CN104587993B - A kind of preparation method of Hydrobon catalyst - Google Patents
A kind of preparation method of Hydrobon catalyst Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of Hydrobon catalyst.The method includes the preparation of carrier and the load of hydrogenation active metals, wherein the preparation process of carrier is to be mixed by a certain percentage by the plan thin aluminum water stone serosity of preparation under two kinds of different conditions, carry out aging the most at a higher temperature, introduce adjuvant component the most before ageing, obtain boehmite dry glue powder, then make alumina support.The carrier that this catalyst uses has that pore volume is high, aperture is big, mechanical strength is high, pore distribution concentration, the acidity feature such as suitably, and the catalyst thus prepared has higher activity when processing height and doing diesel oil and mix refining VGO or intractable secondary operations oil.
Description
Technical field
The present invention relates to the preparation method of a kind of Hydrobon catalyst, be particularly suitable for processing height and do and secondary adds
Work oil produces the preparation method of the Hydrobon catalyst of ultra-low sulfur clean diesel.
Background technology
Aluminium oxide is important catalyst carrier, in terms of Industrial Catalysis, during particularly the refining at oil is processed, has
Market application widely.Aluminium oxide self has the features such as good heat stability, loose structure and suitable surface acidity,
It it is excellent catalyst for hydrogenation of fraction oil carrier.Process height do diesel oil and mix refining VGO or intractable secondary add
During work oil, it is desirable to carrier hole structure has that pore volume is high, aperture big, and support strength and the suitable feature of surface acidity, it is thus possible to
Enough it is well adapted for diffusion and the reaction of macromole sulfide, to meet the production of ultra-low-sulphur diesel.
US4448896 proposes to add white carbon black in forming process and expands carrying alumina body aperture as expanding agent,
US4102822 then propose add starch as expanding agent, EP237240 then selects carbon fiber to form bigger pore structure.
CN1768946A selects starchy material as expanding agent.The reaming mechanism of above-mentioned expanding agent is that expanding agent is in carrier molding
Journey occupies certain volume, is decomposed into gas effusion when alumina support high-temperature roasting, thus forms macroporous structure.This kind of
Expanding agent is to mix with aluminum oxide dry glue powder with solid forms in adding procedure, and carrier hole can be caused to be distributed disperse, and machinery is strong
Degree reduces.The expanding agent that above-mentioned patent is added not with aluminium oxide generation chemical reaction, therefore referred to as physics expanding agent.
CN1160602A proposes to add carbon black pellet in aluminum oxide dry glue powder kneading process as physics expanding agent and can
Using the water-soluble phosphorus having an effect with aluminium oxide, silicon, boron compound as chemical enlargement agent, preparation can meet residual oil demetalization or
Hydrodesulfurization catalyst support.But this method still needs to add substantial amounts of carbon black pellet, and carbon black pellet is relatively big, the hole to carrier
Footpath distribution influence is relatively big, causes the reduction of carrier mechanical strength, and sintering temperature is higher simultaneously, affects the surface acidity of carrier.Cause
This is not suitable for as the carrier producing ultra-low-sulphur diesel catalyst.
CN1727063A proposes a kind of preparation method preparing alumina supporter.The method includes water
Close aluminium oxide mix with aluminium carbonate ammonium, molding roasting.But the macropore obtained by the method is nearly micron level, aperture mistake
Greatly, the hydrodesulfurization reaction of diesel oil it is not suitable for.
Big pore volume alumina support prepared by above method, owing to its boehmite presoma takes the way of reaming,
All have that to be difficult to extruded moulding, support strength low, pore size distribution disperse, the shortcoming that peptizer consumption is big.
CN97121771.8 discloses the preparation method of a kind of aluminium oxide, is continuously added to aluminium compound and acidity the most simultaneously
Or alkaline solution, pH value controls a certain steady state value in the range of 6～11, carries out and flow plastic, generates seed crystal of aluminium hydroxide.So
Rear add acid or alkaline solution, to pH value<4 or>11, dissolve amorphous hydroted alumina and fine particle, add alkalescence or
Acid solution, adjusts pH value to 6～11, and the aluminium ion making dissolving and the aluminium ion being newly added precipitate under crystal seed effect again.Weight
Multiple above-mentioned steps 1～20 times.Through aging, wash, filter, be dried, molding, after roasting, obtain alumina product.
