CN109439364A - Unsaturated C5Distillate hydrogenation process - Google Patents

Unsaturated C5Distillate hydrogenation process Download PDF

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Publication number
CN109439364A
CN109439364A CN201811285986.6A CN201811285986A CN109439364A CN 109439364 A CN109439364 A CN 109439364A CN 201811285986 A CN201811285986 A CN 201811285986A CN 109439364 A CN109439364 A CN 109439364A
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catalyst
silica
hydrogenation
nickel
lanthanum
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CN109439364B (en
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肖真勇
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Lanzhou Jinrunhongcheng New Material Technology Co ltd
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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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • 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
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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

Abstract

The invention relates to an unsaturated C5The fraction hydrogenation method adopts a fixed bed reactor; the catalyst is a nickel hydrogenation catalyst, and the catalyst is firstly reduced by hydrogen or hydrogen-containing gas, and the reduction temperature is 350-500 ℃. The catalyst comprises main active components of molybdenum, nickel, cobalt, potassium and a silicon oxide-aluminum oxide composition. The hydrogenation process conditions are as follows: the inlet temperature of the reactor is 30-60 ℃, the reaction pressure is 1.5-6.0 MPa, and the liquid volume space velocity is 1.0-6.0 h‑1The volume ratio of hydrogen to oil is 100-400. Unsaturated C of the invention5The fraction hydrogenation method uses a nickel-based saturated hydrogenation catalyst which has higher hydrogenation activity, can carry out hydrogenation reaction at a lower temperature, and has the characteristics of good sulfur resistance, water resistance and colloid resistance.

Description

A kind of unsaturation C5Cut fraction hydrogenation method
Technical field
The present invention relates to a kind of unsaturation C5Cut fraction hydrogenation method, by industrial C5Alkynes, diene hydrogenation are at corresponding in fraction Alkane.
Background technique
C4、C5In unsaturated hydrocarbons contain more alkadienes, under certain reaction temperature, alkadienes except itself polymerization in addition to, It can also react with other hydro carbons, generate the cokings precursors such as colloid.And polymerization is easy by alkene, monoolefine is easy plus hydrogen Saturation.While alkadienes in hydrogenation and removing feedstock oil, olefin polymerization is avoided or reduced.
Preparing ethylene by steam cracking and a large amount of C of refinery's by-product4、C5Fraction, yield is with composition with the kind of cracking stock Class, cracking severity and cracking technology are different and different.Wherein C4、C5Separation of hydrocarbons goes out after diolefin uses as industrial chemicals, Remaining small part is for fields such as alkylate oil, Petropols, and extra can only regard fuel, and added value of product is low.To raffinate C4And C5Fraction carries out saturated hydrogenation, and products therefrom can be used as good cracking stock, solvent, foaming agent and other chemical products Base stock, that is, improve C4And C5The added value of fraction, and alleviate ethylene raw problem in short supply.But due to each factory Family's process conditions are different, cause raffinate C4And C5Fraction fractional composition changes greatly, some C4And C5Remaining alkadienes in fraction It is higher with alkynes content, while C4Often contain part water in fraction, causes catalyst to be easily poisoned, easy coking.For C4、C5It evaporates Point, two-stage hydrogenation technique is often used, after removing alkadienes and alkynes by one-stage hydrogenation, produces and is saturated using secondary hydrogenation Alkane.If needing the saturated hydrogenation catalyst that hydrogenation activity is high, hydrogenation depth is good using one section of saturated hydrogenation technique.
Due to C4Water content is higher in fraction, C5Diene content is high in fraction, therefore it is required that being used for C4Fraction, C5Fraction The catalyst of saturated hydrogenation hydrogenation activity with higher simultaneously, has the impurity performances such as preferable sulfur resistive, water, while having good Good thermal stability, is able to bear high temperature reduction, regeneration treatment.If catalyst thermostabilization is bad, high temperature reduction can be made for the first time It is reduced at catalyst activity component utilization rate, and frequent high temperature regeneration processing will cause under the expendable activity of catalyst Drop, therefore and more catalyst changeout, causing producer, increased production cost.
It is used in saturated hydrogenation reaction by the catalyst of active component of Pt, Pd noble metal, due to past in unsaturated hydro carbons Toward certain sulphur, colloid is contained, above-mentioned catalyst poisoning is caused to inactivate.CN200810222182.1 discloses a kind of selectivity and adds Hydrogen catalyst and preparation method thereof.The selective hydrocatalyst, using aluminium oxide as carrier, include active component palladium, Cu additives, Auxiliary agent X1With auxiliary agent X2, in terms of total catalyst weight 100%: containing palladium 0.1~0.5%, copper 0.1~6%, X10.5~15%, X2 0.5~5%, 0~2% is selected from one of cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium, neodymium or a variety of promoter metals；Wherein X1Choosing From IVA element, X2Selected from or mixtures thereof alkali metal, alkaline-earth metal.The catalyst after Butadiene Extraction especially suitable for being rich in The selection acetylene hydrogenation of alkynes salvage stores.Alkali metal is introduced in the invention and/or alkaline-earth metal is used for the surface of modulation carrier Acid-base property, to reach the trend for inhibiting unsaturated hydrocarbons polymerization.
