CN103657709A - Reaction adsorption desulfurization-aromatization reaction process and catalyst thereof - Google Patents
Reaction adsorption desulfurization-aromatization reaction process and catalyst thereof Download PDFInfo
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- CN103657709A CN103657709A CN201210331262.7A CN201210331262A CN103657709A CN 103657709 A CN103657709 A CN 103657709A CN 201210331262 A CN201210331262 A CN 201210331262A CN 103657709 A CN103657709 A CN 103657709A
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Abstract
The invention relates to a reaction adsorption desulfurization-aromatization reaction process and a catalyst thereof. The catalyst has a reaction adsorption desulfurization function while a catalytic gasoline raw material is hydrotreated, is capable of coupling a reaction adsorption desulfurization reaction and an aromatization reaction so that the octane number of a product is not obviously reduced while deep desulfurization is achieved when the researched process and the catalyst are used for modifying the catalytic gasoline raw material. The purposes that the S content of the gasoline of the product is less than 10ppm, the olefin content is reduced by 10 percent, the RON (Research Octane Number) loss is less than 1 and the gasoline yield is more than 95 percent are achieved by using FCC (Fluid Catalytic Cracking) gasoline with S content of 300-800ppm as a raw material.
Description
Technical field
The present invention relates to a kind of method of deep desulfuration and aromatization modification of catalytically cracked gasoline.Specifically a kind of catalytically cracked gasoline of sulfur-bearing is converted into the method for ultra-low sulfur clean fuel, belongs to the deep processing field of oil product.Catalyst hydrogenation not only has reaction adsorption desulfurize function while processing catalytically cracked gasoline raw material, and can react and aromatization by coupled reaction adsorption desulfurize, make the technique of development and catalyst thereof when raw material catalytic cracking gasoline is carried out to upgrading, when can reach deep desulfuration there is not obvious reduction in the octane number of product.
Background technology
The environmental regulation of increasingly stringent is to the particularly more and more stricter requirement of sulfur content proposition of motor petrol quality, the research and development of deep desulfurization of gasoline production technology have become the task of top priority, in addition, the production that develops call " without sulphur " fuel oil rapidly of fuel cell, this has higher requirement to desulfur technology.The existing most of refineries of China are substantially by the domestic heavy low-sulfur paraffinic base crude oil design of processing, sulfur crude processing ability is very low, catalytic cracking (FCC) ratio is excessive, add that the device working abilities such as catalytic reforming, alkylation isomerization, etherificate are low, cause China's the quality on gasoline and diesel generally lower.FCC gasoline accounts for the 80wt%(mass fraction of motor petrol blend component) left and right, sulphur and olefin(e) centent are higher, and therefore, the key of gasoline desulfur is FCC gasoline desulfur.For tackle fuel oil without sulfuration trend, multiple desulfur technology has been developed in countries in the world, can be divided into hydrodesulfurization (HDS) and non-hydrodesulfurization (Non-HDS).FCC gasoline HDS skill is current more ripe clear gusoline production technology, but exist, one-time investment is large, operating cost is high, need to consume the shortcomings such as a large amount of hydrogen, causes oil product cost significantly to rise; In addition,, still there are some difficult problems in depth H DS aspect: 1. FCC gasoline selective hydrodesulfurizationmodification technology (SHDS), although substantially can meet 50 μ g/g sulfur content standards (Europe IV), but cannot tackle gasoline without sulfuration trend (<10 μ g/g, Europe V); 2. in desulfurization, the hydrogenation that alkene occurs is to a certain degree saturated, causes the loss of octane number and liquid yield; When 3. FCC gasoline carries out hydrodesulfurization, product H
2s is easy to generate mercaptan with olefine reaction, and the management that how to realize mercaptan is also a stubborn problem; Non-HDS technology receives much concern always, obtain in recent years certain achievement, as adsorption desulfurize technology (ADS), can optionally remove the sulfur-containing compound in gasoline, and do not affect olefin(e) centent wherein, thereby avoided the octane number that in unifining process, olefin saturated causes to reduce problem.Therefore for the feature of China petroleum refining industry, two schemes that propose are both at home and abroad expected to overcome the above problems, and a kind of is reaction adsorption desulfurize technology, and another kind is aromatization modification scheme.
