CN109364934A - A kind of nickel system selective hydrocatalyst and preparation method - Google Patents
A kind of nickel system selective hydrocatalyst and preparation method Download PDFInfo
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- CN109364934A CN109364934A CN201811182784.9A CN201811182784A CN109364934A CN 109364934 A CN109364934 A CN 109364934A CN 201811182784 A CN201811182784 A CN 201811182784A CN 109364934 A CN109364934 A CN 109364934A
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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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
- C10G45/08—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 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
Abstract
The present invention relates to a kind of nickel system selective hydrocatalysts, catalyst includes silicaalumina carrier and the metal active constituent nickel, molybdenum and the potassium that are carried on carrier, it include following components: nickel oxide content 9-25wt% on the basis of the total weight of catalyst, the content of molybdenum oxide is 2.5-8wt%, and potassium oxide content is 0.02~2.5%；Silicaalumina carrier content is 75-91wt%.Catalyst anticol matter, anti-arsenic, sulfur resistive, water resistant ability are strong.
Description
Technical field
The present invention relates to one kind to be used for unsaturated hydrocarbons selective hydrocatalyst and preparation method, especially a kind of nickel system choosing
Selecting property hydrogenation catalyst is used for 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.
CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves existing
Have and there is technical issues that be difficult to the full-cut fraction pyrolysis gasoline progress high to colloid and free water content in technology.
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, are being reacted
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 is
Under conditions of 60~120: 1, raw material is contacted with catalyst, is reacted, and diolefin and alkylene aromatic component in raw material are made
It is converted to monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, at least
The element or its oxide of a kind of IA in the periodic table of elements or IIA, at least one IVA in the periodic table of elements or VA
Element or its oxide, 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 the industry of full-cut fraction pyrolysis gasoline selective hydrogenation
In production.CN200610118522.7 is related to a kind of Raney nickel with composite pore structural for selective hydrogenation, mainly
The low temperature active that catalyst exists in the prior art in solution is low, anti-interference ability is weak, appearance glue ability is low, stability is poor, resistance to free
Aqueous technical problem that can be poor.The present invention by using including following components by weight percentage: (a) 5.0~40.0%
Metallic nickel or its oxide；(b) 0.01~20.0% be selected from least one of molybdenum or tungsten element or its oxide；(c)
0.01~10.0% selected from least one of rare earth element or its oxide；(d) 0.01~2.0% be selected from period of element
At least one of IA or IIA element or its oxide in table；(e) 0~15.0% in silicon, phosphorus, boron or fluorine at least
A kind of element or its oxide；(f) 0~10.0% at least one of IVB element in the periodic table of elements or its oxidation
Object；(g) alumina catalyst support of surplus, wherein the total pore volume of carrier is 0.5~1.2 ml/g, the Kong Rong that 30 nanometers of bore dia <
The 5~65% of total pore volume are accounted for, the Kong Rong that 30~60 nanometers of bore dia accounts for the 20~80% of total pore volume, the hole that 60 nanometers of bore dia >
Hold 20~50% technical solution for accounting for total pore volume and preferably solve the problems, such as this, can be used for the work of drippolene selective hydrogenation
In industry production.
The CN201210349977.5 present invention is a kind of drippolene nickel system selective hydrocatalyst and preparation method thereof.
Belong to the catalyst comprising metal or metal oxide or hydroxide.It is characterized in that having mesopore-macropore or double mesoporous multiple
Duct is closed, carrier is made with aluminium oxide, with nickel for main active constituent, molybdenum is to help active component, and metal oxide is auxiliary agent, the cracking
The weight percent composition of gasoline nickel system selective hydrocatalyst is as follows: nickel oxide 15~19, molybdenum oxide 6.5~20.0, auxiliary agent,
2.2~4.5, aluminium oxide surplus；The auxiliary agent is one of potassium oxide, magnesia, lanthana or it is two or more groups any
It closes.Drippolene is when using Al2O3When for carrier, during high temperature reduction nickel ion, it is easy to cause nickel aluminate or meta-aluminic acid
Nickel generates, and then reduces catalyst activity selectivity, poor catalyst stability.