CN98119913.5 discloses the preparation method of a kind of aluminium oxide, at a temperature of at least 50 DEG C, at a kind of aluminium hydroxide
Serosity is sequentially added into a kind of acid reagent and a kind of alkaline reagent, first makes the pH value of serosity drop to less than 5, then make serosity pH
Value goes back up to 9.4 ~ 10.4, filters, washs, is dried, obtains boehmite, then roasting, obtain gama-alumina.Both the above
Method is required to the swing condition of complexity, just can prepare the aluminium oxide that granule is more uniform, pore-size distribution is relatively concentrated, and aperture is inclined
Low.
CN201110313848.6 describes the preparation method of a kind of alumina support.The method is that same is intended thin water
Extruded moulding is mixed after the roasting at different temperatures of aluminum stone.The method can reduce lacking of large aperture boehmite not easy-formation
Fall into and the peptizer destruction to pore structure.But when if sintering temperature change is less, to structure of similar to thin diaspore qualitative change
Not quite, if sintering temperature changes greatly, easily cause boehmite generation crystal phase transition so that it is activity reduces.
CN200910176631.8 discloses the preparation method of a kind of alumina support.By two kinds of different boehmites
Dry glue powder mix homogeneously, then carries out peptization, molding, is dried, in 1-5 hour prepared carrying alumina of 550 DEG C ~ 1200 DEG C roastings
Body.Wherein the pore volume of the first boehmite is between 0.50ml/g ~ 0.80ml/g, additional proportion account for the aluminium oxide 5% of feeding intake ~
50%；The pore volume of the second boehmite is between 0.85ml/g ~ 1.50ml/g.Aluminium oxide prepared by the method has mesoporous
With macropore two peak structure, macropore (> 200nm) duct be not suitable for the desulfurization of diesel component sulfide.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides the preparation method of a kind of Hydrobon catalyst.This catalysis
The carrier that agent uses has that pore volume is high, aperture big, pore distribution concentration and mechanical strength is high and surface acidity is suitable feature, special
It is not applicable to process height do and secondary operations oil production ultra-low sulfur clean diesel.
The preparation method of Hydrobon catalyst of the present invention, including preparation and the load of hydrogenation active metals of carrier, its
The preparation process of middle carrier includes:
(1) boehmite serosity A1 is prepared: use acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature control
System is at 5 ~ 30 DEG C, and plastic pH value is 7 ~ 10；
(2) boehmite serosity A2 is prepared: use acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature control
System is at 50 ~ 90 DEG C, and plastic pH value is 7 ~ 10；
(3) step (1) obtains boehmite serosity A1 and the boehmite serosity A2 that step (2) obtains is with Al2O3
After 1:8 ~ 1:1 mixing pressed by meter, then carrying out aging, aging temperature is higher than the gelling temperature of step (2) 30 ~ 120 DEG C, and preferably 50
~ 100 DEG C, aging temperature is 80 ~ 180 DEG C, preferably 100 ~ 180 DEG C, and the time is 6h ~ 96h, washs, is dried after aging end,
To boehmite dry glue powder；
(4) the boehmite dry glue powder that step (3) obtains is shaped, is dried and roasting, obtains alumina support.
Either step in wherein before step (1), step (2) and step (3) are aging or several step add and helps
The precursor of agent component, one or more in silicon, boron, phosphorus of adjuvant component.The precursor of adjuvant component, i.e. silicon source is selected from
One or more in sodium silicate, Ludox, ammonium fluosilicate, boron source be selected from boric acid, ammonium borate, phosphorus source selected from phosphoric acid, ammonium phosphate,
One or more in ammonium hydrogen phosphate etc., adjuvant component addition in terms of oxide accounts for alumina support with Al2O3Meter weight
1wt% ~ 35wt%, preferably 5 wt% ~ 15wt%.
