CN103285842A - Tooth-spherical alumina carrier, tooth-spherical hydrotreating catalyst and preparation methods thereof - Google Patents
Tooth-spherical alumina carrier, tooth-spherical hydrotreating catalyst and preparation methods thereof Download PDFInfo
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Abstract
The invention relates to a tooth-spherical alumina carrier, a tooth-spherical hydrotreating catalyst and preparation methods thereof. The tooth-spherical alumina carrier comprises the following components in parts by weight: 0.5-4 parts of a peptizing agent, 0.2-2 parts of a lubricant, 0.2-3 parts of a dispersant, 0.3-4 parts of a pore-enlarging agent, and 100 parts of aluminum hydroxide. Because various additives such as the peptizing agent, the pore-enlarging agent, the dispersant, the anionic surfactant and the like in the tooth-spherical alumina carrier disclosed by the invention are greatly reduced, the cost of the tooth-spherical alumina carrier is saved, and the tooth-spherical alumina carrier also has the advantages of large specific surface area, high mechanical strength, and the like.
Description
Technical field
The present invention relates to a kind of tooth ball-aluminium oxide carrier, the spherical hydrotreating catalyst of tooth and preparation method thereof, belong to the technical field of hydrogenation catalyst.
Background technology
Along with development and national economy, people are increasing for the demand of the energy, and oil is as one of important energy source, because it is non-renewable, petroleum resources particularly light oil resource reduce just day by day.Along with the minimizing of light oil resource, the ratio of mink cell focus increases in the world oil output, and the content of residual oil is up to more than 60% in the mink cell focus, and therefore, the lighting of mink cell focus is one of very important work in the present petroleum refining industry.The hydrotreatment of mink cell focus is one of important means of light materialization of heavy oil.The hydrotreatment of so-called mink cell focus refers under the condition that high pressure hydrogen, catalyst for hydroprocessing of heavy oil exist, mink cell focus is carried out processing procedures such as hydrodesulfurization, thereby production low-sulphur fuel, or carry out partial cracking simultaneously is for catalytic cracking or hydrocracking are supplied raw materials.When hydrotreatment, in the mink cell focus in the crude oil of enrichment trace meters such as the vanadium, iron, nickel of the overwhelming majority can deposit to the surface of catalyst and influence the catalytic performance of catalyst, therefore, the hydrodynamics state of the aperture of catalyst, pore size distribution, specific area and catalyst surface all exerts an influence to the hydrotreatment of mink cell focus.In the prior art, catalyst for hydroprocessing of heavy oil is many with γ-Al
2O
3Be carrier, Common Shape has cylinder bar shaped, sphere, cloverleaf pattern etc., wherein, compared to cylinder bar shaped and sphere, cloverleaf pattern γ-Al
2O
3Carrier has advantages such as bulk density is little, specific area is big, bed pressure drop is low because of its features of shape.In recent years, tooth spherical gamma-Al
2O
3Carrier becomes the research focus gradually as a kind of new bearer type, and this is because tooth spherical gamma-Al
2O
3Carrier is compared with the cloverleaf pattern carrier, and except reducing the bed pressure drop, also comprise following characteristics: (1) specific area is big, and according to calculating, when its peripheral radius r=1, the surface area of individual particle tooth ball type carrier is 13.3368; When r=x, the surface area of individual particle tooth ball type carrier is 13.3368x
2As a comparison, when r=1, the surface area of individual particle cloverleaf pattern carrier is 12.5664, and when r=x, the surface area of individual particle cloverleaf pattern carrier is 12.5664x
2Porosity is big when (2) loading, bed pressure drop is low, the reacting fluid resistance is little, according to the gas-liquid two-phase flow test in the cold mould trickle bed reactor, when superficial gas velocity is 0.1027m/s, the actual measurement pressure drop gradient of tooth ball type carrier is 531.3433Pa/m, and the actual measurement pressure drop gradient of cloverleaf pattern carrier is 618.0488Pa/m; (3) the carrier rollability is good, and evenly mixed packing is effectively avoided because filling is uneven influencing every performance of catalyst; (4) activity component load quantity is big, and the reactant diffusion velocity is fast, the utilization rate height of catalyst, and reaction temperature is low, effectively avoids catalyst because of hot-spot coking, long service life.
