CN102139217B - Selective hydrogenation catalyst and preparation method thereof - Google Patents
Selective hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102139217B CN102139217B CN 201010106259 CN201010106259A CN102139217B CN 102139217 B CN102139217 B CN 102139217B CN 201010106259 CN201010106259 CN 201010106259 CN 201010106259 A CN201010106259 A CN 201010106259A CN 102139217 B CN102139217 B CN 102139217B
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Abstract
The invention provides a selective hydrogenation catalyst. Nickel serves as an active component; silicon-containing alumina serves as a carrier; based on 100% of the total weight of the catalyst, the selective hydrogenation catalyst comprises 10-20wt% of nickel oxide, 0-10wt% of cerium oxide and/or cerium oxide, 0-8wt% of alkali metal and/or alkaline-earth metal oxides and 3.1-36wt% of silicon oxide; the specific surface area of the catalyst is 60-180m2/g; and the pore volume of the catalyst is 0.4-0.7ml/g. The precursor of the carrier of the silicon-containing alumina is pseudo-boehmite containing amorphous silica-alumina, which is prepared by the following steps of: firstly preparing amorphous silica-alumina seriflux and pseudo-boehmite seriflux; mixing and ageing the two seriflux; and performing a post-processing process comprising filtering and drying on the mixture. The catalyst has high hydrogenation activity, high selectivity and good stability, is suitable for the selective hydrogenation of medium-low distillate oil, and is particularly suitable for the selective hydrogenation of unsaturated hydrocarbon such as diene and the like in an oil product.
Description
Technical field
The present invention relates to a kind of selective hydrocatalyst and preparation method thereof.This catalyst is applicable to the selection hydrogenation of medium-low distillate oil, is specially adapted to the selection hydrogenation of diene class unsaturated hydrocarbons in the oil product.
Background technology
In recent years, along with the increasingly stringent of environmental legislation, more and more harsher to the requirement of Sulfur Content in Petroleum Products and nitrogen content; Simultaneously since crude quality worse and worse, the impurity contents such as sulphur, nitrogen are more and more higher, and are therefore also more and more higher to the requirement of hydrotreating catalyst.For example when coker gas oil is carried out hydrotreatment, the nitrogen compound of high level especially basic nitrogen compound can be adsorbed on the acidic site of catalyst, cause the catalyst desulfurizing denitrification activity to descend, and the emphasis of raising hydrotreating catalyst imurity-removal ability is a kind of novel carriers material of exploitation or improve the catalyst activity constituent content.People are when being optimized alumina support specific area, pore volume and aperture, by introducing the modifying elements such as silicon, titanium, phosphorus, come the modulation alumina support surface acidity, improve the strong interaction between active component and alumina support or new cooperative effect occurs.Have the amorphous aluminum silicide specific area height that divergence hole distributes, anti-sintering property is good, and has certain surface acidity, therefore often be used in the hydrotreating catalyst preparation process, but there is the relatively poor defective of mouldability in amorphous aluminosilicate.At present, the preparation method of silicon-containing alumina is a lot, is summed up and is mainly two kinds, and a kind of is to add a small amount of aluminium oxide in alumino-silicate (2～10wt%) as structural promoter; Another kind is to add a small amount of alumino-silicate in aluminium oxide, comes the modulation alumina surface acid, improves its specific area.
US4721696 discloses the method that a kind of pH of employing swing method prepares silicon-containing alumina, mainly be used as the carrier of sulfur-bearing and metal impurities material hydrotreating catalyst, silicone content generally is no more than 15wt%, and silica mainly is as structural stabilizing agent rather than to provide more acid centre as purpose.
CN1267187C discloses a kind of silica-alumina that contains structure of similar to thin diaspore, described carrier silica content is high, and be with silicon-containing compound solution directly or and stream be incorporated in the boehmite slurries, purpose is that the aluminium content that increases four-coordination improves the amount of aluminium oxide acid strength and acid, the silicon-containing alumina of preparation has very high cracking activity, but higher cracking activity has reduced liquid yield as catalyst carrier for hydrgenating.
CN1074303C has proposed the manufacture method of a kind of aluminium oxide and monox composite oxides, it mixes the solution in salic source and the solution in silicon oxide-containing source first, then in mixed solution, add hydrochloric acid and obtain colloidal sol, add again NaOH in the colloidal sol and obtain gel, alumina source in the gel and silica source are reacted under high temperature, high pressure obtain the powdery alumino-silicate.But the composite oxides of the method preparation have a large amount of micropores, are unsuitable for the carrier as the medium-low distillate oil hydrotreating catalyst.
CN1048957C discloses and has prepared method amorphous, the catalytic activity silica-alumina, adopt tetraalkylammonium hydroxide, tri-alkoxy aluminium and positive silicic acid tetraalkyl ester hydrolysis and gel to obtain, this gel has the hole dimension that can control, and its specific area is at least 500m
2/ g, the mol ratio of silica and alundum (Al2O3) is at least 30: 1.This silica-alumina gel is mainly used in lighter hydrocarbons isomery and oligomerizing.
CN1306977C discloses a kind of silica-alumina and preparation method thereof, concrete steps are to adopt coprecipitation to prepare first a kind of salic water mixed liquid, introduce again a kind of solution of silicon-containing compound, be a kind of mother liquor of synthesis of molecular sieve, make silica-alumina through aging, drying.This carrier is mainly used in the preparation of catalytic cracking catalyst.
Summary of the invention
The object of the present invention is to provide a kind of hydrogenation activity and selective high, the Catalysts and its preparation method of good stability, this catalyst are applicable to the selection hydrogenation of medium-low distillate oil, are specially adapted to the selection hydrogenation of diene class unsaturated hydrocarbons in the oil product.The presoma of catalyst carrier is the boehmite that contains amorphous aluminum silicide, and it has the two-fold advantage of amorphous aluminum silicide and boehmite, easy-formation simultaneously.
