CN109207188A - A kind of light FCC gasoline mercaptan etherification method - Google Patents
A kind of light FCC gasoline mercaptan etherification method Download PDFInfo
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- CN109207188A CN109207188A CN201811193163.0A CN201811193163A CN109207188A CN 109207188 A CN109207188 A CN 109207188A CN 201811193163 A CN201811193163 A CN 201811193163A CN 109207188 A CN109207188 A CN 109207188A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The present invention relates to a kind of light FCC gasoline mercaptan etherification methods, using fixed bed reactors, gasoline is first cut into light and heavy fractions oil, cutting temperature is 70 DEG C, under the action of catalyst, gasoline light fraction enters reactor and carries out mercaptan etherification reaction, and catalyst includes complex carrier and metal active constituent nickel, molybdenum and magnesium.Reaction condition: reaction pressure is 0.1MPa~4.5MPa, and hydrogen to oil volume ratio 2: 1~35: 1, reaction temperature is 60 DEG C~180 DEG C, and air speed is 0.5~7h‑1.Catalyst has mercaptan etherification activity high, and the low feature of loss of octane number is adaptable to different material.
Description
Technical field
The present invention relates to a kind of light FCC gasoline mercaptan etherification methods.
Background technique
Increasingly strict with environmental regulation, countries in the world, which propose the quality of refinery products, to be increasingly stringenter
It is required that being especially increasingly stringenter to the limitation of refinery products sulfur content.Vulcanize owner contained in oils
It to be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, not only has foul smell, very strong
Corrosivity also will affect the stability of product.
In recent years, thioetherification method has been widely used for the mercaptan in removing oil plant hydrocarbon fraction, i.e., using in raw material
Reaction between component removes mercaptan.Specifically, the alkene in certain hydrocarbon fractions containing mercaptan and high reaction activity
With alkadienes (such as butylene, isoprene), thioetherification reaction is by reacting mercaptan between mercaptan and active olefin
It is converted into high boiling thioether, then is fractionated and will be formed by high boiling sulfide compound and be separated from hydrocarbon-fraction, into
And achieve the purpose that remove mercaptan from raw material.The thioetherification technology of hydro carbons has numerous patent reports at present.For example, patent
US 5851383 discloses a kind of light olefin removal of mercaptans and process for selective hydrogenation, which generate catalytic cracking unit
C3-C5Fraction and hydrogen are mixed into fixed bed reactors, under thioetherification catalyst effect, diene and mercaptan in distillate
Reaction generates high boiling thioether, and extra diene is monoene by selective hydrogenation saturation；Reaction product imports destilling tower and carries out
Fractionation, the light component for removing mercaptan are flowed out from tower top, and thioether and heavy constituent are enriched with and are discharged in tower bottom.In specific embodiment
In, catalyst employed in fixed bed reactors is the Ni base catalyst using aluminium oxide as carrier, can realize the sulphur of mercaptan
The selective hydrogenation of etherification reaction and diene.Thioetherification reaction temperature is 125 DEG C, pressure 4100kPa.The sulphur of the patent disclosure
Etherification reaction temperature is excessively high, causes part monoolefin hydrogenation saturation and isomerization, alkene utilization rate is low, is largely not engaged in
In thioetherification reaction.
Patent US 7638041 discloses a kind of technique for handling FCC naphtha comprising the thioether of light naphtha fraction
Change removal of mercaptans, the selective hydrogenation of midbarrel.Full fraction cat cracked naphtha and hydrogen are mixed into destilling tower, and are divided
It is segmented into light components (LCN), intermediate species (MCN) and heavy component (HCN).The rectifying section of destilling tower is equipped with thioetherification catalyst
Agent, the alkadienes in LCN and mercaptan react to form higher boiling thioether herein, and enter stripping section by distillation, in tower
Bottom is concentrated.LCN after removal of mercaptans is discharged from tower top.MCN enters side stripper tower with side run-off, and tower is built-in selective
Hydrogenation catalyst, the light fraction in MCN enter front end destilling tower from side line top of tower, meanwhile, the selective hydrogenation of dienes in MCN
For monoene, product is discharged from tower bottom or mixes discharge with the HCN including sulfur-containing compound of distillation tower bottom.Wherein, sulphur
Catalyst used in etherification reaction is support type Ni base catalyst.Catalyst used in selective hydrogenation unit is load palladium catalysis
Agent.The patent do not refer to can thioetherification reaction for reference process conditions and case study on implementation.