Acid aluminium salt described in step (1) and step (2) is the one in aluminum sulfate, aluminum nitrate, aluminum chloride or several
Kind.Alkaline solution can use alkali aluminate soln, it would however also be possible to employ alkaline sedimentation agent solution, and wherein basic aluminate is inclined
One or more in sodium aluminate, potassium metaaluminate, alkaline precipitating agent is the one in sodium hydroxide, potassium hydroxide, ammonia, carbamide
Or it is several.
In step (3), boehmite serosity A1 that step (1) obtains and the boehmite serosity that step (2) obtains
A2 mixes, and both mixed weight ratios are with Al2O31:8 ~ 1:1 pressed by meter, preferably 1:5 ~ 1:2.Aging condition described in step (3)
For: aging temperature is 80 ~ 180 DEG C, ageing time be 6h ~ 96h, preferably aging temperature be 80 ~ 180 DEG C, ageing time be 6h ~
96h.Described washing can use conventional method to carry out, and washs preferably with deionized water.Described drying condition is as follows:
Baking temperature is 90 ~ 150 DEG C, and drying time is 2 ~ 8h.
In step (4), described boehmite dry glue powder, in forming process, can add shaping assistant as required,
One or more in such as extrusion aid, peptizer etc..Extrusion aid is in methylcellulose, sesbania powder, starch, polyvinyl alcohol
One or more.Peptizer is one or more in formic acid, acetic acid, succinic acid, citric acid, tartaric acid, nitric acid etc., adds weight
Amount is boehmite dry glue powder in terms of butt the 1% ~ 5% of quality.
In step (4), described drying condition is as follows: baking temperature is 90 ~ 150 DEG C, and drying time is 2 ~ 8h, roasting bar
Part is as follows: sintering temperature is 400 ~ 800 DEG C, and roasting time is 2 ~ 8h.
In the inventive method, hydrogenation active metals is group VIB and/or group VIII metal.Wherein vib is preferably molybdenum
And/or tungsten, group VIII metal is preferably nickel and/or cobalt.On the basis of the weight of catalyst, vib metals oxide
Content is 10% ~ 30%, and the content of group VIII metal-oxide is 2% ~ 10%.
In the inventive method, the carrying method of hydrogenation active metals component can use conventional method, typically uses kneading
Method, infusion process, it is preferred to use infusion process can use saturated infusion process, supersaturation infusion process, complexation infusion process etc. is the most excellent
Choosing uses saturated infusion process.When preparing dipping solution, needed for group VIB metal and group VIII metal, active component raw material is general
For type compounds such as metallic salt, metal-oxide or acid, if molybdenum source is in molybdenum oxide, ammonium tetramolybdate, ammonium heptamolybdate
Plant or several；Tungsten source is ammonium metatungstate；Nickel source is one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate；Cobalt source is nitre
One or more in acid cobalt, cobalt carbonate, basic cobaltous carbonate.In described impregnation liquid, it is also possible to containing phosphorus-containing compound, as
One or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.After dipping, being dried with roasting condition such as of catalyst
Under: described drying condition is as follows: baking temperature is 90 ~ 150 DEG C, and drying time is 2 ~ 8h, and roasting condition is as follows: sintering temperature
Being 400 ~ 800 DEG C, roasting time is 2 ~ 8h.
The character of the alumina support that the inventive method obtains is as follows: pore volume is 0.5 ~ 1.0mL/g, and preferably 0.6 ~ 0.8
ML/g, specific surface area is 250 ~ 400m2/ g, preferably 280 ~ 350 m2/ g, average pore diameter is 4.5 ~ 12.5nm, preferably 5 ~
9nm, mechanical strength is at more than 13N/mm, and meleic acid amount is 0.3 ~ 1.0mmol/g, preferably 0.5 ~ 0.9mmol/g, and pore size distribution is such as
Under: bore dia is that the pore volume shared by 5-10nm accounts for the 65% ~ 90% of total pore volume.