Relative to noble metal catalyst, with non-precious metal catalyst that nickel is main active component due to design feature itself, It is insensitive to impurity, from catalyst cost and add in hydrogen effect advantageously.Mainly there is support type at present and uses co-precipitation side The nickel-base catalyst of method preparation, but general more demanding nickel content guarantees the activity of catalyst.CN95111774.2 is disclosed The method of the saturated hydrogenation of raffinating oil of by-product light dydrocarbon, is prepared using coprecipitation in a kind of naphtha pyrolysis process of producing ethylene The atomic ratio of Ni-Cu/ diatomite catalyst, nickel and copper is 9, and the total amount of nickel and copper accounts for the 40% of catalyst, monoolefine in raw material 90%, alkane 8.5%, diolefin 1.5%, 130 DEG C of temperature, pressure 0.6MPa, hydrogen/oil mol ratio 7, liquid hourly space velocity (LHSV) 0.3h-1, single Olefin conversion 87%, pentane yield 90%.The catalyst is higher using temperature, and air speed is lower.
ZL200610064904.6 discloses a kind of nickel series hydrogenating catalyst, using aluminium oxide or with silica as carrier, adopts It is made with the method for co-precipitation, mainly contains active component Ni, it is characterised in that catalyst is by active constituent Ni, La, auxiliary agent X1 With carrier X2The weight formed with catalyst: O composition contains NiO 40~70%, La2O32~5%, X1O 2~ 5%, X2O 20~50%, wherein X1Selected from the one or more of Cu, Mg, Zr, X2Selected from Al or and Si；Its specific surface area 80~ 200m2/ g, 0.4~0.8ml/g of specific pore volume.The catalyst is suitable for monoolefin hydrogenation, is especially suitable for cracking C9Fraction adds hydrogen, With certain sulfur poisoning-resistant, anticol matter performance, the requirement that colloid 500mg/100ml raw material adds hydrogen, catalyst hydrogenation are adapted to Active high, stability is good.
US4956328 has studied the mixed aqueous solution of nickel, aluminium, zirconates, under conditions of being higher than 60 DEG C, pH value 7~10, uses Alkali compounds co-precipitation, prepare catalyst suitable for aromatic hydrocarbon, nitrogen-containing hydrocarbons, alkene plus hydrogen, this catalyst activity is not good enough. US5258346 discloses a kind of aromatic hydrocarbon hydrogenation catalyst of reduced nickel as active component, can be applied to various oil products especially The hydrogenation aromatics-removing of heavier hydrocarbon ils.The catalyst is prepared with coprecipitation, and nickel oxide content is 10~90%, also contains alkali metal Oxide, alkaline earth oxide or rare-earth oxide or their mixture.The sulfuration resistant ability of the proprietary catalysts Limited, industrially application has certain difficulty.
CN02104336.1 discloses a kind of catalysis for reaching olefin(e) centent in controlling reduction gasoline by alkene oligomerization Agent and process with the catalyst, by using mesoporous and macropore gama-alumina and mix a certain amount of silica as Carrier selects nickel as active component, by changing to load capacity, the type of auxiliary agent to improve alkene oligomerization/oligomerisation activity And selectivity, gained polymer gasoline olefin(e) centent decline 10~50 percentage points, overlapping diesel yield is 10~50%.Using this Impurity content is limited in catalyst requirement raw material: water is less than 100 μ g/g, and sulphur is less than 5 μ g/g, and alkadienes is less than 0.1%；Reaction Temperature is at 60 DEG C or more.
CN200710176670.9 discloses a kind of selective nickel series hydrogenating catalyst and preparation method thereof, is with aluminium oxide Carrier, it is characterised in that by catalyst weight be 100% in terms of, contain 14~20% nickel oxide of active component, 2~8% lanthanas And/or cerium oxide and 1~8% VI B oxides additive, 2~8% silica, 1~8% alkaline earth oxide, catalyst ratio 60~150m of surface20.4~0.6ml/g of/g, Kong Rong.The catalyst is suitable for medium-low distillate oil diene selective hydrogenation, has The ability of anti-impurity and anticol matter.
