CN103084183B - Fixed bed catalyst preparation method and fixed bed catalyst - Google Patents
Fixed bed catalyst preparation method and fixed bed catalyst Download PDFInfo
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- CN103084183B CN103084183B CN201110332501.6A CN201110332501A CN103084183B CN 103084183 B CN103084183 B CN 103084183B CN 201110332501 A CN201110332501 A CN 201110332501A CN 103084183 B CN103084183 B CN 103084183B
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Abstract
The invention discloses a fixed bed catalyst preparation method and a fixed bed catalyst. The method comprises that a molded carrier contacts a metal compound solution in an impregnation machine, and the molded carrier after contacting is dried and calcined, wherein the impregnation machine comprises an obliquely-arranged roller (10), the roller (10) comprises a rotatable cylinder (1) and a spray device (2), the inner wall of the cylinder (1) is provided with a spiral blade, and the spray device (2) is fixedly arranged and extends into the internal space of the cylinder (1). According to the method, a molded carrier is conveyed into the cylinder (1), and a metal compound solution is sprayed on the molded carrier with the spray device (2). With the method, the fixed bed catalyst with characteristics of good impregnation uniformity and low impregnation breaking rate can be obtained, automatic catalyst impregnation control can be achieved, production cost can be reduced, and requirements of large-scale industrial production can be met.
Description
Technical field
The present invention relates to the preparation method of catalyst and the fixed bed catalyst that prepared by the method for a kind of fixed bed.
Background technology
Due to the rapid expansion of oil refining hydrogenation plant scale, the demand of domestic hydrogenation catalyst maintains sustained and rapid growth.On the one hand, need to expand hydrogenation catalyst production capacity, need on the other hand to provide the hydrogenation catalyst product of better quality, meet the demand of the environmentally friendly energy in market.
Infusion process is to produce the most frequently used method of hydrogenation catalyst.By catalyst carrier is contacted with maceration extract, a certain amount of active component is entered in the micropore of catalyst carrier.Active component is to duct inwall infiltration, diffusion, then adsorbs with carrier surface, deposition or ion-exchange, and chemical reaction even occurs, and makes active constituent loading on described catalyst carrier.In dipping process, if maceration extract is just absorbed completely by carrier, be called saturated dipping.This method not only can be removed the filter operation of unnecessary maceration extract from, and can accurately control the content of active component in catalyst.Along with the maximization of hydrogenation catalyst process units and the increase of kind, the saturated infusion process of general employing is produced hydrogenation catalyst at present.Saturated infusion process production equipment is few, can save great amount of investment.In addition, saturated infusion process constant product quality, is applicable to large-scale production.
The requirement of hydrogenation catalyst dipping process, the one, dipping good uniformity.Described uniformity refer between particle and the outer surface Active components distribution of particle itself whether even, whether appearance color consistent.The 2nd, dipping percentage of damage is low.In hydrogenation catalyst dipping process, due between catalyst granules and the collision of catalyst and impregnator wall, also have the impact of heat of adsorption, cause producing in hydrogenation catalyst dipping process certain Fragmentation Phenomena.Broken later catalyst can not enter finished product, can only recycle.
At present, the dipping method of production hydrogenation catalyst mainly contains double conical rotary vessel dipping, V-type rotary drum dipping and stirs rotary drum impregnating.
Conventionally, double conical rotary vessel dipping is most widely used a kind of impregnation method at present, and the inside of double conical rotary vessel is not provided for the device of spray and stirring etc., thereby while carrying out impregnation process, can only radially mix carrier material, can not axially mix.And because the medium position of rotary drum is lower, dipping solution and carrier easily gather at this, the two ends dipping solution of rotary drum is less, thereby causes the dipping of carrier material inhomogeneous.Thereby the thickness of the middle part carrier bed of material of rotary drum reaches 500-800mm, carrier material is difficult for stirring, and thermal diffusivity is not good, and while causing flooding, temperature is higher, affects the intensity of catalyst carrier.In addition, while adopting double conical rotary vessel dipping, material running status is for sliding and rolling, and because most of material accumulates in the middle part of rotary drum, the collision between material is herein stronger, easily causes percentage of damage to increase.In addition, it is 200-300kg that the list of double conical rotary vessel impregnator is criticized production capacity, and not only production capacity is less, and the expansion of production capacity is difficult for realizing, and the enlarged meeting of production capacity is accompanied by the increase that mixes inhomogeneities and percentage of damage.