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 nickel system selective hydrocatalyst, is used for one-stage selective hydrogenation of gasoline splitting.The catalysis
The activity of agent in the reaction is higher, and selectivity is more preferable, and anticol matter, water resistant ability are good, and anti-arsenic, sulfur resistive ability are strong, the load of catalyst
Body is a kind of silicaalumina carrier, includes nickel doped lanthanum ferrite in carrier, and active component includes nickel, and catalyst is especially suitable
For one-stage selective hydrogenation of gasoline splitting.
The present invention provides a kind of nickel system selective hydrocatalyst, is used for unsaturated hydrocarbons selective hydrogenation, the catalyst packet
Metal active constituent nickel, molybdenum and the potassium for including silicaalumina carrier and being carried on carrier, using the total weight of catalyst as base
Standard includes following components: nickel oxide content 9-25wt%, and the content of molybdenum oxide is 2.5-8wt%.Potassium oxide content is 0.02
~2.5%；Silicaalumina carrier content is 65-85wt%, includes 0.1~12wt%'s in silicaalumina carrier
Silica, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.1~2.5wt%, carrier is mesoporous to account for the 3~75% of total hole, greatly
The 1.5~60% of the hole hole Zhan Zong.Micropore, mesoporous, macropore uneven distribution in carrier.
It preferably, include following components: nickel oxide content 9-20wt%, molybdenum oxide on the basis of the total weight of catalyst
Content be 3.5-8wt%.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.
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..When containing high-content Al2O3 in drippolene catalyst, during high temperature reduction nickel ion, it is easy to cause aluminic acid
Nickel or meta-aluminic acid nickel generate, and then reduce catalyst activity, poor catalyst stability.Contain simultaneously in carrier of the present invention and is added with
The silica and nickel doped lanthanum ferrite of machine polymer effectively inhibit the generation of nickel aluminate or meta-aluminic acid nickel, improve Raney nickel
Activity stability.
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: nickel nitrate, potassium nitrate, ammonium molybdate solution oxide impregnation silicon-alumina support is prepared, through 110~160
DEG C drying 3~9 hours, 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 resistive, water resistant
Performance, the nickel molybdenum series catalyst of preparation effectively improve alkynes or diolefin hydrogenation selectivity.The preparation of silicaalumina carrier
In the process, the organic polymer of unit content contains than organic polymer in silicon-aluminium-organic admixture in alumina precursor
High 2 times or more is measured, is different from simple reaming, can not only improve the pore structure of carrier, and make carrier micropore, mesoporous, macropore
Uneven distribution improves catalyst anticol mass-energy power, improves the stability and service life of catalyst, be conducive to device long period
Operating；And carrier surface is promoted to produce more active sites load centres, improve Raney nickel 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 2.5g potassium nitrate, and mixing is 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
Nickel nitrate, potassium nitrate, ammonium molybdate solution impregnated carrier 1 are configured, 6 hours dry at 140 DEG C, 560 DEG C of roastings 5 are small
When, obtain catalyst 1.1 nickel oxide content of catalyst is 18.2wt%, and the content of molybdenum oxide is 4.5wt%, the content of potassium oxide
For 0.61wt%.
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 method of catalyst 2
With embodiment 1,2 nickel oxide content of catalyst is 10.3wt%, and the content of molybdenum oxide is 5.28wt%, and the content of potassium oxide is
2.1wt%.
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 method of catalyst 3 is same
Embodiment 1,3 nickel oxide content of catalyst are 21.1wt%, and the content of molybdenum oxide is 3.3wt%, and the content of potassium oxide is
0.30wt%.
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 2.5wt%, 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.The preparation side of catalyst 3
Method is with embodiment 1, and 4 nickel oxide content of catalyst is 14.5wt%, and the content of molybdenum oxide is 2.8wt%, and the content of potassium oxide is
1.45%wt.
