The method of drippolene selective hydrogenation
Technical field
The present invention relates to a kind of methods of one-stage selective hydrogenation of gasoline splitting.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene
It forms very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine
With the organic compound of heavy metal etc., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no
Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline
And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation
Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present
Pd system or Ni series catalysts, midbarrel (C6~C8Hydrocarbon compound fraction) plus hydrogen or full fraction (C5Hydrocarbon~do is 204 DEG C
Hydrocarbon compound fraction) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene is former
Material composition difference is larger, and especially (it is anti-that polymerization occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid
The high molecular polymer that should be generated) and As, content of beary metal there are larger differences;Some device raw pyrolysis gasoline dienes, glue
Matter is high, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, and individual device slightly cracks vapour
The toxic contents such as oily diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao
At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3
Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life,
The catalyst mode for having industrial application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound
The carrier, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use
Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material
When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on carrier
On metal active constituent, the active component is in the microemulsion without cosurfactant containing high molecular polymer water phase
It is prepared in law system;The carrier is selected from aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolinite
At least one of soil, cordierite;The active component is main active component and helps active component, wherein main active component is
Palladium, content are 0.01wt%~1.0wt% of carrier gross weight, and the high molecular polymer is water-soluble high molecular polymerization
Object.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and preparation process is easy, catalyst
Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its fraction selective hydrogenation
Palladium-silver/alumina-silica titanium catalyst, the catalyst include the aluminium oxide-titanium oxide compound as carrier, and load
In active component Pd and Ag on the carrier, wherein the content of Pd is based on the total catalyst weight as 0.15-0.5 weight
% is measured, it is 0.8-4.5 weight % that the content of Ag, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis
Agent can be used for drippolene or its fraction plus hydrogen, low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and
It is activity stabilized.CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves
It exists in the prior art and is difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content and carries out the technology of selective hydrogenation ask
Topic.The present invention is by using with C5The drippolene and hydrogen of the hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C are raw material, anti-
Answering temperature is 30~80 DEG C, and reaction pressure is 2.0~3.0MPa, and green oil air speed is 2.5~5.0 hours- 1, hydrogen/oil volume ratio
Under conditions of 60~120: 1, raw material is contacted with catalyst, is reacted, and diolefin and alkylene aromatic hydrocarbons group in raw material are made
Point it is converted to monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, extremely
Element or its oxide, at least one IVA or VA in the periodic table of elements of few a kind of IA in the periodic table of elements or IIA
Element or its oxide, carrier specific surface area be 40~160 meters2/ gram, total pore volume is 0.3~1.2 ml/g, and carrier has
There is the technical solution of compound pore size distribution, preferably solve the problems, such as this, can be used for the work of full-cut fraction pyrolysis gasoline selective hydrogenation
In industry production.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique: first with it is a kind of can be with dipping
Liquid that liquid dissolves each other presoaks carrier, then with salt solution impregnation containing palladium, and the carrier after dipping is washed, dry, in air
300~600 DEG C roast up to oxidative catalyst finished product.Finished catalyst only need to lead in the reactor hydrogen reducing and can make
With.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant mesoporous.The present invention
Catalyst be used for full-cut fraction pyrolysis gasoline selective hydrogenation when have good low temperature active, selectivity and stability, and
And there is good anti-interference, resistance to high colloid and high-content free water performance.In 40 DEG C of inlet temperature, reaction pressure
2.7Mpa, hydrogen/oil volume are than 80: 1, and green oil air speed 3.8 hours-1Under the conditions of, be 150 milligrams/100 grams oil to gum level,
Free water content is the full fraction (C of 1000ppm5The hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C) drippolene selected
Hydrogenation reaction, outlet diene average value are 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, achieve preferable technology
Effect.The preparation method of the invention carrier include aluminium oxide and modifying agent, peptizing agent, water are mixed in the desired amount, extruded moulding
Afterwards, first 1~24 hour dry at 50~120 DEG C, it is then roasted 1~10 hour at 800~1150 DEG C, obtains carrying alumina
Body.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour
Oily catalyst has anticol matter, water resistant ability good, the strong characteristic of anti-arsenic, sulfur resistive ability.
