CN100484625C - Diene selection hydrogenation catalyst, and preparation method - Google Patents
Diene selection hydrogenation catalyst, and preparation method Download PDFInfo
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- CN100484625C CN100484625C CNB2006100726305A CN200610072630A CN100484625C CN 100484625 C CN100484625 C CN 100484625C CN B2006100726305 A CNB2006100726305 A CN B2006100726305A CN 200610072630 A CN200610072630 A CN 200610072630A CN 100484625 C CN100484625 C CN 100484625C
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Abstract
A selective hydrocatalyst wit high hydrogenating activity, selectivity and stability for the low-temp selective hydrogenation of diene is composed of the carrier gamma-Al2O3 calcined at 900-1200 deg.C and the active component Ni (5-25 Wt %). Its low-temp preparing process is also disclosed.
Description
Technical field
The present invention relates to a kind of diene selection hydrogenation catalyst and preparation method thereof, especially relate to a kind of catalytic cracking light petrol or C of being used for
5Cut is selected the Catalysts and its preparation method of hydrogenation under the low-temp reaction condition.
Background technology
Olefin(e) centent is higher in the catalytically cracked gasoline, generally at 30～60v%, for improving and improve the quality of motor petrol, need further process to handle and reduce olefin(e) centent.All to use strongly acidic catalyst or acid carrier to make alkene be converted into high-octane non-olefinic component in the technology that processing is handled at present, as catalytic cracking light petrol (doing) or C less than 75 ℃ or less than 100 ℃, to call catalytic light gasoline in the following text
5Alkene in the cut generates high-octane tert-alkyl ether compound with methyl alcohol or ethanol generation etherification reaction under the effect of highly acidic resin catalyst; Under the catalytic action of acid carrier or acidic molecular sieve, catalytic light gasoline or C
5Alkene generation isomerization in the cut, aromatization generate high-octane isohydrocarbon and aromatic hydrocarbons; Under the concentrated sulfuric acid or hydrofluoric acid or highly acidic resin or strong solid acids effect, make C
5Alkene generation alkylated reaction in the cut generates high-octane alkylation component etc.But, at catalytic light gasoline or C
5Except that the alkene that contains a large amount of further processing and utilizations, also there are high unsaturated hydrocarbons such as a spot of alkadienes, alkynes in the cut.Oligomerisation reaction very easily takes place in these high unsaturated hydrocarbons under the effect of acidic catalyst or acid carrier, generate big molecule colloid, be present in the quality that reduces oil product in the gasoline on the one hand, can be deposited on the surface of acidic catalyst on the other hand, acidic catalyst inactivation or acid consumption are increased, reduce the service life and the cycle of acidic catalyst, also cause environmental pollution.Therefore, realize catalytic light gasoline or C
5Cut carries out preliminary treatment and removes high unsaturated hydrocarbons such as alkadienes in the raw material, does not also reduce olefin(e) centent simultaneously, is beneficial to follow-up process, just requires catalyst that good diolefin hydrogenation activity is not only arranged, and requires to have very high hydrogenation selectivity.
To catalytic light gasoline or C
5It is selective hydrogenation that cut carries out the common technology that preliminary treatment removes high unsaturated hydrocarbons, what usually use in these selection hydrogen addition technologies is the catalyst that is loaded with precious metals pd, adopts precious metals pd selection of catalysts hydrogen addition technology (Oil ﹠amp as IFP (IFP); GasJ, 1992; 90 (41): 51-54), selection hydrogen addition technology (NPRAAnnual Meeting, 1991 of H ü ls company of Germany; AM-91-17) etc.US 5489565, US 6576586, US 4330679, US 5141525, US 4950820, GB 1090177, CN 1429889, CN 1385496, CN 1410515 etc. also have relevant record; Also there are some technology to adopt Ni as the catalyst of selecting hydrogenation master active component, be mainly used in steam cracking gasoline and select hydrogenation, as the record of US 3234298, US 3847835, US5417844, CN 1218822, CN 1056068, EP 0490571, EP 0559183 etc.