Reaction adsorption desulfurize adopts the load type adsorbing agent with reactivity worth, as the Phillips patent adsorbent (CN1658964 of the S-Zorb of U.S. Cophi Co., Ltd technique use, CN1930271A), the mixture of zinc oxide, silica, aluminium oxide of take is carrier, floods active Ni(or Co, Cu) component obtains reacting adsorption desulfurizing agent by high-temperature roasting.Reaction adsorption mechanism is carried out according to " automatic regeneration " mechanism (autoregenerative), and the Ni atom of reduction-state is as desulphurizing activated position, and ZnO takes on the role of sulfur-donor as the acceptor of sulphur.First, the NiO on NiO/ZnO adsorbent surface is at H
2effect under be transformed into the active Ni of reduction-state, because the S atom in sulfur-containing compound molecule presents electronegativity relatively, under inducing action, move closer to Ni atom, form transition state; Subsequently, between the two, adsorb by force under the effect of potential energy, the C-S bond fission in sulfide, S atom departs from hydro carbons part, forms class NiS state with Ni; Finally, at H
2under effect, S atom shifts and forms ZnS to ZnO surface, and it is desulphurizing activated that Ni recovers.
Technology of aromatization is utilize the acidity of molecular sieve catalyst and select type, and the hydrocarbon fraction in optionally gasoline being formed is converted into high-octane aromatic hydrocarbons, thereby realizes the improvement of desulfurization and octane number.
Chinese patent 02133112.X provides a kind of aromatization catalyst for catalytic gasoline and application process thereof, and the percentage by weight of catalyst of take is benchmark, and it consists of: bullion content is 0.1m%～1.0m%; K type zeolite content is 50.0m%～90.0m%; Wherein K2O content is 1.0m%～5.0m%; Surplus is binding agent.This catalyst can be applied in the hydrodesulfurization of catalytic gasoline.Thereby when reaching desulfurization and reducing olefin(e) centent, the anti-knock index of product loses less object.
Chinese patent 02133130.8 provides a kind of and has produced the technique of low-sulfur, low alkene clean gasoline and the catalyst that this technique is used by catalytically cracked gasoline.Process using hydrofinishing/aromatisation process integration of the present invention, wherein aromatisation adopts the little crystal grain hydrogen type molecular sieve catalyst that comprises IA family metal, magnesium-yttrium-transition metal and lanthanide rare metal oxide, and molecular sieve is that grain size is within the scope of 20nm～800nm.It is short that this invention aromatization of gas catalyst has duct, acid suitable, can reduce cracking reaction, improved the yield of gasoline, reduced the carbon deposit of catalyst simultaneously.Invented technology adopts hydrofinishing/aromatisation to process FCC gasoline, is reaching when desulfurization and reducing olefin(e) centent, and the anti-knock index loss of product is less; Meanwhile, unifining process has removed the alkadienes of easy coking under high temperature, improves the stability of the aromatization catalyst with octane value recovering function.
