CN104650967A - Deep desulfurization method of gasoline by catalysis of Ni-containing catalyst - Google Patents
Deep desulfurization method of gasoline by catalysis of Ni-containing catalyst Download PDFInfo
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- CN104650967A CN104650967A CN201310597737.1A CN201310597737A CN104650967A CN 104650967 A CN104650967 A CN 104650967A CN 201310597737 A CN201310597737 A CN 201310597737A CN 104650967 A CN104650967 A CN 104650967A
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Abstract
The invention relates to a deep desulfurization method of gasoline by catalysis of a Ni-containing catalyst. According to the deep desulfurization method, a gasoline raw material enters a first reactor to undergo selective hydrodesulfurization, and then deep desulfurization is further carried out in a second reactor. A hydrodesulfurization catalyst adopted in the second reactor is the Ni-containing catalyst. The catalyst has a certain desulfurization activity. Meanwhile, olefin saturation is little. After combination with the first reactor and when deep desulfurization is further realized, reaction severity of the first reactor can be remarkably reduced, and octane loss and hydrogen consumption are optimized.
Description
Technical field
The present invention relates to a kind of method of deep desulfurization of gasoline, particularly relate to a kind ofly increases the method for the second hydrodesulphurisatioreactors reactors for deep desulfurization of gasoline after the first hydrodesulphurisatioreactors reactors.
Background technology
Oil is one of of paramount importance energy, has become " blood " of current world economy development.Along with the fast development of global economy, automobile pollution grows with each passing day.By in September, 2011, Global Auto recoverable amount breaks through 1,000,000,000, and China's automobile pollution also breaks hundred million first, and vehicle exhaust becomes the primary pollution source of many urban air pollutions, has a strong impact on people's productive life and healthy all causing.At present, legislations of environmental protection is increasingly strict, and countries in the world propose more and more high requirement to vehicular engine quality of fuel, and China also accelerates the paces of quality of gasoline upgrading.China will implement integrally state IV gasoline emission standard the end of the year 2013, will implement in full state V gasoline standard the end of the year 2017, and quality of gasoline upgrading is extremely urgent, and the high standard Technology for Producing Clean Gasoline demand that exploitation meets market demand is urgent.
China's gasoline is formed based on FCC gasoline component (accounting for more than 80% of China's gasoline product), has the feature of high-sulfur, high olefin.Hydrogen addition technology is the important means of sulphur in effective elimination FCC gasoline, main based on selective hydrodesulfurization technology at present.Wherein, the Prime-G+ technology of AXENS company has obtained the Europe of industrial application production comparatively widely V clean gasoline.But due to the difference of domestic and international oil property, for process China high-sulfur, high olefin FCC gasoline, when carrying out ultra-deep hydrodesulfuration, adopt independent hydrogenating desulfurization technology can bring alkene significantly hydrotreated lube base oil, cause loss of octane number comparatively large, economy is poor.At present, the domestic production still lacking mature technology and be used for state V standard clean gasoline.
US6,692635 describe a kind of low-sulphur oil production technique, and be characterized in full cut catalytic gasoline raw material first selectively removing diolefine in selective hydrogenation reactor (the first reactor), olefines double bond isomerizing, mercaptan is 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), and then, saturated sulphidic conversion is H by hydrogenation on the NiO/Al2O3 catalyzer in second reaction zone
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 technical need 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, and the first step, by sulfide hydrotreated lube base oil unsaturated in FCC gasoline, is converted into mercaptan compound, and saturated sulfide hydrodesulfurizationconversion conversion is H2S by second step again.Its advantage is the full cut FCC gasoline of processing, and do not need to carry out fractionation, weak point is the remaining sulfide major part of the finished product is mercaptan sulfur compounds, causes mercaptan sulfur in product defective.