ZL200610064905.0 discloses a kind of Hydrobon catalyst preparation method and application, and catalyst is with molybdenum, cobalt, nickel For active component, auxiliary agent is added, is in terms of 100% by total catalyst weight, catalyst contains molybdenum oxide 14 using aluminium oxide as carrier ~20%, cobalt oxide 1~6%, nickel oxide 1~4%, the oxide content of auxiliary agent alkali metal is 1~3%, auxiliary agent P or/and Sb Oxide content be 1~5%, Si or/and the oxide content of tin is 2~6%；The Kong Rongwei 0.45 of catalyst~ 0.65cm3/ g, specific surface are 150~280m2/g.The catalyst can be used for the hydrofinishing of medium-low distillate oil, in hydrodesulfurization Hydrogen can be added to be saturated monoolefine to the maximum extent simultaneously, adapt to the requirement of the changeable oil product of sulfur content and high-speed, but to diene Hydrocarbon does not have hydrogenation selectivity.
Therefore, it is necessary to develop the saturated hydrogenation catalyst of a kind of high activity, high stability, and catalyst have it is good The characteristics of resistant to sulfur, water resistant, anticol matter, anti-coking, to adapt to the saturated hydrogenation of unsaturated hydrocarbon raw material.
Summary of the invention
The present invention provides a kind of unsaturation C5Cut fraction hydrogenation method, this method use the metal oxides such as including Ni, Co, Mo The nickel catalyst of component, by petroleum hydrocarbon cracking C5Alkynes, diene hydrogenation are at corresponding alkane, used catalyst in fraction Have the characteristics that high activity, sulfur resistive, water resistant, anticol mass-energy power is strong, side reaction is few, stability is good.
A kind of unsaturation C5Cut fraction hydrogenation method, using fixed bed reactors；Used catalyst is nickel series hydrogenating catalyst, Reducing catalyst first, under the conditions of 350~500 DEG C, with hydrogen or hydrogen-containing gas reducing catalyst, 12~40h of recovery time, 70~180 DEG C are cooled to, reduction carries out in hydrogenator, and logical nitrogen cools to 30~70 DEG C, and reduction terminates；Into unsaturation C5Fraction carries out hydrogenation reaction, by C5Alkynes, diene hydrogenation are at corresponding alkane in fraction；Nickel series hydrogenating catalyst includes master Active component molybdenum, nickel, cobalt, potassium and silica-alumina composition, by weight percentage, the oxidation including 26-36wt% Nickel, the molybdenum oxide of 0.05-2.5wt%, 0.1~2.5wt% cobalt oxide, the potassium oxide of 2.5-7.5wt%, 0-2.2wt% are selected from Strontium, manganese one or both of oxide auxiliary agent；Silica-alumina composition content is 35-70wt%, silica- It include the silica of 0.1~16wt%, the nickeliferous lanthanum-magnesium aluminate of 0.5~15wt%, 60~86.0wt% in alumina composition Aluminium oxide；Hydrogenation process conditions are as follows: 30~60 DEG C of reactor inlet temperature, 1.5~6.0MPa of reaction pressure, liquid volume is empty 1.0~6.0h of speed-1, hydrogen to oil volume ratio is 100~400.
Preferably, hydrogenation process conditions are as follows: 30~50 DEG C of reactor inlet temperature, 1.5~4.5MPa of reaction pressure, liquid 1.0~4.0h of volume space velocity-1, hydrogen to oil volume ratio is 100~350.
Preferably, by weight percentage, the nickel oxide including 26~35wt%, 0.01-2.2wt% is selected from catalyst Strontium, manganese one or both of oxide auxiliary agent.
The comparision contents of aluminium oxide are high in nickel catalyst, under the high temperature conditions, nickel aluminate easy to form, nickel aluminium point The formation of spar can reduce catalyst reaction activity, lead to poor catalyst stability.In silica-alumina composition of the present invention Nickeliferous lanthanum-magnesium aluminate is introduced, the formation of nickel aluminate in catalyst is effectively inhibited, improves the activity stability of Raney nickel, It is able to bear under hot conditions and carries out reduction treatment and regeneration.
The present invention also provides a kind of preparation methods of Ni-based saturated hydrogenation catalyst, the specific steps are as follows:
The soluble-salt of active component and auxiliary agent is dissolved in water, sodium carbonate or potassium carbonate and polyacrylic acid or polypropylene is added Sour sodium, temperature are controlled at 40~100 DEG C, under agitation, are adjusted pH 8.0~9.5, are obtained active component presoma；It is poly- Acrylic acid or Sodium Polyacrylate are added in dust technology with silica-alumina composition powder in the ratio of 1.1~2.1:1 of volume It is uniformly mixed, active component presoma is then added, with ammonium hydroxide tune pH value to 8.0~9.0, agitated reaction 0.5~2.0h, 1- It is filtered, washed, forms for 5 times, drying, 400~600 DEG C of 3~8h of roasting obtain catalyst.Using urging for the method for the present invention preparation Agent nickel should not reunite, good dispersion.
