CN1506163A - Aluminia carrier and hydrogenating catalyst with the carrier - Google Patents

Aluminia carrier and hydrogenating catalyst with the carrier Download PDF

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CN1506163A
CN1506163A CNA021552126A CN02155212A CN1506163A CN 1506163 A CN1506163 A CN 1506163A CN A021552126 A CNA021552126 A CN A021552126A CN 02155212 A CN02155212 A CN 02155212A CN 1506163 A CN1506163 A CN 1506163A
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alumina
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carrier
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roasting
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CN1219600C (en
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刘百军
郑宇印
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China University of Petroleum Beijing
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Abstract

The present invention relates to alumina carrier for high activity hydrogenating catalyst and the hydrogenating catalyst with the carrier. The alumina carrier of the present invention is prepared through mixing alumina sol and alumina, drying and roasting. The alumina carrier has average pore size 2-10 nm, porosity of 0.5-1.0 ml/g and specific surface area 200-400 sq m/g. The hydrogenating catalyst of the present invention is prepared through soaking the carrier to obtain Mo and Ni as active components, drying and roasting. The hydrogenating catalyst is suitable for use in hydrodesulfurization and hydrodenitrification of light oil fraction and heavy oil fraction and hydro-saturation of aromatic hydrocarbon.

Description

Alumina supporter and the hydrogenation catalyst that utilizes this carrier to obtain
Technical field
The present invention relates to the preparation of hydrogenation catalyst, relate to a kind of can be used for the preparing alumina supporter of high-activity hydrogenation catalyst and the hydrogenation catalyst that utilizes this carrier to obtain specifically.
Background of invention
Al 2O 3Have bigger serface, high stability and be used as support of the catalyst, be used widely, relevant Al at oil, chemical field 2O 3The preparation of carrier and modification technology research are one of important contents of scientific worker and each big catalyst Co. research always, and its performance as support of the catalyst also is greatly improved.
United States Patent (USP) (USP 4,820,679) has been introduced a kind of preparation method of catalyst carrier for hydrgenating aluminum oxide.This method uses alkaline aqueous solution (as NaAlO 2) and one or more acid aluminium salt aqueous solution [Al for example 2(SO 4) 3], at 20～90 ℃, pH neutralizes under 5.5～10 conditions, and in pH is 11～12 scopes aging 150 minutes, in the washing and Al (OH) 3The water-sol is with nickel salt and molybdenum or tungsten salt brine solution, with Al (OH) 3Hydrogel is 4～10 times pulps at 25～100 ℃, pH, makes metal adsorption, contains NiO 1～6% and MoO up to final catalyzer 38～22% or WO 310～40%, extruded moulding then is 300～900 ℃ of roastings.The specific surface area that finally obtains catalyzer is greater than 300m 2/ g, at least 70% pore volume concentrate on＜aperture 7nm.
European patent (EP 0,201,949) has been introduced narrow pore distribution Al 2O 3The preparation process of carrier.This preparing carriers method is (as H with the P contained compound bialuminate aqueous solution 3PO 4+ AlCl 3) and basic aluminate (NaAlO 2Or KAlO 2), neutralize under 5.5～10 conditions at 20～90 ℃, pH, again 20～90 ℃ aging 15 minutes at least, and after-filtration, repetitive scrubbing and filtration again, in removing and the time impurity that brings, in 50～150 ℃ of dryings, roasting in 300～900 ℃ of scopes, make γ-Al 2O 3This Al 2O 3The carrier specific surface area is greater than 300m 2/ g, pore volume 0.35～0.65mL/g, at least 80% or 90% aperture is less than 5nm, this Al 2O 3Contain P 0.1～4.5% (wt).
United States Patent (USP) (USP 3,864,461) has reported that heap is than little Al 2O 3The preparation method of carrier.To contain Al 2O 32～7.5% NaAlO 2The aqueous solution is added in 12～35 ℃ or 45～70 ℃ of scopes and contains Al 2O 32～6% Al 2(SO 4) 3In the aqueous solution, make Al earlier 2(SO 4) 3Residue 10%, most of Al (OH) that forms under acidic conditions 3Precipitation then adds superfluous 10%NaAlO 2Solution in pH7.3～10 scopes, makes aluminium salt be precipitated as Al (OH) fully 3, Al in the slurries 2O 3Content 2～7%, filtration, washing, filter cake are dry under＜100 ℃, 300～400 ℃ of roastings.
