CN103785405B - A kind of Hydrodemetalation catalyst and preparation method thereof - Google Patents
A kind of Hydrodemetalation catalyst and preparation method thereof Download PDFInfo
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Abstract
Open a kind of Hydrodemetalation catalyst of the present invention and preparation method thereof.This catalyst is with aluminium oxide as carrier, and with Mo and Ni as metal component, content meter by weight in final catalyst, containing the MoO of 4 ~ 11%3, the NiO of 0.5 ~ 3.5%, the specific surface area of described catalyst is 90 120m2/ g, pore volume is 0.8 1.2ml/g, can several apertures be 40 60nm, and mechanical strength is 10 ~ 20N/mm, and in pore size distribution, the aperture of ＞ 30nm accounts for the 60 ~ 90% of total pore volume.The preparation method of a kind of Hydrodemetalation catalyst, first prepares the boehmite mixed liquor of 20 ~ 100g/L, and the pH value adjusting mixed liquor is 7 ~ 8, and encapsulation process 0.5 ~ 5h at a temperature of 100 ~ 300 DEG C；Then the mixed liquor after processing filters, washs, is dried, molding and roasting obtain alumina support；Finally use infusion process load active component Mo and Ni on the alumina support of preparation, prepare Hydrodemetalation catalyst.This catalyst preparation process is simple, and the Hydrodemetalation catalyst of preparation has bigger aperture, higher mechanical strength and suitable pore size distribution and specific surface area.
Description
Technical field
The present invention relates to a kind of Hydrodemetalation catalyst and preparation method thereof, relate in particular to one and be suitable for heavy
Hydrodemetalation catalyst of distillate especially residual hydrocracking process and preparation method thereof.
Background technology
It is known that activity stabilized to catalyst of catalyst carrier properties such as most probable pore size, surface area, average pore size
Property plays an important role.For heavy distillate especially residual oil, metal impurities (such as Ni, V etc.) content is high, if catalyst
The aperture of carrier is little (less than 15nm), and the aperture resulting in catalyst is little, causes the metal in heavy distillate especially residual oil
Impurity is deposited near catalyst aperture, blocking catalyst aperture, makes catalyst activity reduction, stability reduce.Therefore, heavy
Distillate especially residual oil catalyst for demetalation is it is generally required to have bigger pore volume, aperture, suitable pore size distribution and specific surface
Long-pending.
The physics expanding agents such as the white carbon black such as US4448896, US4102822, starch expand the aperture of alumina support.But
This alumina support pore size distribution is not concentrated, bad mechanical strength.CN1209355A proposes a kind of macropore alumina supporter and preparation thereof
Method, under conditions of higher than room temperature, carries out peptization or ripening to boehmite raw material, and the material after molding is with containing ammonium ion
Compound process, prepare carrier hole a diameter of 10 ~
The pore volume of 20nm accounts for the 70 ~ 85% of total pore volume.Its processing procedure is more complicated.CN200410000953 uses organic expansion
Hole agent method is prepared the aperture of more than 100nm in large-pore alumina carrier, and carrier and is only accounted for total pore volume 7 ~ 25%.The method
Using organic polymer as expanding agent, relative price costly, is unfavorable for carrier commercial Application.
CN1164563A, US4562059 etc. disclose a kind of swing method and prepare the preparation method of catalyst carrier for hydrgenating.Should
Method, during preparing carrier, needs to swing repeatedly, relatively complicated, is industrially difficulty with.
CN1141821A discloses the preparation method of a kind of catalyst carrier for hydrgenating.Its neutralize with aging under the same conditions
Carrying out, in the range of the catalyst carrier hole of preparation is concentrated mainly on 7～12nm, for catalyst for demetalation, aperture is less,
It is not suitable as the carrier of demetalization desulfurization.
CN101088605 discloses the preparation method of a kind of catalyst carrier for hydrgenating.Carrier aperture prepared by the method is
18～22nm, it is unfavorable for desulphurizing activated raising, is not suitable as the carrier of high activity demetalization desulphurization catalyst.
CN200810010253 discloses the preparation method of a kind of hydrogenation catalyst.The method is to utilize two kinds of different routes
The alumina dry glue of method carries out carrier to be prepared.Its shortcoming is that preparation process is more complicated.
