CN1236851C - Method for preparing hydrofining catalyst carrier - Google Patents

Method for preparing hydrofining catalyst carrier Download PDF

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CN1236851C
CN1236851C CN 02148856 CN02148856A CN1236851C CN 1236851 C CN1236851 C CN 1236851C CN 02148856 CN02148856 CN 02148856 CN 02148856 A CN02148856 A CN 02148856A CN 1236851 C CN1236851 C CN 1236851C
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alumina
carrier
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gama
aluminium oxide
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CN1502676A (en
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刘百军
黄伟莉
郑宇印
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China National Petroleum Corp
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China National Petroleum Corp
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Abstract

The present invention relates to a method for preparing hydrofining catalyst carriers prepared by mixing eta-aluminum oxide with gamma-aluminum oxide. In the preparation method, precursors AlCl3 of the eta-aluminum oxide are loaded to the surface of the gamma-aluminum oxide by an immersion method at normal temperature and are washed after being treated by ammonia water, and the hydrofining catalyst carriers are prepared by drying for 1 to 24 hours at 80 to 150 DEG C and calcining for 2 to 24 hours at 300 to 700 DEG C. The average pore size of the obtain carriers is from 5 to 10 nm, and the pore volumes of the obtain carriers are from 0.6 to 1.2 ml/g; the specific surface areas of the obtained carriers are from 150 to 400 m. The present invention is suitable for catalyst carriers of hydrodesulphurization, hydrodenitrogenation and aromatic saturation of diesel oil and hydrofining catalyst carriers of heavy distillate oil.