Patent US20100059413 discloses a kind of for removing the thioetherification technique of mercaptan from gas fraction.Having
In the embodiment of body, the sulphur impurities such as hydro carbons and ethyl mercaptan such as alkene, alkadienes and alkynes are contained in feed gas.Unstripped gas
Gas phase and hydrogen is kept to be mixed into thioetherification reaction device, under the effect of the catalyst, mercaptan and active olefin react life
At higher boiling thioether, reaction product is passed through fractionating column and is separated, and the gas fraction without mercaptan is discharged from tower top, heavy constituent sulphur
Ether is enriched with and is discharged in tower bottom.Thioetherification catalyst used by the technique is the catalyst containing palladium, silver-colored isoreactivity metal,
Thioetherification reaction temperature is 176 °F, reaction pressure 150psig.But the patent is not directed to more about thioetherification catalyst
The information of aspect.CN201711190484.0 discloses a kind of heavy oil floating bed hydrocracking catalyst and preparation method thereof, catalysis
Agent includes the ore composition powder after Zinc oxide powder and vulcanization, and the ore composition powder after vulcanization includes nickel-containing ore, tungstenic
Ore, and/or iron-stone, wherein the content of zinc oxide is 10~56wt%.Ore composition powder and zinc oxide after vulcanization
Dry-mixed, obtained catalyst coking yield is low, liquid yield is high, desulfurization degree is high, the impurity ability such as sulfur resistive, anti-metal, nitrogen, carbon residue
By force, for the slurry-bed hydrocracking of inferior heavy oil.The catalyst is used for hydrocracking heavy oil desulphurization reaction, realizes heavy oil
Effectively conversion is not suitable for mercaptan conversion.
The composition and comparision contents of above-mentioned catalyst are more, and preparation process is complicated, and produce catalyst prod matter in enormous quantities
Amount is difficult to control.
For the defect for overcoming the above prior art, a kind of completely new mercaptan etherification catalyst is found, mercaptan etherification activity is high,
Stability is good, and the low characteristic of loss of octane number, is one of the most urgent problems to be solved by those skilled in the art.
Summary of the invention
The present invention provides a kind of light FCC gasoline mercaptan etherification method, removes mercaptan and alkadienes, and side reaction is few, living
Property it is high, loss of octane number is low.The mercaptan being especially applicable in catalytically cracked gasoline, catalytic cracking gasoline and coker gasoline etc. and two
Olefine reaction generates sulfide compound.
The present invention provides a kind of light FCC gasoline mercaptan etherification method, and using fixed bed reactors, gasoline is first cut
For light and heavy fractions oil, cutting temperature is 70 DEG C, and under the action of catalyst, gasoline light fraction enters reactor and carries out mercaptan etherificate instead
It answers, makes mercaptan and alkadienes in gasoline stocks that thioetherification reaction occur, catalyst includes complex carrier and metal active constituent
Nickel, molybdenum and magnesium, on the basis of the weight of catalyst, the content of nickel oxide is 2%~18wt%, the content of molybdenum oxide is 2~
20wt%, the content of magnesia are 0.01~1.5wt%, and complex carrier content is 65-85wt%；Complex carrier includes oxidation
Silicon-alumina support and ZSM-5 molecular sieve, silicaalumina carrier content is 65-90wt% in complex carrier, ZSM-5 points
Son sieve content is 10-35wt%, includes the silica of 0.1~12wt% in silicaalumina carrier, 0.1~10wt%'s
Nickel doped lanthanum ferrite, the potassium oxide of 0.1~4.0wt%, carrier is mesoporous to account for the 3~75% of total hole, macropore account for total hole 1.5~
60%, micropore, mesoporous, macropore uneven distribution in carrier；Reaction condition: reaction pressure is 0.1MPa~4.5MPa, hydrogen oil body
For product than being 2: 1~35: 1, reaction temperature is 60 DEG C~180 DEG C, and air speed is 0.5~7h-1。
Preferably, reaction pressure is 1MPa~4MPa, and hydrogen to oil volume ratio 2: 1~25: 1, reaction temperature is 70 DEG C~180
DEG C, volume space velocity is 2~6h-1。
It preferably, include following components: nickel oxide content 5-15wt%, molybdenum oxide on the basis of the total weight of catalyst
Content be 5.5-16wt%, carrier is mesoporous to account for the 3~65% of total hole, and macropore accounts for the 1.5~50% of total hole.