Selective hydrocatalyst of the present invention, take nickel as active component, take silicon-containing alumina as carrier, take total catalyst weight as 100%, contain nickel oxide 10～20wt%, (preferably 2～10wt%), (preferably 2～8wt%), silica 3.1～36wt% (preferably 3.1～27wt%) for alkali metal and/or alkaline earth oxide 0～8wt% for cerium oxide and/or lanthana 0～10wt%; Specific surface area of catalyst 60～180m
2/ g, pore volume 0.4～0.7ml/g; The presoma of silicon-containing alumina carrier is the boehmite that contains amorphous aluminum silicide, it is by at first preparing amorphous aluminum silicide slurries and boehmite slurries, then these two kinds of slurries are mixed, aging, and include that the last handling process of filtrations, drying obtains.This catalyst is specially adapted to the selection hydrogenation of medium-low distillate oil.
The most outstanding characteristics of selective hydrocatalyst of the present invention are that the presoma of the employed silicon-containing alumina carrier of catalytic amount is the boehmite that contains amorphous aluminum silicide, having selected it is to mix, wear out with preparing first amorphous aluminum silicide slurries and boehmite slurries, and include filtration, dry last handling process obtains, the mixed process of these amorphous aluminum silicide slurries and boehmite slurries, both being different from simple and mechanical mixing of two kinds of powders of amorphous aluminum silicide and boehmite, is not again the structure of amorphous aluminum silicide coated alumina type.With two bursts of mixing of materials, one side amorphous aluminum silicide and boehmite reciprocation; On the other hand, also be accompanied by a small amount of free aluminum ion and the reaction between the silicate ion.If reach ideal state, in this process, the control of the control of pH value, aging temperature and ageing time is extremely important to the product that obtains, and can obtain the boehmite that contains amorphous aluminum silicide of desired particular characteristic by adjusting control pH value, aging temperature, ageing time.
The present invention also provides a kind of preparation method who contains the boehmite of amorphous aluminum silicide, it is characterized in that amorphous aluminum silicide slurries and boehmite slurries and stream mix or a kind of material joined in the another kind of material mixing, mix complete after, aging 10～30min, filter, wash to sodium ions content less than 0.5wt%, at 80～120 ℃ of lower dry 2～20h, obtain containing the boehmite of amorphous aluminum silicide.
The preparation process of pseudoboehmite that contains amorphous aluminum silicide provided by the invention comprises the preparation of amorphous aluminum silicide slurries and the preparation of boehmite slurries, and with these two kinds of slurries mixing, the mixing of two kinds of slurries can be adopted and flow to mix or a kind of slurries are joined in the another kind of slurries and mix, then aging, more after filtration, washing, the last handling process such as dry obtain containing the boehmite of amorphous aluminum silicide.PH value of solution is preferably 9.0～10.5 when aging, and temperature is preferably 20～65 ℃, and the time is preferably 10～25min.Baking temperature is preferably 80～120 ℃.
The present invention is not particularly limited the preparation method of amorphous aluminum silicide slurries and boehmite slurries, adopts current techique to get final product, and can adopt existing nitrate method or carbonizatin method such as the preparation of boehmite slurries.
The present invention provides a kind of preparation method of amorphous aluminum silicide slurries simultaneously, comprising:
(a) compound concentration is 10～150gAl
2O
3The sodium metaaluminate of/L or sodium aluminate solution are added in the plastic cans, 15～50 ℃ of control plastic cans temperature.
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L joins silicon-containing compound solution in the solution of (a), control pH value 11.5～13.
(c) under the condition of low whipping speed greater than 250r/min, pass into continuously concentration greater than the carbon dioxide of 20v%, the flow of control carbon dioxide is at 1～10Nm
3/ h, with time 20～40min, control endpoint pH 7.5～9.5 neutralizes and finishes in the control.
(d) in pH value 7.5～9.5, the solution 5～20min of aging (c) preparation obtains the amorphous aluminum silicide slurries under the condition that temperature is 25～40 ℃.
Preferably with carbon dioxide process preparation, silicon-containing compound can be waterglass, Ludox to amorphous aluminum silicide slurries of the present invention, waterglass preferably, and concentration of sodium silicate is counted 50～200gSiO with silica
2/ L is preferably 80～120gSiO
2/ L; The concentration of sodium metaaluminate or sodium aluminate solution is counted 10～150gAl with aluminium oxide
2O
3/ L is preferably 35～110gAl
2O
3/ L; Ageing time preferably is controlled at 5～15min; Control silica alumina ratio 40～60wt% in the final amorphous aluminum silicide.
The present invention also provides a kind of preparation method of boehmite slurries.Sodium metaaluminate or sodium aluminate solution are added in the plastic cans, pass into carbon dioxide through becoming glue, the aging boehmite slurries that obtain with intermittence or continuous mode.The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2O
3/ L; The concentration of carbon dioxide is preferably between 40～100v% greater than 20v%, and the flow of carbon dioxide is 1～10Nm
3/ h; Become 20～65 ℃ of glue temperature, best 30～45 ℃; Become glue endpoint pH 9.0～10.5; Become glue and ageing time altogether preferably to be no more than 40min, be advisable with 25～35min.
In the preparation process of boehmite slurries of the present invention, become glue terminal point pH preferably to be controlled at 9.0～10.5, the pH value is lower than at 9.0 o'clock, easy and the reaction of sodium bicarbonate generation silk sodium stone structure of the boehmite that forms, the silk sodium stone that generates is a kind of insoluble salt, hinder the washing of sodium ion, affected aluminium oxide as the serviceability of carrier.