The inventive method is to be mixed by a certain percentage by the plan thin aluminum water stone serosity of preparation under two kinds of different conditions, then exists
Carry out aging at a temperature of higher, and introduce adjuvant component before ageing, obtain boehmite dry glue powder, then make aluminium oxide
Carrier, uses conventional method load hydrogenation active metals component, obtains catalyst.The carrier that this catalyst uses has pore volume
High, aperture is big, mechanical strength is high and surface acidity suitable, the feature of pore distribution concentration, urge with hydrofinishing prepared by this carrier
Agent has higher activity when processing height and doing diesel oil and mix refining VGO or intractable secondary operations oil.
Detailed description of the invention
Further illustrate the present invention program and effect below by embodiment, but be not intended that limitation of the present invention.This
In invention, wt% is mass fraction.
Embodiment 1
By 1 L aluminum sulfate solution (concentration is 0.2 mol/L) and 1 L sodium aluminate solution (concentration is 0.3 mol/L) point
It is not placed in head tank, retort places 1 L pure water as end liquid, by cooling water circulation retort temperature controlled be
9 DEG C, add a small amount of sodium hydroxide and make solution ph be 8.5.Aluminum sulfate solution is injected retort with the speed of 10 mL/min,
It is injected simultaneously into sodium aluminate solution and regulates its speed, making retort solution ph be constant at 8.8.In N-process the most also
Stream adds sodium silicate aqueous solution, and addition is with SiO2Meter accounts for 12 wt%(of total boehmite serosity A1+A2 weight with Al2O3
Meter), terminate after 60min to neutralize, obtain boehmite serosity A1.
Similar, prepare boehmite serosity A2 in another retort simultaneously, reaction temperature is 70 DEG C, and pH value is 8.5,
But it is added without sodium silicate aqueous solution.
By two kinds of boehmite serosity mixing, mixed proportion is boehmite serosity A1: boehmite serosity A2=
1:5(is with Al2O3Meter).Mixed serum is placed in 135 DEG C of autoclaves after aging 24h, takes out filtration, be dried, obtain intending thin water aluminum
Stone dry glue powder.
Extruded moulding after extrusion aid and peptizer mix homogeneously is added in boehmite dry glue powder；Molding materials is done
Alumina support C1 is obtained after dry, roasting.
Embodiment 2
Similar with embodiment 1, simply the reaction temperature of boehmite serosity A1 changes 12 DEG C into, and auxiliary agent precursor changes into
Phosphoric acid, phosphoric acid addition accounts for 8 wt%(of total boehmite serosity A1+A2 weight with Al in terms of phosphorus pentoxide2O3Meter), A1
In serosity and pH value be 9.0；The reaction temperature of boehmite serosity A2 changes 60 DEG C into, in A2 serosity and pH value be 8.0；Mixing
Ratio is boehmite serosity A1: boehmite serosity A2=1:4(is with Al2O3Meter).Aging temperature changes 150 DEG C into, aging
Time changes 10h into.The named C2 of alumina support obtained.
Embodiment 3
Similar with embodiment 1, simply the reaction temperature of boehmite serosity A1 changes 20 DEG C into, in A1 serosity and pH value
It is 8.0；Auxiliary agent precursor changes boric acid into and adds A2 plastic when, and boric acid addition accounts for the thin water of total plan in terms of boron oxide
The 10wt%(of aluminum stone serosity A1+A2 weight is with Al2O3Meter), the reaction temperature of boehmite serosity A2 changes 80 DEG C into, A2 serosity
Neutralizing pH value is 9.0；Mixed proportion is boehmite serosity A1: boehmite serosity A2=1:3(is with Al2O3Meter).Aging
Temperature changes 175 DEG C into, and ageing time changes 6h into.The named C3 of alumina support obtained.
Comparative example 1
By thin for the plan in embodiment 1 aluminum water stone serosity A1 and A2 135 DEG C of aging rear sucking filtration of difference, it is dried, dried plan
Boehmite dry glue powder mixes extrusion, the named B1 of alumina support obtained in 1:5 ratio.