The silica-alumina composition the preparation method is as follows: the silicon source of 55%-75% is taken to mix with sesbania powder It is even, acid solution and expanding agent 1 is added, the additional amount of expanding agent 1, which accounts for, is added the 15~30% of quality of alumina, it mediates uniformly, then Nickeliferous lanthanum-magnesium aluminate is added, is uniformly mixed and obtains the mixture (1) containing aluminium and nickeliferous lanthanum-magnesium aluminate；Silicon source and 25%~45% Silicon source is uniformly mixed, and adds binder and expanding agent 2, the additional amount of expanding agent 2 accounts for the aluminium oxide and siliconoxide mass of addition 0.1~8%, obtain silicon-aluminium mixture (2)；By mixture (1) and silicon-aluminium mixture (2) containing aluminium and nickeliferous lanthanum-magnesium aluminate It is uniformly mixed, through extrusion, molding, drying, 400~650 DEG C of 3~12h of roasting, crushing, grinding, obtains silica-alumina group Close object.The silicon source is one or both of silica gel, sodium metasilicate or silicon powder, diatomite.Source of aluminium be aluminium oxide, intend it is thin One or more of diaspore, aluminum sulfate.Silicon source can also be selected from one of montmorillonite, kaolin, perlite, rectorite Or it is several.The binder is clay, Aluminum sol or the silica solution of silicon-aluminum containing, includes in control silica-alumina composition The silica of 0.1~16wt%, the nickeliferous lanthanum-magnesium aluminate of 0.5~15wt%, the aluminium oxide of 60~86.0wt%.
The preparation process of above-mentioned silica-alumina composition, the expanding agent 1 are polyvinyl alcohol, polyacrylic acid, poly- third One or more of olefin(e) acid sodium, polyethylene glycol, polyacrylate.The expanding agent 2 is methylcellulose, polymethyl One or more of acid, ammonium acrylate, glucose, chitosan etc..
Preferably, the content of nickeliferous lanthanum-magnesium aluminate is 0.5~10wt% in above-mentioned silica-alumina composition, nickeliferous Nickel mass content is 0.1~12% in lanthanum-magnesium aluminate.Control the oxygen in silica-alumina composition comprising 0.1~16wt% SiClx, the nickeliferous lanthanum-magnesium aluminate of 0.5~15wt%, the aluminium oxide of 60~86.0wt%.
Deionized water is added in above-mentioned nickeliferous lanthanum-magnesium aluminate powder materials, obtains high dispersive through high-speed stirred or ultrasonic oscillation Then nickeliferous lanthanum-magnesium aluminate slurry adds in mixture (1).The viscous of silicon-aluminum containing can be also introduced in nickeliferous lanthanum-magnesium aluminate slurry The one or more such as soil, Aluminum sol, silica solution, dosage account for the 0.1~18% of nickeliferous lanthanum-magnesium aluminate slurry gross mass.
Prepare nickeliferous lanthanum-magnesium aluminate LaMgAl11O19Process it is as follows: basic magnesium carbonate, lanthanum carbonate and aluminium hydroxide are pressed LaMgAl11O19Stoichiometric coefficient than be uniformly mixed, be added deionized water in, stir evenly, add nickel nitrate, mix Uniformly, it after spray-dried, under the conditions of blowing air, is roasted 2~10 hours through 1200~1400 DEG C, is crushed, ball milling, obtained Nickeliferous lanthanum-magnesium aluminate powder materials.
Preparing ethylene by steam cracking and a large amount of C of refinery's by-product4、C5Fraction, yield is with composition with the kind of cracking stock Class, cracking severity and cracking technology are different and different.C4、C5Contain more alkadienes in fraction, in certain reaction temperature Under, alkadienes can also react in addition to polymerization itself with other hydro carbons, generate the cokings precursors such as colloid.In hydrogenation and removing While alkadienes in feedstock oil, olefin polymerization is avoided or reduced.Due to C4Water content is higher in fraction, C5Fraction Middle diene content is high, therefore it is required that being used for C4Fraction, C5The catalyst of fraction saturated hydrogenation hydrogenation activity with higher it is same When, there is the impurity performances such as preferable sulfur resistive, anticol matter, water resistant, while there is good thermal stability, is able to bear high temperature also Former, regeneration treatment.If catalyst thermostabilization is bad, high temperature reduction will cause the reduction of catalyst activity component utilization rate for the first time, And frequent high temperature regeneration processing will cause the expendable activity decline of catalyst, therefore and more catalyst changeout, cause producer Increased production cost.