Above-mentioned amorphous aluminum silicide slurries are mixed, wear out according to the ratio of silica content 5～40wt% with the boehmite slurries, and ageing time is 10～30min, the boehmite that then filter, wash, drying obtains containing amorphous aluminum silicide.
The boehmite specific area 250～400m that contains amorphous aluminum silicide of the present invention's preparation
2/ g, pore volume 0.7～1.4ml/g, the surface acidity position is take the weak acid position as main, infrared acidity 0.28～0.55mmol/g.
The boehmite that contains amorphous aluminum silicide that the present invention selects namely has the high acidity of amorphous aluminum silicide, the characteristic of high-specific surface area, contains simultaneously the advantage of boehmite, has overcome the poor problem of amorphous aluminum silicide moulding.The aluminium oxide that contains amorphous aluminum silicide of preparation is specially adapted to do the carrier, the particularly carrier of midbarrel oil hydrogenating treatment catalyst of hydrogenation catalyst.
Can contain alkali metal and/or alkaline-earth metal in the catalyst of the present invention, content is 0～8wt%, is preferably 2～8wt%.Alkali metal and/or alkaline-earth metal are among one among Li, Na, K, Be, Mg, Ca, the Sr or multiple, one or more among preferred Li, K, the Mg.When catalyst is used for medium-low distillate oil selection hydrogenation, alkene is the one of the main reasons that causes catalysqt deactivation in the polymerisation of catalyst surface, alkene in the oil product, the easy polymerization of alkadienes form colloid, cover on the hydrogenation sites of catalyst, reduced the number of active center of catalyst surface; On the other hand, the duct of the polymer plugging catalyst of generation affects the diffusion of reactant and product molecule.Therefore, hydrogenation activity and stabilized hydrogenation can be improved by adjusting the catalyst surface Acidity of Aikalinity, by adding alkali metal and/or alkaline-earth metal, the Acidity of Aikalinity on catalyst carrier surface can be changed, be conducive to reduce the deposition of carbonaceous in the hydrogenation process, colloid, thus the service life of extending catalyst.Alkali metal and/or alkaline-earth metal preferably add with the form of solubility nitrate, acetate or citrate among the present invention.
Can contain rare-earth element cerium and/or lanthanum in the catalyst of the present invention, content is 0～10wt%, is preferably 2～10wt%.After adding cerium and/or lanthanum, catalyst carrier grain growth in the time of can suppressing high-temperature roasting, the decentralization of raising active component nickel strengthens carrier surface alkalescence, improves hydrogenation selectivity and the stability of catalyst.Cerium and/or lanthanum preferably add with the form of solubility nitrate among the present invention.
The present invention does not do detailed restriction to the preparation method of catalyst, as adopting the equi-volume impregnating preparation.
Catalyst carrier of the present invention is to adopt the current techique preparation, and the present invention is not limited.Catalyst carrier can add one or more in alkali metal, alkaline-earth metal, the rare earth element before extruded moulding.The method of recommend adoption one of the following obtains:
Method one: will contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 800～1100 ℃ of roasting 3～6h obtain catalyst carrier.
Method two: will contain predecessor, nitric acid, the water mixer kneader of boehmite and alkali metal and/or the alkaline-earth metal of amorphous aluminum silicide, extruded moulding, 80～140 ℃ of oven dry, 800～1100 ℃ of roasting 3～6h obtain the catalyst carrier of modification.
Method three: in containing the boehmite of amorphous aluminum silicide, add after nitric acid, water mediates, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble-salt solution of alkali metal and/or alkaline-earth metal, 80～120 ℃ of oven dry, 800～1100 ℃ of roasting 4～6h make modified catalyst supports.
The present invention also provides a kind of preparation method of this catalyst, and the aqueous solution of nickeliferous soluble-salt be impregnated on the carrier, dry after at 300～500 ℃ of lower roasting 3～6h.
Alkali metal and/or alkaline-earth metal and rare-earth element cerium and/or lanthanum all can add when the preparation carrier, also can be after the carrier moulding, and nickel is added in the carrier before adding in advance, can also be when dipping nickel, adds simultaneously with nickel.The present invention does not get rid of yet and contain other active component again except nickel.
Active component nickel is to add with the form of soluble-salt among the present invention, such as nickel nitrate, nickel acetate, nickel chloride or nickelous sulfate, and preferred nickel nitrate, nickel acetate.
Hydrogenation catalyst hydrogenation activity of the present invention and selective high, chemical stability and Heat stability is good, coke content is low, long service life.
Catalyst of the present invention was preferably in 380～420 ℃ with hydrogen reducing 8～12 hours before using,
Hydrogenation catalyst of the present invention is applicable to the selection hydrogenation of medium-low distillate oil, is specially adapted to C
6～C
8The selection hydrogenation of diene class unsaturated hydrocarbons in the cut.
When hydrogenation catalyst of the present invention was applied to medium-low distillate oil selection hydrogenation, its suitable hydrogenation technique condition was: 50～80 ℃ of inlet temperatures, air speed 1.0～4.5h
-1, pressure is greater than 2.7MPa, hydrogen and oil volume ratio: 100～400 (volume ratio is in green oils).
The specific embodiment
The raw materials used source of Kaolinite Preparation of Catalyst and specification:
Industry amorphous aluminum silicide: the safe photoinitiator chemical in Zibo Co., Ltd
Industry boehmite: Zibo Wanlin Chemical Technology Co., Ltd.
