CN103450935B - A kind of method of producing super low-sulfur oil - Google Patents
A kind of method of producing super low-sulfur oil Download PDFInfo
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Abstract
The invention discloses a kind of method that inferior patrol produces super low-sulfur oil.Full cut bad gasoline is divided into lighting end and last running through prefractionation; Lighting end is fixed an oxidation deodorizing, and deodorization lighting end is carried out solvent absorbing fractionation and obtained refining petroleum naphtha; Last running is carried out selective hydrodesulfurization and is obtained refining heavy petrol; Refining petroleum naphtha and refining heavy petrol are mixed to get super low-sulfur oil.The inventive method is by complex optimum desulfurization process of gasoline flow process, select low temperature high-selective and hydrogenating desulfurization catalyst, adopt simple method can realize the target of production sulphur content ≯ 10 μ g/g gasoline products, particularly while realizing deep desulfuration, make the loss that product octane value keeps less.
Description
Technical field
The present invention relates to a kind of method that super low-sulfur oil is produced in inferior patrol cut selective hydrodesulfurization, specifically, the present invention relates to the fractionation of inferior patrol cut, mercaptan removal and hydrodesulfurization method.
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%, Europe comes into effect sulphur content after 2009 and is less than 10 μ g/g " super low-sulfur oil (ULSG) " European V emission 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; On July 1st, 2008, the major area clean gasolines such as BeiJing, China perform sulphur content and are equivalent to European IV emission standard (sulphur content ≯ 50 μ g/g); After 2013, execution sulphur content is equivalent to European V emission standard by the clean gasolines such as Beijing, Shanghai, Guangzhou.The sulphur content of the following gasoline in countries in the world requires will be more and more lower.
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 ((R+M)/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.
In above-mentioned technique, organic sulfide can generate a large amount of hydrogen sulfide (H in hydrodesulfurization process
2s) by product, under normal circumstances, H in the hydrogen of reactant
2s content is 1000 ~ 5000 μ g/g.Owing to still containing a certain amount of alkene in HDS product, H
2easily there is secondary rearrangement reaction and again generate more macromolecular mercaptan in S and alkene.Zhao Le equality people [seeing refining of petroleum and chemical industry, 2006,37 (7): 1 ~ 5] is even if result of study thinks H
2h in gas
2s is 1700 μ g/g, compared with raw material, and C in product
7mercaptan sulfur content increases by 46.6%.Although mercaptan sulfur can be reduced to lower than 10 μ g/g through conventional fixed bed oxidation deodorizing technique (as Merox technique), but, deodorizing technology is only mercaptan sulfur is converted into disulphide and is present in product, do not reduce the total sulfur content of product, therefore, limit the desulfurization depth of final product, can not meet the technology needs that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
CN101307255B describes a kind of method of producing low-sulphur oil.Full cut bad gasoline is first fixed an oxidation deodorizing by the method, mercaptan sulfur is converted into disulphide, then smelly gasoline fraction is cut into lighting end and last running, last running carries out selective hydrodesulfurization reaction under hydrodesulfurization reaction condition, then lighting end mixes with heavy fractioning hydrogenation desulfurization product, obtains sulphur content ≯ 10 μ g/g clean gasoline.The shortcoming of the method needs first to be reduced to about 40 DEG C from FCC apparatus stabilizer tower temperature at the full cut FCC gasoline raw material inferior of about 100 DEG C to enter fixed bed oxidation deodorizing, the full cut of deodorization FCC gasoline raw material inferior also needs to reheat 100 DEG C to carry out being cut into lighting end and last running with enterprising preliminary fractionator, therefore, full cut FCC gasoline raw material inferior needs cooling and heats up, and causes the method energy consumption higher.In addition, oxidation deodorizing process is easily by the Na of trace
+bring reaction unit into, affect sweetening effectiveness and the work-ing life of catalyzer.