Silicon oxide-containing-alumina composition high content nickel series hydrocatalyst of coprecipitation preparation of the present invention, oxidation Nickeliferous lanthanum-magnesium aluminate is added in silicon-alumina composition preparation process, is able to suppress catalyst under the high temperature conditions, forms nickel Aluminate, and then catalyst reaction activity is reduced, lead to poor catalyst stability.The preparation of silica-alumina composition Process, aluminium oxide are divided into two parts addition, mix respectively with nickeliferous lanthanum-magnesium aluminate and silica, and introduce in mixture different Expanding agent, the content of expanding agent is also different, and the expanding agent mass content in aluminium oxide and nickeliferous lanthanum-magnesium aluminate mixture (1) is high The expanding agent mass content in aluminium oxide and aktivton (2).Alkene is able to suppress using catalyst prepared by this method It polymerize plastic, within certain reaction time, reduces the production quantity of colloid, improve catalyst anticol mass-energy power, reduce catalyst Surface coking process, catalyst diene and alkynes hydrogenation selectivity are high.Be conducive to device long-term operation；And promote oxidation Silicon-alumina composition and nickel molybdenum cobalt isoreactivity component act synergistically, and improve Raney nickel hydrogenation activity.
Catalyst of the invention does not limit its shape, and the preferable shape of catalyst is 1.5~3 × 1~10mm of Φ Cylinder, can be obtained by extrusion mode.
Petroleum hydrocarbon cracking C of the present invention5The saturation hydrogenation method of fraction, the Ni-based saturated hydrogenation catalyst used have compared with High hydrogenation activity can carry out hydrogenation reaction at a lower temperature, and the spy with good sulfur resistive, water resistant, anticol matter Point, coking rate is low, and stability is good.By C5Alkynes, diene hydrogenation are at corresponding alkane in fraction.
Specific embodiment
All raw materials of the present invention come from commercial product.
Embodiment 1
(1) preparation of silica-alumina composition 1
1, nickeliferous lanthanum-magnesium aluminate LaMgAl is prepared11O19Process it is as follows:
7.8 grams of basic magnesium carbonates, 25 grams of lanthanum carbonates and 70.5 grams of aluminium hydroxides are taken, are uniformly mixed, are added in deionized water Formed high dispersive suspension, add 8 grams of nickel nitrates, it is spray-dried, 140 DEG C drying 5 hours, be placed in air atmosphere 1300 DEG C roast 4 hours, then obtain nickeliferous lanthanum-magnesium aluminate powder within ball milling 18 hours.Nickeliferous lanthanum-magnesium aluminate powder adds water, through super The nickeliferous lanthanum-magnesium aluminate slurry of high dispersive is obtained after sound wave shock.
2, silica-alumina composition is prepared
It takes the boehmite of 150g to be uniformly mixed with 24g sesbania powder, dust technology is added, adds 26g Sodium Polyacrylate Nitric acid solution, and be uniformly mixed, nickeliferous lanthanum-magnesium aluminate slurry is then added, is uniformly mixed, obtains containing aluminium and nickeliferous lanthanum-magnesium aluminate Mixture (1)；18g silicon powder is uniformly mixed with the boehmite of 65g, and 7.5g water soluble chitosan is added, adds silicon Colloidal sol obtains silicon-aluminium mixture (2)；By containing aluminium and nickeliferous lanthanum-magnesium aluminate mixture (1) and silicon-aluminium mixture (2) mix it is equal It is even, through extrusion, molding, drying, 580 DEG C of roasting 5h, crushing, grinding, obtain silica-alumina composition.
(2) preparation of catalyst
Nickel nitrate, cobalt nitrate, potassium nitrate, ammonium molybdate solution are configured, is uniformly mixed, adds Sodium Polyacrylate, sodium carbonate Solution adjusts pH value 8.5, obtains active component presoma；Sodium Polyacrylate is added in dust technology and silica-alumina composition Powder is uniformly mixed in the ratio of volume 1.2:1, and active component presoma is then added, agitated with ammonium hydroxide tune pH value to 8.6 React 0.5h.It is filtered, washed, dried, for extrusion at the cylindrical type of 3 × 6mm of Φ, 480 DEG C of roasting 5h obtain catalyst 1, are catalyzed The composition of agent is shown in Table 1.
Embodiment 2
(1) preparation of silica-alumina composition 2
The preparation of nickeliferous lanthanum-magnesium aluminate takes 68% with embodiment 1 with embodiment 1, the preparation of silica-alumina composition Boehmite be uniformly mixed with sesbania powder, the additional amount of 1 polyacids sodium of expanding agent account for be added quality of alumina 19%, reaming The additional amount of 2 chitosan of agent account for addition aluminium oxide and siliconoxide mass 4%.Include in silica-alumina composition The silica of 6.1wt%, the nickeliferous lanthanum-magnesium aluminate of 5.8wt%.
