CN100496719C - Heavy fractional oil hydrogenation catalyst and production thereof - Google Patents
Heavy fractional oil hydrogenation catalyst and production thereof Download PDFInfo
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- CN100496719C CN100496719C CN 200510046348 CN200510046348A CN100496719C CN 100496719 C CN100496719 C CN 100496719C CN 200510046348 CN200510046348 CN 200510046348 CN 200510046348 A CN200510046348 A CN 200510046348A CN 100496719 C CN100496719 C CN 100496719C
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Abstract
The invention puts a kind of heavy-oil hydrogenation catalyst and the method of preparation and application to the view. The carrier of this kind of catalyst is made up of macroporous alumina that contains silicon and boron and minipore alumina with carrying at least one kind of VIB metallic elements and one kind of VII metallic elements. The percentage composition of VIB metallic elements in that is 10-30wt% according to oxides and the percentage composition of VII metallic elements in that is 1-15wt% according to oxides. The silicon and boron of the carrier are put into the macroporous alumina with the fractional jellied method and dispersed in the face of the macroporous alumina in order to making full use of team work. Besides, the proper pH of the catalyst helps it show high activity of hydrogen denitrification and good stabilization.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-processing heavy distillate and preparation method thereof, especially contain heavy oil hydrogenating treatment catalyst of a kind of siliceous and boron aluminium oxide and preparation method thereof.
Background technology
Hydrotreatment is meant hetero atoms such as the S, the N that remove in the various feedstock oils, O, metal, simultaneously the catalytic hydrogenation process process of unsaturated hydro carbons such as saturated aromatic hydrocarbons, alkene.For the heavy-oil hydrogenation processing procedure, generally comprise hydrodesulfurization (HDS), hydrodenitrogeneration (HDN), aromatic hydrocarbons saturated (HDA) and HDM main chemical reactions such as (HDM), wherein hydrodenitrogeneration is the most difficult.Therefore, the hydrodenitrogeneration ability is taken as the evaluation hydrotreating catalyst, especially the leading indicator of hydrocracking pretreatment catalyst.
The hydrotreating catalyst that industrial application is comparatively successful mostly is aluminium oxide or silica-alumina support and supports nickel, molybdenum, phosphorus component and make, as US4,446,248, US4,568,449, US4,513,097 is disclosed, and its basic skills is that drying, roasting, dipping, drying and roasting made after alumina hydrate powder was shaped.In order further to improve the activity and the activity stability of hydrotreating catalyst, various methods have been taked, as by improving preparation condition, carrier is carried out modification, add auxiliary agent and wait the pore structure of optimizing catalyst, improve the surface electrical character of catalyst, increase the quantity and the activated centre intensity in activated centre.Wherein selected auxiliary agent has silicon, phosphorus, fluorine, boron, zirconium, titanium etc., and the method for adding auxiliary agent has coprecipitation, mechanical kneading method and infusion process.
The comparatively common practice is in catalyst preparation process alumina catalyst support to be carried out modification, for example adopts infusion process, coprecipitation or solution melt method that auxiliary agents such as F, Si, B are joined in the carrier.SiO2 is carrier component or the modified additive of using always, itself acidity is very weak or do not have acidity, but with the acidity and the heat endurance that can improve aluminium oxide after the aluminium oxide combination, can also improve simultaneously the interaction of carrier and active metal component, distribute mutually thereby change activity, thus the hydrogenation activity and the stability of raising catalyst.
Chinese patent CN 1048037C discloses a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, and this catalyst supports molybdenum or tungsten and nickel metallic element by siliceous and alumina support phosphorus and makes.Described siliceous and alumina support phosphorus is to be mixed by a kind of siliceous and macroporous aluminium oxide and a kind of little porous aluminum oxide phosphorus, and wherein the silicon in the macroporous aluminium oxide is to adopt substep to become the glue method to add with phosphorus.This modified aluminas is that to adopt silicon and phosphorus be auxiliary agent, and total acidity is low, awaits further to improve with the hydrogenation activity of the catalyst of its carrier.
Chinese patent CN 1082387C discloses a kind of mesoporous aluminas gel, can evenly disperse one or more oxides that are selected from silica, boron oxide, phosphorous oxide in this alumina substrate, and general formula is VIII and/or the group vib metal oxide of MOx.The specific area of this mesoporous aluminas gel is 260-700m
2/ g, pore volume are 0.2-1.0cm
3/ g, average pore diameter is 2-7nm.Preparation process adopts organic aluminium salt and alkaline solution to be hydrolyzed into the glue method, this preparation method's cost is very high, and the oxide of described silicon, boron and phosphorus joins in the carrier by coprecipitation, can exist equally most of silicon, boron and P elements be dispersed in alumina body mutually in, can not give full play to the problem of its effect.Coprecipitation is that multiple material precipitates simultaneously in addition, and identical deposition condition can not be the best deposition condition of multiple material simultaneously, thereby influences the physical and chemical performance of final carrier.And the alumina gel bore dia that this method makes is less, is only applicable to the carrier of catalyst for hydrorefining distillate oil.