Summary of the invention
The object of the invention is to propose a kind of method of producing super low-sulfur oil.The fractionation of inferior patrol cut, deodorization and hydrodesulfurization specifically, can reach inferior patrol cut production sulphur content ≯ 10 μ g/g clean gasoline, the double effects that loss of octane number is less simultaneously.
The square formula of ultimate principle of the present invention (1).Although, mercaptan sulfur is only converted into disulphide by oxidation deodorizing, do not reduce total sulfur content, but product disulphide boiling point is much higher than raw material mercaptan, such as, in FCC gasoline <80 DEG C of lighting end Major Sulfides ethanethio, its boiling point only 35 DEG C, be oxidized to diethyl disulfide boiling point and bring up to 110 DEG C, therefore just it can be removed from <80 DEG C of lighting end by simple distillation again, thus greatly reduce the total sulfur content of <80 DEG C of lighting end.
（1）。
The method that a kind of inferior patrol cut of the present invention produces super low-sulfur oil comprises the following steps:
(1), full cut bad gasoline is carried out prefractionation and is divided and be cut into lighting end and last running;
(2), by step (1) gained lighting end be fixed an oxidation deodorizing, mercaptan sulfur is converted into disulphide;
(3), by step (2) gained deodorization lighting end carry out solvent absorbing fractionation, disulphide is transferred in solvent and goes, reduce the total sulfur content of deodorization lighting end, obtain refining petroleum naphtha;
(4), by step (1) gained last running mix with hydrogen, and through low temperature high-selective and hydrogenating desulfurization catalyst bed, under hydrodesulfurization reaction condition, carry out selective hydrodesulfurization reaction, obtain refining heavy petrol;
(5), by step (3) gained refine petroleum naphtha to mix with the refining heavy petrol obtained in step (4), obtain the super low-sulfur oil of sulphur content ≯ 10 μ g/g.
Lighting end described in step (1) and the cut point of last running are 40 DEG C ~ 100 DEG C.Described prefractionation can adopt conventional distillation mode to carry out fractionation.
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.
Solvent absorbing fractionation described in step (3) refers to and deodorization lighting end to be mixed with lyosorption and to carry out the process of fractionation.The initial boiling point of lyosorption described in step (3) does 5 ~ 100 DEG C, as being one or more in kerosene, heavy naphtha, solar oil and aromatic hydrocarbons generally higher than lighting end.The initial boiling point of lyosorption is generally 85 DEG C ~ 200 DEG C.Obtain refining petroleum naphtha total sulfur content in step (3) and generally can reach ≯ 10 μ g/g, mercaptan sulfur content generally can reach ≯ 5 μ g/g.The lyosorption being rich in disulphide obtained after absorbing fractionation can go the devices such as diesel oil hydrogenation to carry out desulfurization process.
H in the hydrogen that hydrogenating desulfurization described in step (4) uses
2s content is general ≯ 100 μ L/L, preferably ≯ 10 μ L/L, generally adopt recycle hydrogen de H
2s realizes.In described low temperature high-selective and hydrogenating desulfurization catalyst, the general content by changing active metal in catalyzer is to regulate the desulphurizing activated of catalyzer.In catalyzer, hydrogenation active metals content is generally 5.0wt% ~ 25.0wt% with oxide basis, preferred 8.0wt% ~ 20.0wt%, and hydrogenation active metals is generally selected from one or more in W, Mo, Ni and Co.Can conven-tional adjuvants be contained, as one or more in K, Ca, P, Si, F, B, Ti and Zr in described low temperature high-selective and hydrogenating desulfurization catalyst.Auxiliary agent content is 3.0wt% ~ 15.0wt%, is preferably greater than 6.0wt% to 12.0wt%, most preferably is 6.1wt% ~ 12.0wt%.Step (1) gained last running material refines total sulfur content in heavy petrol by the hydrogenation products obtained after low temperature high-selective and hydrogenating desulfurization catalyst can reach ≯ 10 μ g/g.