Summary of the invention
The present invention provides a kind of one-stage selective hydrogenation of gasoline splitting method, is particularly suitable for drippolene C6-C8Fraction choosing
Selecting property adds hydrogen.The process uses load type palladium catalyst, and carrier is that the silica-alumina comprising nickel doped lanthanum ferrite carries
Body, strong to different arsenic contents, different sulfur contents, water content, the drippolene adaptability to raw material of gum level, catalyst is reacting
In low temperature active it is higher, selectivity is more preferable.
A kind of one-stage selective hydrogenation of gasoline splitting method, catalyst include silicaalumina carrier and are carried on load
Metal active component palladium on body, the content of palladium are 0.15-0.45wt%, silica-oxidation based on the total weight of the catalyst
In alumina supporter include 0.1~12wt% silica, the nickel doped lanthanum ferrite of 0.1~10wt%, the magnesium of 0.05~7.8wt%,
Carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for the 1.5~60% of total hole.Micropore, mesoporous, macropore uneven distribution in carrier.
Hydrogenation process conditions: reaction inlet temperature≤45 DEG C, reaction pressure 2.5-4.5MPa, hydrogen to oil volume ratio 60~450;Liquid volume
Air speed 3.0-5.5h-1.
Preferably, the hydrogenation process conditions: liquid volume air speed 3.0-4.5h-1, react inlet temperature≤40 DEG C, reaction
Pressure 2.5-4.0MPa, hydrogen to oil volume ratio 60~300.
The above-mentioned preferred 0.20-0.35wt% of Palladium Content in Catalyst.Preferably, mesoporous to account for the 3~65% of total hole, macropore accounts for
The 3~45% of total hole.
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 magnesium source, 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..
The preparation method of catalyst by active component palladium dipping, can spray to oxidation using the methods of dipping, spraying
On silicon-carrier, then catalyst is dried, roasts and obtains the catalyst.Such as it can prepare and urge according to the following steps
Agent: preparing palladium-containing solution oxide impregnation silicon-alumina support, dries 3~9 hours through 110~160 DEG C, 400~650 DEG C of roastings
It burns 4~9 hours, finally obtains catalyst prod.
In the preparation method of catalyst of the present invention, palladium compound used can be any one disclosed in prior art
Suitable for the palladium compound of palladium catalyst processed, such as palladium chloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, four nitre
Base palladium acid sodium, acylate such as oxalic acid palladium of palladium etc..To prepare solvent used in palladium compound solution do not have it is any specifically limited,
As long as it can dissolve used palladium compound.Preferred solvent be for example water, dilute hydrochloric acid, dust technology, dilute sulfuric acid or
Their mixed liquor.
Nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistive, water repelling property, improves alkynes
Hydrocarbon or diolefin hydrogenation selectivity.In the preparation process of silicaalumina carrier, unit content is organic in alumina precursor
Polymer 2 times or more higher than the content of organic polymer in silicon-aluminium-organic admixture can not only improve the hole knot of carrier
Structure makes carrier micropore, mesoporous, macropore uneven distribution, improves catalyst anticol mass-energy power, improves the stability of catalyst and makes
With the service life, be conducive to device long-term operation;And carrier surface is promoted to produce more active sites load centres, improve palladium
Catalyst hydrogenation activity.
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
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
Enter into kneader, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, nickel doping is then added
Cadmium ferrite is uniformly mixed, obtains alumina precursor.5g Sodium Polyacrylate is dissolved in nitric acid, adds 38g silicon powder and 50g
Boehmite powder, stirs evenly, and obtaining silicon powder-boehmite-Sodium Polyacrylate mixture, (brief note silicon-aluminium-is organic
Object mixture).Silicon-aluminium-the organic admixture for taking 1/8 adds above-mentioned alumina precursor and 4.2g magnesium nitrate, mediates equal
It is even, it is clover shape by kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain nickeliferous doping
The carrier 1 of the silica-alumina of cadmium ferrite.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, catalyst is prepared
Palladium solution impregnating carrier 1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.It urges
1 palladium content of agent is 0.29wt%.
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 magnesium of 1.2wt%, 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 method of catalyst 2
With embodiment 1, palladium amount is 0.35wt%.
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 magnesium of 2.1wt%, 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 method of catalyst 3 is same
Embodiment 1, palladium amount are 0.21wt%.