For hydrodenitrogenation catalyst, it has been generally acknowledged that aluminium oxide or siliceous alumina support support that to add effect of boron again after the hydrogenation activity component better, and boron additive adopts normally the method for dipping to be downloaded on the carrier, sees Chinese patent CN 92112511.9.U.S. Pat 6,037,300 disclose a kind of hydrotreating catalyst and preparation method thereof.This catalyst is a carrier with aluminium oxide or siliceous aluminium oxide, is active component with Co, Ni, Mo, W metal, adds B as auxiliary agent.Its preparation method is to prepare the molybdenum nickel aqueous solution and ammonium borate or borosilicate solution respectively earlier, carries out graded impregnation, drying and roasting then.Boron or borosilicate component add the employing double-steeping and add preparation method's complexity, and cost height.Have again, adopt above-mentioned soak earlier reactive metal, after soak boron mode, make boron additive improve active ability of disperseing mutually a little less than, activity of such catalysts awaits further to improve.
Summary of the invention
The purpose of this invention is to provide a kind of highly active hydrotreating catalyst, silicon and boron element contained in its carrier are enriched in carrier surface, and have bigger specific surface and pore volume.Another object of the present invention provides a kind of preparation method of hydrotreatment catalyst.
Hydrotreating catalyst provided by the invention comprises a kind of alumina support of siliceous and boron, and supports at least a group vib metallic element and at least a VIII family metallic element.Wherein said alumina support is made up of the macroporous aluminium oxide of siliceous and boron and aperture aluminium oxide, and macroporous aluminium oxide wherein is siliceous with SiO
2Meter 1wt%-15wt%, boracic is with B
2O
3Meter 2wt%-18wt%, specific area 350m
2/ g-500m
2/ g, pore volume 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm; Aperture aluminium oxide specific area 200m wherein
2/ g-300m
2/ g, pore volume 0.3ml/g-0.6ml/g, average pore diameter 2nm-10nm.
In catalyst of the present invention, be benchmark with the weight of catalyst, siliceous and boron macroporous aluminium oxide accounts for 10wt%-60wt%, and little porous aluminum oxide accounts for 10wt%-60wt%; The group vib element accounts for 10wt%-30wt% in oxide, and VIII family element accounts for 1w%-15w% in oxide, and phosphorus is with P
2O
5Meter accounts for 0.5wt%-5.0wt%.
Preparation method of hydrotreatment catalyst of the present invention is as follows:
Adopt and become the glue method to prepare siliceous and macroporous aluminium oxide boron continuously, this aluminium oxide and little porous aluminum oxide, adhesive and extrusion aid are pinched through mixing, are rolled, extrusion, drying, roasting are made carrier, make catalyst of the present invention with active metal component solution impregnation, drying, roasting again.
Above-mentioned siliceous and the macroporous aluminium oxide of boron are to adopt to become continuously the preparation of glue method, and introduce silicon and boron step by step, help the Si and the dispersion of B auxiliary agent on alumina surface of low content, comprise the steps:
(1) fills in the container of water one, under agitation constantly add and contain aluminum ions acidic salt solution, add alkaline solution simultaneously and be carried out to glue;
(2) behind reinforced the end, above-mentioned system wears out a period of time, adds the alkali metal soln of the siliceous oxygen anion of metering then, continues aging;
(3) filter and wash to anion/Al
2O
3Less than 2wt%;
(4) add the boron-containing compound that measures;
(5) filter also drying, obtain siliceous and macroporous aluminium oxide boron.
Make siliceous and macroporous aluminium oxide boron and have following character after roasting: the weight with butt is benchmark, and is siliceous with SiO
2Meter 1wt%-15wt%, boracic is with B
2O
3Meter 2wt%-18wt%, specific surface (BET method) is 350m
2/ g-500m
2/ g, pore volume are 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm.
Used little porous aluminum oxide is aluminium chloride-ammoniacal liquor method, carbonizatin method or the boehmite of aluminum sulfate method production and the SB alumina powder of Zlegler synthetic reaction accessory substance etc. in the method for preparing catalyst of the present invention.
Macroporous aluminium oxide, the aperture aluminium oxide of above-mentioned siliceous and boron are mixed, add that adhesive and extrusion aid (citric acid or sesbania powder) back are mixedly pinched, rolled, make catalyst carrier of the present invention after the moulding, drying, roasting; Described baking temperature is 40 ℃-180 ℃, is preferably 100 ℃-150 ℃, and be 0.5h-24h drying time, is preferably 1h-8h; Described sintering temperature is 400 ℃-700 ℃, is preferably 500 ℃-600 ℃, and roasting time is 0.5h-24h, is preferably 1h-8h.
Described adhesive comprises little porous aluminum oxide and peptizing agent, as the little porous aluminum oxide of binding agent with roasting after the weight of carrier be benchmark, be 5wt%-30wt% in aluminium oxide content.Described peptizing agent is one or more in aluminum nitrate, citric acid, nitric acid, acetic acid and the oxalic acid.Also can add zirconia, titanium oxide, magnesia and their mixture in the described adhesive component.
Carrier can be sheet, spherical, cylinder bar and special-shaped bar (clover, bunge bedstraw herb) after the described moulding, preferably cylinder bar and special-shaped bar (clover, bunge bedstraw herb), can be diameter 0.8mm-2.5mm slice and the thick bar of 2.5mm.
Active metal component of the present invention supports on the carrier by infusion process, can be step impregnation, also floods altogether, preferably a step dipping.