In the preparation method of catalyst of the present invention, the compound of nickel used and molybdenum can be prior art disclosed
A kind of what compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, ammonium molybdate, molybdenum oxide.
Mercaptan etherification catalyst of the present invention is applied in the etherified device of fixed bed gasoline sulfur needs vulcanizing treatment, including as follows
Step: at 100 DEG C~200 DEG C, start to be passed through vulcanizing agent, air speed is 1~8h-1, pressure is 0.1MPa~5MPa, and curing temperature is
200 DEG C~300 DEG C, constant temperature 1h~10h.The vulcanizing agent is selected from carbon disulfide, dimethyl disulfide, ethyl mercaptan or propanethiol etc..
The silicaalumina carrier the preparation method is as follows: boehmite and sesbania powder are added to kneader
In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds nickel doped lanthanum ferrite, mixing is equal
It is even to obtain alumina precursor, it is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains
Silicon source-boehmite-organic polymer mixture, the organic polymer of unit content is more quasi- than silicon source-in alumina precursor
The high 2 times or more of content of organic polymer in boehmite-organic polymer mixture (brief note silicon-aluminium-organic admixture),
Then by silicon source -- boehmite-organic polymer mixture is mixed with alumina precursor, adds potassium resource, through extrusion,
Molding, dry, roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon powder.Silicon-aluminium-is organic
Aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in object mixture.
The preparation process of above-mentioned silicaalumina carrier, the organic polymer are polyvinyl alcohol, polyacrylic acid, gather
One or more of sodium acrylate, polyethylene glycol, polyacrylate.
Preferably, in above-mentioned silicaalumina carrier nickel doped lanthanum ferrite be 0.1~12wt%, more preferable 0.2~
8wt%, nickel accounts for 0.1~8wt% of cadmium ferrite in nickel doped lanthanum ferrite.
The preparation method of the nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then by nitric acid
Lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polyacrylic acid is added in stirring and dissolving
The additional amount of sodium, polyacrylate or polyacrylic acid is the 0.1~10wt%, preferably 0.1~8.0wt% of nickel doped lanthanum ferrite.
Nickel compound containing is added, stirs, obtains finished product through drying, roasting, grinding.The nickel compound containing includes nickel nitrate, acetic acid
Nickel etc..
Complex carrier the preparation method is as follows: silicaalumina carrier is added to ZZSM-5 molecular sieve, sesbania powder pinches
It in conjunction machine, is added, Sodium Polyacrylate nitric acid solution obtains complex carrier through kneading, molding, drying, roasting.
