CN103059966B - Method for producing low sulfur gasoline - Google Patents
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Abstract
The invention discloses a method for producing low sulfur gasoline. The method comprises: subjecting catalytic cracking gasoline to fractionation in a fractionating tower first to obtain gasoline light fraction and heavy fraction, conducting fixed bed oxidation deodorization on the light fraction, converting mercaptan into a disulfide, mixing the deodorized product with thermocatalytic diesel oil from a catalytic cracking distillation tower, subjecting the mixture to fractionation in a prefractionator so as to obtain light fraction and diesel oil fraction; carrying out selective hydrodesulfurization on the heavy fraction, and mixing the desulfurization product with the light fraction fractionated after deodorization to obtain a clean gasoline product. Compared with the prior art, with the method disclosed in the invention, the sulfur content of catalytic cracking gasoline can be reduced to less than 10 micrograms/g, the octane number loss is small, and the mercaptan content is up to the standard. At the same time, the colloid generated by oxidation deodorization can be prevented from entering a heavy fraction selective hydrogenation unit, pressure drop of a hydrogenation device can be avoided, and the device operating cycle can be prolonged. The method provided in the invention has the advantages of wide raw material adaptability and flexibility, mature technology, and high reliability.
Description
Technical field
The present invention relates to a kind of method of producing low-sulphur oil, specifically, the present invention relates to a kind of new technological flow method of production low-sulphur oil of prolong operating period.
Background technology
Reduce the quantity discharged that content of sulfur in gasoline can reduce objectionable impurities in vehicle exhaust significantly, therefore, countries in the world clean gasoline new standard proposes more and more stricter restriction to sulphur content.Europe IV class automobile exhaust emission standard (EU2005 standard) specifies the sulphur content ≯ 50 μ g/g of gasoline after 2005, olefin(e) centent ≯ 18v%, within 2009, implements sulphur content afterwards and is less than 10 μ g/g " sweet gasoline (ULSG) " new standard.U.S.'s U.S.EPA Tier 2-II standard specifies the sulphur content ≯ 80 μ g/g of U.S.Clean gasoline after 2006, and olefin(e) centent ≯ 14v%, U.S.EPA Tier 2-III standard specifies the sulphur content ≯ 30 μ g/g of U.S.Clean gasoline after 2008; China in 2005 national gasoline on July 1 performs European II emission standard (sulphur content ≯ 500 μ g/g), and major area performs Euro III emission standard (sulphur content ≯ 150 μ g/g); On July 1st, 2007 ~ 2008, the whole nation performed Euro III emission standard, and major area performs European IV emission standard (sulphur content ≯ 50 μ g/g); On July 1st, 2010 ~ 2011, the whole nation performed European IV emission standard.Before and after 2013, the big city such as Beijing, Shanghai clean gasoline will perform Europe V standard, requires sulphur content ≯ 10 μ g/g.
At present, catalytic cracking (FCC) is the important sources of gasoline, and if the ratio in Chinese refinery gasoline product shared by FCC gasoline is more than 80%, and in FCC gasoline, sulphur content is generally 200 ~ 1000 μ g/g, and mercaptans content is generally 20 ~ 100 μ g/g.Therefore, FCC gasoline sulphur and mercaptans content are all higher, and the sulphur content and the mercaptans content that reduce FCC gasoline are the keys meeting more stringent clean specification gasoline.
Hydrogenating desulfurization (HDS) technique is the important means of effective elimination FCC gasoline sulphur and mercaptan, but adopt traditional catalyzer and technique, while FCC gasoline hydrogenating desulfurization, alkene significantly hydrotreated lube base oil can cause larger loss of octane number.In order to reduce the loss of sweet gasoline octane value, develop many selective hydrodesulfurizations (HDS) raw catalyst and technique both at home and abroad.
U.S.Pat.6,692,635 describe a kind of low-sulphur oil production technique.Be characterized in full cut catalytic gasoline raw material first selectively removing diolefine in selective hydrogenation reactor (the first reactor), olefines double bond isomerizing and mercaptan are converted into higher boiling sulfur compound.Then, the fractionation in a separation column of selective hydrogenation product is lighting end and last running.The MoO of last running first in the first reaction zone of hydrogenator (the second reactor)
3-CoO/Al
2o
3hydrogenation on catalyzer, is converted into saturated sulfide (as tetramethylene sulfide or mercaptan) by unsaturated sulfide (as thiophene and alkylated substituted thiazoline fen thereof), then, and the NiO/Al in second reaction zone
2o
3hydrogenation on catalyzer, is converted into H by saturated sulfide (as thiophene and alkylated substituted thiazoline fen thereof)
2s.The desulfurization degree of this patented method is generally 80.0% ~ 92.0%, and product sulphur content is generally 96 μ g/g ~ 240 μ g/g, and research octane number (RON) (RON) loses 1.4 ~ 3.0 units.Its shortcoming can not meet the technology needs that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
EP1031622 discloses the method for a kind of full cut FCC gasoline hydrogenating desulfurization.The first step, by sulfide hydrotreated lube base oil unsaturated in FCC gasoline, is converted into mercaptan sulfur compounds, and saturated sulphur compound hydrodesulfurizationconversion conversion is H by second step again
2s.Its advantage is the full cut FCC gasoline of processing, and do not need to carry out fractionation, weak point is the sulphur compound major part that the finished product are remaining is mercaptan sulfur compounds, causes mercaptan sulfur in product defective.
