CN104587993A - Preparation method for hydrorefining catalyst - Google Patents
Preparation method for hydrorefining catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method for a hydrorefining catalyst. The method comprises a step of preparation of a carrier and a step of loading of a hydrogenation active metal; and the carrier is prepared by mixing two pseudo-boehmite slurries prepared under two different conditions according to a certain ratio, then carrying out aging at a high temperature so as to obtain dry pseudo-boehmite glue powder and preparing the alumina carrier, wherein preferably, an auxiliary component is introduced before aging. The carrier used by the catalyst has the characteristics of high pore volume, large pore diameter, high mechanical strength, centralized distribution of pores, proper acidity, etc., so the prepared catalyst has high activity in treatment of diesel with a high dry point and in blending of VGO or secondary processing oil difficult to treat.
Description
Technical field
The present invention relates to a kind of preparation method of Hydrobon catalyst, be particularly applicable to process high doing and the oily preparation method producing the Hydrobon catalyst of ultra-low sulfur clean diesel of secondary operations.
Background technology
Aluminium oxide is important catalyst carrier, in Industrial Catalysis, particularly in the refining processing of oil, has market application widely.Aluminium oxide self has the features such as good heat endurance, loose structure and suitable surface acidity, is excellent catalyst for hydrogenation of fraction oil carrier.Process high do diesel oil and mix refining VGO or unmanageable secondary operations oil time, pore volume is high, aperture is large to require carrier hole structure to have, and the feature that support strength and surface acidity are suitable for, thus diffusion and the reaction of large molecular sulfur compound can be adapted to well, to meet the production of ultra-low-sulphur diesel.
US4448896 proposes in forming process, to add carbon black as expanding agent to expand carrying alumina body aperture, and US4102822 then proposes to add starch as expanding agent, and EP237240 then selects carbon fiber to be formed larger pore structure.CN1768946A selects starchy material as expanding agent.The reaming mechanism of above-mentioned expanding agent is that expanding agent occupies certain volume in carrier forming process, is decomposed into gas effusion, thus forms macroporous structure when alumina support high-temperature roasting.This kind of expanding agent is mix with aluminum oxide dry glue powder with solid forms in adding procedure, and can cause carrier hole distribution disperse, mechanical strength reduces.The expanding agent that adds of above-mentioned patent not with aluminium oxide generation chemical reaction, therefore be referred to as physics expanding agent.
CN1160602A propose add in aluminum oxide dry glue powder kneading process carbon black pellet as physics expanding agent and can have an effect with aluminium oxide water-soluble phosphorus, silicon, boron compound as chemical enlargement agent, preparation can meet residual oil demetalization or hydrodesulfurization catalyst support.But this method still needs to add a large amount of carbon black pellets, and carbon black pellet is comparatively large, and comparatively large on the pore-size distribution impact of carrier, cause the reduction of carrier mechanical strength, sintering temperature is higher simultaneously, affects the surface acidity of carrier.Therefore the carrier as producing ultra-low-sulphur diesel catalyst is not suitable for.
CN1727063A proposes a kind of preparation method preparing alumina supporter.The method comprise hydrated alumina is mixed with aluminium carbonate ammonium, shaping and roasting.But the macropore that the method obtains is nearly micron level, and aperture is excessive, be not suitable for the hydrodesulfurization reaction of diesel oil.
, because its boehmite presoma takes the way of reaming, all there is not easily extruded moulding, support strength low, pore size distribution disperse, the shortcoming that peptizing agent consumption is large in large pore volume alumina support prepared by above method.
CN97121771.8 discloses a kind of preparation method of aluminium oxide, and add aluminium compound and acid or alkaline solution continuously, pH value controls a certain steady state value in 6 ~ 11 scopes, carries out and flows plastic, generates seed crystal of aluminium hydroxide first simultaneously.Then acidity or alkaline solution is added, to pH value <4 or >11, dissolve amorphous hydroted alumina and fine particle, add alkalescence or acid solution again, adjust pH, to 6 ~ 11, makes the aluminium ion of dissolving and the aluminium ion that newly adds again precipitate under crystal seed effect.Repeat above-mentioned steps 1 ~ 20 time.Through aging, washing, filter, after dry, shaping, roasting, obtain alumina product.CN98119913.5 discloses a kind of preparation method of aluminium oxide, at the temperature of at least 50 DEG C, a kind of acid reagent and a kind of alkaline reagent is added successively in a kind of slurries of aluminium hydroxide, the pH value of slurries is first made to drop to less than 5, make slurry pH value go back up to 9.4 ~ 10.4 again, filtration, washing, drying, obtain boehmite, roasting again, obtains gama-alumina.Above two kinds of methods all need complicated swing condition, just can prepare the aluminium oxide that particle is more homogeneous, pore-size distribution is comparatively concentrated, and aperture are on the low side.