Analytical method:
Oil distillation: adopt oil product test method SYB-2110-60 to measure;
Bromine valency: adopt the IC1 method to measure, show with gram bromine/100 gram oil meters;
Diene: adopt apple acid anhydrides method to measure, show with gram iodine/100 gram oil meters;
Arsenic: adopt the DV-4300 Atomic Emission Spectrometer AES to measure;
Sulphur: adopt the WK-2B Microcoulomb instrument to measure;
Colloid: adopt oil product test method SYB-2103-60 to measure;
Catalyst crystalline phases: adopt BRUKER D
8ADVERCE type X-ray diffractometer is measured;
Infrared acidity: adopt pyridine-infrared mensuration;
Specific area, pore volume: adopt low temperature N
2The method of adsorption-desorption is measured.
Embodiment 1:
Configuration 2L concentration is 100gAl
2O
3The sodium aluminate solution of/L places plastic cans, and 40 ℃ of control plastic cans temperature under stirring condition, pass into 60v%CO
2The mist of+40v% air, the flow of carbon dioxide is 2Nm in the gaseous mixture
3/ h.Stop to pass into mist when the pH value reaches 10.5, then aging 25min obtains the boehmite slurries.
Configuration 4L concentration is 100gAl
2O
3The sodium aluminate solution of/L places plastic cans, then adds 2L 100gSiO
2The sodium silicate solution of/L, 30 ℃ of control plastic cans temperature pass into 60v%CO
2The mist of+40v% air, CO in the gaseous mixture
2Flow be 3Nm
3/ h, the control endpoint pH is 9.5, aging 10min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 3L amorphous aluminum silicide slurries are joined in the 1L boehmite slurries, 40 ℃ of control mixing temperatures, aging 10min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 500 ℃ of roasting 3h use the saturated impregnated carrier of potassium nitrate solution, 120 ℃ of oven dry, and 950 ℃ of roasting 4h obtain siliceous and alumina support potassium.Nickel nitrate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 5, is impregnated on the 100g carrier 120 ℃ of oven dry, 400 ℃ of roasting 4h obtain containing the catalyst C-1 of nickel oxide 14.8wt%, cerium oxide 5.6wt%, silica 19.3wt%, potassium oxide 2.5wt%.
Embodiment 2:
The preparation of amorphous aluminum silicide is carried out according to embodiment 1.
Configuration 2L concentration is 150gAl
2O
3The sodium aluminate solution of/L places plastic cans, 35 ℃ of control plastic cans temperature, and under stirring condition, passing into concentration is 70v%CO
2The mist of+30v% air, the flow of carbon dioxide is 4Nm in the gaseous mixture
3/ h stops to pass into mist when the pH value reaches 10.0, aging 20min obtains the boehmite slurries.
Under the condition that constantly stirs, 2L boehmite slurries are joined in the 3L amorphous aluminum silicide slurries, 30 ℃ of control mixing temperatures, aging 15min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 9h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, lanthanum nitrate, cerous nitrate water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 980 ℃ of roasting 4h obtain the alumina support of siliceous, lanthanum and cerium.Nickel acetate, magnesium nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.6, be impregnated on the 100g carrier, 120 ℃ of oven dry, 420 ℃ of roasting 4h obtain containing the catalyst C-2 of nickel oxide 16wt%, cerium oxide 2.6wt%, lanthana 2.4wt%, silica 12.7wt%, magnesia 3.2wt%.
Embodiment 3:
The preparation of boehmite slurries is carried out according to embodiment 1.
Configuration 2L concentration is 130gAl
2O
3The sodium aluminate solution of/L places plastic cans, then adds 2L 80gSiO
2The sodium silicate solution of/L, 20 ℃ of control reaction temperatures pass into 50v%CO
2The mist of+50v% air, CO in the mist
2Flow be 5Nm
3/ h, the control endpoint pH is 9.0, aging 20min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 1L boehmite slurries and 3L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 35 ℃ of control mixing temperatures, aging 15min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, lithium acetate, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 1000 ℃ of roasting 3h obtain siliceous and alumina support lithium.With nickel acetate, the lanthanum nitrate maceration extract of making soluble in water, regulator solution pH value is 4.2, is impregnated on the 100g carrier 120 ℃ of oven dry, 450 ℃ of roasting 4h obtain containing the catalyst C-3 of nickel oxide 11.5wt%, lanthana 4.0wt%, silica 23.3wt%, lithia 3.8wt%.
Embodiment 4:
The preparation of amorphous aluminum silicide slurries and boehmite slurries is carried out according to embodiment 1.
Under the condition that constantly stirs, 1L boehmite slurries and 1.5L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 40 ℃ of control mixing temperatures, aging 18min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 100 ℃ of dry 10h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 500 ℃ of roasting 4h use the saturated impregnated carrier of strontium nitrate solution, 120 ℃ of oven dry, 980 ℃ of roasting 4h obtain siliceous and alumina support strontium.Nickel nitrate, cerous nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 5, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h obtain containing the catalyst C-4 of nickel oxide 15wt%, cerium oxide 1.8wt%, lanthana 2.4wt%, silica 15.3wt%, strontium oxide strontia 4.5wt%.
Embodiment 5:
Configuration 2L concentration is 80gAl
2O
3The sodium aluminate solution of/L places plastic cans, and control plastic cans temperature is 50 ℃, and under the condition that constantly stirs, passing into concentration is 80v%CO
2The mist of+20v% air, the flow of carbon dioxide is 5Nm in the gaseous mixture
3/ h stops to pass into mist when the pH value reaches 10.0, aging 20min obtains the boehmite slurries.