Described active metal component mainly refers to the molybdenum element of nickel and/or cobalt, particularly group vib of the molybdenum of group vib and/or tungsten and VIII family and the nickel element of VIII family, is benchmark with the weight of catalyst, and molybdenum element content is that 10wt%-30wt% is (with MoO
3Meter), nickel element content is 1wt%-15wt% (in NiO).
The used dipping solution of the present invention is the aqueous solution that contains Mo, Ni and/or P simultaneously, forms with nickel compound containing, molybdate compound, phosphorus-containing compound mixed configuration.Wherein nickel compound containing is one or more in water soluble carbonate, nitrate, oxalates and the subcarbonate, molybdate compound is ammonium molybdate and/or molybdenum oxide, and phosphorus-containing compound is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium phosphate.
With the aqueous solution dipping said catalyst carrier that contains molybdenum, nickel and/or phosphorus-containing compound, catalyst of the present invention is made in dipping back drying, roasting; Wherein said baking temperature is 60 ℃-180 ℃, is preferably 100 ℃-150 ℃, and be 0.5h-24h drying time, is preferably 1h-8h; Described sintering temperature is 300 ℃-700 ℃, is preferably 350 ℃-600 ℃, and roasting time is 0.5h-24h, is preferably 1h-8h.
The macroporous aluminium oxide of the siliceous and boron additive that catalyst of the present invention is used is to adopt substep to become the preparation of glue method, compares with kneading method with coprecipitation, and the inventive method can make two kinds of auxiliary agents all be dispersed in the surface of aluminium oxide, and gives full play to the effect of auxiliary agent; And adopt siliceous and aluminium oxide boron additive, and make the specific surface of carrier and pore volume increase, the aperture increases, pore distribution concentration, and then improved the pore structure of catalyst, make catalyst more help the hydrodenitrogeneration reaction.
The present invention adopts the aluminium oxide of silicon and boron additive modification to have higher acidity, thereby increases the acidity of carrier and catalyst surface.In addition, because the electronegativity of boron makes Al than the height of aluminium
2O
3-B
2O
3The B-OH acidity on surface is stronger than Al-OH, makes Mo
7O
24 6-At B
3+On dispersion compare Al
3+Better, and easier reduction and sulfuration, help the formation of the active phase of Ni-Mo-S in the sulphurized catalyst, increased the intensity in activated centre quantity and activated centre, make catalyst have higher hydrogenation activity and hydrodenitrogenationactivity activity.
The specific embodiment
According to Preparation of catalysts method provided by the invention, its concrete steps are as follows respectively:
(a) preparation of siliceous and boron macroporous aluminium oxide
The macroporous aluminium oxide of used siliceous and boron in the alumina support of the present invention, concrete preparation process is as follows:
(1) adds a certain amount of deionized water at a container, under uniform temperature and stirring condition, add and contain aluminum ions acidic salt solution, these contain the solution that aluminum ions salting liquid can be aluminium chloride, aluminum sulfate or aluminum nitrate, its concentration is 2g/100ml-8g/100ml, is preferably 3g/100ml-6.0g/100ml (with Al
2O
3Meter), add ammoniacal liquor simultaneously and be carried out to glue, ammonia concn is 6g/100ml-15g/100ml; When described acidic salt solution is aluminum sulfate solution, can not add ammoniacal liquor and add sodium aluminate solution and be carried out to glue, wherein sodium aluminate solution concentration is 10g/100ml-25g/100ml, is preferably 12g/100ml-20g/100ml; Become glue process control pH value 7.0-11.0, be preferably 7.5-9.5, temperature is controlled at 30 ℃-90 ℃, is preferably 40 ℃-70 ℃; Charging time is controlled at 0.5h-4h, is preferably 0.5h-2h.
(2) stop reinforced after, above-mentioned system is aging 10min-120min under pH value identical with becoming the adhesive tape part and temperature, preferably aging 20min-100min adds sodium metasilicate or the solution of sodium metasilicate through that measures then, and concentration is that 4g/100ml-10g/100ml is (with SiO
2Meter), is preferably 5g/100ml-8g/100ml, continues aging 10min-240min, be preferably 30min-60min.
(3) behind aging the end, filter and wash to anion/Al
2O
3＜2.0wt% is preferably＜0.3wt%.
(4) add the boron-containing compound that measures, as boric acid or borate, 30 ℃-90 ℃ of control temperature are preferably 40 ℃-70 ℃, and the time is 15min-75min, is preferably 30min-60min.Boron-containing compound can add in the following way: a, with after the filter cake making beating joins boron-containing compound in the slurries; B, will the boron-containing compound water join in the wet cake after the dissolving.
(5) filter after, with filter cake at 110 ℃ of-130 ℃ of dry 12h-24h.
In the above-mentioned steps, the inventory of silicon and boron element is all undertaken by the content ratio in the macroporous aluminium oxide of final siliceous and boron.
The macroporous aluminium oxide of above-mentioned obtained siliceous and boron with determination of nitrogen adsorption specific surface, pore volume, average pore size and pore size distribution, has following characteristics behind 500 ℃ of-700 ℃ of roasting 0.5h-10h:
Specific surface 350m
2/ g-500m
2/ g, preferably 400m
2/ g-450m
2/ g;
Pore volume 0.8ml/g-1.3ml/g, preferably 0.9ml/g-1.1ml/g;
Average pore diameter 8nm-13nm, preferably 8nm-11nm;
Infrared acidity ≮ 0.700mmol/g is preferably 0.700mmol/g-0.960mmol/g, is preferably 0.700mmol/g-0.930mmol/g.
