CN103059953B - Technological method for producing super-clean gasoline - Google Patents
Technological method for producing super-clean gasoline Download PDFInfo
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Abstract
The invention discloses a technological method for producing super-clean gasoline. The method comprises: introducing catalytic cracking gasoline into a hydrogenation prefractionator to undergo fractionation so as to obtain light fraction and heavy fraction, subjecting the light fraction to fixed bed oxidation deodorization, converting mercaptan into a disulfide, mixing the deodorized product with thermocatalytic diesel oil, subjecting the mixture to fractionation in a fractionating tower so as to obtain light fraction and diesel oil fraction; and subjecting the catalytic cracking gasoline heavy fraction to hydrodesulfurization through a high activity/low activity combined hydrogenation catalyst, and mixing the desulfurization product with the deodorized light fraction 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 processing method of producing ultra-clean gasoline, specifically, the present invention relates to a kind of prolong operating period, and produce the processing method of ultra-clean gasoline.
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.
US6,692,635 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 anti-knock index ((RON+MON)/2) loss of gasoline is not more than 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 processing method of producing ultra-clean gasoline, adopts the method for staging treating, 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 ultra-clean gasoline 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) lighting end in step (1) is fixed an oxidation deodorizing, mercaptan sulfur is converted into disulphide;
(3) by gained oxidation deodorizing product in step (2) and the mixing of thermocatalysis diesel oil distillate, fractionate out gasoline lighting end and diesel oil distillate through separation column, diesel oil distillate is as diesel hydrotreating unit charging, and doing of gasoline lighting end is 40 DEG C ~ 80 DEG C;
(4) in step (1), the last running of gained gasoline mixes with hydrogen, by high reactivity/low activity combined hydrogenation desulfurization catalyst bed, under hydrodesulfurization reaction condition, carries out selective hydrodesulfurization reaction;
(5) hydrogenation products step (4) obtained and the clean gasoline product lighting end of step (3) gained gasoline being mixed to get sulphur content and being 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; Or alkali-free sweetening technology can be adopted to carry out mercaptan removal, and 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 general control ≯ 300 μ L/L, preferably ≯ 50 μ L/L are general by adopting recycle hydrogen de H
2s realizes.Control hydrodesulfurization process and use 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 g/g, preferably ≯ 10 μ g/g, control hydrodesulfurization process and use CO in hydrogen
2and/or the content of CO, effectively can control the hydrogenating desulfurization rate of catalyzer.
In high reactivity described in step (4)/low activity combined hydrogenation desulfurization catalyst bed, the general content by changing active metal in catalyzer is to regulate the hydrodesulfurization activity of catalyzer.In catalyzer, active metallic content can differ 5.0wt% ~ 18.0wt% with oxide basis, preferably differs 8.0wt% ~ 15.0wt%.Hydrogenation active metals is generally selected from one or more in W, Mo, Ni and Co, can contain conven-tional adjuvants, as one or more in K, Ca, P, Si, F, B, Ti and Zr in catalyzer.In described high activity hydrogenation and desulphurization catalyst, active metallic content take oxide basis as 8.0wt% ~ 20.0wt%, is preferably 10.0wt% ~ 18.0wt%; Auxiliary agent content is 1.0wt% ~ 6.0wt%, particularly 1.5wt% ~ 5.0wt%; In low activity Hydrobon catalyst, metal content take oxide basis as 1.0wt% ~ 12.0wt%, particularly 3.0wt% ~ 10.0wt%, and auxiliary agent content is 1.0wt% ~ 6.0wt%, particularly 1.5wt% ~ 5.0wt%.Reaction mass is successively by high activity hydrogenation and desulphurization catalyst and low activity Hydrobon catalyst.
The grating mode of described high reactivity/low activity combined hydrogenation desulfurization catalyst bed is: along Flow of Goods and Materials direction, high activated catalyst is positioned at upstream, and low activity catalyst is positioned at downstream.Wherein the ratio of the admission space of high activated catalyst/low activity catalyst is 20/80 ~ 80/20.
Step (3) introduces the thermocatalysis diesel oil distillate that catalytic cracking unit fractionates out, be used for dissolving the higher disulphide of boiling point that alkali-free sweetening unit generates and a small amount of coke precursor, 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 separation column simultaneously, both decreased the cooling load of upstream device fractionation unit, and further provided the heat needed for this device separation column, and reduce further the operation energy consumption of separation column and gasoline selective hydrogenation unit.
Total sulfur content in the lighting end that step (3) oxidation deodorizing product fractionation goes out can reach ≯ (being 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, U.S.Pat.5961819, CN1028765C, CN1031854A and 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 hydrogenation preliminary fractionator 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 cut point temperature obtaining lighting end from separation column fractionation after oxidation deodorizing 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.