Configuration 3L concentration is 95gAl
2O
3The sodium aluminate solution of/L places plastic cans, then adds 2L65gSiO
2The sodium silicate solution of/L, 25 ℃ of control reaction temperatures pass into 60v%CO
2The mist of+40v% air, CO in the gaseous mixture
2Flow be 4Nm
3/ h, the control endpoint pH is 9.5, aging 15min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 2L boehmite slurries and 2L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 60 ℃ of control mixing temperatures, aging 10min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use potassium nitrate and the saturated impregnated carrier of strontium citrate solution, 120 ℃ of oven dry, 960 ℃ of roasting 4h obtain the alumina support of siliceous, potassium and strontium.Nickel nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, be impregnated on the 100g carrier, 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst C-5 of nickel oxide 13wt%, lanthana 5.5wt%, silica 17.2wt%, potassium oxide 1.5wt%, strontium oxide strontia 3.5wt%.
Embodiment 6:
The configuration of boehmite slurries and amorphous aluminum silicide slurries is carried out according to embodiment 5.
Get 3L amorphous aluminum silicide slurries and 1L boehmite slurries and stream and join in the plastic cans, 25 ℃ of control reaction temperatures, aging 25min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of lower dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use the saturated impregnated carrier of lithium citrate solution, 120 ℃ of oven dry, 1050 ℃ of roasting 4h obtain siliceous and alumina support lithium.Nickel acetate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, is impregnated on the 100g carrier 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst C-6 of nickel oxide 16wt%, lanthana 2.5wt%, silica 27.7wt%, lithia 5.5wt%.
Embodiment 7:
The preparation of boehmite slurries is carried out according to embodiment 5.
Configuration 2L concentration is 150gAl
2O
3The sodium aluminate solution of/L places plastic cans, adds 1L120gSiO
2The sodium silicate solution of/L, 35 ℃ of control reaction temperatures pass into 50v%CO
2The mist of+50v% air, CO in the gaseous mixture
2Flow be 6Nm
3/ h, the control endpoint pH is 9.5, aging 5min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 1L boehmite slurries and 3L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 40 ℃ of control mixing temperatures, aging 30min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use the saturated impregnated carrier of magnesium acetate solution, 120 ℃ of oven dry, 1000 ℃ of roasting 4h obtain siliceous and alumina support magnesium.Nickel acetate, lanthanum nitrate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.2, be impregnated on the 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h obtain containing the catalyst C-7 of nickel oxide 14.2wt%, cerium oxide 2.4wt%, lanthana 3.6wt%, silica 17.6wt%, magnesia 6.3wt%.
Embodiment 8:
The preparation of boehmite slurries is carried out according to embodiment 1.
Configuration 2L concentration is 130gAl
2O
3The sodium aluminate solution of/L places plastic cans, then adds 2L 80gSiO
2The sodium silicate solution of/L, 20 ℃ of control reaction temperatures pass into 50v%CO
2The mist of+50v% air, CO in the mist
2Flow be 5Nm
3/ h, the control endpoint pH is 9.0, aging 20min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 1L boehmite slurries and 3L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 35 ℃ of control mixing temperatures, aging 15min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, lithium acetate, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 1000 ℃ of roasting 3h obtain siliceous and alumina support lithium.With the nickel acetate maceration extract of making soluble in water, regulator solution pH value is 4.2, be impregnated on the 100g carrier, and 120 ℃ of oven dry, 450 ℃ of roasting 4h obtain containing the catalyst C-8 of nickel oxide 11.5wt%, silica 24.5wt%, lithia 3.8wt%.
Embodiment 9:
The preparation of amorphous aluminum silicide slurries and boehmite slurries is carried out according to embodiment 1.
Under the condition that constantly stirs, 1L boehmite slurries and 1.5L amorphous aluminum silicide slurries and stream are joined in the plastic cans, 40 ℃ of control mixing temperatures, aging 18min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 100 ℃ of dry 10h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 980 ℃ of roasting 4h obtain siliceous alumina support.Nickel nitrate, cerous nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 5, be impregnated on the 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h obtain containing the catalyst C-9 of nickel oxide 15wt%, cerium oxide 1.8wt%, lanthana 2.4wt%, silica 16.2wt%.
Comparative Examples 1:
Be 100gAl with 2L concentration
2O
3The sodium aluminate solution of/L places plastic cans, 40 ℃ of control plastic cans temperature, and under the condition that constantly stirs, passing into concentration is 60v%CO
2The mist of+40v% air, the flow of carbon dioxide is 2Nm in the gaseous mixture
3/ h stops to pass into gaseous mixture when the pH value reaches 10.5, aging 25min obtains the boehmite slurries.
Be 100gAl with 4L concentration
2O
3The sodium aluminate solution of/L places plastic cans, then adds 2L10gSiO
2The sodium silicate solution of/L, 30 ℃ of control reaction temperatures pass into 60v%CO
2The mist of+40v% air, CO in the gaseous mixture
2Flow be 3Nm
3/ h, the control endpoint pH is 9.5, aging 10min obtains the amorphous aluminum silicide slurries.
Under the condition that constantly stirs, 3L amorphous aluminum silicide slurries are joined in the 1L boehmite slurries, 40 ℃ of control mixing temperatures, aging 10min, filtration washing is to Na
+Content obtains containing the boehmite of amorphous aluminum silicide less than 0.5%, 120 ℃ of dry 8h.
To contain the boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 500 ℃ of roasting 3h use the saturated impregnated carrier of potassium nitrate solution, 120 ℃ of oven dry, and 950 ℃ of roasting 4h obtain siliceous and alumina support potassium.Nickel nitrate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 5, is impregnated on the 100g carrier 120 ℃ of oven dry, 400 ℃ of roasting 4h obtain containing the catalyst S-1 of nickel oxide 14.8wt%, cerium oxide 5.6wt%, silica 2.47wt%, potassium oxide 2.5wt%.