Comparative example 2
Using the boehmite A1 in embodiment 2 as crystal seed, adding in end liquid prepared by A2, addition is A2 to be prepared
The 1/4 of amount, then according to the method for embodiment 2, boehmite is prepared in 80 DEG C of neutralizations, aging temperature 175 DEG C, sucking filtration, be dried,
Extrusion, the named B2 of alumina support obtained.
Comparative example 3
By thin for the plan in embodiment 1 aluminum water stone serosity A1 at 175 DEG C aging, ageing time 6h.Then sucking filtration, be dried,
Obtain boehmite dry glue powder.
Extruded moulding after extrusion aid and peptizer mix homogeneously is added in boehmite dry glue powder；Molding materials is done
Alumina support B3 is obtained after dry, roasting.
Comparative example 4
By aging at 135 DEG C after thin for the plan in embodiment 3 aluminum water stone serosity A2 plastic, ageing time 6h.Then sucking filtration, dry
Dry, obtain boehmite dry glue powder.
Extruded moulding after extrusion aid and peptizer mix homogeneously is added in boehmite dry glue powder；Molding materials is done
Alumina support B4 is obtained after dry, roasting.
Table 1 embodiment and comparative example carrier Main physical character
It can be seen in table 1 that compared with comparative example, the bulk property of carrier prepared by the present invention is improved, and especially divides
It is distributed in the hole showed increased of 5 ~ 10nm, higher acid amount, higher mechanical strength, is highly suitable for height and does diesel oil and mix refining two
The removing of secondary processing oil raw oil sulfide.
Comparative example carrier B 1, B2, B3, B4 and embodiment support C 1, C2, C3 are made respectively diesel oil hydrofining catalysis
Agent.
It is immersed in saturated for the impregnation liquid containing equivalent Mo-Co-P component on carrier B 1, B2, B3, B4, C1, C2, C3, warp
After crossing 110 DEG C of dry 4h, 460 DEG C of roasting 3h, respectively obtain catalyst Cat-B1, Cat-B2, Cat-B3, Cat-B4, Cat-C1,
Cat-C2, Cat-C3, catalyst composition is shown in Table 2.
Catalyst composition prepared by table 2
Evaluating catalyst is carried out on 100ml small hydrogenation device, first catalyst is carried out presulfurization before activity rating.Urge
It is pressure 6.0 MPa, volume space velocity 2.0h during liquid that agent evaluates process conditions-1, hydrogen to oil volume ratio 300:1, reaction temperature is 350
℃.Activity rating raw oil character is shown in Table 3, and Activity evaluation is shown in Table 4.
Table 3 raw oil character
Table 4 Activity evaluation
| Catalyst | Cat-B1 | Cat-B2 | Cat-B3 | Cat-B4 | Cat-C1 | Cat-C2 | Cat-C3 |
| The most desulphurizing activated, % | 82 | 84 | 67 | 76 | 100 | 105 | 96 |
| Denitrification activity, % relatively | 86 | 79 | 72 | 80 | 100 | 103 | 94 |
Claims (14)
1. a preparation method for Hydrobon catalyst, including preparation and the load of hydrogenation active metals, the Qi Zhongzai of carrier
The preparation process of body includes:
(1) boehmite serosity A1 is prepared: using acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls
5 ~ 30 DEG C, plastic pH value is 7 ~ 10；
(2) boehmite serosity A2 is prepared: using acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls
50 ~ 90 DEG C, plastic pH value is 7 ~ 10；
(3) step (1) obtains boehmite serosity A1 and the boehmite serosity A2 that step (2) obtains is with Al2O3Meter is pressed
After the mass ratio mixing of 1:8 ~ 1:1, then carrying out aging, aging temperature is higher than the gelling temperature of step (2) 30 ~ 120 DEG C, aging
Temperature is 80 ~ 180 DEG C, and ageing time is 6h ~ 96h, washs, is dried, obtain boehmite dry glue powder after aging end；
(4) the boehmite dry glue powder that step (3) obtains is shaped, is dried and roasting, obtains alumina support.