Chinese patent 0133561.6 provides a kind of ultrafine particle zeolite aromatized catalyst and preparation method thereof and the application in full cut FCC gasoline hydrofinishing/aromatisation group technology.The weight of catalyst of take is benchmark, the composition of this catalyst comprises: transition metal oxide and lanthanide rare metal oxide content sum are 1.0wt%～10.0wt%, ultrafine particle zeolite content is 50.0wt%～90.0wt%, surplus is inorganic oxide adhesive, and the grain size of ultrafine particle zeolite is 20nm～800nm.Because this ultrafine particle zeolite aromatized catalyst total acid content is low, particularly L acid amount is lower, duct is more unimpeded, therefore, this catalyst anti-coking performance is strong, good stability, and can, when reducing the sulfur content and olefin(e) centent of FCC gasoline, guarantee that anti-knock index ((R+M)/2) loss of gained gasoline product is less
The advantage of reaction adsorption desulfurize is to realize ultra-deep desulfurization, the product sulfur content can be reduced to below 10ppm, the problem existing is that reaction must be carried out under hydro condition, is difficult to the loss of octane number of avoiding olefins hydrogenation to bring, and adsorption desulfurizing agent needs frequent regeneration in addition; The advantage of aromatization process is that alkene can improve the octane number of product gasoline to the conversion of aromatic hydrocarbons, and the problem of existence is catalyst carbon deposition inactivation, and reaction time is short, desulphurizing activated not high in addition.
Summary of the invention
Object of the present invention is avoided above-mentioned the deficiencies in the prior art part exactly, adopt a kind of can coupled reaction adsorption desulfurize and technique and the catalyst thereof of aromatization, adopt this technique and catalyst hydrogenation thereof process catalytically cracked gasoline can be in the desulfurization of reaction adsorption deeply alkene generation aromatization, make product gasoline there is ultra-low sulfur and octane number is not subject to the object significantly reducing.This technical process adopts fixed bed reactors, and Catalyst packing is in reactor middle part, and the prereduction of catalyst and desulphurization reaction carry out on same device, first carry out prereduction after Catalyst packing, and reducing condition is: T=400 ℃, P
h2=0.5MPa, H
2flow is 200mlmin
-1, time 4.0h; After reduction, be cooled to catalytic reaction temperature, switch and evaluate raw material, carry out deep desulfuration and aromatization.
The coupled reaction adsorption desulfurize reaction of this invention and the function catalyst of aromatization consist of NiM/ZnO-ZSM-5, wherein one or both the combination such as M=Pb, Cu, Zn adds few alumina dry glue as binding agent in shaping of catalyst process.In the composition of catalyst, the content of ZSM-5 is at 20-40%(wt), the content of ZnO is at 30-50%(wt), the content of Ni is at 1-10%(wt), alumina dry glue is 1-5%(wt), surplus is M.The reaction of coupled reaction adsorption desulfurize and aromatization technological reaction condition are that reaction temperature is 350-450 ℃, and pressure is 0.5-1.6MPa, and hydrogen to oil volume ratio is that 100-300, air speed are 2-10h
-1.Molecular sieve ZSM-5 in the function catalyst of the reaction of coupled reaction adsorption desulfurize and aromatization is the step porous molecular sieve with micropore-mesopore-macropore in addition, and this molecular sieve is to adopt the diatomaceous original position solid phase crystallization conversion with macroporous structure to obtain.Reaction adsorption desulfurize component is first by low-temperature solid-phase method, to synthesize nano zine oxide (the surface area 35-50m of high-ratio surface
2g
-1, pore volume is 0.15-0.20cm
3g
-1grain size is 20-40nm), then by nickel and promoter metal, the form with ion is impregnated on zinc oxide surface respectively to adopt infusion process, then reduction and obtain the nano-complex of nickel, promoter metal and zinc oxide in super-dry, roasting and hydrogen, nickel and promoter metal are incorporated in zinc oxide crystalline phase with the form knot of alloy and present equably and disperse.
The specific embodiment
Below in conjunction with specific embodiment, carry out enumeration technical characterstic of the present invention.The raw material diatomite adopting in example is Changbai Mountain diatomite, and it is pure that other reagent is analysis.
