined feed total feed) is generally 1.0h
-1~ 8.0h
-1, preferred 1.5h
-1~ 5.0h
-1, hydrogen oil standard state lower volume ratio is 100 ~ 3000, preferably 600 ~ 1500.The volume ratio (recycle ratio) of the first reaction zone circulation oil mass and fresh feed oil is 0.1:1 ~ 5.0:1, is preferably 0.2:1 ~ 2.0:1.Supergravity reactor can arrange one, also can arrange 2 ~ 5 series connection and use.
The noble metal catalyst that the arene saturating activity that noble metal catalyst described in step b is familiar with by those skilled in the art is high, generally with platinum and/or palladium for active metal ancestral divides, with one or more mixtures of zeolite, inorganic oxide, activated carbon, clay etc. for carrier, the active ingredient of noble metal catalyst is generally Pt and/or Pt, and content is generally 0.1% ~ 3% by weight.
The fixed-bed reactor of the second reaction zone described in step b are conventional fixed bed hydrogenation reactor, its reaction conditions is: reaction pressure is 2.0MPa ~ 15.0MPa, be preferably 3.0MPa ~ 10.0MPa, temperature of reaction is 250 DEG C ~ 500 DEG C, be preferably 300 DEG C ~ 400 DEG C, during liquid, volume space velocity is generally 0.1h
-1~ 5.0h
-1, preferred 0.5h
-1~ 3.0h
-1, hydrogen oil standard state lower volume ratio is 100 ~ 3000, is preferably 300 ~ 1000.
Advantage of the present invention is:
1, the first reaction zone adopts hypergravity hydrogenator, under the effect of super gravity field, gas-liquid is improved greatly by the speed of beds, compared with the reactor under gravity field, liquid flooding curve has raising by a relatively large margin, therefore higher vapour-liquid ratio can be adopted to operate, higher hydrogen partial pressure can be obtained, promote the saturated reaction of aromatic hydrocarbons, take a large amount of reaction heat out of reactor simultaneously, prevent reactor overtemperature.
2, under the condition of hypergravity, speed of relative movement due to counter fluid becomes large, huge shearing stress can overcome surface tension, contact area between hydrogen and liquid phase material is increased, thus cause alternate transmittance process greatly to be strengthened, hypergravity hydrogenator mass-transfer efficiency is far above the fixed bed hydrogenation reactor under gravity field, and gas-liquid handling capacity also strengthens greatly, so can adopt the operator scheme of high hydrogen to oil volume ratio and circulation.
3, reasonably make use of the constructional feature of hypergravity hydrogenator, by H before second reaction zone
2s and NH
3remove, cancel stripping system, technical process is simple.
Accompanying drawing explanation
Fig. 1 is present invention process method flow schematic diagram.
In figure: 1-fresh feed oil, 2-fixed bed hydrogenation reactor, material is discharged in 3-first reaction zone, and 4-hydrogen, the mixing hydrogen-rich gas of 5-first reaction zone, 6-hypergravity hydrogenator, 7-beds rotor, 8-turning oil, 9-generates oil.
Embodiment
For setting forth specific features of the present invention further, will be illustrated by reference to the accompanying drawings.
By reference to the accompanying drawings 1, a kind of technological process of the present invention is:
Fresh feed oil 1 enters the hypergravity hydrogenator 6 of the first reaction zone, carries out deep hydrodesulfurizationof reaction and the reaction of part aromatic saturation.The fixed bed hydrogenation reactor 2 entering second reaction zone after material 3 mixes with hydrogen 4 is discharged in first reaction zone.Hydrogen 4 is entered by the outside housing of hypergravity hydrogenator, is flowed out by shaft sleeve.The liquid phase of the first reaction zone feeds is driven by the high speed rotating of beds rotor 7, forms counter current contact with hydrogen, and the gas phase that supergravity reactor hydrogenation reaction generates flows out with hydrogen at shaft sleeve place.The material part that first reaction zone is discharged enters second reaction zone, and a part is circulated to the first reaction zone entrance.
For further illustrating the solution of the present invention and effect, enumerate following examples and comparative example:
Embodiment 1
The present embodiment is a kind of embodiment of diesel oil hydrogenation process, and operating process schematic diagram is with reference to accompanying drawing 1.
The present embodiment first reaction zone supergravity reactor adopts non-precious metal catalyst, and second reaction zone fixed-bed reactor adopt noble metal catalyst.The main character of catalyzer is in table 1, and feedstock property is in table 2.
Table 1 catalyzer physico-chemical property.
| Project | Non-precious metal catalyst | Noble metal catalyst |
| Catalyst activity component | Mo、Ni、W | Pt |
| With oxide basis active component content, wt% | 13/6/10 | 0.78 |
| Carrier | Aluminum oxide | USY molecular sieve |
| Shape | Trifolium | Bar shaped |
| Diameter | 3.1 | 2.0 |
| Pore volume/mLg -1 | 0.41 | 0.39 |
| Specific surface area/m 2·g -1 | 235 | 143 |
Table 2 stock oil main character.
| Density (20 DEG C), g/cm 3 | 0.8765 |
| Ultimate analysis | |
| S，μg/g | 7610 |
| N，μg/g | 635 |
| Aromatic hydrocarbons, volume % | 55.8 |
| Boiling range scope, DEG C | 183～377 |
Table 3 hydrofining technology condition.