In described high activity hydrogenation and desulphurization 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%; In SA Hydrobon catalyst, metal oxide content is 1.0wt% ~ 12.0wt%, particularly 3.0wt% ~ 10.0wt%, and 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.High reactivity and low activity Hydrobon catalyst can adopt identical active metal, also can adopt different active metals.Hydrobon catalyst adopts pickling process to prepare usually, 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.Described Hydrobon catalyst can select commercial goods catalyzer, or is prepared according to the Conventional wisdom of this area as required.
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 ~ 300 DEG C, and during liquid, volume space velocity is preferably 1.0h
-1~ 5.0h
-1, hydrogen to oil volume ratio is preferably 200: 1 ~ 700: 1.
In the present invention, Hydrobon catalyst system filling feature is in the reactor that high activated catalyst is positioned at upstream along logistics direction, and low activity catalyst is positioned at downstream, and reaction mass first contacts with high activated catalyst, contacts afterwards with low activity catalyst.Hydrodesulfurization process can produce a large amount of reaction heat, makes reactor lower part temperature higher (beds temperature rise), and industrial is generally by portion's injection is a large amount of in the reactor.The method of cold hydrogen controls beds temperature rise.The catalyzer of lower catalytic activity is placed on downstream by the present invention, can note cold hydrogen less, even not use cold hydrogen, not only save hydrogen usage, effectively utilize system thermal, but also achieve avoid high temperature under hydrogenation excessive, suppress olefins hydrogenation, reduce the object of loss of octane number.
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.
The inventive method process and effect is further illustrated below in conjunction with drawings and Examples.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 refining petroleum naphtha 6 and catalytic diesel oil 7 in separation column D, catalytic diesel oil 7 removes diesel hydrotreating unit 10 after interchanger C heat exchange.The refining petroleum naphtha 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 refining petroleum naphtha 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 high reactivity 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, joins the deionized water that ammonia content is 8%, 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 high activated catalyst, is called for short HAC.Nitrogen absorption under low temperature BET method measures specific surface area of catalyst, pore volume character in table 1.
example 2
This example adopts co-impregnation to prepare a kind of low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2o (2.0wt%)/Al
2o
3catalyzer.
Support of the catalyst is prepared with reference to example 1.
By MoO on catalyzer
3content is 3.0wt%, CoO content is 1.0wt% and K
2o content is 2.0wt%, gets quantitative ammonium molybdate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and saltpetre, adds the deionized water of ammonia content 16%, is made into 110mL steeping fluid, then, sprays in the said catalyst carrier of 165g.Drying 8 hours at 120 DEG C, at 500 DEG C, roasting 4 hours, prepares low activity catalyst.This catalyzer is called for short LAC, nitrogen absorption under low temperature BET method and measures specific surface area of catalyst, pore volume character in table 1.
The physical property of table 1 example 1 and 2 catalyzer
| Project | Example 1 | Example 2 |
| Catalyzer is numbered | HAC | LAC |
| MoO 3，wt% | 13.0 | 3.0 |
| CoO，wt% | 4.0 | 1.0 |
| K 2O，wt% | 2.0 | 2.0 |
| P 2O 5，wt% | 1.5 | — |
| Specific surface area, m 2/g | 220 | 240 |
| Pore volume, mL/g | 0.40 | 0.45 |
| Tap density, g/mL | 0.79 | 0.73 |
example 3
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 catalytic gasoline lighting end oxidation deodorizing:
<50 DEG C of catalytic gasoline lighting end oxidation deodorizing catalyzer adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 35 DEG C, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/petroleum naphtha) 1: 1 condition.
(3), lighting end oxidation deodorizing product prefractionation:
<50 DEG C of catalytic gasoline lighting end oxidation deodorizing product, is mixed into separation column with thermocatalysis diesel oil and fractionates out <50 DEG C of lighting end (doing 52 DEG C).<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 hydrogenation preliminary fractionator, the <50 DEG C of FCC gasoline lighting end separated from separation column after >50 DEG C FCC gasoline last running and oxidation deodorizing and thermocatalysis bavin oil properties.
(4), >50 DEG C of catalytic gasoline heavy fractioning hydrogenation desulfurization:
Evaluation test carries out on the device of fixed-bed reactor, and load 50mL high reactivity HAC and low activity LAC catalyzer in reactor, HAC/LAC volume ratio is 40/60.
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 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), the desulfurization of >50 DEG C of gasoline heavy fractioning hydrogenation mixes with <50 DEG C of gasoline 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 3, 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 3 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 | 11.5 | 22.5 |
| Research octane number (RON) | 92.4 | 88.8 | 91.5 |
| C 5 +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 22.5v% by 25.6v%, and research octane number (RON) RON loses 0.9 unit, C
5 +yield of gasoline 99.9wt%, can be processed as sulphur content ≯ 10 μ g/g high-quality cleaning product by FCC gasoline inferior, simultaneously can long-term operation.
comparative example 1
This comparative example provides a kind of FCC gasoline sweetening effectiveness inferior.