It is the method for the diene selection hydrogenation catalyst of active constituent loading on alumina support with nickel sulfide or cobalt sulfide that US 3234298 (1966) and US 3847835 (1974) disclose a kind of preparation, and discloses this catalyst and more than 160 ℃ diolefin hydrogenation is had preferably active, selectivity and stability in reaction temperature.It is that auxiliary agent, Ni are that active component, aluminium oxide are the diolefin hydrogenation catalyst of carrier with Li or alkaline-earth metal that CN 1218822 has narrated a kind of, be mainly used in the hydrogenation process of steam cracking gasoline, it is as modified additive alumina support to be implemented modification with Li or alkaline-earth metal, through high-temperature process, make described auxiliary agent in conjunction with entering in the structure of alumina support, obtain stable carrier back loading Ni active component, obtain described catalyst through higher temperature and the processing of long period.EP0490571 (1991) has proposed can be applicable to C
5The Ni catalyst of the alumina load of cut diene selection hydrogenation, but the diolefin hydrogenation conversion data of this patent record was being descended low less than 80 ℃ of reaction temperatures, can not 100% diene is carried out hydrogenation, in other words, the activity of hydrogenation catalyst when lower temperature of this patent record is not good.It is that active component, aluminium oxide are the diene selection hydrogenation catalyst of carrier with Ag and Ni that EP 0559183 (1993) has narrated a kind of, and it makes C
5C in the cut
5The temperature of diene 100% hydrogenation will reach more than 90 ℃.US 5417844 (nineteen ninety-five) has described the selective hydrocatalyst of a kind of Ni on aluminium oxide, be characterized in that the Ni catalyst for preparing is not just vulcanizing before the process hydrogen reducing, thereby obtain selectivity and all high catalyst of stability, but this catalyst also is to be applicable to drippolene.
As can be seen, when present diene selection hydrogenation catalyst reacts at the catalysis diolefin hydrogenation, reaction condition is had relatively high expectations, and its diolefin hydrogenation activity, selectivity and stability are still waiting further raising.
Summary of the invention
The main technical problem to be solved in the present invention is researched and proposed a kind of hydrogenation catalyst exactly, and it realizes the selective hydrogenation to the high unsaturated hydrocarbons in the light fraction gasoline under condition as mild as a dove, and has very high selectivity and stability.
Another aspect of the present invention also provides a kind of above-mentioned method with selective hydrogenation of dienes catalyst for preparing, each stage of preparation process is low temperature process and short time operation, makes the catalyst that obtains have active and good selectivity and the stability of very high diolefin hydrogenation.
For reaching above-mentioned purpose, the present invention at first provides a kind of diene selection hydrogenation catalyst, and it is the γ-Al that adopts through 900 ℃～1200 ℃ of roastings
2O
3For carrier, metal Ni are that active component constitutes, activity component load quantity is 5～25%wt.
In the catalyst of the present invention, used carrier γ-Al
2O
3Be to pass through specific high-temperature process, the inventor discovers, γ-Al
2O
3After through 900 ℃～1200 ℃ high-temperature process, its performance will improve, and compare with processed conventionally carrier, and most acid centres are eliminated, and can have very high specific area and rational pore structure.With such Al
2O
3Can play the effect of dispersed active metal as carrier, and help the mass transfer of liquid phase reactor thing.
After measured, the γ-Al after the process high-temperature process of the present invention's use
2O
3Carrier, its bulk specific weight are 0.65～0.75g/mL, pore volume 0.4～0.5mL/g, and the aperture accounts for more than 70% greater than the hole of 4nm, and specific area (BET area) is greater than 100m
2/ g.
Another characteristics of catalyst of the present invention are only to be made up of carrier and active component, and this active component is non-noble metal Ni, by adjusting suitable load capacity, reach the purpose of selecting hydrogenation.The load capacity of metallic nickel on carrier is 5～25%, and for obtaining stable high hydrogenation activity, the preferred negative carrying capacity of metallic nickel is 8～20%wt.
This catalyst can be drying, 0～2 hour product of 250 ℃～350 ℃ roastings behind the carrier to load metal nickel.This catalyst can also be described γ-Al
2O
3Product after handling through hydrogen reducing and presulfurization behind the carrier to load metal Ni, the user obtains to need not further processing behind this catalyst and can directly use.
The catalyst of putting down in writing in catalyst of the present invention and the prior art is compared another characteristics and is exactly, and the load of this catalyst and heat treatment all are to handle low temperature, short time, and active component Ni is in metastable state in the product that obtains.So catalyst of the present invention is used for catalytic light gasoline and C
5Diolefin hydrogenation processing procedure in the cut not only has very high low temperature diolefin hydrogenation activity (can realize 100% hydrogenation under 55 ℃), also has very high selectivity and stability simultaneously.
It is a kind of to catalytic light gasoline or C that the present invention also provides
5Cut carries out pretreated method, comprise and adopt diene selection hydrogenation catalyst of the present invention to contact with pending oil product, the reaction of realization selective hydrogenation of dienes, Gu this selective hydrogenation is to carry out under gas/liquid/three-phase condition, its pressure limit is 1.0MPa～4.0MPa, temperature is higher than 55 ℃, hydrogen to oil volume ratio (STP, that is, under the NPT) scope is 10: 1～60: 1, with the catalyst volume is benchmark, and the long-pending air speed scope of liquid can be 2～10h
-1(STP).