Chinese patent literature CN101497044B discloses a kind of teeth spherical heavy oil hydrotreating catalyst and preparation thereof, its preparation may further comprise the steps: the preparation of (1) alumina support precursor: add peptizing agent, expanding agent and shaping assistant in the aluminium hydroxide, after mixing, add deionized water and nitric acid, mix, make magma shape plastic; Described peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or aforementioned two or more mixture arbitrarily, expanding agent is carboxymethyl cellulose, Sodium Polyacrylate, starch derivatives or methylcellulose or aforementioned two or more mixture arbitrarily, and shaping assistant is sesbania powder or polyethylene glycol or its mixture; (2) preparation of tooth ball-aluminium oxide carrier: the magma shape plastic that step (1) is made adds in the skewed slot of extruder, extrudes by the spherical orifice plate of tooth, through pelletizing, health, drying, roasting, makes tooth ball-aluminium oxide carrier; (3) preparation of catalyst impregnating solution: active component and deionized water mix and are mixed with active component solution, add auxiliary agent, are warming up to 60-150 ℃, are incubated 0.5-3 hour, mix, and make catalyst impregnating solution; Obtain the wet bulb carrier, take out back health, drying, roasting, make teeth spherical heavy oil hydrotreating catalyst.Handle catalyst in order to obtain the spherical heavy hydrogenated of tooth that specific area is big, pore volume is big, intensity is high among the above-mentioned preparation method, when in step (1), preparing the alumina support precursor, it is 11%, 4%, 4% that the amount of adding peptizing agent, expanding agent and shaping assistant accounts for the mass percent of aluminium hydroxide higher, though this is because the addition of peptizing agent, expanding agent and shaping assistant will increase production cost virtually, but have only the peptizing agent that adds capacity just can make alumina powder jointed mixing, and then form the measured colloid of matter; Add the expanding agent of capacity and shaping assistant simultaneously to increase pore volume and the specific area of carrier, and adding the capacity shaping assistant also can make the required material of preparation carrier realize in the mixed grind process fully, evenly mix, realize extruding of control material then, finally obtain the carrier of forming.Yet discover that the interpolation of peptizing agent, expanding agent and shaping assistant also can have a negative impact simultaneously, is mainly reflected in: add excessive pore volume and the specific area that will seriously reduce carrier of peptizing agent proportion; Diffused auxiliary agents such as sesbania powder and methylcellulose are by CO in the carrier roasting process
2Effusion produces a large amount of micropores and makes the specific area of carrier and pore volume increase, but will cause the reduction of support strength simultaneously, for methylcellulose, can reduce pore volume and the specific area of carrier on the contrary when adding is excessive.In sum, during preparation tooth ball-aluminium oxide carrier, when the every performance that guarantees the acquisition carrier is up to standard, reduce the addition of components such as peptizing agent, expanding agent and shaping assistant as far as possible.
Summary of the invention
Technical problem to be solved by this invention is when preparing tooth ball-aluminium oxide carrier in the prior art, because it is bigger that the addition of components such as peptizing agent, expanding agent and shaping assistant accounts for the mass percent of aluminium hydroxide, and the performance that makes tooth ball-aluminium oxide carrier is had a negative impact, thereby provide a kind of novel tooth ball-aluminium oxide carrier and preparation method thereof.
Further, the present invention also provides a kind of tooth based on described tooth ball-aluminium oxide carrier spherical hydrotreating catalyst.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of tooth ball-aluminium oxide carrier, it comprises following component:
Peptizing agent, the 0.5-4 weight portion;
Dispersant, the 0.2-3 weight portion;
Expanding agent, the 0.3-4 weight portion;
Anion surfactant, the 0.2-5 weight portion;
Aluminium hydroxide, 100 weight portions.