| Reaction zone | One | Two |
| Processing condition: | ||
| Reaction hydrogen pressure/MPa | 6.5 | 6.5 |
| Recycle ratio (turning oil/fresh feed) | 0.5 | |
| Hydrogen to oil volume ratio | 850:1 | 450:1 |
| Volume space velocity/h -1(each reaction zone total reactor feed) | 1.5 | 1.2 |
| Temperature of reaction/DEG C | 360 | 345 |
| Product property: | ||
| S，μg/g | 13.9 | 1.8 |
| N，μg/g | 1.3 | 1.0 |
| Aromatic hydrocarbons, volume % | 34.8 | 6.0 |
| Boiling range scope, DEG C | 180～373 | 179～371 |
As can be seen from the above results, the generation oil sulphur of the inventive method, nitrogen content are very low, and aromaticity content is only 6.0%, and aromatic hydrocarbons extrusion rate reaches 89.25%.When cancelling stripping separation system, achieve good hydrogenation effect.
Claims (9)
1. the treatment process of an in-depth dearomatization of diesel oil fraction, include two reaction zones: the first reaction zone and second reaction zone, it is characterized in that: the first reaction zone comprises the hypergravity hydrogenator of a hypergravity hydrogenator or 2 ~ 5 series connection, second reaction zone comprises conventional fixed bed hydrogenation reactor, specifically comprises following content:
A () stock oil enters the hypergravity hydrogenator of the first reaction zone, in reactor, filling non-precious metal catalyst, adopts gas-liquid counter current operating method, carries out deep hydrodesulfurizationof, denitrogenation and the reaction of part aromatic saturation; The liquid phase material part that first reaction zone is discharged enters second reaction zone, and a part is circulated to the first reaction zone entrance;
The hypergravity hydrogenator of step (a) is rotary hearth structure of reactor, catalyst bed rotates with rotating shaft, rotating shaft is tube-in-tube structure, rotating shaft inner core arranges material distribution hole, rotating shaft urceolus and catalyst bed are fixed as one, urceolus has material stream passed opening, and urceolus top arranges gaseous phase materials exhaust channel; Hydrogen is entered by the outside housing of hyper-gravity gas hydrogenator, flowed out by the urceolus of shaft sleeve, stock oil enters hypergravity hydrogenator by the inner core of shaft sleeve, stock oil is driven by the high speed rotating of beds rotor, form counter current contact with hydrogen, reacted gas phase flows out at the urceolus of shaft sleeve;
Directly enter the fixed bed hydrogenation reactor of second reaction zone b () step (a) liquid effluent phase materials mixes with hydrogen after in the mode also flowed, contact the deep hydrogenation carrying out aromatic hydrocarbons with noble metal catalyst saturated.
2. in accordance with the method for claim 1, it is characterized in that: the non-precious metal catalyst of step (a) with aluminum oxide, amorphous silicon aluminium and/or molecular sieve for carrier, with the oxide compound of VIB and group VIII metal for active ingredient, in the content of oxide weight active metal component for 20% ~ 60%, non-precious metal catalyst carries out sulfuration before use.
3. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of step (a) hypergravity hydrogenator is 2.0MPa ~ 15.0MPa, and temperature of reaction is 250 DEG C ~ 500 DEG C, and during liquid, volume space velocity is 1.0h
-1~ 8.0h
-1, hydrogen oil standard state lower volume ratio is 100 ~ 3000.
4. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of step (a) hypergravity hydrogenator is 3.0MPa ~ 10.0MPa, and temperature of reaction is 300 DEG C ~ 380 DEG C, and during liquid, volume space velocity is 1.5h
-1~ 5.0h
-1, hydrogen oil standard state lower volume ratio is 600 ~ 1500.
5. in accordance with the method for claim 1, it is characterized in that: the volume ratio of the first reaction zone circulation oil mass and fresh feed oil is 0.1:1 ~ 5.0:1.
6. in accordance with the method for claim 5, it is characterized in that: the volume ratio of the first reaction zone circulation oil mass and fresh feed oil is 0.2:1 ~ 2.0:1.
7. in accordance with the method for claim 1, it is characterized in that: the noble metal catalyst of step (b) with platinum and/or palladium for active metal component, with one or more mixtures in zeolite, inorganic oxide, activated carbon, clay for carrier, the active ingredient Pt of noble metal catalyst and/or Pt by weight content is 0.1% ~ 3%.
8. in accordance with the method for claim 1, it is characterized in that: the fixed bed reaction condition of step (b) second reaction zone is: reaction pressure is 2.0MPa ~ 15.0MPa, temperature of reaction is 250 DEG C ~ 500 DEG C, and during liquid, volume space velocity is 0.1h
-1~ 5.0h
-1, hydrogen oil standard state lower volume ratio is 100 ~ 3000.
9. in accordance with the method for claim 1, it is characterized in that: the fixed bed reaction condition of step (b) second reaction zone is: reaction pressure is 3.0MPa ~ 10.0MPa, temperature of reaction is 300 DEG C ~ 400 DEG C, and during liquid, volume space velocity is 0.5h
-1~ 3.0h
-1, hydrogen oil standard state lower volume ratio is 300 ~ 1000.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN102041069A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Gas-liquid countercurrent hydrogenation method for desulfurization, denitrification and aromatic hydrocarbon of diesel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN102041069A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Gas-liquid countercurrent hydrogenation method for desulfurization, denitrification and aromatic hydrocarbon of diesel |
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