Weight with butt is benchmark, and is siliceous (with SiO
2Meter) 1wt%-15wt% is preferably 1wt%-13wt%; Boracic is (with B
2O
3Meter) 2wt%-18wt% is preferably 5wt%-15wt%.
Infrared acidity among the present invention is to adopt U.S. Buddhist nun high-tensile strength company's Fourier infrared spectrograph (FIR-560 type) to measure.
(b) preparation of siliceous and boron alumina support
After the siliceous of above-mentioned preparation and boron macroporous aluminium oxide and part aperture aluminium oxide mixed, the little porous aluminum oxide of another part is made adhesive with peptizing agent, water add the back and mix with extrusion aid and pinch, roll that (siliceous and boron macroporous aluminium oxide and aperture alumina weight are than being 10:1-1:10), extruded moulding.Used peptizing agent can be one or more in aluminum nitrate, nitric acid, acetic acid and the oxalic acid.Support shapes can be cylindric, clover or bunge bedstraw herb, is preferably clover or bunge bedstraw herb.The bar of extruding is at 100 ℃ of-150 ℃ of dry 1h-8h, pelletizing and behind 500 ℃ of-600 ℃ of following roasting 1h-8h, and measuring with n2 absorption apparatus has following characteristics:
Specific surface 250m
2/ g-350m
2/ g;
Pore volume 0.4ml/g-0.8ml/g;
Average pore diameter 6nm-10nm is preferably 7nm-9nm.
The used little porous aluminum oxide of the present invention, the little porous aluminum oxide as SB aluminium oxide, carbonizatin method aluminium oxide and Fushun catalyst plant are produced with aluminium chloride and ammoniacal liquor method requires it to contain the gibbsite amount and is no more than 5.0wt%, changes into γ-Al
2O
3After have following characteristics:
The general range preferred range
Pore volume (Ethanol Method) 0.3ml/g-0.6ml/g 0.35ml/g-0.55ml/g
Specific surface (BET method) 200m
2/ g-300m
2/ g 220m
2/ g-270m
2/ g
(c) contain the preparation of modified aluminas hydrotreating catalyst
The used group vib metallic element of the present invention is generally tungsten or molybdenum, is preferably molybdenum element, and in metal oxide, content accounts for the 10wt%-30wt% of catalyst; The used VIII family metallic element of the present invention is generally iron, cobalt, nickel element, is preferably nickel element, and in metal oxide, content accounts for the 1wt%-15wt% of catalyst.
Catalyst V IB family of the present invention and VIII family metallic element are downloaded on the carrier by infusion process, generally are to adopt one-step method that molybdenum, nickel, phosphorus co-impregnated solution are impregnated on the carrier.Molybdenum, nickel, phosphorus solution preferably by molybdenum oxide or ammonium molybdate, basic nickel carbonate or nickel nitrate, phosphoric acid or (with) ammonium dihydrogen phosphate (ADP) is common formulated.
Catalyst of the present invention can be by the method preparation of spraying dipping or circulation dipping.Bar behind the dipping behind dry 4h-24h under 100 ℃ of-150 ℃ of conditions, is carried out the roasting second time at 350 ℃-600 ℃, promptly make catalyst of the present invention.
Catalyst activity constituent content of the present invention:
General range (wt%) the suitableeest scope (wt%)
MoO
3(or WO
3) 10-30 15-28
NiO (or CoO) 1-15 3-10
P 0.5—5 0.8—2.0
Catalyst of the present invention is the same with other hydrogenation catalyst, must vulcanize before use, can be by inject H in nitrogen atmosphere
2S, CS
2, CH
3-S-CH
3Or CH
3-S-S-CH
3Mode carry out dry method sulfuration, also can under the condition that feeds hydrogen, bring organic sulfur compound into liquid hydrocarbon and carry out the wet method presulfurization.
Catalyst of the present invention is suitable for fixed bed most, can be used for hydrogenation preliminary treatment mink cell focus, comprises that normal pressure four lines, decompression two wires, decompression are three-way, shale deasphalted oil, catalytic cracking recycle oil, wax tailings etc.Most typical be subtract two, subtract three, burnt wax miscella, raw material does＜580 ℃ (best＜560 ℃).
Catalyst of the present invention can use under the process conditions below: reaction pressure is 3.5MPa-30MPa, is preferably 6MPa-20MPa, volume space velocity 0.3h
-1-15h
-1, be preferably 0.5h
-1-6h
-1, hydrogen to oil volume ratio is 200-2000, is preferably 300-1500.
Under these conditions, can be according to different material, different product requires to carry out the hydrofinishing of different depth.As at one section prerefining of hydrocracking, can make and generate oily nitrogen content＜5 μ g/g or 10 μ g/g, can make the oily nitrogen content of generation be controlled at 10 μ g/g-100 μ g/g one section of mild hydrocracking, and can make the oily nitrogen content of generation satisfy catalytic cracking charging requirement in the processing wax tailings separately, generate oily nitrogen content less than 1000 μ g/g.