The rotary drum of V-type rotary drum impregnator is roughly " V " type, and rotary drum is comprised of two parts cylindrical shell.Compare with conventional drum, V-type rotary drum impregnator not only has certain axial mixed function, also has certain axial immixture, so dipping uniformity is better than conventional drum.But when adopting V-type rotary drum impregnator dipping, the collision between material is very violent, causes the percentage of damage of carrier higher, therefore, is only applicable to flood the catalyst of high strength carrier.In addition, it is 100-200kg that the list of V-type rotary drum impregnator is criticized production capacity, and production capacity is little, is not suitable for the requirement of large-scale production.
Stirring rotary drum impregnator is to use for reference concrete-agitating mixer structure, has increased maceration extract spray system, and become hydrogenation catalyst, stirs rotary drum impregnator.Not only radially mixed function is good to stir rotary drum impregnator, and has certain axially mixed function, and dipping uniformity is better.But when adopting stirring rotary drum impregnator dipping, the collision between carrier is more violent, the carrier percentage of damage when percentage of damage of carrier and employing double conical rotary vessel impregnator dipping is suitable.In addition it is 200-300kg that the list that, stirs rotary drum impregnator is criticized production capacity.Because the dipping percentage of damage of carrier is higher, further improve production capacity and lose more than gain.
In sum, there is following shortcoming in the hydrogenation catalyst dipping technique of application at present: the first production capacity is low.The list of existing impregnating equipment is criticized production capacity between 100-300kg, can not meet the needs of hydrogenation catalyst large-scale production far away.If carry out the simple energy that expands on existing impregnating equipment basis, cause catalyst prod Quality Down, and the dipping percentage of damage of carrier be high, has increased Catalyst Production cost.The second dipping is inhomogeneous.During existing impregnating equipment operation, only have radially and mix, do not possess axial mixed function.Or carrier is only more abundant at rotary drum middle part with contacting of maceration extract.And rotary drum two ends are because relative position is higher, carrier is less with contacting of maceration extract, thereby causes impregnating metal skewness.The 3rd dipping percentage of damage is high.At present, the catalyst breakage rate of the impregnating equipment of prior art is in 2% left and right, and when main cause is dipping, radiating effect is poor, and the collision of carrier and rotating cylinder is more serious.Thermal effect that scatters is poor.At present, the middle part thickness of feed layer of the impregnating equipment of prior art between 500-800mm, material turning weak effect during dipping, heat of adsorption is difficult to timely discharge, causes dipping temperature high, affects catalyst strength.
Summary of the invention
The object of the invention is to overcome above-mentioned defect of the prior art, and provide a kind of to the lower fixed bed of the dipping good uniformity of carrier, catalyst breakage rate the preparation method with catalyst, thereby improved fixed bed catalyst prod quality, reduce production cost, and met the needs of large-scale industrial production.
To achieve these goals, the invention provides the preparation method of catalyst for a kind of fixed bed, wherein, the method comprises shaping carrier metallizing thing solution is contacted in impregnator, the dry and roasting by the shaping carrier after contact; Described impregnator comprises the cylinder 10 being obliquely installed, and this cylinder 10 comprises rotating cylindrical shell 1 and spray equipment 2, on the inwall of described cylindrical shell 1, is provided with helical blade, and described spray equipment 2 is fixedly installed and extend in the inner space of described cylindrical shell 1; The method comprises shaping carrier is sent in described cylindrical shell 1, by described spray equipment 2, described metal compound solution is sprayed onto on shaping carrier.
The present invention also provides a kind of fixed bed catalyst, and wherein, described fixed bed is what by method provided by the invention, prepare with catalyst.
