CN109364945A - A kind of method of full-cut fraction pyrolysis gasoline selective hydrogenation - Google Patents
A kind of method of full-cut fraction pyrolysis gasoline selective hydrogenation Download PDFInfo
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- CN109364945A CN109364945A CN201811182822.0A CN201811182822A CN109364945A CN 109364945 A CN109364945 A CN 109364945A CN 201811182822 A CN201811182822 A CN 201811182822A CN 109364945 A CN109364945 A CN 109364945A
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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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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- 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 full-cut fraction pyrolysis gasoline process for selective hydrogenation, using adiabatic reactor reactor, catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, total weight of the content of palladium based on the catalyst is 0.15-0.45wt%, it include the silica of 0.1~12wt% in silicaalumina carrier, the nickel doped lanthanum ferrite of 0.1~10wt%, the magnesium of 0.05~7.8wt%, hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction pressure 2.0-4.5MPa, hydrogen to oil volume ratio 60~450；Liquid volume air speed 3.0-5.0h‑1.Catalyst anticol mass-energy power is good, and anti-arsenic, sulfur resistive, water resistant ability are strong.
Description
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/
Al2O3Two kinds of catalyst.Pd series catalysts have initial temperature low, and hydrogenation activity is big, adapt to air speed height, and long service life etc. is excellent
Point, 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,
Reaction 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
Under conditions of being 60~120: 1, raw material is contacted with catalyst, is reacted, and makes diolefin and alkylene aromatic hydrocarbons in raw material
Component is converted to monoolefine and alkylaromatic hydrocarbon, wherein catalyst include alumina support, activity component metal palladium or its oxide,
Element or its oxide, at least one IVA in the periodic table of elements of at least one IA in the periodic table of elements or IIA
Or the element or its oxide of VA, carrier specific surface area are 40~160 meters2/ gram, total pore volume is 0.3~1.2 ml/g, and
Carrier has the technical solution of compound pore size distribution, preferably solves the problems, such as this, can be used for full-cut fraction pyrolysis gasoline and selectively adds
In the industrial production of hydrogen.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique: first with a kind of energy
The liquid to dissolve each other with maceration extract presoaks carrier, then with salt solution impregnation containing palladium, the carrier after dipping is washed, it is dry,
It roasts in air up to oxidative catalyst finished product for 300~600 DEG C.Finished catalyst only need to lead in the reactor hydrogen reducing
It can be used.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant mesoporous.This
The catalyst of invention has good low temperature active, selectivity and stabilization when being used for full-cut fraction pyrolysis gasoline selective hydrogenation
Property, 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, using adiabatic reactor reactor, in a hydrogen atmosphere to catalyst
It is adjusted to reaction process condition after being restored, into full-cut fraction pyrolysis gasoline feedstock oil, carries out selective hydrogenation；Catalyst
Including silicaalumina carrier and the metal active component palladium being carried on carrier, the content of palladium is based on the total of the catalyst
Weight is 0.15-0.45wt%, includes the silica of 0.1~12wt% in silicaalumina carrier, 0.1~10 wt%'s
Nickel doped lanthanum ferrite, the magnesium of 0.05~7.8wt%, 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.Hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction pressure
2.0-4.5MPa hydrogen to oil volume ratio 60~450；Liquid volume air speed 3.0-5.0h-1。
Preferably, the hydrogenation process conditions: liquid volume air speed 3.0-4.5h-1 reacts inlet temperature >=55 DEG C, instead
Answer pressure 2.5-4.0MPa, hydrogen to oil volume ratio 60~400.
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, in temperature 130
DEG C, 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 C5-C9
Fraction, diene content is 40.79g iodine/100g oil, iodine number 119.43g iodine/100g, colloid in full-cut fraction pyrolysis gasoline feedstock oil
Content is 132mg/100ml oil, free water content 1203ppm, sulfur content are 122ppm and arsenic content is 59ppb；React work
Skill condition are as follows: 50 DEG C of inlet temperature, hydrogen to oil volume ratio 230: 1, reaction pressure 2.8MPa, green oil air speed 3.2h-1；Operate 200h
The average diene of 1 hydrogenated products of catalyst is 1.58 grams of iodine/100 gram oil, iodine number 43.67g iodine/100g, diolefin hydrogenation rate
89.1%.The average diene of 2 hydrogenated products of catalyst is 1.28 grams of iodine/100 gram oil, iodine number 42.54g iodine/100g, diolefin hydrogenation
Rate 89.6%.The average diene of 3 hydrogenated products of catalyst is 1.94 grams of iodine/100 gram oil, and iodine number 43.02g iodine/100g, diene adds
Hydrogen rate 89.0%.The average diene of 4 hydrogenated products of catalyst is 1.58 grams of iodine/100 gram oil, iodine number 42.23g iodine/100g, diene
Hydrogenation rate 89.4%.The average diene of 1 hydrogenated products of comparative catalyst be 4.31 grams of iodine/100 gram oil, iodine number 48.76g iodine/
100g, diolefin hydrogenation rate 77.1%.；The anti-arsenic of comparative catalyst 1, sulfur resistive, water repelling property are poor, and diolefin hydrogenation is selectively low；Than urging
Agent 79.4%.；2 anticol mass-energy power of comparative catalyst is poor, and activity is low.Catalyst 1-4 activity is higher, and selectivity is more preferable, anticol
Matter, water resistant ability are more preferable, and anti-arsenic, sulfur resistive ability are strong.