Comparative Examples 2:
This Comparative Examples prepares silica-alumina according to the 3 described methods of embodiment among the CN1267187C, and concrete steps are as follows:
Take by weighing the 1000g aluminum nitrate, be dissolved into 2L aluminum nitrate solution a3 (Al with deionized water
2O
3Concentration is 65g/L); The 500ml concentrated ammonia liquor is diluted to 1500ml solution b3 with deionized water; Preparation 500ml89.6SiO
2The sodium silicate solution c3 of/L; Get 35g NaOH, be dissolved into 150ml solution d3 with deionized water.
In plastic cans, add first the 1.7L deionized water, stirring also is heated to 40 ℃, then and stream add solution a3 and b3, it is 8 that adjust flux makes the pH value of reaction system, after the reaction end again pH be 8, aging 60min under the temperature 45 C condition, behind aging the end, under stirring condition, add successively solution c3 and d3, and control pH is 8.2, then temperature 50 C is warming up to 95 ℃ and also filters behind the constant temperature 20h.Filter cake washs 4 times with deionized water, and 120 ℃ of dry 15h obtain the silica-alumina composite granule.
With silica-alumina composite granule and nitric acid, lithium acetate, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 1000 ℃ of roasting 3h obtain siliceous and alumina support lithium.With nickel acetate, the lanthanum nitrate maceration extract of making soluble in water, regulator solution pH value is 4.2, is impregnated on the 100g carrier 120C oven dry, 450 ℃ of roasting 4h obtain containing the catalyst S-2 of nickel oxide 11.5wt%, lanthana 4.0wt%, silica 23.3wt%, lithia 3.8wt%.
Comparative Examples 3:
This Comparative Examples prepares the silica-alumina composite oxides according to the 1 described method of embodiment among the CN1074303C, and concrete steps are as follows:
First in 150ml, 55 ℃ of distilled water with 30.5g sodium metasilicate (Na
2SiO
3) fully dissolving, with 152.5g sodium aluminate (NaAlO
2) also be dissolved in the 700ml distilled water.Then, sodium aluminate solution is slowly poured in the sodium silicate solution.In mixed process, mixed liquor is in 55 ℃ of laser heatings and simultaneously stirring.After two kinds of solution mix fully, add 6N HCl until reactant mixture is transparent.Then in clear solution, add 6N NaOH until pH value of solution reaches 10, then keep 60min to obtain gel.Gel is put into reative cell keep 1h at 100 ℃ of pressure 100psi of temperature, product filters with vacuum equipment, is deposited in 100 ℃ of dry 24h and obtains the powdery alumino-silicate.
With powdery alumino-silicate and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use the saturated impregnated carrier of magnesium acetate solution, 120 ℃ of oven dry, 1000 ℃ of roasting 4h obtain siliceous and alumina support magnesium.Nickel acetate, lanthanum nitrate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.2, be impregnated on the 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h obtain containing the catalyst S-3 of nickel oxide 14.2wt%, cerium oxide 2.4wt%, lanthana 3.6wt%, silica 14.7wt%, magnesia 6.3wt%.
Comparative Examples 4:
This Comparative Examples prepares silica-alumina according to the 3 described methods of embodiment among the CN1267187C, and concrete steps are as follows:
Take by weighing the 1000g aluminum nitrate, be dissolved into 2L aluminum nitrate solution a3 (Al with deionized water
2O
3Concentration is 65g/L); The 500ml concentrated ammonia liquor is diluted to 1500ml solution b3 with deionized water; Preparation 500ml89.6SiO
2The sodium silicate solution c3 of/L; Get 35g NaOH, be dissolved into 150ml solution d3 with deionized water.
In plastic cans, add first the 1.7L deionized water, stirring also is heated to 40 ℃, then and stream add solution a3 and b3, it is 8 that adjust flux makes the pH value of reaction system, after the reaction end again pH be 8, aging 60min under the temperature 45 C condition, behind aging the end, under stirring condition, add successively solution c3 and d3, and control pH is 8.2, then temperature 50 C is warming up to 95 ℃ and also filters behind the constant temperature 20h.Filter cake washs 4 times with deionized water, and 120 ℃ of dry 15h obtain the silica-alumina composite granule.
With silica-alumina composite granule and nitric acid, lithium acetate, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 1000 ℃ of roasting 3h obtain siliceous and alumina support lithium.With the nickel acetate maceration extract of making soluble in water, regulator solution pH value is 4.2, be impregnated on the 100g carrier, and 120 ℃ of oven dry, 450 ℃ of roasting 4h obtain containing the catalyst S-4 of nickel oxide 11.5wt%, silica 24.6wt%, lithia 3.8wt%.
Comparative Examples 5:
This Comparative Examples prepares silica-alumina according to the 4 described methods of embodiment among the CN1306977C, and concrete steps are as follows:
Adopt water intaking glass 100ml, add high alkalinity sodium metaaluminate 75ml under the room temperature, stir 1h, leave standstill 6h, silica content is 235g/L in this solution, and alumina content is 6.7g/L.Get this solution 65ml, add water to 300ml, obtain the mother liquor of synthesis of molecular sieve, wherein SiO
2Content is 5.1g/100ml.
With concentration be 10% aluminum nitrate solution 385ml and concentration be 8% ammonia spirit 390ml and concentration be 8% ammonia spirit 390ml with and the mode of stream join simultaneously in the retort of a 2L, put in advance 0.5L water in the tank, the flow of aluminum nitrate solution is 1.1L/h, regulate the flow of ammonia spirit, the pH value that makes mixed liquor is 7.0 ± 0.3, and mixed liquor is collected in an ageing can.Under agitation the mother liquor with the 50ml synthesis of molecular sieve joins in this mixed liquor, makes silica-alumina colloid slurries, is warming up to 65 ℃, stir lower aging 1h, after filtering, filter cake washs 3 times with deionized water, 120 ℃ of dry 5h obtain the silica-alumina composite granule in baking oven.