CN02133136.7 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.The shortcoming of this patented method is, owing to generating more macromolecular mercaptan containing H2S and the rearrangement reaction of alkene secondary in heavy fractioning hydrogenation desulfurization product, on the one hand, to reduce the degree of depth of hydrogenating desulfurization, on the other hand, follow-uply must carry out mercaptan removal process.The method desulfurization degree is generally 80.0% ~ 90.0%, and product sulphur content is generally 50 μ g/g ~ 200 μ g/g, and research octane number (RON) (RON) loss ≯ 2.0 units, can not meet the requirement that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
CN02121594.4 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 the gasoline of 200 μ g/g, and the uprising index ((R+M)/2) of gasoline loses ≯ 2.0 units.Its shortcoming is, cannot meet the technical need that oil refining enterprise produces clean gasoline sulphur content ≯ 10 μ g/g.
In sum, from the retrieval of patent documentation, the more gasoline hydrodesulfurizationmethod technology of current investigation and application mainly for the production of the product of sulphur content ≯ 150 μ g/g, and there are no can the report of technology of production sulphur content ≯ 10 μ g/g product.Therefore, remove the sulphur in product further, reduce difficult point and focus that product loss of octane number is current technological development., find in research, because mercaptan sulfur proportion in product is comparatively large, so for the clean gasoline product of production sulphur content ≯ 10 μ g/g, removing of mercaptan sulfur is also the problem that current technology needs to solve meanwhile.
Summary of the invention
The object of this invention is to provide a kind of method containing Ni catalyst deep desulfurization of gasoline.Gasoline stocks is after the first reactor, enter the second reactor, further hydrogenating desulfurization is carried out to the mercaptan in hydrogenating desulfurization product, thioether, disulphide and thiophene sulphur, the clean gasoline of production sulphur content ≯ 20 μ g/g, while realizing deep desulfuration, significantly can reduce the first reactor reaction severity, the extending catalyst cycle of operation, reduce the loss of octane number that olefin saturated brings, realize octane value and hydrogen consumption optimization.
Second reactor of the present invention adopts a kind of high-selective and hydrogenating desulfurization catalyst, and catalyzer is made up of carrier and active ingredient two portions.Carrier is the one of aluminum oxide or silicon oxide or two kinds, and active metal component is NiO.In catalyst weight percent, the composition content of catalyzer is: active metal component NiO content is 7-20%, and all the other are the one of aluminum oxide or silicon oxide or two kinds.The specific surface area of catalyzer is 50-200m
2/ g, pore volume 0.2-0.6ml/g.
Of the present inventionly provide a kind of preparation method with the high-selective and hydrogenating desulfurization catalyst of relay desulfidation, its concrete preparation process is as follows:
(1) one of aluminum oxide or silicon oxide or two kinds are mixed with sesbania powder, add binding agent, deionized water, kneading, extruded moulding, 100-150 DEG C of dry 3-6h, 500-900 DEG C of roasting 3-6h, obtained support of the catalyst;
(2) active ingredient nickel salt is dissolved in one or both complexing agents of citric acid or ammoniacal liquor, be made into stable active metal component complex solution, then active metal component solution incipient impregnation support of the catalyst is used, dipping 12-24h, through 100-150 DEG C of dry 3-6h, after 400-600 DEG C of roasting 3-6h, obtained high-selective and hydrogenating desulfurization catalyst finished product.
According to above-mentioned preparation method, in step (1), the one of optional aluminum oxide or silicon oxide or two kinds are as carrier, and count by weight percentage, the content of silicon oxide is at 0-15%.
Above-mentioned steps (2) nickel salt used can be one or more in nickelous nitrate, nickelous acetate, basic nickel carbonate.
Above-mentioned steps (2) complexing agent used is one or both of citric acid or ammoniacal liquor, wherein, and citric acid: ammoniacal liquor volume ratio is 0-2.
Above-mentioned steps (2) activity component impregnation method used is incipient impregnation, namely at room temperature carries out load by the dipping solution amount being equal to support of the catalyst water-intake rate to carrier.
High-selective and hydrogenating desulfurization catalyst provided by the invention is applicable to deep desulfurization of gasoline reaction.Catalyzer in gasoline needs to carry out sulfuration before using, and cure conditions is: curing temperature 230-320 DEG C, curing time 12-36h, hydrogen-oil ratio 100:1-300:1, pressure 1.0-3.0MPa; The processing condition that catalyzer uses are: hydrogen pressure 1.0-3.0MPa, temperature 250-350 DEG C, air speed 1.0-10.0h-1, hydrogen-oil ratio 100:1-500:1.