CN201110313848.6 describes a kind of preparation method of alumina support.The method mixes extruded moulding by after same boehmite at different temperatures roasting.The method can reduce large aperture boehmite not the defect of easy-formation and peptizing agent to the destruction of pore structure.But when if sintering temperature change is less, little to structure of similar to thin diaspore change of properties, if when sintering temperature changes greatly, easily cause boehmite generation crystal phase transition, make its active reduction.
CN200910176631.8 discloses a kind of preparation method of alumina support.Two kinds of different boehmite dry glue powders are mixed, then carry out peptization, shaping, dry, in 550 DEG C ~ 1200 DEG C roasting 1-5 hour obtained alumina supports.Wherein the pore volume of the first boehmite is between 0.50ml/g ~ 0.80ml/g, and additional proportion accounts for the aluminium oxide 5% ~ 50% that feeds intake; The pore volume of the second boehmite is between 0.85ml/g ~ 1.50ml/g.Aluminium oxide prepared by the method has mesoporous and macropore two peak structure, and the duct of macropore (>200nm) is not suitable for the desulfurization of diesel component sulfide.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of Hydrobon catalyst.The carrier that this catalyst adopts has that pore volume is high, aperture is large, pore distribution concentration and the feature that mechanical strength is high and surface acidity is suitable, is specially adapted to that processing is high to be done and ultra-low sulfur clean diesel produced by secondary operations oil.
The preparation method of Hydrobon catalyst of the present invention, comprise the preparation of carrier and the load of hydrogenation active metals, wherein the preparation process of carrier comprises:
(1) boehmite slurries A1 is prepared: adopt acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls at 5 ~ 30 DEG C, and plastic pH value is 7 ~ 10;
(2) boehmite slurries A2 is prepared: adopt acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls at 50 ~ 90 DEG C, and plastic pH value is 7 ~ 10;
(3) the boehmite slurries A2 that obtains of the boehmite slurries A1 that obtains of step (1) and step (2) is with Al
2o
3after 1:8 ~ 1:1 mixing pressed by meter, then carry out aging, aging temperature is higher than the gelling temperature of step (2) 30 ~ 120 DEG C, be preferably 50 ~ 100 DEG C, aging temperature is 80 ~ 180 DEG C, is preferably 100 ~ 180 DEG C, time is 6h ~ 96h, washs, dry after aging end, obtains boehmite dry glue powder;
(4) undertaken shaping by the boehmite dry glue powder that step (3) obtains, dry and roasting, obtains alumina support.
Add the precursor of adjuvant component in arbitrary step in wherein before step (1), step (2) and step (3) are aging or several step, adjuvant component be selected from silicon, boron, phosphorus one or more.The precursor of adjuvant component, namely silicon source is selected from one or more in sodium metasilicate, Ludox, ammonium fluosilicate, boron source is selected from boric acid, ammonium borate, phosphorus source be selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate etc. one or more, adjuvant component accounts for alumina support with Al with the addition of oxide basis
2o
31wt% ~ the 35wt% of meter weight, is preferably 5 wt% ~ 15wt%.
Step (1) and the acid aluminium salt described in step (2) are one or several in aluminum sulfate, aluminum nitrate, aluminium chloride.Alkaline solution can adopt alkali aluminate soln, also alkaline sedimentation agent solution can be adopted, wherein basic aluminate is one or more in sodium metaaluminate, potassium metaaluminate, and alkaline precipitating agent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, urea.