With silica-alumina composite granule and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use potassium nitrate and the saturated impregnated carrier of strontium citrate solution, 120 ℃ of oven dry, 960 ℃ of roasting 4h obtain the alumina support of siliceous, potassium and strontium.Nickel nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, be impregnated on the 100g carrier, 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst S-5 of nickel oxide 13wt%, lanthana 5.5wt%, silica 23.3wt%, potassium oxide 1.5wt%, strontium oxide strontia 3.5wt%.
Comparative Examples 6:
This Comparative Examples prepares silica-alumina according to the 4 described methods of embodiment among the CN1306977C, and concrete steps are as follows:
Adopt water intaking glass 100ml, add high alkalinity sodium metaaluminate 75ml under the room temperature, stir 1h, leave standstill 6h, silica content is 235g/L in this solution, and alumina content is 6.7g/L.Get this solution 65ml, add water to 300ml, obtain the mother liquor of synthesis of molecular sieve, wherein SiO
2Content is 5.1g/100ml.
With concentration be 10% aluminum nitrate solution 385ml and concentration be 8% ammonia spirit 390ml and concentration be 8% ammonia spirit 390ml with and the mode of stream join simultaneously in the retort of a 2L, put in advance 0.5L water in the tank, the flow of aluminum nitrate solution is 1.1L/h, regulate the flow of ammonia spirit, the pH value that makes mixed liquor is 7.0 ± 0.3, and mixed liquor is collected in an ageing can.Under agitation the mother liquor with the 50ml synthesis of molecular sieve joins in this mixed liquor, makes silica-alumina colloid slurries, is warming up to 65 ℃, stir lower aging 1h, after filtering, filter cake washs 3 times with deionized water, 120 ℃ of dry 5h obtain the silica-alumina composite granule in baking oven.
With the silica-alumina composite granule with nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, 960 ℃ of roasting 4h obtain siliceous alumina support.Nickel nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, is impregnated on the 100g carrier 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst S-6 of nickel oxide 13wt%, lanthana 5.5wt%, silica 24.8wt%.
Comparative Examples 7:
With industrial amorphous aluminum silicide and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use the saturated impregnated carrier of lithium citrate solution, 120 ℃ of oven dry, 1050 ℃ of roasting 4h obtain siliceous and alumina support lithium.Nickel acetate, cerous nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, is impregnated on the 100g carrier 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst S-7 of nickel oxide 16wt%, lanthana 2.5wt%, silica 34.2wt%, lithia 5.5wt%.
Comparative Examples 8:
With industrial boehmite and nitric acid, water mixer kneader, behind the extruded moulding, 120 ℃ of oven dry, then 480 ℃ of roasting 4h use potassium nitrate and the saturated impregnated carrier of strontium citrate solution, 120 ℃ of oven dry, 960 ℃ of roasting 4h obtain the alumina support of potassium and strontium.Nickel nitrate, lanthanum nitrate be dissolved in the water jointly make maceration extract, regulator solution pH value is 4.5, is impregnated on the 100g carrier 120 ℃ of oven dry, 500 ℃ of roasting 3h obtain containing the catalyst S-8 of nickel oxide 13wt%, lanthana 5.5wt%, potassium oxide 1.5wt%, strontium oxide strontia 3.5wt%.
Evaluating catalyst
The employing drippolene is raw material, and feedstock property sees Table 1, and embodiment catalyst C1-C7 and Comparative Examples catalyst S 1-S5 are carried out activity rating at 100ml adiabatic reactor hydrogenation plant.Estimate respectively 500h, every 12h sample analysis bromine valency and diene, average data sees Table 2.
Evaluating catalyst carries out at 100ml adiabatic reactor hydrogenation reaction device, and catalyst at first reduced 10 hours under 380～420 ℃ of hydrogen, then cooled to 60 ℃, with the laggard feedstock oil of cyclohexane passivation 2h that contains DMDS 1000ppm.Estimate process conditions: reaction pressure: 2.8MPa, inlet temperature: 60 ℃, fresh feed oil air speed: 3.5h
-1, hydrogen and oil volume ratio: 200: 1 (volume ratio is in green oil).
Table 1 hydrogenating materials oil (C
6～C
8) index
| Color | Bromine valency * 10 -2(g/g) | Diene 10 -2 (g/g) | Boiling range (℃) | Sulfur content (ppm) | Colloid * 10 -2 (mg/ml) | Density (g/ml) | Arsenic content (ppb) |
| Yellow | 62.5 | 25 | 65～180 | 116 | 11 | 0.837 | Less than 20 |
The evaluating catalyst average data sees Table 2.
Embodiment and Comparative Examples catalyst composition and physico-chemical property are as shown in table 3.
Claims (10)
1. selective hydrogenation catalyst, it is characterized in that take nickel as active component, take silicon-containing alumina as carrier, take total catalyst weight as 100%, contain nickel oxide 10～20wt%, cerium oxide and/or lanthana 0～10wt%, alkali metal and/or alkaline earth oxide 0～8wt%, silica 3.1～36wt%; Specific surface area of catalyst 60～180m
2/ g, pore volume 0.4～0.7ml/g; The presoma of silicon-containing alumina carrier is the boehmite that contains amorphous aluminum silicide, it is by at first preparing amorphous aluminum silicide slurries and boehmite slurries, then these two kinds of slurries are mixed, aging, and include that the last handling process of filtrations, drying obtains; PH value of solution is 9.0～10.5 when aging, and temperature is 20～65 ℃.