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, comparative catalyst 1 is prepared
Nickel nitrate, potassium nitrate, ammonium molybdate solution impregnated carrier 1-1 are configured, 6 hours dry at 140 DEG C, 560 DEG C of roastings 5
Hour, comparative catalyst 1 is obtained, 1 nickel oxide content of comparative catalyst is 18.2wt%, and the content of molybdenum oxide is 4.5wt%, oxygen
The content for changing potassium is 0.61wt%.
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, comparative catalyst 2 is prepared
Nickel nitrate, potassium nitrate, ammonium molybdate solution impregnated carrier 1-1 are configured, 6 hours dry at 140 DEG C, 560 DEG C of roastings 5
Hour, obtain comparative catalyst 2.2 nickel oxide content of comparative catalyst is 18.2wt%, and the content of molybdenum oxide is 4.5wt%, oxygen
The content for changing potassium is 0.61wt%.
Catalyst 1-4 and comparative catalyst 1 and 2 are respectively charged into 100ml insulation bed reaction device, at 440 DEG C of temperature
It is restored 8 hours under hydrogen atmosphere, is passivated 3 hours laggard feedstock oil, drippolene C with hexamethylene after cooling to 50 DEG C5-C9Fraction,
Diene content is 31.23g iodine/100g oil, iodine value is 76.4g iodine/100g oil, gum level is 75mg/100ml oil, free water
Content is 937ppm, sulfur content is 121ppm and arsenic content is 104ppb；Reaction process condition are as follows: 50 DEG C of inlet temperature, hydrogen oil
Volume ratio 110: 1, reaction pressure 2.8MPa, green oil air speed 3.5h-1；After operating 180h, the diene of 1 hydrogenated products of catalyst is
0.73 gram of iodine/100 gram oil, iodine value are 33.5g iodine/100g oil, diolefin hydrogenation rate 99.3%；The diene of 2 hydrogenated products of catalyst
For 1.02 grams of iodine/100 gram oil, iodine value is 34.5g iodine/100g oil, diolefin hydrogenation rate 98.8%；Pair of 3 hydrogenated products of catalyst
Alkene is 0.80 gram of iodine/100 gram oil, and iodine value is 32.8g iodine/100g oil, diolefin hydrogenation rate 99.1%；4 hydrogenated products of catalyst
Diene is 0.89 gram of iodine/100 gram oil, and iodine value is 35.1g iodine/100g oil, diolefin hydrogenation rate 98.9%.Catalyst activity is high, choosing
Selecting property is good, and the anti-arsenic of anticol matter, water resistant, sulfur resistive ability are strong.The diene of 1 hydrogenated products of comparative catalyst is 5.34 grams of iodine/100 gram
Oil, iodine value are 44.1g iodine/100g oil, diolefin hydrogenation rate 85.5%；The diene of 2 hydrogenated products of comparative catalyst be 4.56 grams of iodine/
100 grams of oil, iodine value are 42.1g iodine/100g oil, diolefin hydrogenation rate 87.1%；Comparative catalyst's activity is low, poor selectivity, anticol
Matter, water resistant, anti-arsenic, sulfur resistive ability are poor.It is organic containing adding simultaneously in catalyst carrier of the present invention compared to comparative catalyst 1 and 2
The silica and nickel doped lanthanum ferrite of polymer effectively inhibit the generation of nickel aluminate or meta-aluminic acid nickel, improve the work of Raney nickel
Property stability.
After catalyst 1 and 3 operates 500h, the diene of 1 hydrogenated products of catalyst is 0.78 gram of iodine/100 gram oil, and iodine value is
34.0 iodine/100g oil, diolefin hydrogenation rate 99.1%；The diene of 3 hydrogenated products of catalyst is 0.83 gram of iodine/100 gram oil, and iodine value is
33.2g iodine/100g oil, diolefin hydrogenation rate 99.0%.Contain nickel doped lanthanum ferrite in catalyst carrier, is conducive to inhibit alkadienes
And polymerization reaction occurs for the unsaturated component such as styrene；Catalyst is insensitive to impurity such as water, colloids, and catalyst anticol matter resists
Outlet capacity is good, and anti-arsenic, sulfur resistive ability are strong, stable in catalytic performance.Catalyst carrier micropore, mesoporous, macropore uneven distribution, catalysis
Agent activity is good, and stability is good, long service life, is conducive to device long-term operation.