Described aluminium hydroxide is selected from a kind of or its mixture in macropore aluminium hydroxide that carbonizatin method produces, the aperture aluminium hydroxide that nitrate method is produced.
The aperture of described macropore aluminium hydroxide is 15-20nm, and the aperture of described aperture aluminium hydroxide is 5-12nm.
Described peptizing agent is one or more the mixture in nitric acid, citric acid, acetic acid or the tartaric acid, described dispersant is one or both the mixture in ethyl cellulose or the hydroxyethylcellulose, and described expanding agent is one or more the mixture in polyvinyl alcohol, Sodium Polyacrylate, starch derivatives or the carbon black.
Also comprise lubricant.
Described lubricant is one or both the mixture in sesbania powder or the stearic acid.
Described anion surfactant is one or both the mixture in dodecylphosphoric acid monoesters or fourth octyl group two thioesters.
Further, a kind of method for preparing described tooth ball-aluminium oxide carrier, it comprises the steps:
(1) aluminium hydroxide that will select weight portion mixes with dispersant, expanding agent, mixes the back and adds described peptizing agent and anion surfactant, adds deionized water at last, mixes, and makes plastic;
(2) the described plastic of step (1) is carried out moulding, pelletizing, health, drying, calcination process successively, make tooth ball-aluminium oxide carrier.
Described step also is added with lubricant in (1).
Incorporation time is 20-60 minute described in the step (1).
Health temperature is room temperature described in the described step (2), and the time is 30-60 minute; Described baking temperature is 80-150 ℃, and be 3-4 hour described drying time; Described sintering temperature is 400-1100 ℃, and described roasting time is 2-3 hour.
Further, also provide a kind of tooth based on described tooth ball-aluminium oxide carrier spherical hydrotreating catalyst, its composition comprises active component, auxiliary agent and tooth ball-aluminium oxide carrier, described active component comprises cobalt oxide, nickel oxide, tungsten oxide, zirconia and/or chromium oxide, described auxiliary agent is phosphorus pentoxide, each component is benchmark with the gross weight of hydrotreating catalyst, cobalt oxide 1-7%, nickel oxide 1-8%, zirconia 1-5%, tungsten oxide 1-5%, chromium oxide 1-6%, phosphorus pentoxide 0.2-3.5%, all the other are tooth ball-aluminium oxide carrier.
The dispersant that also comprises 0.1-3% during the spherical hydrotreating catalyst of described tooth is formed.
Described dispersant is one or more the mixture in polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyphosphate sodium or the tertiary sodium phosphate.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) tooth ball-aluminium oxide carrier of the present invention, its raw material comprises: the peptizing agent of 0.5-4 weight portion, 0.2-3 the dispersant of weight portion, the expanding agent of 0.3-4 weight portion, the aluminium hydroxide of the anion surfactant of 0.2-5 weight portion and residuals weight part; When being benchmark with the quality of aluminium hydroxide in the prior art, add the percentage composition of peptizing agent, dispersant, expanding agent respectively up to 11%, 4%, 4%, the present invention is owing to added described anion surfactant in raw material, thereby described tooth ball-aluminium oxide carrier is implemented in when reducing various auxiliary component addition, makes that also specific area increases to 246m
2/ g is far above the 202m of prior art
2/ g also makes other every performances comprise that bulk density, pore volume, crushing strength, pore-size distribution etc. are optimized simultaneously; In addition, because the reduction of various auxiliary component additions, saving production cost simultaneously, also effectively avoided in the prior art since component additions such as peptizing agent, expanding agent and shaping assistant to account for the mass percent of aluminium hydroxide bigger, and the performance that makes tooth ball-aluminium oxide carrier is had a negative impact.