Adopt technique scheme of the present invention, the drum-inclined setting of the described impregnator for the preparation of catalyst, on the inwall of cylindrical shell, helical blade is set, while making barrel body rotation, helical blade can stir shaping carrier, mix, can there is radial and axial motion in shaping carrier simultaneously, thereby can make the contact of the abundant metallizing thing of shaping carrier solution mix, make the dipping of carrier more even, and the percentage of damage of the catalyst obtaining is lower, thereby improved the quality of described catalyst prod, and catalyst activity has improved 2% than the catalyst of existing explained hereafter.Under preferable case, because spray equipment extend into the inside of cylindrical shell, and position is fixing does not rotate with the rotation of cylindrical shell, when barrel body rotation is uniformly mixed shaping carrier, spray equipment sprays described dipping solution to the shaping carrier in cylindrical shell, preferred described spraying condition makes dipping solution become spray pattern, the dipping solution of described spray pattern is contacted with shaping carrier and can further guarantee fully contacting of shaping carrier and described dipping solution, therefore, carrier impregnation obtains more even, and the dipping effect of shaping carrier is better.Moreover impregnator of the present invention also comprises drive unit, and utilize described drive unit to drive the rotation of cylindrical shell 1.Described drive unit can drive described cylindrical shell 1 axial rotation, and more preferably, in situation, described drive unit can drive the axial forward of described cylindrical shell 1 and reverse alternate rotation, and for example, forward rotation can make mixing of materials, and rotating backward can discharging.Therefore, it is roll mode that the method that adopts impregnator dipping of the present invention to prepare hydrogenation catalyst makes the motion of described shaping carrier when dipping, therefore, can reduce the percentage of damage of catalyst in dipping process, the percentage of damage of the catalyst obtaining is not more than 0.5%, than adopting the percentage of damage (2.0% left and right) of the catalyst of existing explained hereafter to reduce by 75%, therefore, greatly reduce production cost.Because percentage of damage is low, can also expand cylindrical shell volume, increase the quantity of helical blade, thereby improve the production capacity of impregnator, adapt to the needs of large-scale production, enhance productivity.The 3rd, method of the present invention has improved hydrogenation catalyst list and has criticized production capacity, has realized the large-scale production of hydrogenation catalyst.Make to adopt method of the present invention, dipping process list is criticized production capacity more than 1000kg, has greatly improved the level of production of hydrogenation catalyst.
Other features and advantages of the present invention partly in detail are described the specific embodiment subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with the specific embodiment one below.
In the accompanying drawings:
Fig. 1 is the schematic diagram of catalyst impregnator used for fixed bed of preparing of the present invention.
Description of reference numerals:
1 cylindrical shell 2 spray equipments
2 ' body 3 feed arrangements
4 drawing mechanism 10 cylinders
20 bases
The specific embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
As shown in Figure 1, the method for the invention comprises shaping carrier metallizing thing solution is contacted in impregnator, the dry and roasting by the shaping carrier after contact; Described impregnator comprises the cylinder 10 being obliquely installed, and this cylinder 10 comprises rotating cylindrical shell 1 and spray equipment 2, on the inwall of described cylindrical shell 1, is provided with helical blade, and described spray equipment 2 is fixedly installed and extend in the inner space of described cylindrical shell 1; The method comprises shaping carrier is sent in described cylindrical shell 1, by described spray equipment 2, described metal compound solution is sprayed onto on shaping carrier.
In the present invention, the cylinder 10 of the described impregnator for the preparation of catalyst is obliquely installed, and the angle of inclination of described cylinder 10 can be 10-14 degree, and length can be 4.5-5.5 rice.Described angle of inclination refers to central shaft and the horizontal angle of cylinder.To the interior diameter of cylinder, there is no particular limitation, and the amount of the shaping carrier that can flood is as required selected the interior diameter of suitable cylindrical shell 1, and generally, the interior diameter of cylindrical shell 1 can be 1-2 rice.Described cylindrical shell 1 can be made by various anti-abrasive materials, for example, and steel, rubber or rigid plastics.On the inwall of described cylindrical shell 1, be provided with helical blade, during this impregnator forward rotation, carrier material carried out to hybrid infusion; When impregnator rotates backward, carrier material is discharged in cylindrical shell, make cylindrical shell 1 helical blade when rotating can stir shaping carrier, mix, can there is radial and axial motion in shaping carrier simultaneously, thereby make shaping carrier fully contact mixing with described metal compound solution, make dipping solution even to the dipping of shaping carrier, and the percentage of damage of shaping carrier is lower.