Further specify technical solution of the present invention by the following examples.
Embodiment 1
Add the 1000ml water purification in a container, be warming up to 65 ℃, add the solution 3700ml that contains 310g aluminium chloride, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 8.2, temperature is 62 ℃, the reinforced time is 60min.After stopping to feed in raw material, system is aging 50min under above-mentioned pH value and temperature conditions, adds the 40ml solution that contains the 4.8g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.After filter cake added water purification making beating, add the boric acid of 43g, the control temperature is at 50 ℃, and the time is 40min.After the filtration, filter cake behind 130 ℃ of dry 8h, is crushed to granularity with it and accounts for more than the 95wt% less than 180 orders, obtain modified aluminas L-1.
Get above-mentioned macroporous aluminium oxide 121g, sneak into the SB alumina powder prepared adhesive of 130g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting,, filter behind the molybdenum of 29.1g basic nickel carbonate, 8.0ml85% phosphoric acid, nickel, the phosphorus solution 200ml dipping 120min with containing the 96g molybdenum oxide, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, catalyst C-1.
Embodiment 2
In a container, add the 1000ml water purification, be warming up to 65 ℃, add and contain 560g aluminum sulfate (Al
2(SO
4)
318H
2O) solution 3700ml, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 7.6, temperature is 60 ℃, the reinforced time is 80min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the solution 100ml that contains the 15.3g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filter and wash to SO
4 2-/ Al
2O
3＜1.5wt%.The boric acid of 34.6g is added in the water purification, wait to dissolve the back and add the filter cake making beating, the control temperature is at 55 ℃, and the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95wt% behind 130 ℃ of dry 8h, obtain modified aluminas L-2 less than 180 orders.
Get above-mentioned macroporous aluminium oxide 60g, sneak into the SB alumina powder prepared adhesive of 96g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4mm.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting, after filtering behind the molybdenum that contains 115g molybdenum oxide, 20.4g basic nickel carbonate, 8.0ml85% phosphoric acid, 1.0g ammonium dihydrogen phosphate (ADP), nickel, the phosphorus solution 200ml dipping 120min, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, catalyst C-2.
Embodiment 3
In a container, add the 1000ml water purification, be warming up to 65 ℃, add and contain 300g aluminum sulfate (Al
2(SO
4)
318H
2O) solution 2000ml, adding 1011g concentration simultaneously is 15.0gAl
2O
3The sodium aluminate solution of/100ml, control pH value 8.5, temperature is 64 ℃, the reinforced time is 120min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the solution 245ml that contains the 32.0g sodium metasilicate.System continues aging 45min under above-mentioned pH value and temperature conditions, filtration washing is to SO
4 2-/ Al
2O
3＜1.5wt%.After filter cake added water purification making beating, add the boric acid of 30.0g, the control temperature is at 45 ℃, and the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95w% behind 130 ℃ of dry 8h, obtain modified aluminas L-3 less than 180 orders.
Get above-mentioned macroporous aluminium oxide 100g, sneak into the SB alumina powder prepared adhesive of 105g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting, with containing the 50g molybdenum acid ammonia, the molybdenum of 11.8g basic nickel carbonate, 3.5ml85% phosphoric acid, nickel, the phosphorus solution 89ml dipping of spraying all is sprayed onto solution in 20min in the drum of continuous rotation on the carrier bar.After rotating 30min again, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, catalyst C-5.
Embodiment 4
In a container, add the 1000ml water purification, be warming up to 65 ℃, add and contain 300g aluminum sulfate (Al
2(SO
4)
318H
2O) solution 2000ml, adding 1011g concentration simultaneously is 15.0gAl
2O
3The sodium aluminate solution of/100ml, control pH value 8.0, temperature is 65 ℃, the reinforced time is 120min.After stopping to feed in raw material, system is aging 30min under above-mentioned pH value and temperature conditions, adds the solution 150ml that contains the 11.4g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filter and wash to SO
4 2-/ Al
2O
3＜1.5wt%.The boric acid of 58.6g is added in the water purification, wait to dissolve the back and add the filter cake making beating, the control temperature is at 50 ℃, and the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95wt% behind 130 ℃ of dry 8h, obtain modified aluminas L-4 less than 180 orders.
Get above-mentioned macroporous aluminium oxide 114g, sneak into the SB alumina powder prepared adhesive of 125g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting, with filtering behind the molybdenum that contains 70g molybdenum oxide, 21.2g basic nickel carbonate, 35.5g nickel nitrate, 12.1ml85% phosphoric acid, 15.6g ammonium dihydrogen phosphate (ADP), nickel, the phosphorus solution 200ml dipping 120min, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, catalyst C-4.
Embodiment 5
Add the 1000ml water purification in a container, be warming up to 65 ℃, add the solution 3700ml that contains 310g aluminium chloride, adding concentration simultaneously is 10gNH
3The ammonia spirit of/100ml, control pH value 7.8, temperature is 62 ℃, the reinforced time is 120min.After stopping to feed in raw material, system is aging 15min under above-mentioned pH value and temperature conditions, adds the solution 140ml that contains the 24g sodium metasilicate.System continues aging 75min under above-mentioned pH value and temperature conditions, filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.After filter cake added water purification making beating, add the boric acid of 14.5g, the control temperature is at 55 ℃, and the time is 40min.Filter cake is crushed to granularity with it accounts for more than the 95wt% behind 130 ℃ of dry 8h, obtain modified aluminas L-5 less than 180 orders.