(2) tooth ball-aluminium oxide carrier of the present invention, aluminium hydroxide in the component is selected from a kind of or its mixture in macropore aluminium hydroxide that carbonizatin method produces, the aperture aluminium hydroxide that nitrate method is produced, because the aluminium hydroxide of carbonizatin method production has bigger specific area and pore volume, and select pore-size distribution to concentrate on 15-20nm macropore aluminium hydroxide, thereby when as the preparation catalyst carrier, has higher hydrogenation performance; Though and its specific area of aluminium hydroxide that nitrate method is produced and pore volume are a bit weaker than the aluminium hydroxide of carbonizatin method production, its preparation technology is simpler relatively, and cost is lower; Therefore, in practice process, the mixing that is chosen as independent use or rational proportion in view of the two characteristics is separately used, to reduce production costs to greatest extent reaching under the prerequisite that expection requires index.
(3) the spherical hydrotreating catalyst of tooth of the present invention, add various active components and comprise that the amount of cobalt oxide, nickel oxide, tungsten oxide and/or chromium oxide is less relatively, keeping described hydrotreating catalyst to have under the prerequisite of certain activity, the active component addition is easier to more after a little while realize that it carries out in order in carrier inside, disperses equably, make the inside of carrier own leave certain hole better adsorbing simultaneously, and improve the catalytic activity of catalyst.
The specific embodiment
The preparation of tooth ball-aluminium oxide carrier
Embodiment 1
The described tooth ball-aluminium oxide of present embodiment carrier, its preparation method comprises the steps:
(1) priority takes by weighing macropore aluminium hydroxide 100g, lubricant sesbania powder 1.3g, dispersant ethyl cellulose 3g and the expanding agent Sodium Polyacrylate 4g of the aperture 15-20nm of carbonizatin method production, and after adopting stirring mixer that above-mentioned various components are mixed 20 minutes, salpeter solution 4g, the anion surfactant dodecylphosphoric acid monoesters 5g and the deionized water 15g that add peptizing agent mass concentration 60wt%, then adopt kneading machine to mix 20 minutes, make magma shape plastic;
(2) the magma shape plastic that step (1) is made adds in the extruder skewed slot, extrude by the spherical orifice plate of tooth, again after the cutting knife pelletizing, health at room temperature 40 minutes, in air atmosphere, drying is 3 hours under 120 ℃,, makes (unimodal) tooth ball-aluminium oxide carrier 800 ℃ of following roastings 3 hours.
Embodiment 2
The described tooth ball-aluminium oxide of present embodiment carrier, its preparation method comprises the steps:
(1) priority takes by weighing the macropore aluminium hydroxide 100g of the aperture 5-12nm of carbonizatin method production, lubricant is the mixture 1.3g that sesbania powder and stearic acid are formed with mass ratio 1:1, dispersant is that ethyl cellulose and hydroxyethylcellulose are polyvinyl alcohol with mixture 1.5g and the expanding agent that mass ratio 1:1 forms, Sodium Polyacrylate, the mixture 1.5g that starch derivatives and carbon black are formed with mass ratio 1:1:1:1, and after adopting stirring mixer that above-mentioned various components are mixed 40 minutes, the adding peptizing agent is salpeter solution (mass concentration is 60wt%), citric acid solution (mass concentration is 90wt%), acetic acid solution (mass concentration is 30wt%) and tartaric acid solution (mass concentration is 30wt%) amount to 2g with the mixed acid solution that mass ratio 1:1:1:1 forms, anion surfactant is the mixture 2g that dodecylphosphoric acid monoesters and fourth octyl group two thioesters are formed with mass ratio 1:1, and deionized water 13g, then adopt kneading machine to mix 40 minutes, make magma shape plastic;
(2) the magma shape plastic that step (1) is made adds in the extruder skewed slot, extrude by the spherical orifice plate of tooth, again after the cutting knife pelletizing, health at room temperature 40 minutes, in air atmosphere, drying is 3 hours under 120 ℃,, makes (unimodal) tooth ball-aluminium oxide carrier 800 ℃ of following roastings 3 hours.