Chinese patent (CN 1141821A) has been set forth a kind of preparation method of catalyst carrier for hydrgenating, to contain aluminum ions acidic aqueous solution and contain or do not contain aluminum ions alkaline aqueous solution and add simultaneously in the water purification under stirring, 30～85 ℃ of neutral temperatures, pH6～10 neutralize, after the digestion time 0.25～8 hour, filter, wash, dry under 50～150 ℃, promptly get Al 300～700 ℃ of following roastings 2O 3Carrier.Mean pore size 7～the 12nm of carrier, pore volume 0.7～1.2mL/g, specific surface area 250～500mu/g.
Find out that from above technology formerly the preparation of alumina supporter all is to adopt the ordinary method preparation, the not too big raising of the performance of the aluminum oxide of preparation.
Above-mentioned patent is spoken of with Al (OH) in (USP 4,820,679) 3The water-sol directly is added to aqueous metal salt, makes catalyzer, and following drawback is arranged: the catalyzer crushing strength is low, rate of wear is big; Extruded moulding is difficult; Generate NiAl easily 2O 4Or CoAl 2O 4Spinel is difficult for during sulfuration being reduced to sulfide and influences activity of such catalysts.
Rickle compares Al 2O 3The preparing carriers method, reality is the soda acid swing method, the difference of operational condition can make repeatability relatively poor, the difficult quality guarantee of the alumina supporter of preparation.
The macropore of being set forth among the Chinese patent CN 1141821A, the preparation of alumine with high specific surface area carrier are to adopt aluminum soluble salt as precursor, use P, SiO 2, the zeolite after γ type, X type, ZSM, β zeolite and the modification thereof regulates the acid-basicity of alumina supporter, thereby the preparation cost of carrier is very high.
Summary of the invention
The present invention proposes a kind of alumina supporter that is different from prior art, utilize this carrier can obtain having the higher catalyst activity and the Hydrobon catalyst of excellent stability.
The present invention also provides the preparation method of described alumina supporter.
The invention allows for and utilize the resulting hydrogenation catalyst of above-mentioned alumina supporter load active component, this catalyzer has higher hydrogenation activity and stability.
The present invention is on the basis with macropore, bigger serface, alumina supporter that bulk density is lower, modification by alumina sol, change the pore structure and the surface acid alkalescence matter of alumina supporter, alumina supporter is more suitable in the carrier as catalysts such as gasoline, diesel hydrogenation for removal sulphur, hydrodenitrification, aromatic hydrogenation are saturated.
According to technical scheme of the present invention, with after aluminum oxide mixes, dry, roasting forms described alumina supporter by alumina sol, and the mean pore size of this carrier is 2～10nm, and pore volume is 0.5～1.0mL/g, and specific surface area is 200～400m 2/ g.
Wherein, described alumina sol preferably forms through the hydration dispergation as precursor with pseudo-boehmite, boehmite or amorphous alumina, and aluminum oxide then can directly use and be purchased product.
The present invention also provides the preparation method of alumina supporter, comprise alumina sol is mixed with aluminum oxide afterwards to descend dry 1～48 hour at 70～160 ℃, 300～700 ℃ of following roastings 2～48 hours, wherein the weight ratio of alumina sol and aluminum oxide was 1～200: 100 then.
Reach as previously described, alumina sol of the present invention preferably forms through the hydration dispergation as precursor with pseudo-boehmite, boehmite or amorphous alumina or material with similarity, and this process comprises:
(1) the alumina sol precursor is mixed with water, the blended part by weight is 0.1～20: 100, is preferably 1～20: 100;
(2) the pH value with said mixture is adjusted to 2.5～6.8, is preferably 3.0～5.0, then at 40～100 ℃ of dispergation;
(3) mixture behind the dispergation was 50～100 ℃ of following ageings 3～48 hours; Preferably 60～90 ℃ of following ageings 5～24 hours.