CN 02133136.7 describes a kind of catalyst for selective hydrodesulfurizationof of gasoline and technique, and be characterized in being first lighting end and last running by FCC gasoline prefractionation, last running is at low metal/high metal content MoO
3-CoO/Al
2o
3on combination catalyst after hydrogenating desulfurization, then mix with lighting end.This patented method shortcoming is owing to containing H in last running HDS product
2the more macromolecular mercaptan that S and the rearrangement reaction of alkene secondary generate, on the one hand, reduces the degree of depth of HDS, on the other hand, follow-uply must carry out mercaptan removal process.The desulfurization degree of this patented method is generally 80.0% ~ 90.0%, product sulphur content is generally 50 μ g/g ~ 200 μ g/g, research octane number (RON) (RON) loss ≯ 2.0 units, can not meet the technology needs that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
CN 02121594.4 describes a kind of method of producing low-sulphur oil.The method is that gasoline stocks is cut into lighting end and last running, lighting end is through soda finishing mercaptan removal, last running contacts with Hydrobon catalyst together with hydrogen, carry out selective hydrodesulfurization reaction, gasoline fraction after hydrogenation carries out hydrogenation or non-hydro-sweetening, and light, last running after desulfurization are mixed to get gasoline products.The method energy production sulphur content is lower than 200 μ g/g, and the anti-knock index ((RON+MON)/2) of gasoline loses ≯ 2.0 units.Its shortcoming is, cannot meet the technology needs that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
CN 101307255A describes a kind of method of producing low sulfur gasoline by using by inferior gasoline fractions.The method first full cut bad gasoline is fixed an oxidation deodorizing, mercaptan sulfur is converted into disulphide, then fractionation is lighting end and last running, last running carries out selective hydrodesulfurization through high reactivity/low activity combined hydrogenation desulfurization catalyst, and desulfurization product and lighting end are mixed to get clean gasoline product.The method can the gasoline products of production sulphur content ≯ 10 μ g/g.But fixed bed oxidation deodorizing can cause gasoline component to contact with oxygen, accelerates green coke, is unfavorable for the long-term operation of device.
In the prior art, the subject matter that FCC gasoline produces low sulfur clean gasoline product is that several respects contradiction can not take into account solution simultaneously, as sulfide under the contradiction between desulfurization depth and loss of octane number, hydrodesulfurizationconditions conditions remove and mercaptan generate between contradiction, contradiction etc. between deodorization and desulfurization, make the clean gasoline product that existing Technology can not obtain low-sulfur simultaneously, loss of octane number is few, mercaptan is qualified.In addition, the handiness of art methods is poor, poor to the adaptability of different material, is unfavorable for the long-term operation of device.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of method of producing low-sulphur oil, adopts simple technical process, obtains sulphur content ≯ 10 μ g/g clean gasoline, and loss of octane number is few simultaneously, and device is long for running period.
The method that the present invention produces low-sulphur oil comprises the following steps:
(1) stable gasoline come from catalytic cracking unit enters hydrogenation preliminary fractionator, and extract lighting end out from tower top, separate last running at the bottom of tower, the cutting temperature of described lighting end and last running is 40 DEG C ~ 80 DEG C;
(2) step (1) gained lighting end is fixed an oxidation deodorizing, and mercaptan sulfur is converted into disulphide;
(3) step (2) gained oxidation deodorizing product is entered disulphide separation column together with thermocatalysis diesel oil, tower top goes out gasoline lighting end, extracts diesel oil distillate carrying device out at the bottom of tower;
(4) the gasoline last running fractionated out in step (1) enters hydrogenator, contacts, carry out selective hydrodesulfurization reaction with Hydrobon catalyst;
(5) step (4) gained hydrogenation products mixes after air lift with by step (3) gained lighting end, obtains the clean gasoline product that sulphur content is less than 10 μ g/g.
Light fractions of FCC naphtha described in step (1) and the cut point temperature of last running are 40 ~ 80 DEG C, are preferably 50 ~ 70 DEG C.
The method that fixed bed oxidation deodorizing described in step (2) can adopt this area common is carried out, as with sulfonation titanium cyanines cobalt for catalyzer take air as the oxidation deodorizing process of oxygenant, the sweet gasoline mercaptan sulfur after deodorization process generally can reach ≯ 10 μ g/g.