The most in accordance with the method for claim 1, it is characterised in that: in before step (1), step (2) and step (3) are aging
Either step or several step in add the precursor of adjuvant component, adjuvant component one or many in silicon, boron, phosphorus
Kind.
The most in accordance with the method for claim 2, it is characterised in that: the precursor of adjuvant component i.e. silicon source is selected from sodium silicate, silicon
One or more in colloidal sol, ammonium fluosilicate, boron source is selected from boric acid, ammonium borate, and phosphorus source is selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate
In one or more.
The most in accordance with the method for claim 2, it is characterised in that: adjuvant component addition in terms of oxide accounts for carrying alumina
Body is with Al2O31wt% ~ the 35wt% of meter weight.
The most in accordance with the method for claim 2, it is characterised in that: adjuvant component addition in terms of oxide accounts for carrying alumina
Body is with Al2O35 wt% ~ the 15wt% of meter weight.
The most in accordance with the method for claim 1, it is characterised in that: the acid aluminium salt described in step (1) and step (2) is sulfur
Acid aluminum, aluminum nitrate, aluminum chloride in one or several, alkaline solution use alkali aluminate soln or alkaline precipitating agent molten
Liquid, one or more during wherein basic aluminate is sodium metaaluminate, potassium metaaluminate, alkaline precipitating agent is sodium hydroxide, hydrogen-oxygen
Change one or more in potassium, ammonia, carbamide.
The most in accordance with the method for claim 1, it is characterised in that: in step (3), the boehmite slurry that step (1) obtains
The boehmite serosity A2 mixing that liquid A1 and step (2) obtain, both mixed weight ratios are with Al2O3It is calculated as 1:5 ~ 1:2.
The most in accordance with the method for claim 1, it is characterised in that: the aging condition described in step (3) is: aging temperature is
100 ~ 180 DEG C, ageing time is 6h ~ 96h.
The most in accordance with the method for claim 1, it is characterised in that: the aging temperature described in step (3) is than the plastic of step (2)
A height of 50 ~ 100 DEG C of temperature.
The most in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (3) is as follows: baking temperature
Being 90 ~ 150 DEG C, drying time is 2 ~ 8h.
11. in accordance with the method for claim 1, it is characterised in that: in step (4), described drying condition is as follows: be dried temperature
Degree is 90 ~ 150 DEG C, and drying time is 2 ~ 8h, and roasting condition is as follows: sintering temperature is 400 ~ 800 DEG C, and roasting time is 2 ~ 8h.
12. according to the method described in claim 1 or 2, it is characterised in that: hydrogenation active metals is vib and/or VIII
Race's metal, wherein vib is molybdenum and/or tungsten, and group VIII metal is nickel and/or cobalt.
13. in accordance with the method for claim 12, it is characterised in that: on the basis of the weight of catalyst, vib metals oxygen
The content of compound is 10% ~ 30%, and the content of group VIII metal-oxide is 2% ~ 10%.
14. in accordance with the method for claim 1, it is characterised in that: the carrying method of hydrogenation active metals component uses saturated
Infusion process.
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| CN106311309A (en) * | 2016-08-28 | 2017-01-11 | 山东成泰化工有限公司 | Hydrogenation catalyst carrier |
| CN107999089B (en) * | 2017-11-28 | 2021-02-02 | 万华化学集团股份有限公司 | Catalyst for producing diethyltoluenediamine and preparation method and application thereof |
| CN110038585B (en) * | 2018-01-16 | 2022-03-04 | 中国石油化工股份有限公司 | Preparation method of hydrofining catalyst |
| CN111099646B (en) * | 2018-10-26 | 2022-11-22 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
| CN112547067B (en) * | 2019-09-10 | 2023-06-20 | 中国石油化工股份有限公司 | Preparation method of catalyst for slurry bed methane synthesis reaction |
| CN111001424A (en) * | 2019-11-27 | 2020-04-14 | 浙江石油化工有限公司 | Phosphorus-containing residual oil hydrotreating catalyst and preparation method thereof |
| CN115518663B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
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