(2) preparation of catalyst
The preparation method is the same as that of Example 1 for catalyst, and polyacrylic acid solution and silica-alumina composition powder press volume The ratio of 1.8:1 is uniformly mixed, and the composition of catalyst is shown in Table 1.
Embodiment 3
(1) preparation of silica-alumina composition 3
The preparation of nickeliferous lanthanum-magnesium aluminate takes 72% with embodiment 1 with embodiment 1, the preparation of silica-alumina composition Boehmite be uniformly mixed with sesbania powder, the additional amount of 1 polyacrylate of expanding agent account for be added quality of alumina 21%, The additional amount of 2 methylcellulose of expanding agent account for addition aluminium oxide and siliconoxide mass 2.6%.Silica-alumina combination It include the silica of 4.3wt%, the nickeliferous lanthanum-magnesium aluminate of 5.9wt% in object.
(2) preparation of catalyst
The preparation method is the same as that of Example 1 for catalyst 3, and Sodium Polyacrylate is added in dust technology and combines with silica-alumina Powder is uniformly mixed in the ratio of volume 1.5:1, and the composition of catalyst is shown in Table 1.
Embodiment 4
(1) preparation of silica-alumina composition 4
The preparation of nickeliferous lanthanum-magnesium aluminate takes 61% with embodiment 1 with embodiment 1, the preparation of silica-alumina composition Boehmite be uniformly mixed with sesbania powder, the additional amount of 1 Sodium Polyacrylate of expanding agent account for be added quality of alumina 19%, The additional amount of 2 glucose of expanding agent account for addition aluminium oxide and siliconoxide mass 3.1%.In silica-alumina composition Silica comprising 8.1wt%, the nickeliferous lanthanum-magnesium aluminate of 3.1wt%.
(2) preparation of catalyst
The preparation method is the same as that of Example 1 for catalyst 4, and Sodium Polyacrylate is added in dust technology and combines with silica-alumina Powder is uniformly mixed in the ratio of volume 2.0:1, and the composition of catalyst is shown in Table 1.
Comparative example 1
(1) comparative example silica-alumina composition 1 is prepared
It is as follows to prepare 1 process of silica-alumina composition:
It takes the boehmite of 140g to be uniformly mixed with 22g sesbania powder, dust technology is added, adds 20g Sodium Polyacrylate Nitric acid solution, and be uniformly mixed, obtain (1) containing aluminium mixture；16g silicon powder is uniformly mixed with the boehmite of 60g, is added 7g chitosan, adds silica solution, obtains silicon-aluminium mixture (2)；Aluminium mixture (1) and silicon-aluminium mixture (2) mixing will be contained Uniformly, through extrusion, molding, drying, 550 DEG C of roasting 5h, crushing, grinding, silica-alumina composition is obtained.
(2) comparative catalyst 1 is prepared
Nickel nitrate, cobalt nitrate, potassium nitrate, ammonium molybdate solution are configured, is uniformly mixed, adds Sodium Polyacrylate, sodium carbonate Solution adjusts pH value 8.5, obtains active component presoma；Sodium Polyacrylate is added in dust technology and silica-alumina composition Powder is uniformly mixed in the ratio of volume 1.2:1, and active component presoma is then added, agitated with ammonium hydroxide tune pH value to 8.6 React 0.5h.It being filtered, washed, is dried, for extrusion at the cylindrical type of 3 × 6mm of Φ, 480 DEG C of roasting 5h obtain comparative catalyst 1, The composition of comparative catalyst is shown in Table 1.
Comparative example 2
(1) comparative example silica-alumina composition 2 is prepared
It is as follows to prepare silica-alumina composition process with embodiment 1 for the preparation of nickeliferous lanthanum-magnesium aluminate:
It takes the boehmite of 200g to be uniformly mixed with 22g sesbania powder, dust technology is added, adds 20g Sodium Polyacrylate Nitric acid solution, and being uniformly mixed, is then added nickeliferous lanthanum-magnesium aluminate slurry and 16g silicon powder, is uniformly mixed, through extrusion, molding, Dry, 550 DEG C of roasting 5h, crushing, grinding, obtain silica-alumina composition.
(2) comparative catalyst 2 is prepared
Nickel nitrate, cobalt nitrate, potassium nitrate, ammonium molybdate solution are configured, is uniformly mixed, adds Sodium Polyacrylate, sodium carbonate Solution adjusts pH value 8.5, obtains active component presoma；Sodium Polyacrylate is added in dust technology and silica-alumina composition Powder is uniformly mixed in the ratio of volume 1.2:1, and active component presoma is then added, agitated with ammonium hydroxide tune pH value to 8.6 React 0.5h.It being filtered, washed, is dried, for extrusion at the cylindrical type of 3 × 6mm of Φ, 480 DEG C of roasting 5h obtain comparative catalyst 2, The composition of comparative catalyst is shown in Table 1.