In addition, because spray equipment 2 extend into the inside of cylindrical shell 1, and position is fixed and with the rotation of cylindrical shell 1, does not rotate.When the rotation of cylindrical shell 1 is uniformly mixed shaping carrier, spray equipment 2 sprays described metal compound solution to the shaping carrier in cylindrical shell 1, further make the dipping of shaping carrier more even, so the dipping effect of shaping carrier is better, the quality of the catalyst of production is higher.
Owing to having, the catalyst breakage rate of impregnator of described structure is lower, therefore can expand the volume of cylindrical shell 1, increases the quantity of helical blade, thereby improves the production capacity of impregnator, adapts to the needs of large-scale production, enhances productivity.
As shown in Figure 1, in order to facilitate charging and the discharging of cylindrical shell 1, preferably, described cylinder 10 comprises feed arrangement 3 and the drawing mechanism 4 that is arranged on described cylindrical shell 1 one end, and this feed arrangement 3 and drawing mechanism 4 are communicated with the inner space of described cylindrical shell 1 by the nozzle of described cylindrical shell 1 one end.The charging aperture of described feed arrangement 3 upward, extend to the nozzle of cylindrical shell 1 and extend into the pipeline of cylindrical shell 1 inner space, the pipeline of feed arrangement 3 can be various structures, for example, vertically extend the structure of the backward nozzle bending of certain distance, is convenient to shaping carrier and slips into smoothly cylindrical shell 1 inside.Drawing mechanism 4 is for being arranged on the nozzle outside of cylindrical shell 1 and the casing of encirclement nozzle, and down, the fixed bed of being convenient to obtain after dipping passes through described drawing mechanism 4 from the inner discharge of cylindrical shell 1 with catalyst to its discharging opening, and is convenient to collection.
Because impregnator needs airtight environment when the impregnation process, preferably, described feed arrangement 3 and described drawing mechanism 4 are tightly connected with described cylindrical shell 1 respectively.Feed arrangement 3 is connected with the nozzle of cylindrical shell 1 by sealing device (such as sealing ring, sealing strip and lid etc.) with drawing mechanism 4, guaranteed the sealing of cylinder 10, while having avoided shaping carrier in dipping process to be uniformly mixed, the splashing and the leakage of catalyst carrier or the catalyst that obtains of metal compound solution.In addition, the contact of the solution of shaping carrier metallizing thing is preferably carried out under vacuum condition, described feed arrangement 3 and described drawing mechanism 4 and being tightly connected of described cylindrical shell 1 have also guaranteed to contact sealing and the vacuum condition of dipping process, thereby reduced the surface tension between the solution of shaping carrier metallizing thing, described metal compound solution is more easily entered between the duct, inside of shaping carrier, and discharge the gas producing in dipping process.
Described spray equipment 2 can adopt various suitable version, as shown in Figure 1, preferably, described spray equipment 2 comprises body 2 ' and nozzle, described body 2 ' extends to the other end through the nozzle of described cylindrical shell 1 from one end of described cylindrical shell 1, and it is upper and towards the below of described body 2 ' that described nozzle is arranged on described body 2 '.Because body 2 ' extends to the inner space of whole cylindrical shell 1, make spray equipment 2 metal compound solution can be sprayed onto to each position of cylindrical shell 1 inside, make to be contained in cylindrical shell 1 shaping carrier everywhere and all can absorb solution and evenly be flooded.Due to the nozzle on body 2 ' downward, thereby make to make shaping carrier in the process of upset mixing when driving cylindrical shell 1 to rotate, nozzle still can directly be sprayed onto metal compound solution on shaping carrier so that shaping carrier fully absorbs dipping solution and is fully uniformly mixed, the dipping effect that has guaranteed shaping carrier is better, and uniformity is better.