Embodiment 3
The described tooth ball-aluminium oxide of present embodiment carrier, its preparation method comprises the steps:
(1) taking by weighing the macropore aluminium hydroxide of carbonizatin method production and its mass ratio of aperture aluminium hydroxide of nitrate method production is that the mixture that 1:1 forms amounts to 100g, lubricant sesbania powder 2g, dispersant ethyl cellulose 0.2g and expanding agent CMS 0.3g, and after adopting stirring mixer that above-mentioned various components are mixed 60 minutes, acetic acid solution 0.5g, the anion surfactant fourth octyl group two thioester 0.2g and the deionized water 14g that add peptizing agent mass concentration 30wt%, then adopt kneading machine to mix 60 minutes, make magma shape plastic;
(2) the magma shape plastic that step (1) is made adds in the extruder skewed slot, extrude by the spherical orifice plate of tooth, again after the cutting knife pelletizing, health at room temperature 40 minutes, in air atmosphere, drying is 3 hours under 80 ℃,, makes (bimodal) tooth ball-aluminium oxide carrier 400 ℃ of following roastings 2 hours.
Embodiment 4
The described tooth ball-aluminium oxide of present embodiment carrier, its preparation method comprises the steps:
(1) priority takes by weighing macropore aluminium hydroxide 100g, dispersant ethyl cellulose 1.3g and the expanding agent carbon black 1.5g of the aperture 15-20nm of carbonizatin method production, and after adopting stirring mixer that above-mentioned various components are mixed 40 minutes, citric acid solution 2g, the anion surfactant dodecylphosphoric acid monoesters 2.0g and the deionized water 15g that add peptizing agent mass concentration 90wt%, then adopt kneading machine to mix 50 minutes, make magma shape plastic;
(2) the magma shape plastic that step (1) is made adds in the extruder skewed slot, extrude by the spherical orifice plate of tooth, again after the cutting knife pelletizing, health at room temperature 40 minutes, in air atmosphere, drying is 3 hours under 120 ℃,, makes (unimodal) tooth ball-aluminium oxide carrier 800 ℃ of following roastings 3 hours.
Comparative Examples 1
The described tooth ball-aluminium oxide of this Comparative Examples carrier, its preparation method comprises the steps:
(1) priority takes by weighing macropore aluminium hydroxide 100g, lubricant stearic acid 1.3g, dispersant ethyl cellulose 1.5g and the expanding agent Sodium Polyacrylate 1.5g of the aperture 15-20nm of carbonizatin method production, and after adopting stirring mixer that above-mentioned various components are mixed 30 minutes, the salpeter solution 3g and the deionized water 13g that add peptizing agent mass concentration 60wt%, then adopt kneading machine to mix 50 minutes, make magma shape plastic;
(2) the magma shape plastic that step (1) is made adds in the extruder skewed slot, extrude by the spherical orifice plate of tooth, again after the cutting knife pelletizing, health at room temperature 40 minutes, in air atmosphere, drying is 3 hours under 120 ℃,, makes (unimodal) tooth ball-aluminium oxide carrier 800 ℃ of following roastings 3 hours.
Comparative Examples 2
This Comparative Examples adopts method of the prior art to prepare tooth ball-aluminium oxide carrier, and it comprises the steps:
(1) preparation of tooth ball-aluminium oxide carrier precursor
Commodity aluminium hydroxide 60g, sesbania powder 10g, Sodium Polyacrylate 10g and citric acid powder 13g that the commodity aluminium hydroxide 200g that nitrate method is produced, carbonizatin method are produced, with kolleroang mixed grind 30min, the nitric acid 16g that adds deionized water 80g and 60%, continue mixed grind 40min with kolleroang, make magma shape plastic;
(2) preparation of tooth ball-aluminium oxide carrier
The magma shape plastic that step (1) is made adds in the skewed slot of extruder, extrudes by the spherical orifice plate of tooth, obtains the carrier that is shaped through pelletizing again; Then, health at room temperature 1 hour in 100-110 ℃ time dry 2 hours, is put into Muffle furnace in 500-550 ℃ of following roasting 4 hours in air atmosphere, make the alumina support of tooth sphere.