(1), stock oil oxidation deodorizing
Stock oil oxidation deodorizing catalyzer adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 35 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.
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 |
(3), >50 DEG C of heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, and load 50mL high reactivity HAC and a kind of low activity LAC catalyzer in reactor, the former with the latter volume ratio is 40/60.
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 260 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 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%.
Can find out, compared with comparative example 1, the inventive method can reach higher desulfurization degree, and loss of octane number is less simultaneously.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, effectively extend the steady running cycle of device.
example 4
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 catalytic gasoline lighting end oxidation deodorizing
<70 DEG C of catalytic gasoline lighting end oxidation deodorizing catalyzer 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 catalytic gasoline lighting end oxidation deodorizing product, is mixed into separation column with thermocatalysis diesel oil and fractionates out <70 DEG C of lighting end (doing 71 DEG C).<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 <70 DEG C of FCC gasoline lighting end separated from hydrogenation preliminary fractionator, the <70 DEG C of FCC gasoline lighting end separated from separation column after >70 DEG C FCC gasoline last running and oxidation deodorizing and thermocatalysis bavin oil properties.
The character of FCC gasoline in table 6 example 4, 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 |
(4), >70 DEG C of catalytic gasoline heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, and load 50mL high reactivity HAC and a kind of low activity LAC catalyzer in reactor, the former with the latter volume ratio is 60/40.
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 step (3) obtains.The character of clean gasoline product after table 7 lists raw material FCC gasoline and processes.
The character of table 7 example 4 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 | 18.3 | 27.0 |
| Research octane number (RON) | 93.3 | 90.3 | 92.0 |
| 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 μ g/g by 32.0 μ g/g, olefin(e) centent is reduced to 27.0v% by 31.0v%, and research octane number (RON) RON loses 1.3 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 inferior, simultaneously can long-term operation.
Claims (11)
1. produce a method for ultra-clean gasoline, 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) lighting end in step (1) is fixed an oxidation deodorizing, mercaptan sulfur is converted into disulphide;
(3) by gained oxidation deodorizing product in step (2) and the mixing of thermocatalysis diesel oil distillate, fractionate out gasoline lighting end and diesel oil distillate through separation column, diesel oil distillate is as diesel hydrotreating unit charging, and doing of gasoline lighting end is 40 DEG C ~ 80 DEG C;
(4) the gasoline last running obtained in step (1) mixes with hydrogen, by high reactivity/low activity combined hydrogenation desulfurization catalyst bed, under hydrodesulfurization reaction condition, carries out selective hydrodesulfurization reaction;
(5) hydrogenation products step (4) obtained and the clean gasoline product lighting end of step (3) gained gasoline being mixed to get sulphur content and being less than 10 μ g/g.
2. in accordance with the method for claim 1, it is characterized in that, the light fractions of FCC naphtha described in step (1) and the cut point temperature of last running are 50 ~ 70 DEG C.
3. in accordance with the method for claim 1, it is characterized in that, the 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 330 ~ 380 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, the endpoint control of the described gasoline lighting end of step (3) is 40 ~ 80 DEG C.
5. in accordance with the method for claim 1, it is characterized in that, in high reactivity described in step (4)/low activity combined hydrogenation desulfurization catalyst bed, high activated catalyst differs 5.0wt% ~ 18.0wt% with active metallic content in low activity catalyst with oxide basis.
6. according to the method described in claim 1 or 5, it is characterized in that, in described high activity hydrogenation and desulphurization catalyst, active metallic content take oxide basis as 8.0wt% ~ 20.0wt%, and auxiliary agent content is 1.0wt% ~ 6.0wt%; In described low activity Hydrobon catalyst, metal content take oxide basis as 1.0wt% ~ 12.0wt%, and auxiliary agent content is 1.0wt% ~ 6.0wt%.
7. in accordance with the method for claim 1, it is characterized in that, the grating mode of the high reactivity described in step (4)/low activity combined hydrogenation desulfurization catalyst bed is: along Flow of Goods and Materials direction, high activated catalyst is positioned at upstream, and low activity catalyst is positioned at downstream.
8. in accordance with the method for claim 1, it is characterized in that, wherein high activated catalyst is 20/80 ~ 80/20 with the ratio of the admission space of low activity catalyst.
9. 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.
10. in accordance with the method for claim 1, it is characterized in that, fixed bed oxidation deodorizing described in step (2) adopts with sulfonation titanium cyanines cobalt for catalyzer take air as the oxidation deodorizing process of oxygenant, or adopts alkali-free sweetening technology to carry out mercaptan removal.
11. 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 controls ≯ 300 μ L/L.
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