In the prior art, the subject matter that inferior patrol cut (as 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, does not lose octane value simultaneously; But oxidation deodorizing process can cause gasoline component to contact with oxygen, accelerates green coke, is unfavorable for the long-term operation of device simultaneously.
The present invention first obtains lighting end and last running by prefractionation to catalytically cracked gasoline, an oxidation deodorizing is fixed to lighting end, and mix with lyosorption, the high boiling point disulphide that in lighting end, the conversion of lower boiling mercaptan generates is dissolved in lyosorption, a small amount of coke precursor that simultaneous oxidation deodorising process generates, because boiling range is heavier, is also dissolved in lyosorption.The lyosorption being rich in disulphide obtained after absorbing fractionation can go the device such as diesel oil hydrogenation or kerosene hydrogenation to carry out hydrogenating desulfurization process, indirectly be stripped of coke precursor, thus the coking phenomenon of heavy petrol selective hydrogenation unit can be slowed down, the running period of extension fixture.
Compare with the catalyst for selectively hydrodesulfurizing used in prior art, in the inventive method recommendation low temperature high-selective and hydrogenating desulfurization catalyst in auxiliary agent content higher, be generally and be greater than 6.0wt% to 12.0wt%.The auxiliary agent of high level is the modulation character of catalyzer well, obtained catalyzer is made to have good low temperature hydrodesulfurisation performance, still higher desulfurization degree can be reached when significantly can reduce (general 10 ~ 30 DEG C) in temperature of reaction, and the excessive hydrogenation of alkene can be suppressed saturated, thus effectively reduce the loss of octane number of hydrodesulfurization process.The inventive method is by complex optimum desulfurization process of gasoline flow process, select low temperature high-selective and hydrogenating desulfurization catalyst, adopt simple method can realize producing the target of premium-type gasoline product, particularly while realizing deep desulfuration, make the loss that product octane value keeps less.
Accompanying drawing explanation
Fig. 1 is a kind of block diagram of the inventive method.
Embodiment
Bad gasoline 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 boiling range is generally 30 DEG C ~ 220 DEG C, particularly 30 DEG C ~ 180 DEG C.
Fixed bed oxidation deodorizing technique of the present invention 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 FCC gasoline lighting end of the present invention and last running is 40 DEG C ~ 100 DEG C, preferably 50 ~ 90 DEG C, the yield of lighting end is generally the 20.0wt% ~ 40.0wt% of gasoline stocks, the refining petroleum naphtha total sulfur content ≯ 10 μ g/g that lighting end oxidation deodorizing obtains; The yield of last running is generally the 60.0wt% ~ 80.0wt% of gasoline stocks.
De-H of the present invention
2s recycle hydrogen is control H preferably
2s content ≯ 100 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 hydrogenation active component 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; usually auxiliary agent can also be contained, as one or more in phosphorus, potassium, fluorine.
In low temperature high-selective and hydrogenating desulfurization catalyst of the present invention, active metal oxide content can 5.0wt% ~ 25.0wt%, preferred 8.0wt% ~ 20.0wt%, and hydrogenation active metals is generally selected from one or more in W, Mo, Ni and Co; High-selective and hydrogenating desulfurization catalyst can contain conven-tional adjuvants, as one or more in K, Ca, P, Si, F, B, Ti and Zr.Auxiliary agent content is 3.0wt% ~ 15.0wt%, is preferably greater than 6.0wt% to 12wt%(>6.0wt% ~ 12wt%).This catalyzer can adopt pickling process to prepare, and as adopted 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 method can when research octane number (RON) (RON) loss ≯ 2.0 units production sulphur content ≯ 10 μ g/g, mercaptan sulfur content ≯ 10 μ g/g super low-sulfur oil, meet the technology needs of production sulphur content ≯ 10, oil refining enterprise μ g/g super low-sulfur oil (sweet 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.Wherein, the low temperature height selective hydrodesulfrization catalyzer that reactor D loads generally can be divided into upper bed layer and lower bed layer, and middle liquid hydrogen injection controls the temperature rise between upper bed layer, lower bed layer, to regulate the hydrodesulfurization reaction degree of depth.