The preparation method of catalyst can will be soaked using the methods of dipping, spraying containing the solution of active component nickel, potassium, molybdenum
Stain sprays on silica-carrier, is then dried to catalyst, roasts and obtain the catalyst.Such as can by with
Lower step prepares catalyst: solution oxide impregnation silicon-alumina support containing active component and adjuvant component is prepared, through 110~
160 DEG C dry 3~9 hours, and 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
Compared to cadmium ferrite, nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistance,
The mercaptan thioetherification catalyst of preparation is effectively mentioned using nickel doped lanthanum ferrite silica-alumina and ZSM-5 molecular sieve as carrier
High mercaptan thioetherification is active, and in the preparation process of silicaalumina carrier, unit content is organic poly- in alumina precursor
Object 2 times or more higher than the content of organic polymer in silicon-aluminium-organic admixture is closed, the pore structure of carrier can be not only improved,
Make carrier micropore, mesoporous, macropore uneven distribution, effectively inhibits active olefin polymerization, improve catalyst anticol mass-energy power, improve
The stability and service life of catalyst, are conducive to device long-term operation；And carrier surface is promoted to produce more work
Property position load centre, improve catalyst reaction activity.
Mercaptan etherification catalyst of the present invention is suitable for liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coke
Change mercaptan thioetherification removing mercaptan and the alkadienes in gasoline；Good catalyst activity.The octane number RON loss 0.3~0.4 of gasoline
Point or so, catalyst activity is high, and loss of octane number is low.A kind of light FCC gasoline mercaptan etherification method of the present invention is to different sulphur
The oil product of content, mercaptan sulfur content and olefin(e) centent is adaptable.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain
To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare,
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added to kneading
In machine, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, adds above-mentioned silicon powder-poly- third
Olefin(e) acid sodium mixture is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, by kneading-extrusion
It is shaped to clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the silica-of nickeliferous doped lanthanum ferrite
The carrier 1 of aluminium oxide.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, complex carrier is prepared
Silicaalumina carrier and ZZSM-5 molecular sieve, sesbania powder are added in kneader, and it is molten that Sodium Polyacrylate is added
Liquid obtains complex carrier through kneading, molding, drying, roasting.
4, catalyst is prepared
Nickeliferous, magnesium, molybdenum solution impregnated carrier 1 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, are urged
Agent 1.The composition of catalyst is shown in Table 1.
Embodiment 2
260g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 4.4wt% silica, the nickel doped lanthanum ferrite of 5.7wt%,
The potassium of 1.6wt%, carrier is mesoporous to account for the 64.2% of total hole, and macropore accounts for the 25.6% of total hole.Unit content in alumina precursor
Sodium Polyacrylate it is 3 times higher than the content of Sodium Polyacrylate in silicon source-organic polymer mixture.The preparation of complex carrier is the same as real
Example 1 is applied, the preparation method is the same as that of Example 1 for catalyst 2.
Embodiment 3
220g polyacrylic acid is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite, silicaalumina carrier
Preparation includes the silica of 8.4wt% with embodiment 1, in silicaalumina carrier, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 0.8wt%, carrier is mesoporous to account for the 54.6% of total hole, and macropore accounts for the 33.5% of total hole.Unit content in alumina precursor
Polyacrylic acid it is 3.3 times higher than the content of polyacrylic acid in silicon source-organic polymer mixture.The preparation of complex carrier is the same as implementation
Example 1, the preparation method is the same as that of Example 1 for catalyst 3.
Embodiment 4
280g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 8.4wt% silica, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 3.5wt%, carrier is mesoporous to account for the 49.3% of total hole, and macropore accounts for the 39.4% of total hole.Unit content in alumina precursor
Polyacrylate it is 3.3 times higher than the content of polyacrylate in silicon source-organic polymer mixture.Preparing for complex carrier is same
Embodiment 1, the preparation method is the same as that of Example 1 for catalyst.
Comparative example 1
1, cadmium ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, stir 30min, drying, roasting, grinding obtain nickel doping iron
Sour lanthanum.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain
To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare,
It is spare that citric acid is added in 4.5g cadmium ferrite.300g boehmite powder and 25.0g sesbania powder are added in kneader, added
Enter nitric acid, add 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is mixed to add above-mentioned silicon powder-Sodium Polyacrylate
Object is closed, mediates uniformly, cadmium ferrite and 2.5g potassium nitrate is then added, be uniformly mixed, is cloverleaf pattern by kneading-extruded moulding
Shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the carrier 1-1 of the silica-alumina of Fe-laden acid lanthanum.