In step (3), the boehmite slurries A1 that step (1) obtains and the boehmite slurries A2 that step (2) obtains mixes, and both mixed weight ratios are with Al
2o
31:8 ~ 1:1 pressed by meter, is preferably 1:5 ~ 1:2.Aging condition described in step (3) is: aging temperature is 80 ~ 180 DEG C, and ageing time is 6h ~ 96h, and being preferably aging temperature is 80 ~ 180 DEG C, and ageing time is 6h ~ 96h.Described washing can adopt conventional method to carry out, and preferably adopts deionized water to wash.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, peptizing agent etc.Extrusion aid is one or more in methylcellulose, sesbania powder, starch, polyvinyl alcohol.Peptizing agent is one or more in formic acid, acetic acid, butanedioic acid, citric acid, tartaric acid, nitric acid etc., and adding weight is that boehmite dry glue powder is in 1% ~ 5% of butt quality.
In step (4), 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 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 group vib is preferably molybdenum and/or tungsten, and group VIII metal is preferably nickel and/or cobalt.With the weight of catalyst for benchmark, the content of group vib metal oxide 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 adopt conventional method, generally adopts kneading method, infusion process, preferred employing infusion process can adopt saturated infusion process, supersaturation infusion process, complexing infusion process etc., preferably adopt saturated infusion process further.When preparing dipping solution, needed for group VIB metal and group VIII metal, active component raw material is generally the type compounds such as metallic salt, metal oxide or acid, if molybdenum source is one or more in molybdenum oxide, ammonium tetramolybdate, ammonium heptamolybdate; Tungsten source is ammonium metatungstate; Nickel source is one or more in nickel nitrate, nickelous carbonate, basic nickel carbonate; Cobalt source is one or more in cobalt nitrate, cobalt carbonate, basic cobaltous carbonate.In described maceration extract, can also phosphorus-containing compound be contained, as one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).After dipping, drying and the roasting condition of catalyst are as follows: 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 is 400 ~ 800 DEG C, and 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 be preferably 0.6 ~ 0.8 mL/g, specific area is 250 ~ 400m
2/ g, is preferably 280 ~ 350 m
2/ g, average pore diameter is 4.5 ~ 12.5nm, and be 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 as follows: the pore volume of bore dia shared by 5-10nm accounts for 65% ~ 90% of total pore volume.
The inventive method is mixed by a certain percentage by the plan thin aluminium water stone slurries prepared under two kinds of different conditions, then carry out aging at a higher temperature, and introduce adjuvant component before ageing, obtain boehmite dry glue powder, make alumina support again, adopt conventional method load hydrogenation active metals component, obtain catalyst.The carrier that this catalyst adopts has that pore volume is high, aperture is large, mechanical strength is high and surface acidity is suitable for, the feature of pore distribution concentration, the Hydrobon catalyst prepared with this carrier process high do diesel oil and mix refining VGO or unmanageable secondary operations oil time there is higher activity.
Detailed description of the invention
Further illustrate the present invention program and effect below by embodiment, but be not construed as limiting the invention.In the present invention, wt% is mass fraction.
Embodiment 1
1 L aluminum sulfate solution (concentration is 0.2 mol/L) and 1 L sodium aluminate solution (concentration is 0.3 mol/L) are placed in head tank respectively, 1 L pure water is placed as end liquid in retort, by cooling water circulation, retort temperature is controlled to be 9 DEG C, add a small amount of NaOH and make solution ph be 8.5.Aluminum sulfate solution is injected retort with the speed of 10 mL/min, injects sodium aluminate solution simultaneously and regulate its speed, making retort solution ph be constant at 8.8.In N-process, also stream adds sodium silicate aqueous solution simultaneously, and addition is with SiO
2meter accounts for 12 wt%(of total boehmite slurries A1+A2 weight with Al
2o
3meter), terminate neutralization after 60min, obtain boehmite slurries A1.
Similar, prepare boehmite slurries A2 in another retort, reaction temperature is 70 DEG C simultaneously, and pH value is 8.5, but does not add sodium silicate aqueous solution.
By two kinds of boehmite slurries mixing, mixed proportion is boehmite slurries A1: boehmite slurries A2=1:5(is with Al
2o
3meter).After mixed serum being placed in 135 DEG C of aging 24h of autoclave, taking out filtration, drying, obtain boehmite dry glue powder.