Its specific embodiment is as follows:
Embodiment 1: weigh 200 grams of dried diatomite in beaker, first it is mended to aluminium, concrete process is by 51.64 grams of NaAlO
2, 4.348 grams of templates, 21.74 grams of NaOH be dissolved in the distilled water of 1000 milliliters and be mixed with solution.Diatomite and this solution Agitation and mixing is even, and 80 ℃ dry, obtains modification infusorial earth; Then the modification infusorial earth of gained is placed in to crystallizing kettle, 170 ℃ of crystallization 24 hours.The product centrifuge washing going out after still is neutral to supernatant for several times, and filtration, the dry molecular screen primary powder that obtains obtain Hydrogen ZSM-5 according to conventional method after ammonium sulfate exchange.Analysis result shows that the pore structure of synthesis of molecular sieve presents obvious step pore size distribution, and the BET surface area of synthesis of molecular sieve is 250-300m
2/ g, micropore and mesoporous pore volume (BET method mensuration) are 0.3-0.35cm
3/ g, macropore (>50nm, mercury injection method is measured) pore volume 0.09-0.12cm
3/ g.
Example 2: in 1: 1(mol ratio) ratio accurately takes respectively oxalic acid (H
2c
2o
4, analyze pure) and zinc acetate (Zn (Ac)
22H
2o, analyzes pure), be placed in mortar, fully grind 30-60min, solid product in 70 ℃ of vacuum drying 4h, obtains predecessor ZnC in baking oven
2o
42H
2o.By dried ZnC
2o
42H
2o is placed in muffle furnace and is heated to decomposition temperature 450-500 ℃, keeps 2h, obtains product nano-ZnO.Measure by analysis BET surface area 35-46m
2g
-1, pore volume is 0.15-0.20cm
3-g
-1, grain size is 20-40nm.
Example 3: accurately take 8 grams of 7 grams of nickel nitrates, plumbi nitras and be dissolved in 30 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 50 grams of example 2 methods, and then add 30 grams of ZSM-5 molecular sieves in example 1,10 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 1(Ni-Pb/ZnO-ZSM-5).
Example 4: accurately take 4 grams of 7 grams of nickel nitrates, plumbi nitras and be dissolved in 30 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 40 grams of example 2 methods, and then add 35 grams of ZSM-5 molecular sieves in example 1,15 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 2(Ni-Pb/ZnO-ZSM-5).
Example 5: accurately take 8 grams of 7 grams of nickel nitrates, cobalt nitrate and be dissolved in 30 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 40 grams of example 2 methods, and then add 35 grams of ZSM-5 molecular sieves in example 1,15 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 3(Ni-Co/ZnO-ZSM-5).
Example 6: accurately take 4 grams of 7 grams of nickel nitrates, cobalt nitrate and be dissolved in 20 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 40 grams of example 2 methods, and then add 40 grams of ZSM-5 molecular sieves in example 1,15 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 4(Ni-Co/ZnO-ZSM-5).
Example 7: accurately take 2 grams of 7 grams of nickel nitrates, plumbi nitras and be dissolved in 20 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 40 grams of example 2 methods, and then add 40 grams of ZSM-5 molecular sieves in example 1,15 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 5(Ni-Pb/ZnO-ZSM-5).
Example 8: accurately take 2 grams of 7 grams of nickel nitrates, cobalt nitrate and be dissolved in 20 ml water solution and be mixed with maceration extract, adopt infusion process that the maceration extract preparing is impregnated on the synthetic nano zine oxide of 40 grams of example 2 methods, and then add 40 grams of ZSM-5 molecular sieves in example 1,15 grams of alumina dry glues and a small amount of 1% nitric acid, mix after rear extruded moulding, dry and roasting, obtain catalyst 6(Ni-Co/ZnO-ZSM-5).