On the other hand, the present invention also provides the preparation method of described diene selection hydrogenation catalyst, and it mainly is the γ-Al that adopts through 900 ℃～1200 ℃ of high-temperature roastings
2O
3Be carrier, after the load of water-soluble active metal salt solution, handle (comparing) and prepare described diene selection hydrogenation catalyst with common process through low temperature drying.
The method of the described diene selection hydrogenation catalyst of preparation of the present invention comprises:
With γ-Al
2O
3900 ℃～1200 ℃ roastings 1～5 hour;
Adopt infusion process that metal Ni is carried on the alumina support after the roasting.
γ-Al of the present invention
2O
3Raw material can be purchased, can be microspheric form or other shape, general diameter is φ 1～2mm, heat treatment is after 1～5 hour in 900 ℃～1200 ℃ air, can measure its bulk specific weight is 0.65～0.75g/mL, pore volume 0.4～0.5mL/g, the aperture accounts for (even can reach more than 90%) more than 70% greater than the hole of 4nm, and specific area is greater than 100m
2/ g has preferable specific area and rational pore structure, is suitable as very much the carrier of catalyst of the present invention.
In the impregnation steps, adopt the aqueous solution or the organic solution dipping γ-Al of Ni salt
2O
3Carrier.Wherein, described Ni salt can be the water soluble salt of nickel, for example nitrate, acetate or chlorate etc., can be mixed with the aqueous solution, also can be with anhydrous polar organic solvent (for example propyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, acetate or formic acid etc., preferred alcohol, methyl alcohol or propyl alcohol) dissolving after be mixed with organic solution, afterwards the carrier after the above-mentioned roasting of step is flooded (for example adopting incipient impregnation), active component Ni is carried on the prepared alumina support, the load capacity of this reactive metal Ni is preferably 5～25%wt, more preferably 8～20%wt.
Can be generally drying time about 3～8 hours in 100 ℃～180 ℃ following dryings or vacuum drying after the carrier impregnation active component of the present invention.From being beneficial to the angle of environment, further can carry out the low-temperature bake of short time earlier to the above-mentioned catalyst that obtains, offer the user again, for example can handle 0～2 hour at 250 ℃～350 ℃, can obtain diene selection hydrogenation catalyst of the present invention, it only is made of carrier and active component Ni.
The catalyst that obtains through above-mentioned preparation method also needs to carry out hydrogen reduction and presulfurization processing before use, further improve diolefin hydrogenation activity, selectivity and the long period stability of catalyst of the present invention, promptly, this catalyst that so obtains can offer the user, and it can use after by oneself.Further, in preparation catalyst process, can also comprise above-mentioned diene selection hydrogenation catalyst is reduced and presulfurization with reducing gases, the actual conditions that reduction is handled can for: in nitrogen atmosphere, reduce, 350 ℃～450 ℃ of reduction temperatures, 3～8 hours recovery times, the reduction pressure be normal pressure to 0.3MPa, the reducing gases air speed is 420～600h
-1(STP).Vulcanizing treatment (or claiming presulfurization to handle) is and adopts suitable sulfide treatment catalyst, for example can use ethyl mercaptan or diethyl disulfide or dimethyl disulfide or butyl mercaptan or thiophene or diethyl sulfonic acid fat sulfides solution pretreatment catalyst 0.1～5 hour down at 10 ℃～60 ℃.
As can be seen from the above description, prepare catalyst of the present invention, what adopt is " low, short " change technology, promptly, the low temperatureization of each preparatory phase of catalyst, short time handle, and this just makes active component Ni all be in metastable condition at its each preparatory phase, has very high diolefin hydrogenation activity, also just have good selectivity and stability through after the vulcanizing treatment, can under very gentle condition, realize efficient diene selection hydrogenation.And catalyst of the present invention only is made up of active component and carrier, and preparation method's technology is simple, and is with low cost.
The specific embodiment
Enumerate specific embodiment below and further set forth characteristics, preparation method and the catalytic performance thereof of catalyst of the present invention, understand enforcement of the present invention and the beneficial effect that is produced better with the help reader, but do not constitute any qualification the scope of the present invention.
Embodiment 1
With an amount of diameter is bead γ-Al of φ 1～2mm
2O
3Carrier (Fushun Petrochemical Company catalyst plant) is used for the carrier of subsequent catalyst 1100 ℃ of following roastings of Muffle furnace 4 hours after the cooling, measure its bulk specific weight 0.72g/mL, pore volume 0.41mL/g, and the aperture accounts for 95% greater than the hole of 4nm, specific area 101m
2/ g.