The tooth ball-aluminium oxide support samples that embodiment 1-4 and Comparative Examples 1-2 are made is numbered successively and is A-F, and the Main physical character of described sample is as shown in table 1:
The physical property of the different alumina support samples of table 1
The preparation of the spherical hydrotreating catalyst of tooth
Embodiment 6
The spherical hydrotreating catalyst of the described tooth of present embodiment is to prepare on embodiment 1 described tooth ball-aluminium oxide carrier basis, and its composition comprises: active component, auxiliary agent and tooth ball-aluminium oxide carrier; Wherein, active component comprises cobalt oxide, nickel oxide and tungsten oxide, auxiliary agent is phosphorus pentoxide, dispersant is polyoxyethylene lauryl ether, each component is benchmark with the gross weight of hydrotreating catalyst, its quality percentage composition is respectively: cobalt oxide 4%, nickel oxide 5%, tungsten oxide 3%, phosphorus pentoxide 2%, polyoxyethylene lauryl ether 3%, all the other components are tooth ball-aluminium oxide carrier.
The spherical preparation method of hydrotreatment catalyst of described tooth comprises the steps:
(1) preparation of catalyst impregnating solution: accurately take by weighing basic cobaltous carbonate 12g, nickel nitrate 12.5g and ammonium metatungstate 11g, adding the deionized water that is added with ammoniacal liquor mixes, after mixing, then add 10g auxiliary agent phosphorus pentoxide and 11g dispersant polyoxyethylene lauryl ether, after mixing, be warming up to 100 ℃ and be incubated 2 hours, make catalyst impregnating solution;
(2) Preparation of catalysts: the tooth ball-aluminium oxide carrier of described embodiment 1 preparation of 200g is placed dipping tank, add the catalyst impregnating solution dipping 0.8h that 300g step (1) makes, obtain the wet bulb carrier, health 0.5h at room temperature after the taking-up, put into baking oven in 90 ℃ of dry 3h, put into converter then in 550 ℃ of roastings 2 hours, make the spherical hydrotreating catalyst of unimodal tooth after the cooling.
Embodiment 7
The spherical hydrotreating catalyst of the described tooth of present embodiment is to prepare on embodiment 2 described tooth ball-aluminium oxide carrier bases, and its composition comprises: active component, auxiliary agent and tooth ball-aluminium oxide carrier; Wherein, active component comprises cobalt oxide, nickel oxide and chromium oxide, auxiliary agent is phosphorus pentoxide, dispersant is polyoxyethylene lauryl ether, each component is benchmark with the gross weight of hydrotreating catalyst, its quality percentage composition is respectively: cobalt oxide 7%, nickel oxide 8%, chromium oxide 6%, phosphorus pentoxide 3.5%, all the other components are tooth ball-aluminium oxide carrier.
The spherical preparation method of hydrotreatment catalyst of described tooth comprises the steps:
(1) preparation of catalyst impregnating solution: accurately take by weighing basic cobaltous carbonate 21g, nickel nitrate 20g and chromic nitrate 18g, adding the deionized water that is added with ammoniacal liquor mixes, after mixing, then add 15g auxiliary agent phosphorus pentoxide and 10g dispersant polyoxyethylene lauryl ether, after mixing, be warming up to 100 ℃ and be incubated 3 hours, make catalyst impregnating solution;
(2) Preparation of catalysts: the tooth ball-aluminium oxide carrier of described embodiment 1 preparation of 200g is placed dipping tank, add the catalyst impregnating solution dipping 0.5h that 300g step (1) makes, obtain the wet bulb carrier, health 0.5h at room temperature after the taking-up, put into baking oven in 90 ℃ of dry 3h, put into converter then in 550 ℃ of roastings 2 hours, make the spherical hydrotreating catalyst of unimodal tooth after the cooling.