Thermocatalysis diesel oil distillate described in step (3) comes from the catalytic cracking diesel oil that catalytic cracking unit distillation tower fractionates out, and doing of catalytic diesel oil cut is generally 330 ~ 380 DEG C.The cut point temperature that sweet gasoline described in step (3) and catalytic diesel oil cut are cut into lighting end and last running is 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C, and conventional distillation mode can be adopted to carry out fractionation.
H in the hydrogen that hydrogenating desulfurization described in step (4) uses
2s content ≯ 300 μ L/L, preferably ≯ 50 μ L/L, general employing recycle hydrogen de H
2s realizes, and controls hydrodesulfurization process and uses H in hydrogen
2the content of S, effectively can control the generation of mercaptan in hydrogenation products.
CO in the hydrogen that hydrogenating desulfurization described in step (4) uses
2and/or CO content ≯ 50 μ L/L, preferably ≯ 10 μ L/L, control hydrodesulfurization process and use CO in hydrogen
2and/or the content of CO, effectively can control the hydrogenating desulfurization rate of catalyzer.
The active metal of the Hydrobon catalyst described in step (4) is generally selected from one or more in W, Mo, Ni and Co, and catalyzer can contain conven-tional adjuvants, as one or more in K, Ca, P, Si, F, B, Ti and Zr.In described Hydrobon catalyst, metal oxide content is 8.0wt% ~ 20.0wt%, is preferably 10.0wt% ~ 18.0wt%; Auxiliary agent content is 1.0wt% ~ 6.0wt%, is preferably 1.5wt% ~ 5.0wt%.
Step (3) introduces the thermocatalysis diesel oil distillate that catalytic cracking unit fractionates out, be used for dissolving a small amount of coke precursor that alkali-free sweetening unit generates, thus the coking of heavy petrol selective hydrogenation unit can be slowed down, extend the running period of gasoline hydrodesulfurizationmethod device.Catalytic diesel oil hot feed introduced by preliminary fractionator simultaneously, both decreased upstream device fractionation unit cooling load, and further provided the heat needed for this device preliminary fractionator, and reduce further the operation energy consumption of preliminary fractionator and gasoline selective hydrogenation unit.
Total sulfur content in the lighting end that step (3) oxidation deodorizing product fractionation goes out can reach and be not more than (≯) 10 μ g/g, total sulfur content in step (4) last running selective hydrodesulfurization product also can reach ≯ 10 μ g/g, therefore the total sulfur content of step (5) mix products can reach ≯ 10 μ g/g, and loss of octane number can be less than 1.5 units.
In the prior art, the subject matter that FCC gasoline produces low-sulphur oil product is that the conversion of mercaptan in light boiling range petroleum naphtha, hydrodesulfurization process loss of octane number are many, hydrodesulfurization process is with mercaptan generation etc.Sulfur compound in light boiling range petroleum naphtha mainly mercaptan, and sulfur compound mainly thiophene and other heterocycle sulfocompounds in heavier boiling range naphtha stream, so carry out separation separately through fractionation can not remove mercaptan.If think the clean gasoline of production sulphur content ≯ 10 μ g/g, the sulfide Mercaptan removal in light boiling range petroleum naphtha or conversion must attached most importance to.Mercaptan in light boiling range petroleum naphtha can be transformed the sulfide of attaching most importance to by fixed bed oxidation deodorizing method, do not lose octane value, but oxidation deodorizing process can cause gasoline component to contact with oxygen simultaneously, accelerates green coke, is unfavorable for the long-term operation of device simultaneously.
The present invention first fractionates out lighting end and last running through separation column to catalytically cracked gasoline, an oxidation deodorizing is fixed to lighting end, and mix with thermocatalysis diesel oil, in lighting end, lower boiling mercaptan changes into high boiling disulphide and is dissolved in thermocatalysis diesel oil, a small amount of coke precursor that simultaneous oxidation deodorization generates, because boiling range is heavier, is also dissolved in diesel oil distillate.Using diesel oil distillate as diesel hydrotreating unit charging, be indirectly stripped of coke precursor, slow down the coking of heavy petrol selective hydrogenation unit, prolong operating period.Simultaneously under the condition of deep desulfuration, the loss of octane number of the inventive method is also very low.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
Gasoline stocks described in the inventive method is fluid catalytic cracking (FCC) gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline etc. or its mixture.The preferred raw material of the present invention is FCC gasoline.Described inferior patrol hydrogenating materials can be full cut FCC gasoline, and its boiling range is generally 30 DEG C ~ 220 DEG C, particularly 30 DEG C ~ 180 DEG C.
Fixed bed oxidation deodorizing technique described in the inventive method can adopt arbitrary form of the prior art, as adopted alkali-free sweetening treatment process etc.Fixed bed oxidation deodorizing technique illustrates, as US4033806, US4481106, US4746494, US5741415, US5849656, US5858212, US5961819, CN1028765C, CN1031854A, CN1670134A etc. in many patent documentations.Therefore, any those of ordinary skill in the art can process according to existing method.