Embodiment 2
Take by weighing prepared alumina support among the 165 gram embodiment 1, with 119.3 gram nickel nitrate Ni[(NO
3)
26H
2O] and the solution that is made into of 115.5 ml distilled waters carried out incipient impregnation 2 hours, behind the room temperature preliminarily dried, again 160 ℃ of following constant temperature vacuum drying 7 hours, can prepare metal Ni load capacity is the catalyst A of 14.6%wt.
Embodiment 3
Is bead γ-Al of φ 1～2mm with 130 grams without the diameter of crossing high-temperature process
2O
3Carrier (Fushun Petrochemical Company catalyst plant) prepares the catalyst contrast medium B of identical Ni tenor by the method for embodiment 2.
Embodiment 4
Get the prepared catalyst A of a certain amount of embodiment 2, in Muffle furnace,, promptly get through the Ni catalyst C after the roasting in air, 280 ℃ of following roastings 2 hours.
Embodiment 5
The catalyst A that embodiment 2 is prepared in air, 450 ℃ of following roastings 2 hours, promptly gets the Ni catalyst contrast medium D through the higher temperature roasting in Muffle furnace.
Embodiment 6
Take by weighing prepared alumina support among the 120 gram embodiment 1, with 115.9 gram nickel nitrate Ni[(NO
3)
26H
2O] and the solution that is made into of 86 ml distilled waters carry out incipient impregnation after 2 hours, behind the room temperature preliminarily dried, again 160 ℃ of following constant temperature vacuum drying 7 hours, then in Muffle furnace in air, 300 ℃ of following roastings 2 hours, promptly getting through the Ni tenor after the roasting is the catalyst E of 19.5%wt.
Embodiment 7
Take by weighing prepared alumina support among the 85 gram embodiment 1, with 36.2 gram nickel nitrate Ni[(NO
3)
26H
2O] and the solution that is made into of 63 ml distilled waters carry out incipient impregnation after 2 hours, behind the room temperature preliminarily dried, again 160 ℃ of following constant temperature vacuum drying 7 hours, then in Muffle furnace in air, 280 ℃ of following roastings 2 hours, promptly getting through the Ni tenor after the roasting is the catalyst F of 8.6%wt.
Embodiment 8
It is active and stable to adopt the upper reaches feeding manner to estimate the diolefin hydrogenation of above-mentioned non-precious metal catalyst and contrast medium A～F in the small pressurized fixed-bed reactor.
A certain amount of catalyst is placed the middle part of reactor flat-temperature zone, fill with quartz sand up and down, be warming up to 380 ℃ under the hydro condition, constant temperature reduction 5 hours, reduction pressure is normal pressure, the reducing gases air speed is 420h
-1(STP), then device is cooled to room temperature, with vulcanizing agent butyl mercaptan sulfuration 1 hour.
Afterwards, be warming up to reaction temperature, feed catalytic cracking light petrol reaction raw materials liquid and carry out the diolefin hydrogenation reaction.Facing the hydrogen hydrogenation conditions is: 65 ℃ of reaction temperatures, and reactive hydrogen dividing potential drop 1.2MPa, the liquid under the STP amasss air speed 18.0h
-1(the per hour ratio of liquid feed volume and catalyst system therefor volume), hydrogen to oil volume ratio 33: 1.The content of main component is in the catalytic cracking light petrol reaction raw materials liquid: carbon pentaene hydrocarbon 22.72% (wt), pentadiene 0.538% (wt), C 6 olefin 17.48% (wt), total sulfur 87.4 μ g/g, total nitrogen 5.8 μ g/g.The reaction evaluating result is as shown in table 1.
The diolefin hydrogenation conversion ratio (%) of table 1, non-noble metal Ni catalyst
From the result of table 1 as can be seen, employing of the present invention is through the γ-Al after the specific high-temperature roasting
2O
3As the catalyst (catalyst A) of a certain amount of Ni of carrier impregnation, (contrast medium B) compares with the unfired catalyst of carrier, has higher diolefin hydrogenation activity and stable; Catalyst after the load through the catalyst C after the lower temperature roasting and E with compare through the contrast medium D after the higher temperature roasting, also have higher and more stable high active of hydrogenation catalysis; Even the catalyst F that the active component load capacity is lower compares with D with contrast medium B, also demonstrate more stable catalytic activity.