The present invention has the following advantages:
(1) catalyzer provided by the invention has relay desulfidation, while removing mercaptan sulfur, can remove other Sulfurs, and olefin saturated is few simultaneously, and catalyst HDS selectivity is obviously better than conventional hydrodesulfurization catalyzer;
(2) the first reactor and the second reactor are carried out organic assembling by the present invention adopts technical process first, by the second reactor to the further highly selective deep desulfuration of gasoline hydrodesulfurizationmethod product, reduce the first reactor reaction severity, extended for the first reactor used catalyst cycle of operation, realize loss of octane number and hydrogen consumption optimization.
(3) after the second reactor provided by the invention and the first combination of reactors, can the clean gasoline product of production sulphur content ≯ 20 μ g/g.
Embodiment
Comparative example:
Gasoline enters the first reactor and carries out selective hydrodesulfurization, and wherein, selective hydrodesulfurization reactor catalyst for selectively hydrodesulfurizing used is industrial agent.Operating procedure condition is in table 1, and gasoline stocks and reaction result are in table 2.
Table 1 operating procedure condition
Project | Hydrobon catalyst |
Temperature of reaction, DEG C | 260 |
Reaction pressure, MPa | 2.0 |
Volume space velocity, h-1 | 3.0 |
Hydrogen-oil ratio, V/V | 300:1 |
Table 2 comparative example 1 data
Project | Gasoline stocks | Gasoline products |
Total sulfur/μ g/g | 112.5 | 16.3 |
Mercaptan sulfur/μ g/g | 13.7 | 11.9 |
Alkene/v% | 28.25 | 25.38 |
RON | 90.3 | 87.9 |
RON loses | / | 2.4 |
Table 2 result shows: under table 1 operational condition, and content of sulfur in gasoline is down to 16.3 μ g/g by 112.5 μ g/g, and mercaptan sulfur is 11.9 μ g/g, and alkene reduces 2.87v%, RON and loses 2.4 units.
Embodiment 1:
Take pseudo-boehmite 100g, add 2g sesbania powder, then add 3% aqueous nitric acid, through kneading, extrusion, dry 4h at 120 DEG C, then through 650 DEG C of roasting 4h, obtained support of the catalyst.Conventionally test carrier water-intake rate, then according to incipient impregnation method, carries out the preparation of activity component impregnation liquid according to carrier water-intake rate.First take 45ml ammoniacal liquor, then add 54g nickelous nitrate and be stirred to dissolving, finally carry out constant volume with ammoniacal liquor.Adopt incipient impregnation method to flood carrier, make support of the catalyst abundant assimilating activity component steeping fluid, after then placing 12h, 120 DEG C of dry 4h are carried out to catalyzer, roasting 4h at 600 DEG C, obtained catalyst sample Cat-1#.
Embodiment 2:
Prepare 100g support of the catalyst according to the support preparation method in embodiment 1, then carry out the preparation of activity component impregnation liquid, compound method is identical with embodiment 1.First take 50ml ammoniacal liquor, then add 32g nickelous acetate and be stirred to dissolving, finally carry out constant volume with ammoniacal liquor.Metal active constituent dipping method and drying, roasting condition with embodiment 1, obtained catalyst sample Cat-2#.
Embodiment 3:
Prepare 100g support of the catalyst according to the support preparation method in embodiment 1, then carry out the preparation of activity component impregnation liquid, compound method is identical with embodiment 1.First take 40ml ammoniacal liquor, then add 38g nickelous acetate, 40g nickelous nitrate is stirred to dissolving, finally carry out constant volume with ammoniacal liquor.Metal active constituent dipping method and drying, roasting condition with embodiment 1, obtained catalyst sample Cat-3#.
Embodiment 4: the present embodiment illustrates the application of catalyzer Cat1#-Cat5# in gasoline hydrodesulfurizationmethod adopting the present invention to prepare.