As shown in Figure 1, in order further to improve the uniformity of dipping, preferably, described body 2 ' is along the longitudinal axis setting of described cylindrical shell 1.Metal compound solution is carried by body 2 ', again by nozzles spray out, body 2 ' is arranged on to the center of cylindrical shell 1 inner space, make the metal compound solution of sprinkling more even, to improve as far as possible the amount of the dipping solution on the shaping carrier being sprayed onto, improve the dipping uniformity of shaping carrier.
Described nozzle can arrange in every way, and preferably, described nozzle comprises the many groups nozzle arranging along the axially spaced-apart of described body 2 '.Many group nozzles are set along body 2 ' interval, more preferably, each organizes evenly interval setting between nozzle, make the shaping carrier in cylindrical shell 1 can both absorb the metal compound solution that spray equipment 2 sprays, and solution can be fully absorbed, can also reduce the consumption of metal compound solution, and improve the uniformity of dipping.
Because the radial dimension of cylindrical shell 1 is larger, respectively organizing nozzle and need to spray described solution to a certain amount of shaping carrier vertically, preferably, described in every group, nozzle comprises the circumferential spaced a plurality of nozzles along described body 2 '.A plurality of nozzles along circumferentially towards different directions, thereby along the different radial direction spray solution of cylindrical shell 1, make the shaping carrier of diverse location can be sprayed to solution, thereby more even to the dipping of shaping carrier.
A plurality of nozzles in described every group of nozzle can be towards different radial direction, and preferably, in described every group of nozzle, the jeting area of described a plurality of nozzles is the sector region of 60 °-180 ° of described body 2 ' belows.In the process of rotating at cylindrical shell 1, under Action of Gravity Field, most of shaping carriers are all positioned at body 2 ' below, in order to make full use of described solution, and the uniformity of raising dipping, described a plurality of nozzle is ejected into solution in the sector region of 60 °-180 ° of body 2 ' belows, can as much as possible metal compound solution be sprayed onto on the shaping carrier in cylindrical shell 1.
Shaping carrier in abundant mix and blend cylindrical shell 1, preferably, is provided with at least one helical blade on the inwall of described cylindrical shell 1; Two groups or more helical blade more preferably.Helical blade extends to the other end from one end of cylindrical shell 1, can the shaping carrier material in cylindrical shell 1 be stirred fully and be overturn, described carrier can fully be contacted with described solution, and the percentage of damage of carrier and the catalyst that obtains is lower, the effect of carrier impregnation is improved.When a plurality of helical blade is set, the even interval of common a plurality of helical blades arranges, and more even to the stirring of carrier material, catalyst breakage rate is lower.
Under preferable case, for the ease of operation, and can make mixing more even of the solution of shaping carrier metallizing thing, the impregnator adopting in the method for the invention also comprises drive unit, and utilizes described drive unit to drive the rotation of cylindrical shell 1.Wherein, described drive unit can be the various drive units that can drive cylindrical shell 1 to rotate, for example, for example, motor, more preferably Hydraulic Power Transmission System.Described drive unit can drive described cylindrical shell 1 axial rotation.Under preferable case, for the ease of metal compound solution to the dipping of shaping carrier, mixing, and the discharging of dipping rear catalyst, described drive unit can also drive the axial forward of described cylindrical shell 1 and reverse alternate rotation, for example, while driving described cylindrical shell 1 axial forward rotation, can make the mixing of metal compound solution and shaping carrier, driving described cylindrical shell 1 axially to rotate backward can be so that discharging, thereby the automation that realizes material is controlled.Wherein, described forward rotation preferably refers to clockwise rotate, and rotates backward preferred finger and rotates counterclockwise.
The rotating speed of described cylindrical shell 1 can regulate according to the needs of preparation, and under preferable case, the rotating speed of described cylindrical shell 1 can be 0-10 rev/min.
In addition can also, by regulating the rotating speed of cylindrical shell 1 to regulate the flow of metal compound solution, switch the import and export flow direction and can change impregnator traffic direction.
In order to facilitate the fixing of cylinder 20 and to arrange, as shown in Figure 1, preferably, for the preparation of fixed bed, with the impregnator of catalyst, also comprise base 20, described cylinder 10 is inclined on described base 20.Base 20 is arranged on horizontal plane, and motor, transmission device and cylinder 10 etc. can be set on base 20, make the overall structure of impregnator better, and stability is better.