3, the preparation of complex carrier is the same as embodiment 1.
4, comparative catalyst 1 is prepared
Nickeliferous, magnesium, molybdenum solution impregnated carrier 1-1 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain
Comparative catalyst 1.
Comparative example 2
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite, 350g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.7g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is micro- to add 4.8g silicon
Powder is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, and is three leaves by kneading-extruded moulding
Careless shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the load of the silica-alumina of nickeliferous doped lanthanum ferrite
Body 1-2.
3, the preparation of complex carrier is the same as embodiment 1.
4, comparative catalyst 2 is prepared
Nickeliferous, magnesium, molybdenum solution impregnated carrier 1-2 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain
Comparative catalyst 2.
Catalyst 1-4 and comparative example Catalyst packing are subjected to evaluation catalyst reaction into fixed bed reactors respectively
Performance.Presulfurization, sulfide stress 3.2MPa are carried out to catalyst with sulfurized oil, sulfurized oil volume space velocity is 3.5h-1, vulcanize journey
Sequence is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched to full fraction FCC gasoline replacement Treatment
6h, then gasoline is first cut into light and heavy fractions oil, and cutting temperature is 65 DEG C, and gasoline light fraction enters reactor, is adjusted to react
Process conditions carry out etherificate removal of mercaptans and diene hydrocarbon reaction.523 μ g/g of FCC feedstock content of sulfur in gasoline, 30.3 μ g/g of mercaptan sulfur,
Arsenic content is 27ppb, olefin(e) centent 30.8v%, RON 88.9.Reaction process condition are as follows: 100 DEG C of temperature of reactor, volume is empty
Fast 3.5h-1, hydrogen to oil volume ratio 18:1, reaction pressure 2.4MPa.Sampling analysis after reaction about 60h, reaction result are shown in Table 2.
1 embodiment of table/comparative example catalyst composition/wt%
2 embodiments of table/comparative example reaction 60h result
| Embodiment/comparative example | Mercaptan sulfur content/μ g/g | Olefin(e) centent v% | Loss of octane number | Yield of gasoline wt%； |
| Embodiment 1 | 0.1 | 30.4 | 0.2 | 99.1 |
| Embodiment 2 | 0.1 | 30.3 | 0.3 | 98.8 |
| Embodiment 3 | 0.2 | 30.3 | 0.2 | 98.7 |
| Embodiment 4 | 0.2 | 30.4 | 0.3 | 98.7 |
| Comparative example 1 | 11 | 21.5 | 3.7 | 87.5 |
| Comparative example 2 | 9 | 24.6 | 2.8 | 90.4 |
The result of 3 embodiment of table reaction 600h
| Embodiment | Mercaptan sulfur content/μ g/g | Olefin(e) centent v% | Loss of octane number | Yield of gasoline wt%； |
| Embodiment 1 | 0.1 | 30.3 | 0.2 | 99.0 |
| Embodiment 2 | 0.1 | 30.3 | 0.3 | 98.9 |
Reaction result shows that olefin(e) centent is basically unchanged, and reaction loss of octane number is 0.3~0.4, catalyst etherification activity
Height, arsenic resistance can be good, and loss of octane number is low.Comparative example catalyst activity is low, catalyst may plastic even coking and under activity
Drop.