Embodiment 9
With above-mentioned catalytic cracking light petrol is raw material, catalyst C of the present invention has been carried out 100 hours long-term operation in the small pressurized fixed-bed reactor.Reaction condition is: 65 ℃ of reaction temperatures, and reactive hydrogen dividing potential drop 1.2MPa, liquid amasss air speed 9.0h
-1, hydrogen to oil volume ratio 23: 1.Pentadiene conversion ratio, C
5Alkene reduction and isomery carbon five tertiary olefin increment rates are as shown in table 2 with the Changing Pattern in reaction time.
Table 2, catalyst C are at the long-pending air speed 9.0h of liquid
-1Continuous 100 hours down stability running
From the result of table 2 as can be seen, use catalyst C of the present invention and carry out hydrogenation reaction, the pentadiene hydrogenation conversion up to 100%, C
5The alkene reduction is low to be no more than 1%, and isomery carbon five tertiary olefin increment rates are about 2%; Adopt catalyst A, E and F to carry out above-mentioned test, also obtain similar result.
Illustrate that catalyst of the present invention has higher diolefin hydrogenation activity and selectivity, and have good stable.
Claims (9)
1, a kind of diene selection hydrogenation catalyst, it is the γ-Al that adopts through 900 ℃～1200 ℃ of roastings
2O
3For carrier, metal Ni are that active component constitutes, activity component load quantity is 5～25%wt, and described γ-Al
2O
3Bulk density 0.65～the 0.75g/mL of carrier, pore volume 0.4～0.5mL/g, the aperture accounts for more than 70% greater than the hole of 4nm, and specific area is greater than 100m
2/ g.
2, the described catalyst of claim 1, the load capacity of wherein said reactive metal Ni is 8～20%wt.
3, the described catalyst of claim 1, this catalyst are drying behind the carrier to load metal nickel, 0～2 hour product of 250 ℃～350 ℃ roastings.
4, claim 1 or 3 described catalyst, this catalyst is described γ-Al
2O
3Product after handling through hydrogen reducing and 10-60 ℃ of presulfurization in following 0.1-5 hour behind the carrier to load metal Ni.
5, the preparation method of each described diene selection hydrogenation catalyst of claim 1～4 comprises step:
With γ-Al
2O
3900 ℃～1200 ℃ roastings 1～5 hour;
Adopt infusion process that metal Ni is carried on the alumina support after the roasting;
Dry under 100 ℃～180 ℃, 250 ℃～350 ℃ roastings 0～2 hour.
6, the described preparation method of claim 5, it further comprises the catalyst that obtains is carried out hydrogen reducing and presulfurization step, wherein, the hydrogen reducing condition is for to reduce resulting catalyst 3～8 hours with hydrogen under 350 ℃～450 ℃, the reduction pressure be normal pressure to 0.3MPa, the reducing gases air speed is 420～600h under the STP
-1The presulfurization treatment step is included under 10 ℃～60 ℃ the catalyst after the hydrogen reduction was implemented vulcanizing treatment 0.1～5 hour.
7, the described preparation method of claim 5 wherein, during infusion process carried metal Ni, is mixed with the γ-Al of maceration extract after to roasting with water soluble nickel salt water or anhydrous polar solvent
2O
3Carrier floods.
8, the described preparation method of claim 7, described water soluble nickel salt are nitrate, acetate or the chlorate of Ni; Described anhydrous polar solvent is propyl alcohol, isopropyl alcohol, methyl alcohol, ethanol, acetate or formic acid.
9, to catalytic light gasoline or C
5Cut carries out pretreated method, comprise and adopt the described diene selection hydrogenation catalyst of claim 1 to contact that realize the selective hydrogenation of dienes reaction, the reaction pressure scope is 1.0MPa～4.0MPa with pending oil product, temperature is higher than 55 ℃, and the hydrogen to oil volume ratio scope is 10: 1～60: 1 under the STP.
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Families Citing this family (6)
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| CN102580751A (en) * | 2011-01-11 | 2012-07-18 | 中国石油大学(北京) | Diene selectivity hydrogenation catalyst and preparation method thereof |
| CN102909047A (en) * | 2012-10-25 | 2013-02-06 | 兰州理工大学 | Dinitrotoluene catalytic hydrogenation catalyst and preparation method thereof |
| CN104557408A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A selective hydrogenation method for a light C5 fraction |
| CN106925275B (en) * | 2015-12-31 | 2020-01-07 | 中国石油天然气股份有限公司 | Ti-Fe-Ni selective hydrogenation catalyst, preparation method and application thereof |
| CN107573239B (en) * | 2016-07-05 | 2021-02-12 | 中国石油化工股份有限公司 | Synthetic method of tert-amyl acetate |
| CN114433094B (en) * | 2020-10-20 | 2024-01-09 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
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