CN200410048357 and CN99114574 discloses a kind of support preparation method.The method is to utilize acidifying aluminium salt
Solution and NH4HCO3Deng containing NH3Solution carries out plastic, thus prepares carrier.Its shortcoming is that simple utilization acidifying aluminium salt prepares carbonic acid
Aluminum ammonium, Yield compari@is low, is unfavorable for commercial production, is unfavorable for support strength control.
CN200410050726.2 discloses the preparation method of a kind of catalyst carrier for hydrgenating.The method be acid aluminium salt with
Basic aluminate also flows neutralization, aging in preparation process is carrying out higher than neutral temperature and neutralizing under pH value condition, uses this side
Catalyst carrier pore diameter range prepared by method is 15 ~ 30nm, converts relative or little to asphalitine micelle.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of Hydrodemetalation catalyst and preparation method thereof.This catalysis
Agent preparation process is simple, and the Hydrodemetalation catalyst of preparation has bigger aperture, higher mechanical strength and suitable hole
Distribution and specific surface area.This catalyst demonstrates efficient HDM activity during residual hydrocracking and stablizes
Property.
A kind of Hydrodemetalation catalyst, with aluminium oxide as carrier, with Mo and Ni as metal component, presses in final catalyst
Weight content meter contains the MoO of 4 ~ 11%3, the NiO of 0.5 ~ 3.5%, the specific surface area of described catalyst is 90-120m2/ g, hole
Holding is 0.8-1.2ml/g, can several apertures be 40-60nm, and mechanical strength is 10 ~ 20N/mm, and in pore size distribution, the aperture of ＞ 30nm accounts for
The 60 ~ 90% of total pore volume.
In the present invention, the specific surface area of preferred catalyst is 100～110m2/ g, pore volume is 0.85-1.15ml/g, can several holes
Footpath is 40 ~ 5nm, and mechanical strength is 12 ~ 15N/mm, and in pore size distribution, ＞ 30nm accounts for the 65 ~ 80% of total pore volume.
The preparation method of a kind of Hydrodemetalation catalyst, comprises the steps: first to prepare the thin water of plan of 20 ~ 100g/L
Aluminum stone mixed liquor, the pH value adjusting mixed liquor is 7 ~ 8, and encapsulation process 0.5 ~ 5h at a temperature of 100 ~ 300 DEG C；Then at inciting somebody to action
Mixed liquor after reason filters, washs, is dried, molding and roasting obtain alumina support；Finally use infusion process at the oxygen of preparation
Change load active component Mo and Ni on alumina supporter, prepare Hydrodemetalation catalyst.
Preferably preparing the boehmite mixed liquor of 40 ~ 80g/L in the inventive method, encapsulation process temperature is preferably 150-
250 DEG C, process time preferred 1-4h.
Boehmite described in the inventive method can use commercially available boehmite, it would however also be possible to employ carbonization
The homemade boehmites of conventional method such as method, cocurrent process, swing method.
In the inventive method, the dipping of active component uses spray infusion process, and co-impregnated solution is joined by the composition of pre-prepared catalyst
System, sprays impregnation liquid in the carrier strip prepared, spray step solution to be ensured just loaded body all absorb and without many
Remaining, therefore need to measure the water absorption of carrier before dipping, thus determine to use the concentration of solution.When with molybdenum and nickel as active component
Time, preparation co-impregnated solution can use industry ammonium heptamolybdate, industrial nitric acid nickel to be raw material, and co-impregnated solution compositional range is: MoO3 5.0
～15.0g/100ml, NiO 0.5～3.5g/100ml.Include being dried and roasting process, described dried strip after dipping active component
Part is to be dried 1～10 hour at 100～130 DEG C；Described roasting process is 470 DEG C～550 DEG C of roastings 1～6 hours.
The present invention carries out heat treatment in the boehmite of certain mass concentration and pH value is placed in sealing container, and with warp
Boehmite after suitably processing is raw material, prepares through steps such as molding, roasting, dipping active components and has larger aperture
Hydrodemetalation catalyst.The preparation process of catalyst of the present invention is simple, only need to adjust operating condition, vary without existing preparation
Process, available large aperture big pore volume catalyst.Hydrodemetalation catalyst of the present invention is while having big pore volume aperture, also
Having higher mechanical strength and suitable pore size distribution and specific surface area, this Hydrodemetalation catalyst activity is high, good stability.
Detailed description of the invention
The functions and effects of the present invention are further illustrated below in conjunction with embodiment.