The cut point temperature of the FCC gasoline lighting end separated from the first separation column of the present invention is 40 ~ 80 DEG C, and be preferably 50 ~ 70 DEG C, the yield of lighting end is generally the 20.0wt% ~ 40.0wt% of gasoline stocks.The lighting end cut point temperature that oxidation deodorizing aftercut obtains is 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C, the total sulfur content ≯ 10 μ g/g of the lighting end that oxidation deodorizing aftercut obtains; Total sulfur content ≯ 10 μ the g/g of catalytically cracked gasoline last running selective hydrogenation product.
De-H of the present invention
2s recycle hydrogen is control H preferably
2s content ≯ 50 μ L/L, CO
2and/or CO content preferably ≯ 10 μ L/L.Recycle hydrogen de H
2s method is generally conventional hydramine method.The flow process of alcohol amine method technology is generally: from reactive system containing H
2s hydrogen stream and hydramine adsorption solvent (as ethylene glycol amine) counter current contact in adsorption tower, de-H
2the hydrogen of S is discharged from tower top, after recycle compressor boosting, enter reactive system; Enter into solvent regeneration tower after manipulation of regeneration from the hydramine adsorption solvent of discharging bottom adsorption tower, return in adsorption tower and continue to use.Above-mentioned de-H
2s method is this area general knowledge, and those skilled in the art can process according to existing method.
Hydrobon catalyst of the present invention can be conventional Hydrobon catalyst, be active ingredient by one or more base metals in group vib in the periodic table of elements and/or group VIII, with one or more in amorphous alumina, silicon-containing alumina and titanium-contained aluminum oxide for carrier, can also auxiliary agent be contained, as one or more in phosphorus, potassium, fluorine.
In described Hydrobon catalyst, metal oxide content is 8.0wt% ~ 20.0wt%, particularly 10.0wt% ~ 18.0wt%; Auxiliary agent content is 1.0wt% ~ 6.0wt%, particularly 1.5wt% ~ 5.0wt%; Described active metal be preferably in cobalt, molybdenum, nickel and tungsten one or more.Auxiliary agent be preferably in phosphorus, potassium and fluorine one or more.This catalyzer can adopt pickling process to prepare, and can adopt step impregnation method, also can adopt co-impregnation.Steeping fluid can wait adsorptive capacity to flood, and also can be the excessive dipping of steeping fluid.
The present invention adopts selective hydrogenation desulfurization process condition to be: hydrogen dividing potential drop is generally 0.5MPa ~ 5.0MPa, and temperature of reaction is generally 230 DEG C ~ 330 DEG C, and during liquid, volume space velocity is generally 2.0h
-1~ 15.0h
-1, hydrogen to oil volume ratio is generally 200: 1 ~ 1000: 1; Hydrogen dividing potential drop is preferably 0.8MPa ~ 3.0MPa, and temperature of reaction is preferably 250 DEG C ~ 280 DEG C, and during liquid, volume space velocity is preferably 4.0h
-1~ 10.0h
-1, hydrogen to oil volume ratio is preferably 200: 1 ~ 700: 1.
The inventive method can when research octane number (RON) (RON) loss is not more than (≯) 1.5 units the clean gasoline of production sulphur content ≯ 10 μ g/g, mercaptan sulfur content ≯ 10 μ g/g, meet the technology needs of production sulphur content ≯ 10, oil refining enterprise μ g/g clean gasoline.
Below in conjunction with the further the inventive method process of drawings and Examples and effect.Logistics and each unit operation carry out in the direction of the arrow in order.
Below in conjunction with Fig. 1, the inventive method is described in detail.
Catalytically cracked gasoline 1 fractionates out lighting end gasoline 2 and last running gasoline 3 in hydrogenation preliminary fractionator A.Lighting end gasoline 2 enters oxidation deodorizing unit B and realizes mercaptan conversion, gasoline lighting end 4 after conversion mixes with the hot diesel oil 5 of catalytic cracking come from catalytic cracking fractionating tower, after interchanger C heat exchange, fractionate out light FCC gasoline 6 and catalytic diesel oil 7 in disulphide separation column D, catalytic diesel oil 7 removes diesel hydrotreating unit 10 after interchanger C heat exchange.The light FCC gasoline 6 fractionated out in disulphide separation column D goes product to be in harmonious proportion.The catalytically cracked gasoline last running 3 fractionated out from hydrogenation preliminary fractionator A enters hydrofining reactor E and carries out selective hydrodesulfurization reaction, and reaction product 8 and light FCC gasoline 6 are in harmonious proportion and obtain clean gasoline product 9.