Below in conjunction with Fig. 1, the inventive method is described in detail.
Full distillation gasoline raw material 1 enters preliminary fractionator A and is cut into lighting end 2 and last running 3; Lighting end 2 enters air sweetening in alkali-free sweetening fixed bed oxidation desulfur reaction device B; Oxidation dealcoholysis product and lyosorption 4 are mixed into knockout tower C, and go out refining petroleum naphtha 6 and thick solvent 5 by fractionation separates, the thick solvent 5 being rich in disulphide goes the devices such as diesel oil hydrogenation to carry out desulfurization process; Last running 3 mixes with recycle hydrogen 10 after interchanger G heats heats through process furnace F, reacting by heating thing 7 enters hydrogenating desulfurization in hydrodesulphurisatioreactors reactors D, and reactant flow effluent 8 enters in gas-liquid separator E and is separated into refining heavy petrol 12 and circulation gas 9 after interchanger G lowers the temperature.It is that recycle hydrogen 10 mixes with last running 3 that circulation gas 9 removes hydrogen sulfide rear portion, and a part is squeezed into reactor D from catalyst bed interlayer as cold hydrogen 11.Refining heavy petrol 12 and refining petroleum naphtha 6 are mixed to get super low-sulfur oil product 13.Supplement new hydrogen to introduce at recycle hydrogen pipeline.
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 step impregnation method prepares a kind of low temperature height selective hydrodesulfrization catalyzer MoO
3(13.0wt%)-CoO (4.0wt%)-P (1.6wt%)-K (4.5wt%)/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.
Be 1.6wt%, K content by P content on catalyzer be 4.5wt%, get quantitative phosphoric acid, saltpetre, add deionized water, be made into 120mL steeping fluid, then, spray in the said catalyst carrier of 160g.Drying 10 hours at 120 DEG C, roasting 5 hours at 500 DEG C, prepares P (1.5wt%)-K (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 high reactivity MoO
3(13.0wt%)-CoO (4.0wt%)-P (1.6wt%)-K (4.5wt%)/Al
2o
3catalyzer.This catalyzer is called for short ME-1.Nitrogen absorption under low temperature BET method measures specific surface area of catalyst, pore volume character.
Table 1 lists the physico-chemical property of ME-1 catalyzer.
example 2
This example co-impregnation prepares another kind of low temperature height selective hydrodesulfrization catalyzer MoO
3(10.0wt%)-CoO (3.5wt%)-Ti (8.0wt%)-P (1.3wt%)-K (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 in Ti
2o
3the titanium dioxide of butt 10wt% 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 MoO on catalyzer
3content is 10.0wt%, CoO content be 3.5wt% and P content be 1.3wt%, K content is 2.0wt%, get quantitative ammonium molybdate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and saltpetre, urea, add deionized water, be made into 110mL steeping fluid, then, spray in the said catalyst carrier of 165g.Drying 8 hours at 120 DEG C, at 500 DEG C, roasting 4 hours, prepares MoO
3(10.0wt%)-CoO (3.5wt%)-Ti (8.0wt%)-P (1.3wt%)-K (2.0wt%)/Al
2o
3catalyzer.This catalyzer is called for short ME-2.Nitrogen absorption under low temperature BET method measures specific surface area of catalyst, pore volume character.
Table 1 lists the physico-chemical property of ME-2 catalyzer.
comparative example 1
This comparative example prepares another kind of Hydrobon catalyst MoO according to patent CN101307255B step impregnation method
3(10.0wt%)-CoO (3.5wt%)-P (1.5wt%)-K (2.5wt%)/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.
Be 1.2wt%, K content by P content on catalyzer be 1.5wt%, get quantitative potassium primary phosphate, add deionized water, be made into 120mL steeping fluid, then, spray 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(1.2wt%)-K
2o-(1.5wt%)/Al
2o
3catalyst intermediate.