Description

A kind of preparation method of hydrofining catalyst carrier
Technical field
The invention belongs to preparation method of hydrofining catalyst carrier, is by AlCl 3After mixing with gama-alumina, the alumina support that the η-aluminium oxide that obtains through precipitation, washing, dry, roasting mixes with gama-alumina.
The average pore size of the carrier that η-aluminium oxide of the present invention mixes with gama-alumina is 5 ~ 10nm, and pore volume is 0.6 ~ 1.2ml/g, specific area 150 ~ 400m 2/ g is suitable for the carrier of the Hydrobon catalyst of the carrier of hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbon saturation catalyst of diesel oil and heavy distillate.
The objective of the invention is on basis, to pass through AlCl with macropore, bigger serface, alumina support that bulk density is lower 3Modification, change surface texture, pore structure and the surface acid alkalescence matter of alumina support, alumina support is more suitable in the carrier as diesel oil and mink cell focus hydrodesulfurization, hydrodenitrogeneration, hydrocatalyst for saturating arylhydrocarbon.
Background technology
Al 2O 3Have bigger serface, high stability and be used as catalyst carrier, 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 catalyst carrier also is greatly improved.
EP 0,201, and 949 have introduced narrow pore size distribution Al 2O 3The preparation process of carrier.This preparing carriers method is (as H with the phosphorus-containing 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, then filter, cyclic washing 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 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 P0.1～4.5% (wt).
USP 4,820, and 679 have revealed a kind of method for preparing catalyst, relate to the preparation of alumina support.This method uses alkaline aqueous solution (as NaAlO 2) and one or more acid aluminium salt aqueous solution as [as Al 2(SO 4) 3], at 20～90 ℃, pH is 5.5～10 neutralizations, in pH11～12 scopes aging 150 minutes, and in the washing and Al (OH) 3The hydrosol with nickel salt and molybdenum or tungsten saline solution, is 4～10 times pulps with hydrogel at 25～100 ℃, pH, makes metal adsorption, contains NiO1～6% and MoO up to final catalyst 38～22% or WO 310～40%, extruded moulding then is 300～900 ℃ of roastings.The specific area that obtains catalyst is greater than 300m 2/ g, at least 70% pore volume concentrate on＜aperture 7nm.
USP 3,864, and 461 have 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 acid condition 3Precipitation then adds superfluous 10%NaAlO 2Solution in pH7.3～10 scopes, makes its precipitation fully, Al in the slurries 2O 3Content 2～7%, filtration, washing, filter cake are dry under＜100 ℃, 300～400 ℃ of roastings.
Chinese patent CN1141821A has 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, in and pH6～10, after the ageing time 0.25～8 hour, filter, wash, dry under 50～150 ℃, promptly get Al 300～700 ℃ of following roastings 2O 3Carrier.Average pore size 7～the 12nm of carrier, pore volume 0.7～1.2ml/g, specific area 250～500m 2/ g.
Chinese patent CN1273878A has set forth a kind of preparation method of aluminium oxide-titanium oxide bicomponent.Adopt the solubility titanium salt to add the mixed solution and the NaAlO of aluminum soluble salt 2The aqueous solution also flows the coprecipitation preparation, and in this Ti-Al bi-component, the titanium oxide mass fraction is 0.5～50%.
Find out from above patent, pore distribution concentration aperture＜5nm or＜alumina support of 7nm (EP 0,201,949, USP 4,820,679 and USP 3,864,461) not too is suitable for the hydrotreatment of heavy distillate.
Above-mentioned patent is spoken of with Al (OH) in (USP 4,820,679) 3The hydrosol directly adds aqueous metal salt, makes catalyst, and following drawback is arranged: the catalyst crushing strength is low, rate of wear is big; Extruded moulding is difficult; Generate NiAl easily 2O 4Or CoAl 2O 4Spinelle 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, its repeatability is relatively poor, the difficult quality guarantee of the alumina support of preparation.
The macropore that Chinese patent CN 1141821A is set forth, the preparation of alumine with high specific surface area carrier are to adopt aluminum soluble salt as predecessor, use P, SiO 2, the zeolite after Y type, X type, ZSM, β zeolite and the modification thereof regulates the Acidity of Aikalinity of alumina support, the preparation cost of carrier is very high
The aperture of aluminium oxide-titanium oxide bicomponent carrier is less, and specific area is little, also not too is suitable for the hydrotreatment of heavy distillate.
Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation has the hydrodesulfurization catalyst support of higher catalyst activity and excellent stability.
The objective of the invention is to realize: with the predecessor such as the A1Cl of η-aluminium oxide by following scheme 3Load to the gama-alumina surface by infusion process, after WITH AMMONIA TREATMENT, washing, drying, the alumina support that roasting obtains mixing, last step impregnation active component molybdenum, nickel etc., drying, roasting prepare catalyst.
Concrete preparation method of the present invention:
1. at normal temperatures with the predecessor AlCl of η-aluminium oxide 3Load to the gama-alumina surface by infusion process, after WITH AMMONIA TREATMENT, washing, drying is 1～24 hour under 80～150 ℃, forms in 2～24 hours 300～700 ℃ of following roastings.The average pore size of gained carrier is 5～10nm, and pore volume is 0.6～1.2ml/g, specific area 150～400m 2/ g.
2. the predecessor of η-aluminium oxide is AlCl 3, Al (NO 3) 3, Al 2(SO 4) 3, organo-aluminium etc., be preferably AlCl 3
3. with AlCl 3With the gama-alumina hybrid infusion, the ratio of its mixing is 0.01～10: 100 (wt: wt), be preferably 0.05～5: 100 (wt: wt)
4. with the regulating the pH value with ammoniacal liquor and be adjusted to 9～13 of 3 mixtures that obtain, be preferably 10～12.
5. the mixture that step 3 and 4 is obtained washes with water to no Cl -Ion.
With the mixture of step 5 50～150 ℃ of dryings 3～100 hours, be preferably under 80～110 ℃ of conditions and worked 10～24 hours.
With the mixture of step 6 300～700 ℃ of following roastings 2～24 hours, preferably 300～500 ℃ of following roastings 5～10 hours.
8. the mixed oxidization alumina supporter that step 7 is obtained and the aqueous solution that contains molybdenum, nickel is by the equi-volume process hybrid infusion, and under 80～150 ℃ of conditions dry 2～24 hours, 300～700 ℃ of following roastings were 2～24 hours in the air, promptly get required catalyst.
The aqueous solution of described step 8 molybdenum salt is preferably ammonium molybdate, and the aqueous solution that contains nickel salt is nickel nitrate, nickel acetate, preferably nickel nitrate.
Preferably 400～550 ℃ of described catalyst sintering temperatures, roasting time is 3～6 hours.
(with the weight after the catalyst roasting is benchmark to Zhi Bei catalytic component content, wt%): MoO according to the method described above 310.0～25.0%, NiO2.5～8.0%, surplus is Al 2O 3Preferably: MoO 312.0～20.0%, NiO3.0～5.0%, surplus is Al 2O 3
Catalyst according to alumina support preparation of the present invention is applicable to that hydrodesulfurization, hydrodenitrogeneration and the aromatic hydrogenation of light oil distillate, heavy oil fraction are saturated.Before the reaction, catalyst must be through presulfurization, 280～370 ℃ of reaction temperatures, and pressure 2.0～4.0MPa, liquid air speed 1～10h -1, hydrogen-oil ratio 500～1500, the extrusion rate that can make model compound thiophene phenol is greater than 95%.
Compare with conventional method, the invention has the advantages that: commercially available alumina support is carried out after-treatment, change the surface texture and the surface nature of alumina support,, improved the hydrogenation activity and the stability of catalyst with this carrier as hydrogenation catalyst.
Concrete enforcement
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
With 30mlAlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 10.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 1 that η-aluminium oxide mixes with gama-alumina.
Embodiment 2
With 20ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 10.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 2 that η-aluminium oxide mixes with gama-alumina.
Embodiment 3
With 10ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 10.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 3 that η-aluminium oxide mixes with gama-alumina.
Embodiment 4
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 11.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 4 that η-aluminium oxide mixes with gama-alumina.
Embodiment 5
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 12.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 5 that η-aluminium oxide mixes with gama-alumina.
Embodiment 6
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 9.0,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 6 that η-aluminium oxide mixes with gama-alumina.
Embodiment 7
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 12.5,50 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 7 that η-aluminium oxide mixes with gama-alumina.
Embodiment 8
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 12.5,80 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 8 that η-aluminium oxide mixes with gama-alumina.
Embodiment 9
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 12.5,90 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 120 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained mixed oxidization alumina supporter 9.
Embodiment 10
With 30ml AlCl 3With 100g γ-Al 2O 3Mix, adding ammoniacal liquor adjusting pH value is 12.5,60 ℃ of ageings 10 hours, is washed till no Cl with the 500ml deionized water -Ion, 110 ℃ of dryings 10 hours, 350 ℃ of roastings 5 hours obtained the alumina support 10 that η-aluminium oxide mixes with gama-alumina.
Embodiment 11
Preparation of catalysts.
Get the alumina support 7.0g that η-aluminium oxide of embodiment 1～embodiment 10 mixes with gama-alumina, 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 aluminium 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 catalyst 1 ~ catalyst 10
Comparative example 1
Get commercially available γ-Al 2O 3Carrier 7.0g adds the 8.2ml ammonium molybdate aqueous solution, and 50 ℃ were soaked 3 hours down, 110 ℃ of dryings 10 hours, and roasting is 3 hours in 500 ℃ of air; On the above-mentioned aluminium 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 catalyst 11.
Embodiment 12
Present embodiment is the use experiment of catalyst.
On continuous micro-reactor, come evaluation of catalyst activity with thiophene phenol hydrogenolysis.Catalyst loading amount: 0.20g catalyst (40～60 order) and 1.0g quartz sand (40～60 order) mixing.Feeding contains H 2S10% (volume ratio) H 2S and H 2Mist, 30ml/min is warmed up to 400 ℃ with the heating rate of 20 ℃/min and kept 2 hours, is cooled to 360 ℃ of reaction temperatures then, and the hydrogen sulfide mist is switched to hydrogen, advances reaction oil, reaction oil consist of 10% thiophene phenol and 90% cyclohexane.Volume space velocity 4 ~ 8h -1, hydrogen-oil ratio 600 ~ 1000,5 hours sample analysis after the oil-feed, later per 1 hour sample analysis is once.The evaluation result of all catalyst sees Table 1.The HDS activity is calculated as follows:
Figure C0214885600101
The result finds out from table 1, and with the catalyst of method preparation provided by the invention, its HDS activity is better than the catalyst of art methods preparation.
Table 1 Preparation of Catalyst and HDS activity
Catalyst Chemical composition HDS％ Relative activity
MoO 3 NiO
1 2 3 4 5 6 7 8 9 10 11 13.6 13.6 13.6 13.6 13.6 13.6 13.6 13.6 13.6 13.6 13.6 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 96.5 95.0 94.8 92.3 92.5 93.0 89.8 78.5 75.4 72.0 65.0 148 146 146 142 142 143 138 121 116 111 100