Extrusion aid is added and peptizing agent mixes rear extruded moulding in boehmite dry glue powder; Alumina support C1 is obtained by after molding materials drying, roasting.
Embodiment 2
Similar with embodiment 1, just the reaction temperature of boehmite slurries A1 changes 12 DEG C into, and auxiliary agent precursor changes phosphoric acid into, and phosphoric acid addition accounts for 8 wt%(of total boehmite slurries A1+A2 weight with Al in phosphorus pentoxide
2o
3meter), in A1 slurries and pH value be 9.0; The reaction temperature of boehmite slurries A2 changes 60 DEG C into, in A2 slurries and pH value be 8.0; Mixed proportion is boehmite slurries A1: boehmite slurries A2=1:4(is with Al
2o
3meter).Aging temperature changes 150 DEG C into, and ageing time changes 10h into.The alumina support called after C2 obtained.
Embodiment 3
Similar with embodiment 1, just the reaction temperature of boehmite slurries A1 changes 20 DEG C into, in A1 slurries and pH value be 8.0; Auxiliary agent precursor changes boric acid into and adds when A2 plastic, and boric acid addition accounts for the 10wt%(of total boehmite slurries A1+A2 weight with Al in boron oxide
2o
3meter), the reaction temperature of boehmite slurries A2 changes 80 DEG C into, in A2 slurries and pH value be 9.0; Mixed proportion is boehmite slurries A1: boehmite slurries A2=1:3(is with Al
2o
3meter).Aging temperature changes 175 DEG C into, and ageing time changes 6h into.The alumina support called after C3 obtained.
Comparative example 1
By thin for the plan in embodiment 1 aluminium water stone slurries A1 and A2 difference 135 DEG C of aging rear suction filtrations, drying, dried boehmite dry glue powder mixes extrusion in 1:5 ratio, the alumina support called after B1 obtained.
Comparative example 2
Using the boehmite A1 in embodiment 2 as crystal seed, add in end liquid prepared by A2, addition is will prepare A2 amount 1/4, then according to the method for embodiment 2, boehmite is prepared in 80 DEG C of neutralizations, aging temperature 175 DEG C, suction filtration, drying, extrusion, the alumina support called after B2 obtained.
Comparative example 3
By aging at 175 DEG C for thin for the plan in embodiment 1 aluminium water stone slurries A1, ageing time 6h.Then suction filtration, drying, obtains boehmite dry glue powder.
Extrusion aid is added and peptizing agent mixes rear extruded moulding in boehmite dry glue powder; Alumina support B3 is obtained by after molding materials drying, roasting.
Comparative example 4
By aging at 135 DEG C after thin for the plan in embodiment 3 aluminium water stone slurries A2 plastic, ageing time 6h.Then suction filtration, drying, obtains boehmite dry glue powder.
Extrusion aid is added and peptizing agent mixes rear extruded moulding in boehmite dry glue powder; Alumina support B4 is obtained by after molding materials drying, roasting.
Table 1 embodiment and comparative example carrier Main physical character
As seen from Table 1, compared with comparative example, the bulk property of carrier prepared by the present invention improves, especially the hole showed increased of 5 ~ 10nm is distributed in, higher acid amount, higher mechanical strength, is highly suitable for height and does diesel oil and mix removing of refining secondary operations oil feedstock oil sulfide.
Comparative example carrier B 1, B2, B3, B4 and embodiment support C 1, C2, C3 are made diesel oil hydrofining catalyst respectively.
Be immersed on carrier B 1, B2, B3, B4, C1, C2, C3 by saturated for the maceration extract containing equivalent Mo-Co-P component, after 110 DEG C of dry 4h, 460 DEG C of roasting 3h, obtain catalyst Cat-B1, Cat-B2, Cat-B3, Cat-B4, Cat-C1, Cat-C2, Cat-C3 respectively, catalyst composition is in table 2.
Table 2 Kaolinite Preparation of Catalyst forms
Evaluating catalyst carries out on 100ml small hydrogenation device, first carries out presulfurization to catalyst before activity rating.Evaluating catalyst process conditions are pressure 6.0 MPa, volume space velocity 2.0h during liquid
-1, hydrogen to oil volume ratio 300:1, reaction temperature is 350 DEG C.Activity rating feedstock oil character is in table 3, and Activity evaluation is in table 4.