Example 1
Weighing boehmite (Tianjin FTA-1) 200g, add water purification and be configured to the solution of 50g/L, adjusting pH value is 7.5,
This solution is moved in hermetic container, is warming up to 200 DEG C, encapsulation process 3h；Mixed liquor after processing filters, washs, is dried,
Molding, roasting prepare alumina support；With above-mentioned prepared aluminium oxide as carrier, use spray infusion process supported active metals Mo
And Ni, it is dried 5 hours at 120 DEG C after dipping, at 3 hours prepared Hydrodemetalation catalysts 1 of 500 DEG C of roastings, catalyst
Physico-chemical property is shown in Table 1, and the HDM Activity and stabill of catalyst is shown in Table 4.
Example 2
Weighing boehmite (Tianjin FTA-1) 200g, add water purification and be configured to the solution of 40g/L, adjusting pH value is 7, will
This solution moves in hermetic container, is warming up to 150 DEG C, encapsulation process 2h；Mixed liquor after processing filters, washs, is dried, and becomes
Type, roasting prepare alumina support；With above-mentioned prepared aluminium oxide as carrier, use spray infusion process supported active metals Mo and
Ni, is dried 10 hours after dipping, at 6 hours prepared Hydrodemetalation catalysts 2 of 470 DEG C of roastings, the thing of catalyst at 100 DEG C
Changing character and be shown in Table 1, the HDM Activity and stabill of catalyst is shown in Table 4.
Example 3
Weighing boehmite (Tianjin FTA-1) 200g, add water purification and be configured to the solution of 80g/L, adjusting pH value is 8, will
This solution moves in hermetic container, is warming up to 250 DEG C, encapsulation process 1h；Mixed liquor after processing filters, washs, is dried, and becomes
Type, roasting prepare alumina support；With above-mentioned prepared aluminium oxide as carrier, use spray infusion process supported active metals Mo and
Ni, is dried 1 hour after dipping, at 2 hours prepared Hydrodemetalation catalysts 3 of 550 DEG C of roastings, the thing of catalyst at 130 DEG C
Changing character and be shown in Table 1, the HDM Activity and stabill of catalyst is shown in Table 4.Example 4
Example 4
Weighing boehmite (Tianjin FTA-1) 200g, add water purification and be configured to the solution of 20g/L, adjusting pH value is 7, will
This solution moves in hermetic container, is warming up to 300 DEG C, encapsulation process 1h；Mixed liquor after processing filters, washs, is dried, and becomes
Type, roasting prepare alumina support；With above-mentioned prepared aluminium oxide as carrier, use spray infusion process supported active metals Mo and
Ni, is dried 4 hours after dipping, at 3 hours prepared Hydrodemetalation catalysts 4 of 450 DEG C of roastings, the thing of catalyst at 110 DEG C
Changing character and be shown in Table 1, the HDM Activity and stabill of catalyst is shown in Table 4.
Example 5
Weighing boehmite (Tianjin FTA-1) 200g, add water purification and be configured to the solution of 100g/L, adjusting pH value is 8, will
This solution moves in hermetic container, is warming up to 100 DEG C, encapsulation process 4h；Mixed liquor after processing filters, washs, is dried, and becomes
Type, roasting prepare alumina support；With above-mentioned prepared aluminium oxide as carrier, use spray infusion process supported active metals Mo and
Ni, is dried 5 hours after dipping, at 3 hours prepared Hydrodemetalation catalysts 5 of 500 DEG C of roastings, the thing of catalyst at 120 DEG C
Changing character and be shown in Table 1, the HDM Activity and stabill of catalyst is shown in Table 4.
Comparative example 1
Weighing boehmite (Tianjin FTA-1) 200g, boehmite, without pretreatment, is dried, molding and roasting
Obtain alumina support Deng conventional process, prepare catalyst 6 with this carrier.
The physico-chemical property of table 1. hydrogenation catalyst
| Catalyst | 1 | 2 | 3 | 4 | 5 | 6 |
| S, m2/g | 118 | 110 | 91 | 106 | 100 | 158 |
| V, cm3/g | 0.88 | 0.90 | 1.1 | 0.96 | 1.05 | 0.90 |
| Can several apertures, nm | 45 | 45 | 60 | 45 | 50 | 18 |
| Intensity, N/mm | 14 | 15 | 11 | 14 | 13 | 17 |
| Pore-size distribution, % | ||||||
| 100-60 | 14 | 15 | 26 | 14 | 18 | 2 |
| 60-30 | 58 | 63 | 60 | 66 | 63 | 10 |
| 30-20 | 21 | 17 | 11 | 15 | 14 | 27 |
| ＜ 20 | 7 | 5 | 3 | 5 | 5 | 61 |
| Active component | ||||||
| MoO3, wt% | 8.0 | 7.9 | 8.1 | 8.0 | 8.2 | 8.2 |
| NiO, wt% | 2.0 | 1.9 | 2.2 | 1.8 | 2.1 | 2.1 |
200ml fixed bed hydrogenation assay device activity stability test, raw material oiliness have been carried out to catalyst 1,6
Matter, experimental condition such as table 2,3, result of the test is as shown in table 4.