By MoO on catalyzer
3content is 10.0wt%, CoO content is 3.5wt%, gets quantitative ammonium molybdate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, adds deionized water, 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 MoO
3(10.0wt%)-CoO (3.5wt%)-P (1.2wt%)-K (1.5wt%)/Al
2o
3catalyzer.This catalyzer is called for short R-1.Nitrogen absorption under low temperature BET method measures specific surface area of catalyst, pore volume character.
Table 1 lists the physico-chemical property of R-1 catalyzer.
The physical property of table 1 catalyzer.
| Project | Example 1 | Example 2 | Comparative example 1 |
| Catalyzer is numbered | ME-1 | ME-2 | R-1 |
| MoO 3, wt% | 13.0 | 10.0 | 10.0 |
| CoO, wt% | 4.0 | 3.5 | 3.5 |
| Ti, wt% | / | 8.0 | / |
| K, wt% | 4.5 | 2.0 | 2.5 |
| P, wt% | 1.6 | 1.3 | 1.5 |
| Specific surface area, m 2/g | 210 | 180 | 220 |
| Pore volume, mL/g | 0.48 | 0.43 | 0.49 |
| Tap density, g/mL | 0.79 | 0.82 | 0.78 |
example 3-4
Example 3-4 provides a kind of FCC gasoline sweetening effectiveness inferior.
(1), stock oil prefractionation is lighting end, last running
For cut point temperature, full cut FCC gasoline is separated into <55 DEG C of lighting end and >55 DEG C of last running with 55 DEG C, table 2 lists the character of FCC gasoline, <55 DEG C lighting end and >55 DEG C of last running.
The character of the full cut FCC gasoline of table 2, lighting end and last running.
| Project | Full cut FCC gasoline | < 55 DEG C of lighting ends | > 55 DEG C of last running |
| Cutting ratio, wt% | 100 | 27.0 | 73.0 |
| Density, g/mL | 0.7232 | 0.6456 | 0.7550 |
| Sulphur content, μ g/g | 450 | 40.0 | 610 |
| Mercaptans content, μ g/g | 30.2 | 35.0 | 28.4 |
| Olefin(e) centent, v% | 27.6 | 38.0 | 16.0 |
| Research octane number (RON), RON | 92.4 | 94.8 | 90.5 |
| Boiling range, DEG C (initial boiling point ~ final boiling point) | 32～188 | 30～55 | 50～188 |
(2), <55 DEG C of lighting end mercaptan removal and diesel oil absorption extraction
<55 DEG C of lighting end mercaptan removal oxygenant adopts commodity AFS-12 catalyzer (buying from University of Petroleum), at pressure 0.5MPa, temperature 35 DEG C ~ 45 DEG C, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/catalyzer) 4:1 condition and obtain thick petroleum naphtha.
According to the mass ratio of 50%:50%, thick petroleum naphtha is mixed with catalytic diesel oil, and carry out distillation cutting, obtain refining petroleum naphtha and thick catalytic diesel oil respectively, and sampling analysis.Thick petroleum naphtha, catalytic diesel oil and refining petroleum naphtha, thick catalytic diesel oil character are in table 3.
Table 3 lighting end mercaptan removal and solvent absorbing raw material and product characteristics.
| Project | < 55 DEG C of lighting ends | Catalytic diesel oil | Refining petroleum naphtha | Thick catalytic diesel oil |
| Mass ratio, wt% | 50 | 50 | 50 | 50 |
| Density, g/mL | 0.6456 | 0.94 | 0.6456 | 0.94 |
| Sulphur content, μ g/g | 40.0 | 9010 | 7.0 | 9026 |
| Mercaptans content, μ g/g | 35.0 | / | 3.0 | / |
| Olefin(e) centent, v% | 38.0 | / | 35.0 | / |
| Research octane number (RON), RON | 94.8 | / | 94.8 | / |
| Boiling range, DEG C (initial boiling point ~ final boiling point) | 30～55 | 178～360 | 30～55 | 178～360 |
(3), >55 DEG C of heavy fractioning hydrogenation desulfurization
Heavy fractioning hydrogenation desulfurization test carries out on the device of fixed-bed reactor.Load the ME-1 catalyzer of 50mL in example 3 in reactor, in example 4, in reactor, load the ME-2 catalyzer of 50mL.