Table 3 feedstock oil character
Table 4 Activity evaluation
| Catalyst | Cat-B1 | Cat-B2 | Cat-B3 | Cat-B4 | Cat-C1 | Cat-C2 | Cat-C3 |
| Relatively desulphurizing activated, % | 82 | 84 | 67 | 76 | 100 | 105 | 96 |
| Relative denitrification activity, % | 86 | 79 | 72 | 80 | 100 | 103 | 94 |
Claims (14)
1. a preparation method for Hydrobon catalyst, comprise the preparation of carrier and the load of hydrogenation active metals, wherein the preparation process of carrier comprises:
(1) boehmite slurries A1 is prepared: adopt acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls at 5 ~ 30 DEG C, and plastic pH value is 7 ~ 10;
(2) boehmite slurries A2 is prepared: adopt acid aluminium salt solution and alkaline solution and flow plastic, gelling temperature controls at 50 ~ 90 DEG C, and plastic pH value is 7 ~ 10;
(3) the boehmite slurries A2 that obtains of the boehmite slurries A1 that obtains of step (1) and step (2) is with Al
2o
3meter press 1:8 ~ 1:1 mixing after, then carry out aging, aging temperature is higher than the gelling temperature of step (2) 30 ~ 120 DEG C, and aging temperature is 80 ~ 180 DEG C, and ageing time is 6h ~ 96h, wash after aging end, drying, obtain boehmite dry glue powder;
(4) undertaken shaping by the boehmite dry glue powder that step (3) obtains, dry and roasting, obtains alumina support.
2. in accordance with the method for claim 1, it is characterized in that: the precursor adding adjuvant component in the arbitrary step in before step (1), step (2) and step (3) are aging or several step, adjuvant component be selected from silicon, boron, phosphorus one or more.
3. in accordance with the method for claim 2, it is characterized in that: the precursor of adjuvant component and silicon source be selected from sodium metasilicate, Ludox, ammonium fluosilicate one or more, boron source is selected from boric acid, ammonium borate, phosphorus source be selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate etc. one or more.
4. in accordance with the method for claim 2, it is characterized in that: adjuvant component accounts for alumina support with Al with the addition of oxide basis
2o
31wt% ~ the 35wt% of meter weight.
5. in accordance with the method for claim 2, it is characterized in that: adjuvant component accounts for alumina support with Al with the addition of oxide basis
2o
35 wt% ~ 15wt% of meter weight.
6. in accordance with the method for claim 1, it is characterized in that: step (1) and the acid aluminium salt described in step (2) are one or several in aluminum sulfate, aluminum nitrate, aluminium chloride, alkaline solution adopts alkali aluminate soln or alkaline sedimentation agent solution, wherein basic aluminate is one or more in sodium metaaluminate, potassium metaaluminate, and alkaline precipitating agent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, urea.
7. in accordance with the method for claim 1, it is characterized in that: in step (3), the boehmite slurries A1 that step (1) obtains and the boehmite slurries A2 that step (2) obtains mixes, and both mixed weight ratios are with Al
2o
3count 1:5 ~ 1:2.
8. in accordance with the method for claim 1, it is characterized in that: the aging condition described in step (3) is: aging temperature is 100 ~ 180 DEG C, ageing time is 6h ~ 96h.
9. in accordance with the method for claim 1, it is characterized in that: the aging temperature described in step (3) is higher than the gelling temperature of step (2) is 50 ~ 100 DEG C.
10. in accordance with the method for claim 1, it is characterized in that: the drying condition described in step (3) is as follows: baking temperature is 90 ~ 150 DEG C, drying time is 2 ~ 8h.
11. in accordance with the method for claim 1, it is characterized in that: in step (4), 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 is 400 ~ 800 DEG C, and roasting time is 2 ~ 8h.
12., according to the method described in claim 1 or 2, is characterized in that: hydrogenation active metals is group vib and/or group VIII metal, and wherein group 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 characterized in that: with the weight of catalyst for benchmark, and the content of group vib metal oxide 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 characterized in that: the carrying method of hydrogenation active metals component adopts saturated infusion process.
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