Get above-mentioned macroporous aluminium oxide 100g, sneak into the SB alumina powder prepared adhesive of 107g nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting, with containing the 37.9g molybdenum oxide, the molybdenum of 12.9g basic nickel carbonate, 3.5ml85% phosphoric acid, nickel, the phosphorus solution 89ml dipping of spraying all is sprayed onto solution in 20min in the drum of continuous rotation on the carrier bar.After rotating 30min again, behind 130 ℃ of dry 8h, roasting 4h under 500 ℃ of conditions gets catalyst C-5 with it.
Comparative example 1
C-A is the reference catalyst with reference to CN 1048037C method preparation, and this catalyst is to be carrier with siliceous and aluminium oxide phosphorus, and concrete steps are as follows:
30g boric acid among the embodiment 3 is replaced with 13.4g phosphoric acid, and all the other steps get reference catalyst C-A with embodiment 3.
Comparative example 2
Reference agent C-B is carrier with reference to US 6,037,300 with siliceous aluminium oxide, soaks reactive metal earlier, and the method for soaking ammonium borate again makes, and wherein auxiliary agent B adds in the catalyst by impregnation method, and concrete steps are as follows:
Ammonia spirit among the embodiment 1 is replaced with the ammonia spirit that contains the 35.6g sodium metasilicate, and the control ph value of reaction is 7.2, and temperature is 58 ℃, and the reinforced time is 60min.After stopping to feed in raw material, system is aging 60min under above-mentioned pH value and temperature conditions, and filtration washing is to Cl
-/ Al
2O
3＜0.3wt%.Filter cake behind 130 ℃ of dry 8h, is crushed to granularity with it and accounts for more than the 95wt% less than 180 orders, obtain siliceous aluminium oxide.
Get above-mentioned siliceous aluminium oxide 150g, add concentration 4% aqueous solution of nitric acid peptization, mix pinch 20min after, roll 10min, make the plasticity paste, by the clover orifice plate extrusion of φ 1.4.Behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h.
Get carrier strip 100g after the roasting, with containing the 50g molybdenum acid ammonia, the dipping 11.8g the molybdenum of basic nickel carbonate, 4.3ml85% phosphoric acid, nickel, phosphorus solution 89ml spray, in 20min, solution all is sprayed onto in the drum of continuous rotation on the carrier bar, after rotating 30min again, with its behind 130 ℃ of dry 8h under 520 ℃ of conditions roasting 4h, again with the aqueous solution that contains the 10.1g ammonium borate dipping of spraying, with its behind 130 ℃ of dry 8h under 500 ℃ of conditions roasting 4h, reference catalyst C-B.
The macroporous aluminium oxide that embodiment 1-5 and comparative example 1 obtain is at 520 ℃ of roasting 4h, analyze its character and see Table 1 and table 2, and the character of the catalyst that obtains of embodiment 1-5, comparative example 1 and 2 sees Table 1 and table 2.
In order to compare the present invention siliceous and boron aluminium oxide and siliceous and acid matter phosphorus oxidation aluminium, adopt temperature programmed desorption (TPD-NH
3) method records the total acid content and the sour distributed data of L-1, L-3 and L-A modified aluminas, the results are shown in Table 2.
Table 1 catalyst physico-chemical property of the present invention
| The catalyst numbering | C-1 | C-2 | C-3 | C-4 | C-5 | C-A | C-B |
| The auxiliary agent adding method | Prepare by aluminium chloride ammoniacal liquor method | Prepare by aluminum sulfate ammoniacal liquor method | Prepare by aluminum sulfate sodium metaaluminate method | Same C-3 | Same C-1 | The same C-3 of method | B adds by infusion process |
| The catalyst physicochemical property | |||||||
| Specific surface, m 2/g | 181 | 163 | 171 | 187 | 165 | 160 | 142 |
| Pore volume, ml/g | 0345 | 0.314 | 0.332 | 0.340 | 0.336 | 0.324 | 0.321 |
| NiO，wt％ | 3.92 | 3.21 | 3.98 | 6.98 | 4.02 | 4.10 | 4.02 |
| MoO 3，wt％ | 24.5 | 27.5 | 24.2 | 15.6 | 23.9 | 24.0 | 23.9 |
| P，wt％ | 0.98 | 0.95 | 0.98 | 3.0 | 1.68 | 1.8 | 1.21 |
| Macroporous aluminium oxide character | |||||||
| SiO 2，wt％ | 1.98 | 5.2 | 8.3 | 3.0 | 10.6 | 3.5 | — |
| B 2O 3，wt％ | 16.2 | 8.9 | 6.1 | 11.2 | 3.9 | 3.0 (P 2O 5) | — |
| Specific surface, m 2/g | 401 | 440 | 436 | 445 | 448 | 400 | — |
| Pore volume, ml/g | 1.03 | 1.12 | 0.98 | 1.09 | 1.06 | 1.02 | — |
| Average pore diameter, nm | 10.1 | 11.3 | 10.2 | 9.2 | 10.5 | 10.0 | — |
| Infrared acidity, mmol/g | 0.930 | 0.793 | 0.746 | 0.823 | 0.720 | 0.461 | — |
The acid of table 2 modified aluminas distributes
As shown in Table 2, the present invention adopts silicon and boron additive to significantly improve the acidity of alumina surface, particularly the quantity of weak acid center and middle strong acid center is (in the table 2, the acid amount of 250-400 ℃ of correspondences of acid distribution) increases considerably, promoted the catalytic reaction of this acidic site, especially hydrodenitrogeneration reaction.