Evaluating catalyst process: catalyzer is respectively charged in fixed-bed reactor.First carry out prevulcanized to catalyzer, vulcanized oil is for containing 3wt%CS
2straight-run spirit, sulfide stress 2.0MPa, hydrogen to oil volume ratio 300:1,230 DEG C, 320 DEG C respectively sulfidizing be about 8h.After sulfuration terminates, enter stock oil and react, the technical process taked increases by the second reactor after the first reactor.Wherein, gasoline property and the first reactor used catalyst all identical with comparative example.Each embodiment operating procedure condition identical (see table 3), the reaction result obtained is in table 4.
Table 3 operating procedure condition
Project | First reactor | Second reactor |
Temperature of reaction, DEG C | 260 | 300 |
Reaction pressure, MPa | 2.0 | 2.0 |
Volume space velocity, h-1 | 3.0 | 5.0 |
Hydrogen-oil ratio, V/V | 200:1 | 200:1 |
Table 4 embodiment data
Result shows: comparative example and comparative example operational condition, increase by the second reactor after the first reactor, can reduce the first reactor reaction temperature and hydrogen-oil ratio; Meanwhile, load Cat1#-Cat3# respectively at the second reactor, content of sulfur in gasoline is down to 20 below μ g/g by 112.5 μ g/g, and mercaptan sulfur is down to 10 below μ g/g, and loss of octane number is starkly lower than the independent hydrodesulfurization reaction in comparative example.
Claims (5)
1. the method containing Ni catalyst deep desulfurization of gasoline, it is characterized in that, gasoline stocks enters and enters the second reactor again after the first reactor carries out selective hydrodesulfurization and carry out further deep desulfuration, the composition content of the Hydrobon catalyst that the second reactor adopts is: NiO content is 7-20wt%, and all the other are aluminum oxide or silicon oxide one or both;
The preparation of catalyzer:
(1) one of aluminum oxide or silicon oxide or two kinds are mixed with sesbania powder, add binding agent, deionized water, kneading, extruded moulding, 100-150 DEG C of dry 3-6h, 500-900 DEG C of roasting 3-6h, obtained support of the catalyst;
(2) active ingredient nickel salt is dissolved in one or both complexing agents of citric acid or ammoniacal liquor, be made into stable active metal component complex solution, then active metal component solution incipient impregnation support of the catalyst is used, dipping 12-24h, through 100-150 DEG C of dry 3-6h, after 400-600 DEG C of roasting 3-6h, obtained high-selective and hydrogenating desulfurization catalyst finished product;
Hydrobon catalyst operation reaction conditions is: hydrogen pressure 1.0-3.0MPa, temperature 250-350 DEG C, air speed 1.0-10.0h
-1, hydrogen-oil ratio 100:1-500:1.
2. the method containing Ni catalyst deep desulfurization of gasoline as claimed in claim 1, is characterized in that, the carrier of described high-selective and hydrogenating desulfurization catalyst is the one of aluminum oxide or silicon oxide or two kinds, and the content of silicon oxide is at 0-15wt%.
3. the method containing Ni catalyst deep desulfurization of gasoline as claimed in claim 1, it is characterized in that, the specific surface area of described high-selective and hydrogenating desulfurization catalyst is 50-200m
2/ g, pore volume 0.2-0.6ml/g.
4. the method containing Ni catalyst deep desulfurization of gasoline as claimed in claim 1, it is characterized in that, described gasoline stocks can be cut into 1 ~ 10 cut, and each cut sulphur is different with olefin(e) centent.
5. the method containing Ni catalyst deep desulfurization of gasoline as claimed in claim 1, it is characterized in that, described gasoline stocks can first carry out pre-hydrotreating reaction and remove diolefine, simultaneously by mercaptan heaviness.
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CN101619234A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
CN101905165A (en) * | 2010-08-12 | 2010-12-08 | 中国石油天然气股份有限公司 | Preparation and application of catalyst for selective hydrodesulfurization of gasoline |
CN102757818A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Sulfur-free gasoline production method |
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CN101619234A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
CN101905165A (en) * | 2010-08-12 | 2010-12-08 | 中国石油天然气股份有限公司 | Preparation and application of catalyst for selective hydrodesulfurization of gasoline |
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