Embodiment 8
The spherical hydrotreating catalyst of the described tooth of present embodiment is to prepare on embodiment 3 described tooth ball-aluminium oxide carrier bases, and its composition comprises: active component, auxiliary agent and tooth ball-aluminium oxide carrier; Wherein, active component comprises cobalt oxide, nickel oxide, tungsten oxide and zirconia, auxiliary agent is phosphorus pentoxide, dispersant is polyoxyethylene lauryl ether, each component is benchmark with the gross weight of hydrotreating catalyst, its quality percentage composition is respectively: cobalt oxide 1%, nickel oxide 1%, tungsten oxide 1%, zirconia 1%, phosphorus pentoxide 0.2%, all the other components are tooth ball-aluminium oxide carrier.
The spherical preparation method of hydrotreatment catalyst of described tooth comprises the steps:
(1) preparation of catalyst impregnating solution: accurately take by weighing basic cobaltous carbonate 3g, nickel nitrate 4g, ammonium metatungstate 3.5g and zirconium oxychloride 5g, adding the deionized water that is added with ammoniacal liquor mixes, after mixing, then add 0.2g auxiliary agent phosphorus pentoxide and 3g dispersant polyoxyethylene lauryl ether, after mixing, be warming up to 90 ℃ and be incubated 0.5 hour, make catalyst impregnating solution;
(2) Preparation of catalysts: the tooth ball-aluminium oxide carrier of described embodiment 1 preparation of 200g is placed dipping tank, add the catalyst impregnating solution dipping 1.0h that 300g step (1) makes, obtain the wet bulb carrier, health 0.5h at room temperature after the taking-up, put into baking oven in 90 ℃ of dry 3h, put into converter then in 550 ℃ of roastings 2 hours, make the spherical hydrotreating catalyst of unimodal tooth after the cooling.
Embodiment 9
The spherical hydrotreating catalyst of the described tooth of present embodiment is to prepare on embodiment 4 described tooth ball-aluminium oxide carrier bases, and its composition comprises: active component, auxiliary agent and tooth ball-aluminium oxide carrier; Wherein, active component comprises cobalt oxide, nickel oxide and zirconia, auxiliary agent is phosphorus pentoxide, dispersant is polyoxyethylene lauryl ether, each component is benchmark with the gross weight of hydrotreating catalyst, its quality percentage composition is respectively: cobalt oxide 4%, nickel oxide 5%, zirconia 3%, phosphorus pentoxide 2%, polyoxyethylene lauryl ether 3%, all the other components are tooth ball-aluminium oxide carrier.
The spherical preparation method of hydrotreatment catalyst of described tooth comprises the steps:
(1) preparation of catalyst impregnating solution: accurately take by weighing basic cobaltous carbonate 12g, nickel nitrate 12g and zirconium oxychloride 15g, adding the deionized water that is added with ammoniacal liquor mixes, after mixing, then add 10g auxiliary agent phosphorus pentoxide and 10g dispersant polyoxyethylene lauryl ether, after mixing, be warming up to 100 ℃ and be incubated 2 hours, make catalyst impregnating solution;
(2) Preparation of catalysts: the tooth ball-aluminium oxide carrier of described embodiment 1 preparation of 200g is placed dipping tank, add the catalyst impregnating solution dipping 0.8h that 300g step (1) makes, obtain the wet bulb carrier, health 0.5h at room temperature after the taking-up, put into baking oven in 90 ℃ of dry 3h, put into converter then in 550 ℃ of roastings 2 hours, make the spherical hydrotreating catalyst of unimodal tooth after the cooling.
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being extended out thus or change still are among the protection domain of the invention.