The alumina sol that is obtained by said process mixes the back drying with conventional aluminum oxide and roasting can obtain required alumina supporter, and wherein, used aluminum oxide is preferably γ, η, θ or χ aluminum oxide, preferably uses γ-Al 2O 3
The catalyzer of hydrogenation reactions such as the hydrogenating desulfurization that is suitable for gasoline, diesel oil, hydrodenitrification, the aromatic hydrocarbons that utilize above-mentioned carrier to obtain are saturated is provided according to a further aspect in the invention.Catalyzer of the present invention is to utilize described alumina supporter to form through dipping active ingredient after drying, roasting, and described active ingredient comprises molybdenum and nickel.
Contain in the above-mentioned hydrogenation catalyst of the present invention that (with the weight after the catalyzer roasting is benchmark, wt%): MoO 310.0～25.0%, NiO 2.5～8.0%, surplus is Al 2O 3Preferably, contain in this catalyzer: MoO 312.0-20.0%, NiO 3.0～5.0%, and surplus is Al 2O 3
This hydrogenization catalyst preparation method comprises: with alumina supporter and the aqueous solution that contains molybdenum, nickel salt by the equi-volume process hybrid infusion, 80～150 ℃ dry 2～24 hours down, roasting is 2～48 hours in 300～700 ℃ of air.
The preferred scheme according to the present invention, the described aqueous solution that contains molybdenum salt comprises ammonium molybdate, the aqueous solution that contains nickel salt comprises nickelous nitrate, nickel acetate, preferably nickelous nitrate; Preferably 400～550 ℃ of described maturing temperatures, roasting time is preferably 3～6 hours.
Adopt the hydrogenation catalyst of alumina supporter preparation of the present invention to be applicable to that hydrogenating desulfurization, hydrodenitrification and the aromatic hydrogenation of light oil distillate, heavy oil fraction are saturated.Before the reaction, catalyzer must be through prevulcanized, 280～370 ℃ of temperature of reaction, and pressure 2.0～4.0MPa, liquid air speed 1～10h -1, under the condition of hydrogen-oil ratio 500～1500, the extrusion rate that can make the model compound thiophene is greater than 95%.
Compare with traditional method, creativeness of the present invention is: by commercially available or normally used alumina supporter is carried out secondary treatment, changed the surface tissue and the surface properties of alumina supporter,, improved the hydrogenation activity and the stability of catalyzer with this carrier as hydrogenation catalyst.Actual conditions and operation as for described hydrogenation catalyst preparation all are easy to realize to those skilled in the art.
Specific embodiments
The technical characterstic that the invention is further illustrated by the following examples; the purpose of these embodiment is to help the reader to understand essence of the present invention and the effect that is had better; can not limit practical range of the present invention, any modification made on this basis and change all should be in protection scope of the present invention in every case.
Embodiment 1: the preparation of alumina sol
The 120g pseudo-boehmite is mixed with 1000mL water, and adding the nitre acid for adjusting pH value is 3.5, is warming up to 75 ℃, and continuously stirring 10 hours promptly gets alumina sol.
Embodiment 2: the preparation of alumina supporter
The alumina sol of getting 40mL embodiment 1 preparation mixes with the 40g gama-alumina, soaks 3 hours, and 110 ℃ of dryings 10 hours, roasting was 3 hours in 500 ℃ of air, obtains carrier 1 then.
Embodiment 3: the preparation of alumina supporter
Get the alumina sol of 30mL embodiment 1 preparation, add 10mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 500 ℃ of air, obtains carrier 2.
Embodiment 4: the preparation of alumina supporter
Get the 20mL alumina sol, add 20mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 500 ℃ of air, obtains carrier 3.
Embodiment 5: the preparation of alumina supporter
Get the 10mL alumina sol, add 30mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 500 ℃ of air, obtains carrier 4.
Embodiment 6: the preparation of alumina supporter
Get 5 mL alumina sols, add 35mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 500 ℃ of air, obtains carrier 5.
Embodiment 7: the preparation of alumina supporter
Get the 30mL alumina sol, add 10mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 450 ℃ of air, obtains carrier 6.
Embodiment 8: the preparation of alumina supporter
Get the 30mL alumina sol, add 10mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 400 ℃ of air, obtains carrier 7.
Embodiment 9: the preparation of alumina supporter
Get the 20mL alumina sol, add 20mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 450 ℃ of air, obtains carrier 8.