Embodiment 6
Present embodiment is activity of such catalysts evaluation test of the present invention, and carries out the activity contrast with the hydrotreating catalyst that adopts the distinct methods preparation, mainly investigates the hydrodenitrogeneration performance of catalyst.
The catalyst activity evaluation is carried out on the 200ml small hydrogenation device, and raw materials used oil is Iranian VGO, and main character is listed table 3 in, reaction velocity 1.0h
-1, hydrogen to oil volume ratio 1000:1, hydrogen dividing potential drop 14.7MPa is a fiducial temperature with the reaction temperature, its evaluation result sees Table 4.
Table 3 feedstock oil main character
| Feedstock oil | Iran VGO |
| Density (20 ℃), g/cm 3 | 0.9096 |
| The boiling range scope, ℃ | 325—525 |
| Condensation point, ℃ | 37 |
| Sulphur/nitrogen, μ g/g | 10100/1205 |
Table 4 catalyst of the present invention and the contrast of reference agent nitrogen removal performance
| The catalyst numbering | C-A | C-B | C-1 | C-2 | C-3 | C-4 | C-5 |
| Type | The reference agent | The reference agent | The present invention | The present invention | The present invention | The present invention | The present invention |
| Feedstock oil | Iran VGO | Iran VGO | Iran VGO | Iran VGO | Iran VGO | Iran VGO | Iran VGO |
| The feedstock oil nitrogen content, μ g/g | 1205 | 1205 | 1205 | 1205 | 1205 | 1205 | 1205 |
| Generate oily nitrogen content, μ g/g | 14.0 | 7.0 | 2.2 | 2.1 | 2.8 | 4.2 | 3.0 |
| Relative denitrification activity | 100 | 116 | 142 | 143 | 136 | 127 | 135 |
Annotate: the hydrodenitrogenationactivity activity of regulation reference agent C-A is 100, and all the other are pressed
Relative denitrification activity=[ln (Nf/Np)]/ln (Nf/Npr)] * 100
Wherein: Nf is the raw material nitrogen content, and Npr and Np are respectively catalyst C-A and other catalyst hydrogenation is handled the oily nitrogen content of generation.
Find out by table 4, when supporting same metal, compare with reference catalyst and to have higher hydrodenitrogenationactivity activity with the reference agent through the catalyst of the present invention of silicon, boron additive modification.
The method that adds silicon and boron additive in alumina support provided by the invention has overcome (coprecipitation) silicon and boron major part in the prior art and has been distributed to the shortcoming of alumina body in mutually.Compare with reference catalyst, the present invention adopts the carrier of the aluminium oxide preparation of siliceous and boron, make catalyst have higher pore volume and specific surface, silicon and boron additive in the catalyst carrier are dispersed in carrier surface, make catalyst have suitable surface acid property, thereby have higher hydrotreatment activity.
Embodiment 7
Present embodiment is the life test of catalyst C-3 of the present invention, and used experimental rig, feedstock oil and evaluation process conditions the results are shown in Table 5 with embodiment 6.
Table 5 catalyst stability result of the test of the present invention
| Feedstock oil | Iran VGO | Iran VGO |
| The feedstock oil nitrogen content, μ g/g | 1205 | 1205 |
| Reaction pressure, MPa | 14.7 | 14.7 |
| Volume space velocity, h -1 | 1.0 | 1.0 |
| Reaction temperature, ℃ | 372 | 372 |
| Sampling time, h | 500 | 2000 |
| Generate oily nitrogen content, μ g/g | 2.1 | 4.3 |
Can see by table 5, catalyst of the present invention is a raw material with Iranian VGO,, generates oily nitrogen content and rises to 4.3 μ g/g by 2.1 μ g/g more than 2000 hours 372 ℃ of following steady runnings, average deactivation rate is 0.035 ℃/d, illustrates that catalyst of the present invention has good activity stability.
Claims (16)
1, a kind of heavy oil hydrogenating treatment catalyst, comprise siliceous and alumina support boron, and support at least a group vib metallic element and at least a VIII family metallic element, it is characterized in that described alumina support is made up of siliceous and macroporous aluminium oxide and aperture aluminium oxide boron, macroporous aluminium oxide wherein is siliceous with SiO
2Meter 1wt%-15wt%, boracic is with B
2O
3Meter 2wt%-18wt%, its specific area 350m
2/ g-500m
2/ g, pore volume 0.8ml/g-1.3ml/g, average pore diameter 8nm-13nm; Weight with catalyst is benchmark, and siliceous and macroporous aluminium oxide boron accounts for 10wt%-60wt%, and little porous aluminum oxide accounts for 10wt%-60wt%; The group vib element accounts for 10wt%-30wt% in oxide, and VIII family element accounts for 1w%-15w% in oxide, and phosphorus is with P
2O
5Meter accounts for 0.5wt%-5.0wt%.