Table 2 raw oil character
| Raw oil character | The normal slag in the Middle East |
| S, w% | 3.8 |
| Ni, ug/g | 32.2 |
| V, ug/g | 98.5 |
Table 3 experimental condition
| Reaction temperature, DEG C | 385 |
| Reaction pressure, MPa | 15.7 |
| Volume space velocity, h-1 | 1.0 |
| Hydrogen-oil ratio, V/V | 758 |
Table 4 demetalization performance comparison
As can be seen from the above results, the catalyst prepared by the inventive method can several apertures big, 30 ~ 60nm aperture accounts for always
Pore volume percentage rate is greatly improved.From the point of view of estimation of stability, the catalyst that demetalization good stability is prepared in comparative example.Explanation is pressed
Catalyst prepared by the inventive method can meet mink cell focus especially residuum hydrogenating and metal-eliminating process well.
Claims (10)
1. a Hydrodemetalation catalyst, with aluminium oxide as carrier, with Mo and Ni as metal component, by weight in final catalyst
Amount content meter, containing the MoO of 4 ~ 11%3, the NiO of 0.5 ~ 3.5%, it is characterised in that: the specific surface area of described catalyst is 90-
120m2/ g, pore volume is 0.8-1.2ml/g, can several apertures be 40-60nm, and mechanical strength is 10 ~ 20N/mm, ＞ in pore size distribution
The aperture of 30nm accounts for the 60 ~ 90% of total pore volume.
Catalyst the most according to claim 1, it is characterised in that: the specific surface area of described catalyst is 100～110m2/ g,
Pore volume is 0.85-1.15ml/g, can several apertures be 40 ~ 50nm, and mechanical strength is 12 ~ 15N/mm, and in pore size distribution, ＞ 30nm accounts for always
The 65 ~ 80% of pore volume.
3. the preparation method of catalyst described in claim 1, it is characterised in that: first prepare the boehmite of 20 ~ 100g/L
Mixed liquor, the pH value adjusting mixed liquor is 7 ~ 8, and encapsulation process 0.5 ~ 5h at a temperature of 100 ~ 300 DEG C；Then after processing
Mixed liquor filter, wash, be dried, molding and roasting obtain alumina support；Finally use infusion process at the aluminium oxide of preparation
Supported on carriers active component Mo and Ni, prepare Hydrodemetalation catalyst.
Method the most according to claim 3, it is characterised in that: the boehmite mixed liquor of preparation 40 ~ 80g/L, seal
Treatment temperature is 150-250 DEG C, and the process time is 1-4h.
Method the most according to claim 3, it is characterised in that: described boehmite uses commercially available boehmite
Or use carbonizatin method, cocurrent process, swing method to make by oneself.
Method the most according to claim 3, it is characterised in that: the dipping of active component uses spray infusion process.
7. according to the method described in claim 3 or 6, it is characterised in that: active component comes from ammonium heptamolybdate and nickel nitrate.
Method the most according to claim 3, it is characterised in that: MoO in impregnation liquid3With the content of NiO be respectively 5.0～
15.0g/100ml, 0.5～3.5g/100ml.
Method the most according to claim 3, it is characterised in that: include being dried and roasting process after dipping active component.
Method the most according to claim 3, it is characterised in that: described drying condition be at 100～130 DEG C be dried 1～
10 hours；Described roasting process is 470 DEG C～550 DEG C of roastings 1～6 hours.
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| CN106914251A (en) * | 2015-12-28 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrodesulfurization catalyst and preparation method thereof |
| CN107303492B (en) * | 2016-04-21 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN106994351B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
| CN116060055A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
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| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1164563A (en) * | 1996-05-02 | 1997-11-12 | 中国科学院山西煤炭化学研究所 | Method for preparing alumina as catalyst carrier |
| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN102441368A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst for heavy oil |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
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2012
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| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
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| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN102441368A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst for heavy oil |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
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