Embodiment 10: the preparation of alumina supporter
Get the 20mL alumina sol, add 20mL water, mix with the 40g gama-alumina then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 400 ℃ of air, obtains carrier 9.
Embodiment 11: the preparation of alumina supporter
Get the 30mL alumina sol, add 10mL water, mix with 40g η-aluminum oxide then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 450 ℃ of air, obtains carrier 10.
Embodiment 12: the preparation of alumina supporter
Get the 30mL alumina sol, add 10mL water, mix with 40g θ-aluminum oxide then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 450 ℃ of air, obtains carrier 11.
Embodiment 13: the preparation of alumina supporter
Get the 30mL alumina sol, add 10mL water, mix with 40g χ-aluminum oxide then, soaked 3 hours, 110 ℃ of dryings 10 hours, roasting is 3 hours in 450 ℃ of air, obtains carrier 12.
Table 1 is listed the physical data of above-mentioned 12 kinds of carrier liquid nitrogen determining adsorptions.
The physical data of table 1 alumina supporter
Carrier Specific surface area m 2/g Pore volume mL/g Mean pore size nm
????1 ????202.1 ????0.56 ????5.2
????2 ????225.5 ????0.55 ????5.8
????3 ????240.3 ????0.60 ????5.8
????4 ????290.5 ????0.65 ????4.8
????5 ????350.2 ????0.67 ????6.1
????6 ????235.9 ????0.54 ????6.2
????7 ????240.4 ????0.55 ????6.0
????8 ????246.2 ????0.61 ????6.1
????9 ????262.2 ????0.64 ????7.0
????10 ????208.1 ????0.70 ????6.8
????11 ????285.0 ????0.54 ????4.2
????12 ????213.9 ????0.68 ????4.5
Embodiment 14: Preparation of catalysts
Get the alumina supporter 7.0g for preparing among the embodiment 2-embodiment 13 respectively, add the 8.2mL ammonium molybdate aqueous solution, 50 ℃ were soaked 3 hours down, 110 ℃ of dryings 10 hours, and roasting is 3 hours in 500 ℃ of air; On the above-mentioned aluminum oxide basis that contains ammonium molybdate, add the 8.2mL nickel nitrate aqueous solution then, 50 ℃ were soaked 3 hours down, 110 ℃ of dryings 10 hours, and roasting is 3 hours in 500 ℃ of air, obtains catalyzer 1～catalyzer 12.
Comparative example 1
Get commercially available alumina supporter 7.0g, add the 8.2mL ammonium molybdate aqueous solution, 50 ℃ were soaked 3 hours down, 110 ℃ of dryings 10 hours, and roasting is 3 hours in 500 ℃ of air; On the above-mentioned aluminum oxide basis that contains ammonium molybdate, add the 8.2mL nickel nitrate aqueous solution then, 50 ℃ were soaked 3 hours down, 110 ℃ of dryings 10 hours, and roasting is 3 hours in 500 ℃ of air, obtains catalyzer 13.
The test example
Present embodiment is the use experiment of catalyzer.
On continuous micro-reactor, come evaluation of catalyst activity with the thiophene hydrogenolysis.
Catalyzer loading amount: 0.50g catalyzer (40～60 order) and 2.50g quartz sand (40～60 order) mixing.Feeding contains H 2The H of S 10% (volume ratio) 2S and H 2Mixed gas, 30mL/min is warmed up to 400 ℃ with the temperature rise rate of 20 ℃/min and kept 3 hours, is cooled to 360 ℃ of temperature of reaction then, and the hydrogen sulfide mixed gas is switched to hydrogen, advances reaction mass, reaction mass consist of 10% thiophene and 90% hexanaphthene.Volume space velocity 4～8h -1, hydrogen-oil ratio 600～1000, after the charging 84, the time sampling analysis.The evaluation result of all catalyzer sees Table 1.Hydrodesulfurization reaction (HDS) activity is calculated as follows:
Figure A0215521200111
The result finds out from table 2, and with the catalyzer of method preparation provided by the invention, its HDS activity is better than the catalyzer of art methods preparation.