2. hydrogenation catalyst according to claim 1 is characterized in that cerium oxide and/or lanthana 2～10wt%, and alkali metal and/or alkaline earth oxide 2～8wt%, silica content are 3.1～27wt%.
3. hydrogenation catalyst according to claim 1, the boehmite that it is characterized in that containing amorphous aluminum silicide is by with amorphous aluminum silicide slurries and boehmite slurries and stream mixes or a kind of slurries are joined in the another kind of slurries mix, after mixing is finished, aging 10～30min, filter, washing, 80～120 ℃ of drying 2～20h obtain.
4. hydrogenation catalyst according to claim 1 is characterized in that the amorphous aluminum silicide slurries obtain by following method:
(a) compound concentration is 10～150gAl
2O
3The sodium metaaluminate of/L or sodium aluminate solution join in the plastic cans, 15～50 ℃ of control plastic cans temperature;
(b) compound concentration is 50～200gSiO
2The silicon-containing compound solution of/L joins in the sodium metaaluminate or sodium aluminate solution of (a), control pH value 11.5～13;
(c) under the condition of low whipping speed greater than 250r/min, pass into continuously concentration greater than the carbon dioxide of 20v%, the flow of control carbon dioxide is at 1～10Nm
3/ h, in and time 20～40min, endpoint pH 7.5～9.5, neutralization finishes;
(d) in pH value 7.5～9.5, aging (c) 5～20min obtains the amorphous aluminum silicide slurries under the condition that temperature is 25～40 ℃.
5. hydrogenation catalyst according to claim 1, it is characterized in that the boehmite slurries obtain by following method: sodium metaaluminate or sodium aluminate solution are placed plastic cans, pass into carbon dioxide with intermittence or continuation mode and become glue, the aging boehmite slurries that obtain; The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2O
3/ L; Gas concentration lwevel is greater than 20v%, flow 1～10Nm
3/ h; Become 20～65 ℃ of glue temperature; Become glue endpoint pH 9.0～10.5, become in the glue and time and ageing time altogether less than 40min.
6. hydrogenation catalyst according to claim 1 is characterized in that catalyst carrier is boehmite by will containing amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, and 80～140 ℃ of oven dry, 800～1100 ℃ of roasting 3～6h make.
7. hydrogenation catalyst according to claim 6 is characterized in that catalyst carrier adds one or more in alkali metal, alkaline-earth metal, the rare earth element before extruded moulding.
8. the preparation method of a hydrogenation catalyst claimed in claim 1 is characterized in that the aqueous solution of nickeliferous soluble-salt be impregnated on the carrier, and is dry rear at 300～500 ℃ of lower roasting 3～6h.
9. the preparation method of hydrogenation catalyst according to claim 8, it is characterized in that alkali metal and/or alkaline-earth metal and rare-earth element cerium and/or lanthanum all can add when the preparation carrier, perhaps after the carrier moulding, nickel is added in the carrier before adding in advance, or when dipping nickel, add simultaneously with nickel.
10. the preparation method of hydrogenation catalyst according to claim 8, it is characterized in that carrier be by in containing the boehmite of amorphous aluminum silicide, add nitric acid, water carries out mixer kneader, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble-salt solution of alkali metal and/or alkaline-earth metal, 80～120 ℃ of oven dry, 800～1100 ℃ of roasting 4～6h obtain.
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| CN105080548B (en) * | 2014-05-08 | 2017-09-22 | 中国石油化工股份有限公司 | A kind of method for improving nickel system liquid phase hydrogenating catalyst selectivity and stability |
| CN106732620B (en) * | 2015-11-23 | 2020-02-14 | 中国石油天然气股份有限公司 | Nickel series hydrogenation catalyst and preparation method thereof |
| CN108262047B (en) * | 2016-12-30 | 2021-03-09 | 中国石油天然气股份有限公司 | Nickel-molybdenum series hydrogenation catalyst and preparation method thereof |
| CN108855129B (en) * | 2017-05-15 | 2021-04-30 | 中国石油天然气股份有限公司 | Nickel-silver hydrogenation catalyst and preparation method thereof |
| CN108855128B (en) * | 2017-05-15 | 2021-04-30 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN108865241B (en) * | 2017-05-15 | 2021-01-01 | 中国石油天然气股份有限公司 | Selective hydrogenation method for cracked gasoline carbon eight fractions |
| CN108863696B (en) * | 2017-05-15 | 2021-07-02 | 中国石油天然气股份有限公司 | Method for recovering butene by selective hydrogenation of alkyne |
| CN108864368B (en) * | 2017-05-15 | 2020-09-04 | 中国石油天然气股份有限公司 | Hydrogenation method for C-V petroleum resin |
| CN108864369B (en) * | 2017-05-15 | 2020-09-04 | 中国石油天然气股份有限公司 | Hydrogenation method for C-V petroleum resin |
| CN109289868B (en) * | 2018-10-11 | 2022-04-01 | 烟台百川汇通科技有限公司 | Pyrolysis gasoline selective hydrogenation catalyst and preparation method thereof |
| CN114950470B (en) * | 2022-06-30 | 2023-07-25 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of propyne and propadiene in propylene |
| CN116173968A (en) * | 2023-03-06 | 2023-05-30 | 上海迅凯新材料科技有限公司 | Nickel-based hydrogenation catalyst and preparation method and application thereof |
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| US5609750A (en) * | 1991-06-03 | 1997-03-11 | Akzo Nobel Nv | Boron-containing catalyst |
| CN1597092A (en) * | 2003-09-17 | 2005-03-23 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5609750A (en) * | 1991-06-03 | 1997-03-11 | Akzo Nobel Nv | Boron-containing catalyst |
| CN1597092A (en) * | 2003-09-17 | 2005-03-23 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
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