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 >55 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.6MPa, and use not hydrogen sulfide containing fresh hydrogen, hydrogen to oil volume ratio is 300, and volume space velocity is 3.0h
-1, in 4 hours, be cooled to temperature of reaction 260 DEG C.Steady running 100 hours, obtains refining heavy petrol, and sampling analysis.
(4), refining heavy petrol mixes with refining petroleum naphtha
Refining heavy petrol mixes according to prefractionation lighting end, the last running ratio of cutting with refining petroleum naphtha.The character of clean gasoline product after table 4, table 5 list raw material FCC gasoline and process.
The character of table 4 example 3 oil product.
| Project | Refining petroleum naphtha | Refining heavy petrol | Sweet gasoline |
| Sulphur content, μ g/g | 7.0 | 7.5 | 7.4 |
| Mercaptans content, μ g/g | 3.0 | 3.2 | 3.1 |
| Olefin(e) centent, v% | 35.0 | 9.0 | 17.6 |
| Research octane number (RON), RON | 94.8 | 87.0 | 90.9 |
| Boiling range scope, DEG C | 30～55 | 50～188 | 32～188 |
The character of table 5 example 4 oil product.
| Project | Refining petroleum naphtha | Refining heavy petrol | Sweet gasoline |
| Sulphur content, μ g/g | 7.0 | 8.0 | 7.7 |
| Mercaptans content, μ g/g | 3.0 | 3.0 | 3.0 |
| Olefin(e) centent, v% | 35.0 | 11.5 | 19.6 |
| Research octane number (RON), RON | 94.8 | 88.0 | 91.2 |
| Boiling range scope, DEG C | 30～55 | 50～188 | 32～188 |
As can be seen from table 4,5:
Example 4,5 uses ME-1 and ME-2 catalyzer at 260 DEG C, process >55 DEG C of last running respectively, the sulphur content of FCC gasoline can be reduced to 7.4 μ g/g and 7.7 μ g/g by 450 μ g/g, mercaptan sulfur content is reduced to 3.1 μ g/g and 3.10 μ g/g by 30.2 μ g/g, olefin(e) centent is reduced to 17.6v% and 19.6v% by 27.6v%, research octane number (RON) RON loses 1.5 and 1.2 units, FCC gasoline inferior can be processed as sulphur content ≯ 10 μ g/g super low sulfur cleaning product.
comparative example 2
This comparative example to provide in comparative example 1 FCC gasoline sweetening effectiveness in R-1 catalyst treatment example 3.
(1), >55 DEG C of heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, is respectively charged into R-1 catalyzer 50mL 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, change >55 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.6MPa, and use not hydrogen sulfide containing fresh hydrogen, hydrogen to oil volume ratio is 300, and volume space velocity is 3.0h
-1, in 4 hours, be cooled to temperature of reaction 280 DEG C (condition 1).Steady running 100 hours, obtains refining heavy petrol, and sampling analysis.
Then, temperature of reaction drops to 260 DEG C (conditions 2), and steady running 100 hours, obtains refining heavy petrol, and sampling analysis.
(2), refining heavy petrol mixes with refining petroleum naphtha
Refining heavy petrol mixes according to prefractionation lighting end, the last running ratio of cutting with refining petroleum naphtha.The character of clean gasoline product after table 6-1,6-2 list raw material FCC gasoline and process.