Further illustrate the solution of the present invention and effect below by embodiment, but therefore do not limit the present invention.
example 1
This example adopts step impregnation method to prepare a kind of selective hydrodesulfurization MoO
3(13.0wt%)-CoO (4.0wt%)-P
2o
5(1.5wt%)-K
2o-(2.0wt%)/Al
2o
3catalyzer.
Take 1000g and intend thin water-aluminum hydroxide powder (Al
2o
3contents on dry basis is 78wt%), add and account for Al
2o
3the sesbania powder extrusion aid of butt 5wt%, mass concentration are 10% aqueous nitric acid 200mL, mix and roll and be mixed into plastic powder, prepare with banded extruder the cylindrical bars that diameter is 1.5mm, drying 8 hours at 120 DEG C, at 500 DEG C, roasting 5 hours, prepares support of the catalyst.
By P on catalyzer
2o
5content is 1.5wt%, K
2o content is 2.0wt%, gets quantitative phosphoric acid, saltpetre, adds deionized water, is made into 120mL steeping fluid, then, sprays in the said catalyst carrier of 160g.Drying 10 hours at 120 DEG C, at 500 DEG C, roasting 5 hours, prepares P
2o
5(1.5wt%)-K
2o-(2.0wt%)/Al
2o
3catalyst intermediate.
By MoO on catalyzer
3content is 13.0wt%, CoO content is 4.0wt%, gets quantitative molybdenum oxide, cobaltous dihydroxycarbonate, adds deionized water, is made into 60mL steeping fluid, then, sprays in the above-mentioned catalyst intermediate of 80g.Drying 8 hours at 120 DEG C, at 490 DEG C, roasting 6 hours, prepares highly active MoO
3(13.0wt%)-CoO (4.0wt%)-P
2o
5(1.5wt%)-K
2o-(2.0wt%)/Al
2o
3catalyzer.Nitrogen absorption under low temperature BET method measures specific surface area of catalyst, pore volume character in table 1.
The physical property of table 1 example 1 catalyzer
| Project | Example 1 |
| Catalyzer is numbered | HAC |
| MoO3, wt% | 13.0 |
| CoO, wt% | 4.0 |
| K2O, wt% | 2.0 |
| P2O5, wt% | 1.5 |
| Specific surface area, m2/g | 220 |
| Pore volume, mL/g | 0.40 |
| Tap density, g/mL | 0.79 |
example 2
This example provides a kind of FCC gasoline sweetening effectiveness inferior.
(1), a kind of FCC gasoline is fractionated out <50 DEG C of petroleum naphtha and ﹥ 50 DEG C of heavy petrol through hydrogenation preliminary fractionator.
(2), <50 DEG C of light FCC gasoline oxidation deodorizing:
<50 DEG C of light FCC gasoline mercaptan-eliminating catalyst adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 40 DEG C, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/petroleum naphtha) 1: 1 condition.
(3), petroleum naphtha oxidation deodorizing product prefractionation:
<50 DEG C of light FCC gasoline oxidation deodorizing product, is mixed into preliminary fractionator with thermocatalysis diesel oil and fractionates out <50 DEG C of lighting end and >50 DEG C of last running.<50 DEG C of lighting end goes product to be in harmonious proportion, and >50 DEG C of double distilled is divided into the catalytic diesel oil having dissolved macromole sulfide and the green coke precursor transformed.Table 2 lists the <50 DEG C of FCC gasoline lighting end separated from separation column, the character of the <50 DEG C of FCC gasoline lighting end separated from preliminary fractionator after >50 DEG C FCC gasoline last running and oxidation deodorizing and thermocatalysis bavin oil properties.
(4), >50 DEG C of catalytically cracked gasoline heavy fractioning hydrogenation desulfurization:
Evaluation test carries out on the device of fixed-bed reactor, loads catalyzer prepared by 50mL example 1 in reactor.
Airtight qualified after, first carry out catalyst vulcanization.Vulcanized oil is straight-run spirit, and vulcanizing agent is CS
2, CS
2concentration is 1.0v%; Sulfide stress is 1.6MPa, and circulation hydrogen to oil volume ratio is 300: 1, and vulcanized oil volume space velocity is 2.0h
-1, constant temperature 8 hours at temperature is 230 DEG C, constant temperature 8 hours at 300 DEG C.
After sulfuration terminates, switch >50 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.6MPa, uses not sulfide hydrogen and CO/CO
2fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 260 DEG C.Steady running sampling analysis in 100 hours.
(5), >50 DEG C of heavy fractioning hydrogenation desulfurization mixes with <50 DEG C of lighting end
>50 DEG C of heavy fractioning hydrogenation desulphurization reaction thing mixes according to cutting ratio with the <50 DEG C of lighting end that prefractionation goes out.The character of clean gasoline product after table 3 lists raw material FCC gasoline and processes.