Claims (6)

1. preparation method of hydrofining catalyst carrier, it is to prepare to gama-alumina by dip loading under the predecessor normal temperature of η-aluminium oxide, its characterization step is: 1. will be with AlCl 3, Al (NO 3) 3, Al 2(SO 4) Cl 3, or organo-aluminium be the predecessor and the gama-alumina hybrid infusion of η-aluminium oxide, the predecessor of η-aluminium oxide and the part by weight of gama-alumina are 0.01-10: 100; 2. the mixture that 1. step is obtained is 9-13 with ammoniacal liquor adjusting pH value; 3. step mixture 2. is washed with water to no Cl ion; 4. the mixture of 3. step being removed the Cl ion descended dry 3-100 hour at 80-150 ℃; 5. with the 4. dried mixture of step at 300-700 ℃ of following roasting 2-24 hour, obtaining average pore size is 5-10nm, pore volume is 0.6-1.2ml/g, specific area 150-400m 2The carrier of/g.
2. according to the described preparation method of hydrofining catalyst carrier of claim 1, it is characterized in that the predecessor AlCl3 of η-aluminium oxide of being adopted and the weight ratio of gama-alumina are 0.1-5: 100.
3. according to the described preparation method who adds the refining catalytic agent carrier of claim 1, it is characterized in that the 2. predecessor AlCl of η-aluminium oxide of above-mentioned steps 3With gama-alumina mixture WITH AMMONIA TREATMENT, regulating pH value with ammoniacal liquor is 10-12.
4. described according to claim 1 is preparation method of hydrofining catalyst carrier, it is characterized in that: the drying of the mixture after the 3. middle washing of above-mentioned steps, and its baking temperature is 80-150 ℃, be 3-100 hour drying time.
5. according to the described preparation method of hydrofining catalyst carrier of claim 1, it is characterized in that the 5. roasting of dried mixture of above-mentioned steps, its sintering temperature is 300-700 ℃, roasting time 5-10 hour.
7. according to the described preparation method of hydrofining catalyst carrier of claim 1, it is characterized in that: above-mentioned resulting carrier, with this carrier with the aqueous solution of molybdenum or nickel salt flood prepare be used for diesel hydrogenation for removal sulphur, denitrogenation, aromatic hydrocarbons is saturated and the Hydrobon catalyst of heavy distillate.
CN 02148856 2002-11-22 2002-11-22 Method for preparing hydrofining catalyst carrier Expired - Fee Related CN1236851C (en)

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