Table 2 catalyst property and HDS activity
Catalyzer Chemical constitution ????HDS％ Relative reactivity
????MoO 3 ????NiO
????1 ????13.6 ????4.0 ????97.1 ????149
????2 ????13.6 ????4.0 ????94.5 ????145
????3 ????13.6 ????4.0 ????94.5 ????145
????4 ????13.6 ????4.0 ????92.0 ????141
????5 ????13.6 ????4.0 ????91.5 ????140
????6 ????13.6 ????4.0 ????93.0 ????143
????7 ????13.6 ????4.0 ????78.6 ????121
????8 ????13.6 ????4.0 ????89.8 ????138
????9 ????13.6 ????4.0 ????86.0 ????132
????10 ????13.6 ????4.0 ????77.3 ????119
????11 ????13.6 ????4.0 ????78.1 ????120
????12 ????13.6 ????4.0 ????72.2 ????111
????13 ????13.6 ????4.0 ????65.0 ????100

Claims (11)

1, a kind of alumina supporter, with after aluminum oxide mixes, dry, roasting forms by alumina sol, and the mean pore size of this carrier is 2～10nm, and pore volume is 0.5～1.0mL/g, and specific surface area is 200～400m 2/ g.
2, the described alumina supporter of claim 1, wherein, described alumina sol is to form through the hydration dispergation as precursor with pseudo-boehmite, boehmite or amorphous alumina.
3, the preparation method of the described alumina supporter of claim 1, comprise alumina sol is mixed with aluminum oxide afterwards to descend dry 1～48 hour at 70～160 ℃, 300～700 ℃ of following roastings 2～48 hours, wherein the weight ratio of alumina sol and aluminum oxide was 1～200: 100 then.
4, the described preparation method of claim 3, wherein alumina sol is to form through the hydration dispergation as precursor with pseudo-boehmite, boehmite or amorphous alumina, this process comprises:
(1) the alumina sol precursor is mixed with water, the blended part by weight is 0.1～20: 100;
(2) the pH value with said mixture is adjusted to 2.5～6.8, then at 40～100 ℃ of dispergation;
(3) mixture behind the dispergation was 50～100 ℃ of following ageings 3～48 hours.
5, claim 3 or 4 described preparation methods, wherein, aluminum oxide is γ, η, θ or χ aluminum oxide.
6, claim 1 or 2 application of described alumina supporter in catalyst for hydrogenation.
7, the described application of claim 6, described hydrogenation reaction comprises the hydrogenating desulfurization of gasoline, diesel oil, hydrodenitrification, the hydrogenation reaction that aromatic hydrogenation is saturated.
8, a kind of catalyst for hydrogenation is to utilize claim 1 or 2 described alumina supporters to form through dipping active ingredient after drying, roasting, and described active ingredient comprises molybdenum and nickel.
9, the described catalyzer of claim 8 wherein, contains in this catalyzer: MoO 310.0～25.0%, NiO 2.5～8.0%, surplus is Al 2O 3
10, claim 8 or 9 described Preparation of catalysts methods comprise: with alumina supporter and the aqueous solution that contains molybdenum, nickel salt by the equi-volume process hybrid infusion, 80～150 ℃ dry 2～24 hours down, roasting is 2～48 hours in 300～700 ℃ of air.
11, the described preparation method of claim 10, wherein, the described aqueous solution that contains molybdenum salt comprises ammonium molybdate, the aqueous solution that contains nickel salt comprises nickelous nitrate, nickel acetate.
CN 02155212 2002-12-06 2002-12-06 Aluminia carrier and hydrogenating catalyst with the carrier Expired - Fee Related CN1219600C (en)

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CN100389171C (en) * 2004-08-31 2008-05-21 中国石油化工股份有限公司 Catalytic cracking adjuvant and its preparing method
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CN102259901A (en) * 2011-05-23 2011-11-30 华东理工大学 Hierarchical aluminium oxide and catalysis application thereof
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CN102259901B (en) * 2011-05-23 2013-05-22 华东理工大学 Hierarchical aluminium oxide and catalysis application thereof
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CN105214677A (en) * 2014-07-03 2016-01-06 中国石油化工股份有限公司 Nickel-base catalyst
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CN106512918A (en) * 2016-11-16 2017-03-22 上海绿强新材料有限公司 An alkali-modified alumina material having a high specific surface area, a preparing method thereof and applications of the material
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