The character of FCC gasoline in table 2 example 2, lighting end and last running
| Project | FCC gasoline | < 50 DEG C of lighting ends | > 50 DEG C of last running | < 50 DEG C of lighting ends after deodorization | Fractionation after heat diesel oil distillate |
| Cutting ratio, wt% | 100 | 25.8 | 74.2 | — | — |
| Density, g/mL | 0.7232 | 0.6456 | 0.7550 | 0.6456 | 0.9400 |
| Sulphur content, μ g/g | 460 | 37 | 520 | 10 | 9800 |
| Mercaptans content, μ g/g | 34.2 | 61.9 | 12 | 7 | — |
| Olefin(e) centent, v% | 25.6 | 35.0 | 16.0 | 35.0 | — |
| Research octane number (RON) | 92.4 | 94.8 | 90.5 | 94.8 | — |
| Boiling range, DEG C | 32～188 | 30～52 | 48～190 | 30～52 | 178~360 |
The character of table 3 example 2 oil product
| Project | FCC gasoline | > 50 DEG C of heavy fractioning hydrogenation products | Mixing oil |
| Density, g/mL | 0.7232 | 0.7551 | 0.7233 |
| Sulphur content, μ g/g | 460 | 5.0 | 9.5 |
| Mercaptan sulfur content, μ g/g | 34.2 | 6.0 | 9.2 |
| Olefin(e) centent, v% | 25.6 | 10.3 | 21.0 |
| Research octane number (RON) | 92.4 | 87.5 | 91.2 |
| C5+ yield, wt% | — | 99.8 | 99.9 |
| The steady running cycle, h | — | 8000 | — |
As can be seen from Table 3: the sulphur content of FCC gasoline can be reduced to 9.5 μ g/g by 460 μ g/g by method of the present invention, mercaptan sulfur content is reduced to 9.2 μ g/g by 34.2 μ g/g, olefin(e) centent is reduced to 21.0v% by 25.6v%, and research octane number (RON) RON loses 1.2 units, C
5 +yield of gasoline 99.9wt%, steady running 8000 hours, can be processed as sulphur content ≯ 10 μ g/g high-quality cleaning product by FCC gasoline, simultaneously can long-term operation.
comparative example 1
This comparative example provides a kind of FCC gasoline sweetening effectiveness inferior.
(1), stock oil mercaptan removal
Stock oil mercaptan-eliminating catalyst adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 40 DEG C, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/FCC gasoline) 1: 1 condition.
(2), stock oil lighting end, last running cutting
For cut point temperature, FCC gasoline after deodorization is separated into <50 DEG C of lighting end and >50 DEG C of last running with 50 DEG C, table 4 lists the character of FCC gasoline, <50 DEG C lighting end and >50 DEG C of last running.
(3), >50 DEG C of heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, loads catalyzer prepared by 50mL example 1 in reactor.
Airtight qualified after, first carry out catalyst vulcanization.Vulcanized oil is straight-run spirit, and vulcanizing agent is CS
2, CS
2concentration is 1.0v%; Sulfide stress is 1.6MPa, and circulation hydrogen to oil volume ratio is 300: 1, and vulcanized oil volume space velocity is 2.0h
-1, constant temperature 8 hours at temperature is 230 DEG C, constant temperature 8 hours at 300 DEG C.
After sulfuration terminates, switch >50 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.3MPa, and use not hydrogen sulfide containing fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 280 DEG C.Steady running sampling analysis in 100 hours.
(4), >50 DEG C of heavy fractioning hydrogenation desulfurization mixes with <50 DEG C of lighting end
>50 DEG C of heavy fractioning hydrogenation desulphurization reaction thing mixes according to cutting ratio with the <50 DEG C of lighting end that prefractionation goes out.The character of clean gasoline product after table 5 lists raw material FCC gasoline and processes.
The character of FCC gasoline in table 4 comparative example 1, lighting end and last running
| Project | FCC gasoline | Deodorization FCC gasoline | < 50 DEG C of lighting ends | > 50 DEG C of last running |
| Cutting ratio, wt% | 100 | 100 | 25.8 | 74.2 |
| Density, g/mL | 0.7232 | 0.7232 | 0.6456 | 0.7550 |
| Sulphur content, μ g/g | 460 | 455 | 10 | 590 |
| Mercaptans content, μ g/g | 34.2 | 8.8 | 7 | 10 |
| Olefin(e) centent, v% | 25.6 | 25.6 | 35.0 | 16.0 |
| Research octane number (RON) | 92.4 | 92.4 | 94.8 | 90.5 |
| Boiling range, DEG C | 32～188 | 32～188 | 30～52 | 48～190 |
The character of table 5 comparative example 1 oil product
| Project | FCC gasoline | > 50 DEG C of heavy fractioning hydrogenation products | Mixing oil |
| Density, g/mL | 0.7232 | 0.7551 | 0.7233 |
| Sulphur content, μ g/g | 460 | 18.0 | 16.0 |
| Mercaptan sulfur content, μ g/g | 34.2 | 6.0 | 6.2 |
| Olefin(e) centent, v% | 25.6 | 11.0 | 21.5 |
| Research octane number (RON) (RON) | 92.4 | 88.5 | 91.2 |
| C 5 +Yield, wt% | — | 99.8 | 99.9 |
| The steady running cycle, h | — | 2000 | — |
As can be seen from Table 5: the sulphur content of FCC gasoline can be reduced to 16 μ g/g by 460 μ g/g by this comparative example, mercaptan sulfur content is reduced to 6.2 μ g/g by 34.2 μ g/g, olefin(e) centent is reduced to 21.5v% by 25.6v%, and research octane number (RON) RON loses 1.2 units, C
5 +yield of gasoline 99.9wt%, steady running 2000 hours.