Stability test is carried out to catalyst, reaction operation 600h reaction result is shown in Table 3, and olefin(e) centent is basically unchanged, and is urged
It is good that agent is not easy plastic even coking and deactivation, stability.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. a kind of light FCC gasoline mercaptan etherification method, which is characterized in that use fixed bed reactors, gasoline is first cut into
Light and heavy fractions oil, cutting temperature are 70 DEG C, and under the action of catalyst, gasoline light fraction enters reactor and carries out mercaptan etherificate instead
It answers, catalyst includes complex carrier and metal active constituent nickel, molybdenum and magnesium, and on the basis of the weight of catalyst, nickel oxide contains
Amount is 2%~18wt%, and the content of molybdenum oxide is 2~20wt%, and the content of magnesia is 0.01~1.5wt%, complex carrier
Content is 65-85wt%；Complex carrier includes silicaalumina carrier and ZSM-5 molecular sieve, silica-in complex carrier
Alumina support content is 65-90wt%, and ZSM-5 molecular sieve content is 10-35wt%, includes in silicaalumina carrier
The silica of 0.1~12wt%, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium oxide of 0.1~4.0wt%, carrier is mesoporous to be accounted for
The 3~75% of total hole, macropore accounts for the 1.5~60% of total hole, micropore, mesoporous, macropore uneven distribution in carrier；Reaction condition:
Reaction pressure is 0.1MPa~4.5MPa, and hydrogen to oil volume ratio 2: 1~35: 1, reaction temperature is 60 DEG C~180 DEG C, and air speed is
0.5~7h-1。
2. light FCC gasoline mercaptan etherification method according to claim 1, which is characterized in that reaction pressure 1MPa
~4MPa, hydrogen to oil volume ratio 2: 1~25: 1, reaction temperature are 70 DEG C~180 DEG C, and volume space velocity is 2~6h-1。
3. light FCC gasoline mercaptan etherification method according to claim 1, which is characterized in that the carrier is mesoporous to be accounted for
The 3~65% of total hole, macropore accounts for the 1.5~50% of total hole；The catalyst includes following components on the basis of total weight: oxidation
Nickel content is 5-15wt%, and the content of molybdenum oxide is 5.5-16wt%.
4. light FCC gasoline mercaptan etherification method according to claim 1, which is characterized in that the silica-oxygen
Change being uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader for alumina supporter, inorganic acid is added
Solution and organic polymer are mediated uniformly, then add nickel doped lanthanum ferrite, are uniformly mixed and obtain alumina precursor, standby
With；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, it is organic to obtain silicon source-boehmite-
Polymeric blends, the organic polymer of unit content is more mixed than silicon source-boehmite-organic polymer in alumina precursor
The high 2 times or more of content for closing organic polymer in object, then by silicon source -- boehmite-organic polymer mixture and oxidation
The mixing of aluminium presoma, adds potassium resource, through extrusion, molding, drying, roasting, obtains silicaalumina carrier.
5. light FCC gasoline mercaptan etherification method according to claim 4, which is characterized in that the silicon source is silicon
Glue, sodium metasilicate or silicon powder, in silicon source-boehmite-organic polymer mixture aluminium oxide account for aluminium oxide in carrier 1~
35wt%.
6. light FCC gasoline mercaptan etherification method according to claim 4, which is characterized in that the organic polymer
For one or more of polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
7. light FCC gasoline mercaptan etherification method according to claim 4, which is characterized in that the silica-oxygen
Changing nickel doped lanthanum ferrite in alumina supporter is 0.1~12wt%.
8. described in any item light FCC gasoline mercaptan etherification methods according to claim 1~7, which is characterized in that described
The preparation method of nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then adds lanthanum nitrate and ferric nitrate
Enter in citric acid, stirring and dissolving, Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylate is added
Or the additional amount of polyacrylic acid is 0.1~10wt% of nickel doped lanthanum ferrite, adds nickel compound containing, is stirred, through drying, roasting
It burns, grinding obtains finished product.
9. described in any item light FCC gasoline mercaptan etherification methods according to claim 1~7, which is characterized in that described
The preparation method of catalyst includes the following steps: that the maceration extract dipping of active component will be contained, sprays on carrier, then to catalysis
Agent is dried, roasts and obtains the catalyst.
10. light FCC gasoline mercaptan etherification method according to claim 9, which is characterized in that the catalyst
Preparation process is as follows: nickeliferous, magnesium, molybdenum solution oxide impregnation silicon-alumina support are configured, it is small through 110~160 DEG C of drying 3~9
When, 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
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