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 magnesium of 2.8wt%, 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.The preparation side of catalyst 3
For method with embodiment 1, palladium amount is 0.26wt%.
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 4.2g magnesium 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, comparative catalyst 1 is prepared
Palladium solution impregnating carrier 1-1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.
1 palladium content of comparative catalyst is 0.29wt%.
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 4.2g magnesium 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, comparative catalyst 2 is prepared
Palladium solution impregnating carrier 1-2 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain comparison catalysis
Agent 2.2 palladium content of comparative catalyst is 0.29wt%.
Catalyst 1-4 and comparative catalyst 1 and 2 are respectively charged into 100ml insulation bed reaction device, at 130 DEG C of temperature,
It is restored 7 hours under the conditions of the volume ratio 220:1 of hydrogen and catalyst, cools to 40 DEG C of laggard feedstock oils, drippolene C6-C8It evaporates
Point, diene content is 19.51g iodine/100g oil, bromine valency is 26.76g bromine/100g oil, gum level is 41mg/100ml oil, trip
From water content be 1123ppm, sulfur content is 156ppm and arsenic content is 151ppb;Reaction process condition are as follows: 45 DEG C of inlet temperature,
Hydrogen to oil volume ratio 300: 1, reaction pressure 3.5MPa, green oil air speed 3.5h-1;Operating 1 hydrogenated products of 220h catalyst are averaged
Diene is 0.38 gram of iodine/100 gram oil, and bromine valency is 15.68 grams of bromine/100 gram, diolefin hydrogenation rate 98.7%.2 hydrogenated products of catalyst
Average diene be 0.33 gram of iodine/100 gram oil, bromine valency be 14.56 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.8%;Catalyst 3
The average diene of hydrogenated products is 0.42 gram of iodine/100 gram oil, and bromine valency is 16.54 grams of bromine/100 gram, diolefin hydrogenation rate 98.2%.
The average diene of 4 hydrogenated products of catalyst is 0.40 gram of iodine/100 gram oil, and bromine valency is 15.29 grams of bromine/100 gram oil, diolefin hydrogenation
Rate 98.3%.Catalyst activity is higher, and selectivity is more preferable, and anticol matter, water resistant ability are more preferable, and anti-arsenic, sulfur resistive ability are strong.
After catalyst 1-2 operates 500h, the average diene of 1 hydrogenated products of catalyst is 0.40 gram of iodine/100 gram oil, bromine valency
For 20.25 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.5%;The average diene of 2 hydrogenated products of catalyst is 0.45 gram of iodine/100
Gram oil, bromine valency are 20.48 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.7%.Contain nickel doped lanthanum ferrite in catalyst carrier, has
Polymerization reaction occurs conducive to the unsaturated component of inhibition alkadienes and styrene etc.;Catalyst is insensitive to impurity such as water, colloids, urges
Agent anticol matter, water resistant ability are good, and anti-arsenic, sulfur resistive ability are strong, stable in catalytic performance.Catalyst carrier micropore, mesoporous, macropore are not
It is uniformly distributed, palladium catalyst activity is good, and stability is good, long service life, is conducive to device long-term operation.
Catalyst 1-2 is respectively charged into 100ml insulation bed reaction device, at 125 DEG C of temperature, the body of hydrogen and catalyst
Product cools to 40 DEG C of laggard feedstock oils, drippolene C than restoring 8 hours under the conditions of 250:16-C8Fraction, diene content are
23.32g iodine/100g oil, bromine valency are 24.35g bromine/100g oil, gum level is 104mg/100ml oil, free water content is
1045ppm, sulfur content are 87ppm and arsenic content is 96ppb;Reaction process condition are as follows: 41 DEG C of inlet temperature, hydrogen to oil volume ratio
260: 1, reaction pressure 3.0MPa, green oil air speed 3.0h-1;The average diene for operating 1 hydrogenated products of 200h catalyst is 0.45
Gram iodine/100 gram oil, bromine valency are 16.12 grams of bromine/100 gram, diolefin hydrogenation rate 98.5%.The average diene of 2 hydrogenated products of catalyst
For 0.37 gram of iodine/100 gram oil, bromine valency is 15.13 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.7%;Catalyst contains different sulphur
Amount, free water content, arsenic content, the oil of gum level are adaptable.
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.