Example 9: the benchmark test of reaction process and catalyst thereof carries out on fixed-bed reactor, experimentation is for first packing a certain amount of clean quartz sand in reaction tube bottom, then measure 100 milliliters of catalyst that above-mentioned preparation method obtains and be loaded on reaction tube middle part, upper end is filled up with clean quartz sand again, in filling process, with wooden mallet, beats gently and makes pipe interior closely knit.After installing reaction tube, logical hydrogen detects air-tightness.Whole reacting system pressure is by H
2pressure is controlled, H
2pressure regulates by pressure maintaining valve and counterbalance valve.The prereduction of catalyst and desulphurization reaction carry out on same device, first carry out prereduction after Catalyst packing.Reducing condition is: T=400 ℃, P
h2=0.5MPa, H
2flow is 200mlmin
-1, time 4.0h; After reduction, be cooled to catalytic reaction temperature, switch and evaluate raw material FCC gasoline (taking from China Petroleum Univ.'s Shenghua refinery), carry out deep desulfuration and aromatization, reaction condition is 400 ℃ of temperature, hydrogen dividing potential drop 1.5MPa, hydrogen to oil volume ratio=200/1, and volume space velocity is 2h
-1, sample analysis after stable reaction, result is as following table:
Invention effect
Compare with existing invention, catalyst of the present invention has following features: while adopting catalyst upgrading catalytically cracked gasoline raw material of the present invention, because catalyst has the function of coupled reaction adsorption desulfurize reaction and aromatization, when the upgrading of raw material catalytic cracking gasoline by adsorb-technology of aromatization of reaction can reach deep desulfuration there is not obvious reduction in the octane number of product.
Claims (3)
- One kind can coupled reaction adsorption desulfurize-aromatization catalyst, the composition of this catalyst is NiM/ZnO, ZSM-5 and alumina dry glue, it is characterized in that content that this catalyst weight ratio in forming is ZSM-5 is at 30-40%, the content of ZnO is at 40-50%, the content of Ni is at 1-10%, alumina dry glue is 10-15%, and surplus is M; In NiM/ZnO-ZSM-5, its M is one or both the combination of Pb, Co; Alumina dry glue is as binding agent.
- 2. a kind of catalyst that can coupled reaction adsorption desulfurize-aromatization according to claim 1, be further characterized in that molecular sieve ZSM-5 used is the step porous molecular sieve with micropore-mesopore-macropore, the BET surface area of this step porous molecular sieve is 250-300m 2/ g, micropore and mesoporous pore volume are 0.3-0.35cm 3g -1, macropore pore volume is not less than 0.08-0.10cm 3g -1.
- 3. the technique of coupled reaction adsorption desulfurize reaction and aromatization, it is characterized in that this technical process adopts fixed bed reactors, Catalyst packing is in reactor middle part, the prereduction of catalyst and desulphurization reaction carry out on same device, after Catalyst packing, first carry out prereduction, reducing condition is: T=400 ℃, P h2=0.5MPa, H 2flow is 200mlmin -1, time 4.0h; After reduction, be cooled to catalytic reaction temperature, switch and evaluate raw material, carry out deep desulfuration and aromatization.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974290A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN107974292A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN116355646A (en) * | 2023-04-17 | 2023-06-30 | 天津大学 | Method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon |
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| CN102343276A (en) * | 2011-07-25 | 2012-02-08 | 中国石油大学(华东) | Catalyst for deep desulfuration and octane number increase for gasoline and preparation and application methods thereof |
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2012
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|---|---|---|---|---|
| US6974787B2 (en) * | 1998-08-31 | 2005-12-13 | Exxonmobil Corporation | Gasoline sulfur reduction in fluid catalytic cracking |
| CA2351646A1 (en) * | 1998-11-16 | 2000-05-25 | Mobil Oil Corporation | Deep desulfurization of fcc gasoline at low temperatures to maximize octane-barrel value |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974290A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN107974292A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN107974292B (en) * | 2016-10-21 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN107974290B (en) * | 2016-10-21 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of vapour oil treatment process |
| CN116355646A (en) * | 2023-04-17 | 2023-06-30 | 天津大学 | Method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon |
| CN116355646B (en) * | 2023-04-17 | 2024-05-28 | 天津大学 | Method for synthesizing high-energy-density heat-absorbing aviation fuel by one-step hydrogenation conversion of polycyclic aromatic hydrocarbon |
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