2, catalyst according to claim 1 is characterized in that described macroporous aluminium oxide is siliceous with SiO
2Meter 1wt%-13wt%, boracic is with B
2O
3Meter 5wt%-15wt%, its specific area 400m
2/ g-450m
2/ g, pore volume 0.9ml/g-1.1ml/g, average pore diameter 8nm-11nm.
3, catalyst according to claim 1 and 2 is characterized in that, described macroporous aluminium oxide is after roasting, and its infrared acidity is 0.700mmol/g-0.960mmol/g.
4, catalyst according to claim 1 and 2 is characterized in that, described macroporous aluminium oxide is after roasting, and its infrared acidity is 0.700mmol/g-0.930mmol/g.
5, catalyst according to claim 1, the specific surface that it is characterized in that described catalyst is 160m
2/ g-190m
2/ g, pore volume are 0.3ml/g-0.4ml/g, and average pore diameter is 7.0nm-9.5nm.
6, catalyst according to claim 1 is characterized in that, described group vib metallic element is Mo and/or W, and described VIII family metallic element is Ni and/or Co.
7, the arbitrary described preparation method of hydrotreatment catalyst of claim 1-6 comprises the steps:
(1) preparation of the macroporous aluminium oxide of siliceous and boron:
A) fill in the container of water one, under agitation also stream adds continuously and contains aluminum ions acidic salt solution, adds alkaline solution simultaneously and is carried out to glue;
B) behind reinforced the end, above-mentioned system is aging, adds the alkali metal soln of the siliceous oxygen anion of metering then, continues aging;
C) filter and wash to anion/Al
2O
3＜2.0wt%;
D) add the boron-containing compound that measures;
E) filter also drying, promptly obtain siliceous and aluminium oxide boron;
(2) macroporous aluminium oxide of the siliceous and boron that step (1) is obtained and one or more little porous aluminum oxides and adhesive mix pinch, moulding, drying, roasting make carrier;
(3) promptly make catalyst with containing reactive metal solution impregnation, drying, roasting.
8, preparation method according to claim 7 is characterized in that, the drying condition of described carrier is: 40 ℃-180 ℃ of temperature, time 0.5h-24h; Roasting condition is: 400 ℃-700 ℃ of temperature, time 0.5h-24h; The drying condition of described catalyst is: 60 ℃-180 ℃ of temperature, time 0.5h-24h; Roasting condition is: 300 ℃-700 ℃ of temperature, time 0.5h-24h.
9, preparation method according to claim 7 is characterized in that, described to contain aluminum ions acidic salt solution be aluminium chloride, aluminum sulfate or aluminum nitrate solution, and its concentration is with Al
2O
3Count 2.0g/100ml-8.0g/100ml; Described alkaline solution is an ammoniacal liquor, and its concentration is with NH
3Count 6g/100ml-15g/100ml.
10, preparation method according to claim 7 is characterized in that, described to contain aluminum ions acidic salt solution be aluminum sulfate solution, and described alkaline solution is a sodium aluminate solution, and its concentration is with Al
2O
3Count 10.0g/100ml-25.0g/100ml.
11, preparation method according to claim 7 is characterized in that, the control pH value is 7.5-9.5 in the step a), and temperature is 30 ℃-90 ℃, and charging time is controlled at 30min-240min.
12, preparation method according to claim 7 is characterized in that, the alkali metal soln of described siliceous oxygen anion is sodium metasilicate or sodium metasilicate solution, with SiO
2Meter concentration is 4.0g/100ml-10.0g/100ml.
13, preparation method according to claim 7 is characterized in that, boron-containing compound described in the step d) is boric acid or borate, and its adding mode is: with filter cake making beating, directly add in the slurries or will join in the wet cake after the dissolving of boron-containing compound water.
14, preparation method according to claim 7 is characterized in that, wherein the control temperature is 30 ℃-90 ℃ in the step d).
15, preparation method according to claim 7 is characterized in that, wherein the control temperature is 40 ℃-70 ℃ in the step d).
16, preparation method according to claim 7 is characterized in that, baking temperature is 110 ℃-130 ℃ in the described step e), and be 12h-24h drying time.
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| CN101391224B (en) * | 2007-09-20 | 2010-11-24 | 中国石油化工股份有限公司 | Catalyst for removing nitrogen oxide and use thereof |
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| CN101491768B (en) * | 2008-01-23 | 2011-05-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing silicon and zirconium |
| CN101618346B (en) * | 2008-07-04 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing silicon and zirconium containing aluminum oxide carrier |
| CN101664688B (en) * | 2008-09-04 | 2012-05-09 | 中国石油化工股份有限公司 | Hydrogenation desilicification catalyst and preparation thereof |
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| CN102728373B (en) * | 2011-04-14 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN102728374B (en) * | 2011-04-14 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst |
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| CN107999142B (en) * | 2016-10-28 | 2020-06-16 | 中国石油化工股份有限公司 | Alkaline earth metal-containing hydrated alumina composition, molded body, preparation method and application of hydrated alumina composition, catalyst and preparation method of catalyst |
| 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 |
| CN114471642B (en) * | 2020-10-27 | 2023-07-14 | 中国石油化工股份有限公司 | Hydrodesilicification catalyst containing phosphorus and boron, preparation method thereof and hydrodesilicification method |
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