After catalyst 1-2 operates 600h, the average diene of 1 hydrogenated products of catalyst is 1.64 grams of iodine/100 gram oil, iodine number
43.77g iodine/100g, diolefin hydrogenation rate 89.2%.The average diene of 2 hydrogenated products of catalyst is 1.33 grams of iodine/100 gram oil,
Iodine number 42.98g iodine/100g, diolefin hydrogenation rate 89.4%.Contain nickel doped lanthanum ferrite in catalyst carrier, is conducive to inhibition two
Polymerization reaction occurs for the unsaturation component such as alkene and styrene；Catalyst is insensitive to impurity such as water, colloids, catalyst anticol
Matter, water resistant ability are good, and anti-arsenic, sulfur resistive ability are strong, stable in catalytic performance.Catalyst carrier micropore, mesoporous, macropore unevenly divide
Cloth, 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, full-cut fraction pyrolysis gasoline (C than restoring 8 hours under the conditions of 250:15~C9) diene content
For 40.65g iodine/100g oil, iodine number 132.92g iodine/100g, gum level is 143mg/100ml oil, sulfur content 56ppm, trip
From water content be 1056ppm and arsenic content is 78ppb；Reaction process condition are as follows: 55 DEG C of inlet temperature, hydrogen to oil volume ratio 260: 1,
Reaction pressure 2.5MPa, green oil air speed 4.0h-1；Operate 1 hydrogenated products of 200h catalyst average diene be 1.43 grams of iodine/
100 grams of oil, iodine number 40.68g iodine/100g, diolefin hydrogenation rate 89.4%.The average diene of 2 hydrogenated products of catalyst is 1.37 grams
Iodine/100 gram oil, iodine number 39.32g iodine/100g, diolefin hydrogenation rate 90.7%.Catalyst to different sulfur contents, 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.
Claims (10)
1. a kind of full-cut fraction pyrolysis gasoline process for selective hydrogenation, which is characterized in that adiabatic reactor reactor is used, in hydrogen atmosphere
Under catalyst is restored after be adjusted to reaction process condition, into full-cut fraction pyrolysis gasoline feedstock oil, carry out selective hydrogenation
Reaction；Catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, and the content of palladium is based on should
The total weight of catalyst is 0.15-0.45wt%, includes the silica of 0.1~12wt% in silicaalumina carrier, 0.1
The nickel doped lanthanum ferrite of~10wt%, the magnesium of 0.05~7.8wt%, carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for total hole
1.5~60%, micropore, mesoporous, macropore uneven distribution in carrier；Hydrogenation process conditions: reaction inlet temperature >=50 DEG C, reaction
Pressure 2.0-4.5MPa, hydrogen to oil volume ratio 60~450；Liquid volume air speed 3.0-5.0h-1。
2. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the hydrogenation technique
Condition: liquid volume air speed 3.0-4.5h-1 reacts inlet temperature >=55 DEG C, reaction pressure 2.5-4.0MPa, hydrogen to oil volume ratio
60~400.
3. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the carrier is mesoporous
The 3~65% of total hole are accounted for, macropore accounts for the 3~45% of total hole.
4. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the catalysis
The content of agent palladium is 0.20-0.35wt%.
5. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1, which is characterized in that the silica-
Being uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader for alumina support, is added inorganic
Acid solution and organic polymer are mediated uniformly, then add nickel doped lanthanum ferrite, are uniformly mixed and obtain alumina precursor,
It is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtaining silicon source-boehmite-has
Machine polymeric blends, the organic polymer of unit content is than silicon source-boehmite-organic polymer in alumina precursor
The high 2 times or more of the content of organic polymer in mixture, then by silicon source -- boehmite-organic polymer mixture and oxygen
Change the mixing of aluminium presoma, adds magnesium source, through extrusion, molding, drying, roasting, obtain silicaalumina carrier.
6. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, 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%.
7. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, which is characterized in that the organic polymer
Object is one or more of polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
8. full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 5, which is characterized in that the silica-
Nickel doped lanthanum ferrite is 0.1~12wt% in alumina support.
9. described in any item full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1~8, which is characterized in that institute
The preparation method for stating nickel doped lanthanum ferrite includes the following steps: for citric acid to be dissolved in stirring and dissolving in deionized water, then by nitre
Sour lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polypropylene is added in stirring and dissolving
The additional amount of sour sodium, polyacrylate or polyacrylic acid is 0.1~10wt% of nickel doped lanthanum ferrite, adds nickeliferous chemical combination
Object, stirring, obtains finished product through drying, roasting, grinding.
10. described in any item full-cut fraction pyrolysis gasoline process for selective hydrogenation according to claim 1~8, which is characterized in that institute
The preparation method for stating catalyst includes the following steps: to prepare palladium-containing solution oxide impregnation silicon-alumina support, through 110~160 DEG C
Drying 3~9 hours, 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
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| CN109364929A (en) * | 2018-10-11 | 2019-02-22 | 陈新忠 | The method of drippolene selective hydrogenation |
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