Can find out, under identical processing condition, compared with comparative example, desulfurization degree of the present invention is higher, and loss of octane number is identical.And technical process of the present invention is because only carry out oxidation deodorizing to light fractions of FCC naphtha, the green coke precursor that oxidation deodorizing produces is separated simultaneously, avoid at hydrogenation unit green coke, can steady running cycle of extension fixture.
example 3
This example provides another kind of FCC gasoline sweetening effectiveness inferior.
(1), a kind of FCC gasoline is fractionated out <70 DEG C of petroleum naphtha > 70 DEG C of heavy petrol through hydrogenation preliminary fractionator.
(2), <70 DEG C of light FCC gasoline oxidation deodorizing
<70 DEG C of light FCC gasoline mercaptan-eliminating catalyst adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 40 DEG C, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/petroleum naphtha) 1: 1 condition.
(3), petroleum naphtha oxidation deodorizing product prefractionation
<70 DEG C of light FCC gasoline oxidation deodorizing product, is mixed into preliminary fractionator with thermocatalysis diesel oil and fractionates out <70 DEG C of lighting end and >70 DEG C of last running.<70 DEG C of lighting end goes product to be in harmonious proportion, and >70 DEG C of double distilled is divided into the catalytic diesel oil having dissolved macromole sulfide and the green coke precursor transformed.Table 6 lists the character of the <70 DEG C of FCC gasoline lighting end separated from separation column, the <70 DEG C of FCC gasoline lighting end separated from preliminary fractionator after >70 DEG C FCC gasoline last running and oxidation deodorizing.
(4), >70 DEG C of catalytically cracked gasoline heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, loads catalyzer prepared by 50mL example 1 in reactor.
Airtight qualified after, first carry out catalyst vulcanization.Vulcanized oil is straight-run spirit, and vulcanizing agent is CS
2, CS
2concentration is 1.0v%; Sulfide stress is 1.6MPa, and circulation hydrogen to oil volume ratio is 300: 1, and vulcanized oil volume space velocity is 2.0h
-1, constant temperature 8 hours at temperature is 230 DEG C, constant temperature 8 hours at 300 DEG C.
After sulfuration terminates, switch >70 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.6MPa, uses not sulfide hydrogen and CO/CO
2fresh hydrogen, volume space velocity is 3.0h
-1, in 2 hours, be cooled to 280 DEG C.Steady running sampling analysis in 100 hours.
(5), >70 DEG C of heavy fractioning hydrogenation desulfurization mixes with <70 DEG C of lighting end
>70 DEG C of heavy fractioning hydrogenation desulphurization reaction thing mixes according to cutting ratio with the <70 DEG C of lighting end that prefractionation goes out.The character of clean gasoline product after table 7 lists raw material FCC gasoline and processes.
The character of FCC gasoline in table 6 example 3, lighting end and last running
| Project | FCC gasoline | < 70 DEG C of lighting ends | > 70 DEG C of last running | < 70 DEG C of lighting ends after deodorization | Fractionation after heat catalytic diesel oil |
| Cutting ratio, wt% | 100 | 35.2 | 64.8 | — | — |
| Density, g/mL | 0.7110 | 0.6308 | 0.7510 | 0.6308 | 0.94 |
| Sulphur content, μ g/g | 660 | 118 | 900 | 7 | 9800 |
| Mercaptans content, μ g/g | 32 | 44.6 | 16 | 3 | — |
| Olefin(e) centent, v% | 31.0 | 40.0 | 22 | 40.0 | — |
| Research octane number (RON) | 93.3 | 94.0 | 91.0 | 94.0 | — |
| Boiling range, DEG C | 32～178 | 30～71 | 68～179 | 30～71 | 178～360 |
The character of table 7 example 3 oil product
| Project | FCC gasoline | > 70 DEG C of heavy fractioning hydrogenation products | Mixing oil |
| Density, g/mL | 0.7110 | 0.7511 | 0.7110 |
| Sulphur content, μ g/g | 660 | 9.0 | 8.5 |
| Mercaptan sulfur content, μ g/g | 32.0 | 7.0 | 6 |
| Olefin(e) centent, v% | 31.0 | 13.3 | 26.8 |
| Research octane number (RON) | 93.3 | 89.3 | 91.8 |
| C 5 +Yield, wt% | — | 99.8 | 99.9 |
| The steady running cycle, h | — | 8000 | — |
As can be seen from Table 7: the sulphur content of FCC gasoline can be reduced to 8.5 μ g/g by 660 μ g/g by method of the present invention, mercaptan sulfur content is reduced to 6.0 μ g/g by 32.0 μ g/g, olefin(e) centent is reduced to 26.8v% by 31.0v%, and research octane number (RON) RON loses 1.5 units, C
5 +yield of gasoline 99.9wt%, steady running 8000 hours, can be processed as the high-quality cleaning product of sulphur content ≯ 10 μ g/g by FCC gasoline inferior, simultaneously can long-term operation.