Claims (14)
1. tooth ball-aluminium oxide carrier is characterized in that it is made up of following raw material:
Peptizing agent, the 0.5-4 weight portion;
Dispersant, the 0.2-3 weight portion;
Expanding agent, the 0.3-4 weight portion;
Anion surfactant, the 0.2-5 weight portion;
Aluminium hydroxide, 100 weight portions.
2. tooth ball-aluminium oxide carrier according to claim 1 is characterized in that, described aluminium hydroxide is selected from a kind of or its mixture in macropore aluminium hydroxide that carbonizatin method produces, the aperture aluminium hydroxide that nitrate method is produced.
3. tooth ball-aluminium oxide carrier according to claim 2 is characterized in that, the aperture of described macropore aluminium hydroxide is 15-20nm, and the aperture of described aperture aluminium hydroxide is 5-12nm.
4. according to the arbitrary described tooth ball-aluminium oxide carrier of claim 1-3, it is characterized in that, described peptizing agent is one or more the mixture in nitric acid, citric acid, acetic acid or the tartaric acid, described dispersant is one or both the mixture in ethyl cellulose or the hydroxyethylcellulose, and described expanding agent is one or more the mixture in polyvinyl alcohol, Sodium Polyacrylate, starch derivatives or the carbon black.
5. according to the arbitrary described tooth ball-aluminium oxide carrier of claim 1-4, it is characterized in that described anion surfactant is one or both the mixture in dodecylphosphoric acid monoesters or fourth octyl group two thioesters.
6. according to the arbitrary described tooth ball-aluminium oxide carrier of claim 5, it is characterized in that, also comprise lubricant.
7. tooth ball-aluminium oxide carrier according to claim 6 is characterized in that, described lubricant is one or both the mixture in sesbania powder or the stearic acid.
8. method for preparing the arbitrary described tooth ball-aluminium oxide carrier of claim 1-7, it comprises the steps:
(1) aluminium hydroxide that will select weight portion mixes with dispersant, expanding agent, mixes the back and adds described peptizing agent and anion surfactant, adds deionized water at last, mixes, and makes plastic;
(2) the described plastic of step (1) is carried out moulding, pelletizing, health, drying, calcination process successively, make tooth ball-aluminium oxide carrier.
9. the preparation method of tooth ball-aluminium oxide carrier according to claim 8 is characterized in that, described step also is added with lubricant in (1).
10. according to Claim 8 or the preparation method of 9 described tooth ball-aluminium oxide carriers, it is characterized in that incorporation time is 20-60 minute described in the step (1).
11. according to Claim 8 or the preparation method of 9 described tooth ball-aluminium oxide carriers, it is characterized in that health temperature is room temperature described in the described step (2), the time is 30-60 minute; Described baking temperature is 80-150 ℃, and be 3-4 hour described drying time; Described sintering temperature is 400-1100 ℃, and described roasting time is 2-3 hour.
12. spherical hydrotreating catalyst of the tooth based on the arbitrary described tooth ball-aluminium oxide carrier of claim 1-7, it is characterized in that, form and comprise active component, auxiliary agent and tooth ball-aluminium oxide carrier, described active component comprises cobalt oxide, nickel oxide, tungsten oxide, zirconia and/or chromium oxide, described auxiliary agent is phosphorus pentoxide, each component is benchmark with the gross weight of hydrotreating catalyst, cobalt oxide 1-7%, nickel oxide 1-8%, tungsten oxide 1-5%, zirconia 1-5%, chromium oxide 1-6%, phosphorus pentoxide 0.2-3.5%, all the other are tooth ball-aluminium oxide carrier.
13. the spherical hydrotreating catalyst of tooth according to claim 12 is characterized in that, also comprises the dispersant of 0.1-3% during it is formed.
14. the spherical hydrotreating catalyst of tooth according to claim 13 is characterized in that, described dispersant is one or more the mixture in polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyphosphate sodium or the tertiary sodium phosphate.
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