1 embodiment of table/comparative example composition/wt%
C5The reaction of fraction saturated hydrogenation:
On 100ml adiabatic reactor hydrogenation plant, in a hydrogen atmosphere, by catalyst and comparative example catalyst respectively 360 Reductase 12 4h under the conditions of DEG C.90 DEG C are cooled to, logical nitrogen cools to 30 DEG C.Catalyst and comparative example catalyst after reduction use Industrial C5Fraction is evaluated, C5It is 59mg/100ml oil, sulfur content 82ppm that fraction, which contains gum level, and free water content is 1148ppm；37 DEG C of reactor inlet temperature, reaction pressure 3.5MPa, liquid volume air speed 3.5h-1, hydrogen to oil volume ratio 360: 1.Product form analysis after raw material and catalyst and comparative example catalyst reaction 800h is shown in Table 2.As can be seen from Table 2, it is catalyzed Agent adds hydrogen saturated activity high, and carbon deposition rate is low, and the alkadienes of high-content and alkynes are further hydrogenated into alkane by comparative example catalyst Ability it is weaker, carbon deposition rate is high.Comparative example catalyst alkadienes, alkynes saturated hydrogenation depth are inadequate, and part alkadienes, alkynes are not It can complete hydrogenation.Contain nickeliferous lanthanum-magnesium aluminate in catalyst silica-alumina composition, is conducive to inhibit the insatiable hungers such as alkadienes Polymerization reaction occurs with component, reduces hydrogen consumption, reduces the production quantity of colloid, catalyst is insensitive to impurity such as water, colloids, catalysis Agent anticol matter, water resistant ability are good, and sulfur resistive ability is strong, stable in catalytic performance.
2 raw material of table and COMPARATIVE CATALYST EXAMPLE's catalyst prod composition analysis (ω %)
Alkadienes+alkynes Monoolefine Catalyst carbon deposition
Raw material 51.7 13.2 -
Catalyst 1 0 11.7 3%
Catalyst 2 0 12.0 2%
Catalyst 3 0 11.9 2%
Catalyst 4 0 12.1 3%
Contrast medium 1 17.3 7.4 14%
Contrast medium 2 21.1 8.6 9%
Regeneration treatment is carried out to the catalyst 1,3 after operating 800h, temperature of reactor is down to 90 DEG C, and pressure is down to 0.5MPa, with 55m3/ h is passed through hydrogen, keeps 6h；Reactor inlet temperature is raised to 240 DEG C with 25 DEG C/h, keeps 7h；It drops again Then low reactor temperature starts to restore C to 30 DEG C5Cut fraction hydrogenation reaction.C5It is 59mg/100ml that fraction, which contains gum level, Oil, sulfur content 82ppm, free water content 1148ppm；37 DEG C of reactor inlet temperature, reaction pressure 3.5MPa, liquid bulk Product air speed 3.5h-1, hydrogen to oil volume ratio 360:1.Properties of product analysis after operating 300h is as shown in table 3:
3 product form of catalyst 1 and 3 of table analyzes (ω %)
Alkadienes+alkynes Monoolefine Catalyst carbon deposition
Raw material 51.7 13.2 -
Catalyst 1 0 12.0 2%
Catalyst 3 0 12.3 3%
After high temperature regeneration is handled, the Hydrogenation of catalyst can be restored to fresh catalyst level, and catalyst has Effect inhibit nickel aluminate generation, improve the activity stability of Raney nickel, be able to bear under hot conditions carry out reduction and Regeneration, catalyst have preferable thermal stability.

Claims (10)

1. a kind of unsaturation C5Cut fraction hydrogenation method, which is characterized in that use fixed bed reactors；Used catalyst is that nickel system adds Hydrogen catalyst, first reducing catalyst, under the conditions of 350~500 DEG C, with hydrogen or hydrogen-containing gas reducing catalyst, when reduction Between 12~40h, cool to 70~180 DEG C, reduction carries out in hydrogenator, and logical nitrogen cools to 30~70 DEG C, reduction knot Beam；Into unsaturated C5Fraction carries out hydrogenation reaction, by C5Alkynes, diene hydrogenation are at corresponding alkane in fraction；Nickel series hydrogenating is urged Agent includes main active component molybdenum, nickel, cobalt, potassium and silica-alumina composition, by weight percentage, including 26- The nickel oxide of 36wt%, the molybdenum oxide of 0.05-2.5wt%, 0.1~2.5wt% cobalt oxide, the potassium oxide of 2.5-7.5wt%, 0- 2.2wt% is selected from the auxiliary agent of one or both of oxide of strontium, manganese；Silica-alumina composition content is 35- 70wt% includes the silica of 0.1~16wt%, the nickeliferous magnesium aluminate of 0.5~15wt% in silica-alumina composition Lanthanum, the aluminium oxide of 60~86.0wt%；Hydrogenation process conditions are as follows: 30~60 DEG C of reactor inlet temperature, reaction pressure 1.5~ 6.0MPa, 1.0~6.0h of liquid volume air speed-1, hydrogen to oil volume ratio is 100~400.
2. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that hydrogenation process conditions are as follows: reactor enters 30~50 DEG C of temperature of mouth, 1.5~4.5MPa of reaction pressure.
3. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that hydrogenation process conditions are as follows: liquid volume 1.0~4.0h of air speed-1, hydrogen to oil volume ratio is 100~350.
4. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that the system of the nickel series hydrogenating catalyst Preparation Method includes the following steps: that the soluble-salt by active component and auxiliary agent is dissolved in water, and sodium carbonate or potassium carbonate and poly- third is added Olefin(e) acid or Sodium Polyacrylate, temperature are controlled at 40~100 DEG C, under agitation, are adjusted pH 8.0~9.5, are obtained active group Divide presoma；Polyacrylic acid or Sodium Polyacrylate be added in dust technology with silica-alumina composition powder by volume 1.1~ The ratio of 2.1:1 is uniformly mixed, and active component presoma is then added, with ammonium hydroxide tune pH value to 8.0~9.0, agitated reaction 0.5~2.0h is filtered, washed, forms, and drying, 400~600 DEG C of 3~8h of roasting obtain catalyst.
5. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that the silica-alumina composition The preparation method is as follows: the silicon source of 55%-75% is taken to be uniformly mixed with sesbania powder, acid solution and expanding agent 1, expanding agent 1 is added Additional amount account for be added quality of alumina 15~30%, mediate uniformly, add nickeliferous lanthanum-magnesium aluminate, be uniformly mixed contained The mixture (1) of aluminium and nickeliferous lanthanum-magnesium aluminate；Silicon source is uniformly mixed with 25%~45% silicon source, adds binder and reaming Agent 2, the additional amount of expanding agent 2 account for addition aluminium oxide and siliconoxide mass 0.1~8%, obtain silicon-aluminium mixture (2)；It will Mixture (1) and silicon-aluminium mixture (2) containing aluminium and nickeliferous lanthanum-magnesium aluminate be uniformly mixed, through extrusion, molding, drying, 400~ 650 DEG C of 3~12h of roasting, crushing, grinding, obtain silica-alumina composition.
6. unsaturation C according to claim 55Cut fraction hydrogenation method, which is characterized in that the silicon source be silica gel, sodium metasilicate or One or more of silicon powder.
7. unsaturation C according to claim 55Cut fraction hydrogenation method, which is characterized in that the expanding agent 1 be polyvinyl alcohol, One or more of polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
8. unsaturation C according to claim 55Cut fraction hydrogenation method, which is characterized in that the expanding agent 2 is Methyl cellulose One or more of element, polymethylacrylic acid, ammonium acrylate, glucose, chitosan.
9. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that the catalyst is with weight percent Meter, the nickel oxide including 26~35wt%, 0.01-2.2wt% are selected from the auxiliary agent of one or both of oxide of strontium, manganese.
10. unsaturation C according to claim 15Cut fraction hydrogenation method, which is characterized in that the silica-alumina combination The content of nickeliferous lanthanum-magnesium aluminate is 0.5~10wt% in object, and nickel mass content is 0.1~12% in nickeliferous lanthanum-magnesium aluminate.
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CN114950465A (en) * 2022-06-30 2022-08-30 东营科尔特新材料有限公司 Nickel-based catalyst, preparation method thereof and application thereof in olefin and alkyne saturation hydrogenation

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US20070111884A1 (en) * 2005-11-14 2007-05-17 Laiyuan Chen Catalyst support, supported catalyst, and methods of making and using the same
CN102994144A (en) * 2011-09-09 2013-03-27 中国石油天然气股份有限公司 Saturation hydrogenation method for cracking C4 and C5 fraction by petroleum hydrocarbons

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US20070111884A1 (en) * 2005-11-14 2007-05-17 Laiyuan Chen Catalyst support, supported catalyst, and methods of making and using the same
CN102994144A (en) * 2011-09-09 2013-03-27 中国石油天然气股份有限公司 Saturation hydrogenation method for cracking C4 and C5 fraction by petroleum hydrocarbons

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Publication number Priority date Publication date Assignee Title
CN114950465A (en) * 2022-06-30 2022-08-30 东营科尔特新材料有限公司 Nickel-based catalyst, preparation method thereof and application thereof in olefin and alkyne saturation hydrogenation
CN114950465B (en) * 2022-06-30 2023-08-08 东营科尔特新材料有限公司 Nickel-based catalyst, preparation method thereof and application thereof in alkene and alkyne saturated hydrogenation

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