The character of table 6-1 comparative example 2 condition 1 oil product.
| Project | Refining petroleum naphtha | Refining heavy petrol | Sweet gasoline |
| Sulphur content, μ g/g | 7.0 | 9.5 | 8.8 |
| Mercaptans content, μ g/g | 3.0 | 3.0 | 5.0 |
| Olefin(e) centent, v% | 35.0 | 7.5 | 16.0 |
| Research octane number (RON), RON | 94.8 | 84.8 | 89.4 |
| Boiling range, DEG C (initial boiling point ~ final boiling point) | 30～55 | 50～188 | 32～188 |
The character of table 6-2 comparative example 2 condition 2 oil product.
| Project | Refining petroleum naphtha | Refining heavy petrol | Sweet gasoline |
| Sulphur content, μ g/g | 7.0 | 25.0 | 20.0 |
| Mercaptans content, μ g/g | 3.0 | 13.0 | 10.0 |
| Olefin(e) centent, v% | 35.0 | 9.8 | 18.0 |
| Research octane number (RON), RON | 94.8 | 86.8 | 90.6 |
| Boiling range, DEG C (initial boiling point ~ final boiling point) | 30～55 | 50～188 | 32～188 |
As can be seen from Table 6:
Comparative example R-1 catalyzer processes >55 DEG C of last running at 280 DEG C, the sulphur content of FCC gasoline can be reduced to 8.8 μ g/g(desulfurization degrees 98.0% by 450 μ g/g), mercaptan sulfur content is reduced to 5.0 μ g/g by 30.2 μ g/g, olefin(e) centent is reduced to 16.0v%(olefin saturated rate 42.0% by 27.6v%), research octane number (RON) RON loses 3.0 units.
Can be found out by above-mentioned contrast, the FCC gasoline production sulphur content ≯ 10 μ g/g super low sulfur cleaning product of process sulphur content 450 μ g/g, olefin(e) centent 27.6v%, the inventive method low temperature height hydrogenating desulfurization catalysts selective is compared with comparative example catalyzer, at heavy fractioning hydrogenation desulfurization reaction temperature reduces by 20 DEG C, olefin saturated rate reduces by 31.0%, RON and loses minimizing 1.8 units.
comparative example 3
This comparative example provides a kind of FCC gasoline sweetening effectiveness inferior, and stock oil is with implementing 3.
(1), full cut FCC gasoline air sweetening
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 <55 DEG C of refining petroleum naphtha and >55 DEG C of last running with 55 DEG C, table 7 lists the character of <55 DEG C of refining petroleum naphtha and >55 DEG C of last running.
(3), >55 DEG C of heavy fractioning hydrogenation desulfurization
Evaluation test carries out on the device of fixed-bed reactor, loads R-1 catalyzer prepared by 50mL comparative 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 280 DEG C.
After sulfuration terminates, switch >55 DEG C of double distilled and be divided into stock oil, hydrogen dividing potential drop is 1.6MPa, and use not hydrogen sulfide containing fresh hydrogen, hydrogen to oil volume ratio 300, volume space velocity is 3.0h
-1, in 2 hours, be warming up to temperature of reaction 285 DEG C, steady running sampling analysis in 100 hours.
(4), >55 DEG C of refining heavy petrol mixes with <55 DEG C of refining petroleum naphtha
>55 DEG C of refining heavy petrol mixes according to the ratio of cutting with <55 DEG C of refining petroleum naphtha.The character of clean gasoline product after table 5 lists raw material FCC gasoline and processes.
The character of FCC gasoline in table 7 comparative example 3, refining petroleum naphtha and last running.
| Project | FCC gasoline | < 55 DEG C of refining petroleum naphthas | > 55 DEG C of last running |
| Cutting ratio, wt% | 100 | 27.0 | 73.0 |
| Density, g/mL | 0.7232 | 0.6456 | 0.7550 |
| Sulphur content, μ g/g | 450 | 12.0 | 600 |
| Mercaptans content, μ g/g | 30.2 | 2.0 | 5.0 |
| Olefin(e) centent, v% | 27.6 | 38.0 | 16.0 |
| Research octane number (RON) | 92.4 | 94.8 | 90.5 |
| Boiling range, DEG C | 32～188 | 30～55 | 50～188 |
The character of table 8 comparative example 3 oil product.