Claims (10)
1. a kind of nickel system selective hydrocatalyst, which is characterized in that catalyst includes silicaalumina carrier and is carried on
Metal active constituent nickel, molybdenum and potassium on carrier, include following components on the basis of the total weight of catalyst: nickel oxide content is
9-25wt%, the content of molybdenum oxide are 2.5-8wt%, and potassium oxide content is 0.02~2.5%；Silicaalumina carrier contains
Amount is 65-85wt%, includes the silica of 0.1~12wt%, the nickel doping of 0.1~10wt% in silicaalumina carrier
Cadmium ferrite, the potassium of 0.1~2.5wt%, carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for the 1.5~60% of total hole, in carrier
Micropore, mesoporous, macropore uneven distribution.
2. nickel system according to claim 1 selective hydrocatalyst, which is characterized in that the total weight of the catalyst is
Benchmark includes following components: nickel oxide content 9-20wt%, and the content of molybdenum oxide is 3.5-8wt%.
3. nickel system according to claim 1 selective hydrocatalyst, which is characterized in that the carrier is mesoporous to account for total hole
3~65%, macropore accounts for the 1.5~50% of total hole.
4. nickel system according to claim 1 selective hydrocatalyst, which is characterized in that the silica-alumina carries
Body the preparation method is as follows: by boehmite and sesbania powder be added in kneader be uniformly mixed, be added inorganic acid solution and
Organic polymer is mediated uniformly, then adds nickel doped lanthanum ferrite, is uniformly mixed and obtains alumina precursor, spare；Having
Silicon source is added in the acid solution of machine polymer and boehmite is uniformly mixed, it is mixed to obtain silicon source-boehmite-organic polymer
Object is closed, the organic polymer of unit content in silicon source-boehmite-organic polymer mixture than having in alumina precursor
The high 2 times or more of the content of machine polymer, then by silicon source -- boehmite-organic polymer mixture and alumina precursor
Mixing, adds potassium resource, through extrusion, molding, drying, roasting, obtains silicaalumina carrier.
5. nickel system according to claim 4 selective hydrocatalyst, which is characterized in that the silicon source is silica gel, silicic acid
Sodium or silicon powder, aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in silicon source-boehmite-organic polymer mixture.
6. nickel system according to claim 4 selective hydrocatalyst, which is characterized in that the organic polymer is poly- second
One or more of enol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
7. nickel system according to claim 4 selective hydrocatalyst, which is characterized in that the silica-alumina carries
Nickel doped lanthanum ferrite is 0.1~12wt% in body.
8. described in any item nickel systems selective hydrocatalyst according to claim 1~7, which is characterized in that the nickel doping
The preparation method of cadmium ferrite: being dissolved in stirring and dissolving in deionized water for citric acid, and lemon then is added in lanthanum nitrate and ferric nitrate
In acid, Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylate or poly- third is added in stirring and dissolving
The additional amount of olefin(e) acid is 0.1~10wt% of nickel doped lanthanum ferrite, adds nickel compound containing, is stirred, and through drying, roasts, grinds
Mill obtains finished product.
9. described in any item nickel systems selective hydrocatalyst according to claim 1~7, which is characterized in that the catalyst
Preparation method include the following steps: by contain active component nickel, molybdenum, potassium maceration extract dipping, spray on carrier, then to urging
Agent is dried, roasts and obtains the catalyst.
10. selective hydrogenation catalyst for pyrolysis gasoline according to claim 9, which is characterized in that the system of the catalyst
Standby process is as follows: preparing nickel nitrate, potassium nitrate, ammonium molybdate solution oxide impregnation silicon-alumina support, dries through 110~160 DEG C
3~9 hours, 400~650 DEG C roasted 4~9 hours, finally obtained catalyst prod.
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| CN114829553A (en) * | 2019-12-17 | 2022-07-29 | Ifp 新能源公司 | Selective hydrogenation catalyst obtained from molten salts and organic additives |
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