Claims (9)
1. produce a method for low-sulphur oil, comprise the following steps:
(1) stable gasoline come from catalytic cracking unit enters hydrogenation preliminary fractionator, and extract lighting end out from tower top, separate last running at the bottom of tower, the cutting temperature of described lighting end and last running is 40 DEG C ~ 80 DEG C;
(2) step (1) gained lighting end is fixed an oxidation deodorizing, and mercaptan sulfur is converted into disulphide;
(3) step (2) gained oxidation deodorizing product is entered disulphide separation column together with thermocatalysis diesel oil, tower top goes out gasoline lighting end, extracts diesel oil distillate carrying device out at the bottom of tower; Described thermocatalysis diesel oil comes from the catalytic cracking diesel oil that catalytic cracking unit distillation tower fractionates out, and doing of catalytic cracking diesel oil is 330 DEG C ~ 380 DEG C;
(4) the gasoline last running fractionated out in step (1) enters hydrogenator, contacts, carry out selective hydrodesulfurization reaction with Hydrobon catalyst;
(5) step (4) gained hydrogenation products mixes after air lift with by step (3) gained lighting end, obtains the clean gasoline product that sulphur content is less than 10 μ g/g.
2. in accordance with the method for claim 1, it is characterized in that, the cut point temperature of the light fractions of FCC naphtha described in step (1) and last running is 50 ~ 70 DEG C.
3. in accordance with the method for claim 1, it is characterized in that, doing of the gasoline lighting end described in step (3) is 40 ~ 80 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, the active metal of the Hydrobon catalyst described in step (4) is selected from one or more in W, Mo, Ni and Co, and one or more containing in K, Ca, P, Si, F, B, Ti and Zr of catalyzer are auxiliary agent.
5. according to the method described in claim 1 or 4, it is characterized in that, in described Hydrobon catalyst, metal oxide content is 8.0wt% ~ 20.0wt%, and auxiliary agent content is 1.0wt% ~ 6.0wt%.
6. in accordance with the method for claim 1, it is characterized in that, the described stable gasoline next from catalytic cracking unit comprises the cut that boiling range is 30 DEG C ~ 220 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, the selective hydrogenation desulfurization process condition described in step (4) is: hydrogen dividing potential drop is 0.5MPa ~ 5.0MPa, and temperature of reaction is 230 DEG C ~ 330 DEG C, and during liquid, volume space velocity is 2.0h
-1~ 15.0h
-1, hydrogen to oil volume ratio is 200: 1 ~ 1000: 1.
8. in accordance with the method for claim 1, it is characterized in that, H in the hydrogen that the hydrogenating desulfurization described in step (4) uses
2s content ≯ 300 μ L/L, CO
2and/or CO content ≯ 50 μ L/L.
9. according to the method described in claim 1 or 7, it is characterized in that, described selective hydrogenation desulfurization process condition is, hydrogen dividing potential drop is 0.8MPa ~ 3.0MPa, and temperature of reaction is 250 DEG C ~ 280 DEG C, and during liquid, volume space velocity is 4.0h
-1~ 10.0h
-1, hydrogen to oil volume ratio is 200: 1 ~ 700: 1.
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| US6334948B1 (en) * | 1998-11-18 | 2002-01-01 | Institut Francais Du Petrole | Process for producing gasoline with a low sulphur content |
| CN101220295A (en) * | 2008-02-03 | 2008-07-16 | 天津大学 | Device and method for catalytically cracked gasoline and diesel oil coupling desulfurization |
| CN101307255A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334948B1 (en) * | 1998-11-18 | 2002-01-01 | Institut Francais Du Petrole | Process for producing gasoline with a low sulphur content |
| CN101307255A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Process for producing sweet gas for poor-quality gasoline distillate |
| CN101220295A (en) * | 2008-02-03 | 2008-07-16 | 天津大学 | Device and method for catalytically cracked gasoline and diesel oil coupling desulfurization |
| CN101787307A (en) * | 2009-01-22 | 2010-07-28 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization method |
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