| Project | FCC gasoline | > 55 DEG C of refining heavy petrol | Mixing oil |
| Density, g/mL | 0.7232 | 0.7550 | 0.7232 |
| Sulphur content, μ g/g | 450 | 7.9 | 9.0 |
| Mercaptan sulfur content, μ g/g | 30.2 | 4.0 | 3.5 |
| Olefin(e) centent, v% | 27.6 | 7.0 | 15.7 |
| Research octane number (RON) (RON) | 92.4 | 85.0 | 89.2 |
The full cut FCC gasoline of deodorization processes >55 DEG C of last running through comparative example R-1 catalyzer at 280 DEG C, mix with <55 DEG C of refining petroleum naphtha again, the sulphur content of FCC gasoline can be reduced to 9.7 μ g/g(desulfurization degrees 97.8% by 450 μ g/g), mercaptan sulfur content is reduced to 3.5 μ g/g by 30.2 μ g/g, olefin(e) centent is reduced to 15.7v%(olefin saturated rate 43.1% by 27.6v%), research octane number (RON) RON loses 3.2 units.
Claims (10)
1. produce a method for super low-sulfur oil, comprise the following steps:
(1), full cut bad gasoline carries out prefractionation, is cut into lighting end and last running; Described lighting end and the cut point of last running are 40 DEG C ~ 100 DEG C;
(2), by step (1) gained lighting end be fixed an oxidation deodorizing, mercaptan sulfur is converted into disulphide;
(3), by step (2) gained deodorization lighting end carry out solvent absorbing fractionation, disulphide is transferred in solvent and goes, reduce the total sulfur content of deodorization lighting end, obtain refining petroleum naphtha; The initial boiling point of described solvent does 5 ~ 100 DEG C higher than lighting end;
(4), by step (1) gained last running mix with hydrogen, and through low temperature high-selective and hydrogenating desulfurization catalyst bed, under hydrodesulfurization reaction condition, carry out selective hydrodesulfurization reaction, obtain refining heavy petrol; Described low temperature high-selective and hydrogenating desulfurization catalyst with one or more base metals in group vib in the periodic table of elements and/or group VIII for hydrogenation active metals, with one or more in K, Ca, P, Si, F, B, Ti and Zr for auxiliary agent; With the weight of catalyzer for benchmark, hydrogenation active metals content take oxide basis as 5.0wt% ~ 25.0wt%, and auxiliary agent content, for being greater than 6.0wt%, is less than or equal to 15.0wt%;
(5), by step (3) gained refine petroleum naphtha to mix with the refining heavy petrol obtained in step (4), obtain the super low-sulfur oil of sulphur content ≯ 10 μ g/g.
2. 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 as catalyzer take air as the oxidation deodorizing process of oxygenant.
3. in accordance with the method for claim 1, it is characterized in that, described lyosorption is one or more in kerosene, heavy naphtha, solar oil and aromatic hydrocarbons.
4. 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 ≯ 100 μ L/L, adopts recycle hydrogen de H
2s realizes.
5. in accordance with the method for claim 1, it is characterized in that, with the weight of catalyzer for benchmark, described auxiliary agent content, for being greater than 6.0wt%, is less than or equal to 12.0wt%.
6. in accordance with the method for claim 1, it is characterized in that, described hydrogenation active metals is selected from one or more in W, Mo, Ni and Co.
7. in accordance with the method for claim 1, it is characterized in that, described full cut bad gasoline is fiuidized bed evaporator, catalytic cracking gasoline, coker gasoline, pressure gasoline or its mixture, and boiling range is 30 DEG C ~ 220 DEG C.
8. in accordance with the method for claim 1, it is characterized in that, described full cut inferior patrol is full cut FCC gasoline.
9. in accordance with the method for claim 1, it is characterized in that, the condition of the reaction of selective hydrodesulfurization 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, the lyosorption being rich in disulphide obtained after absorbing fractionation in step (3) goes diesel hydrotreating unit to carry out desulfurization process.
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| 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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| 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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