According to the present invention, the consumption of described metal compound solution and the condition of contact are not particularly limited, as long as preferably make take described fixed bed, by the gross weight of catalyst, are benchmark, and the content of described catalyst carrier is 60-99.8 % by weight; In oxide, the content of described metallic compound is 0.2-40 % by weight.
According to the present invention, the present invention does not have specific (special) requirements to the condition of described shaping carrier metallizing thing solution contact, as long as metallic compound can be loaded on described shaping carrier.For example, the temperature that described contact conditions generally comprises contact is 20-50 ℃, is preferably 20-30 ℃; The time of contact is 20-40 minute, is preferably 30-40 minute.Under preferable case, for the solution that makes described metallic compound with shaping carrier in impregnator contact easier, make the fixed bed obtaining use the uniformity of catalyst better, described contact is carried out under vacuum condition, guarantee that described impregnator is in closed environment, described relative pressure (gauge pressure) can be-0.03MPa to 0MPa.
According to the present invention, the mode of contact of the present invention is for to be sprayed onto on shaping carrier described metal compound solution to flood by described spray equipment 2.The present invention without specific (special) requirements, can be the various impregnation methods of prior art to the mode of described dipping, for example, can be spray dipping, saturated dipping or excessive immersion stain.Under preferable case, in order to make metal compound solution more even to the dipping of shaping carrier, preferably the metal compound solution of spray pattern is contacted with shaping carrier, that is, it is spray pattern that the spraying condition of described spray equipment 2 makes the metal compound solution spraying.Described spray pattern makes liquid dispersion become fine droplet to form by nozzle or with high velocity air, and atomizing pressure is generally 0.3-0.8MPa.The spraying condition that realizes the spray pattern of metallic compound can regulate by variety of way, for example, regulate every group along the number of circumferential spaced a plurality of nozzles of described body 2 ', and in described every group of nozzle, the jeting area of described a plurality of nozzles, as the sector region of 60 °-180 ° of body 2 ' belows as described in being; And the sprinkling amount of adjusting metal compound solution and spray pressure etc.
The present invention to the kind of described metal compound solution without specific (special) requirements, can be the conventional various metallic compound aqueous solution of catalyst field for fixed bed, for example, can be the solution that contains group vib metallic compound or the solution that contains group VIII metallic compound, or the mixed solution that contains group vib metallic compound and group VIII metallic compound.
In the present invention, group VIII metallic compound in the described solution that contains group VIII metallic compound or contain group vib metallic compound and the mixed solution of group VIII metallic compound in the group VIII metallic compound of oxide and the weight ratio of shaping carrier, can in wider scope, select, under preferable case, take the group VIII metallic compound of oxide and the weight ratio of shaping carrier in the described solution that contains group VIII metallic compound or in the mixed solution that contains group vib metallic compound and group VIII metallic compound are 0.001-0.1: 1.
In the present invention, group vib metallic compound in the described solution that contains group vib metallic compound or contain group vib metallic compound and the mixed solution of group VIII metallic compound in the group vib metallic compound of oxide and the weight ratio of shaping carrier, can in wider scope, select, under preferable case, group vib metallic compound in the described solution that contains group vib metallic compound or contain group vib metallic compound and the mixed solution of group VIII metallic compound in take the group vib metallic compound of oxide and the weight ratio of shaping carrier be 0.05-0.6: 1.
The present invention, can carry out with reference to prior art without specific (special) requirements the described solution kind that contains group VIII metallic compound, is preferably the aqueous solution of group VIII metallic compound, or ammonia spirit.
The present invention to the kind of described group VIII metallic compound without specific (special) requirements, for example can be for nickel compound containing, cobalt compound, containing ruthenium compound, iron containing compounds, nickel compound containing, rhodium-containing compound, containing palladium compound with containing one or more in platinum compounds, under preferable case, in order to make catalyst activity and selectively higher for fixed bed of the present invention, described group VIII metallic compound is nickel compound containing, cobalt compound, containing palladium compound with containing one or more in platinum compounds.
The present invention without specific (special) requirements, for example, can be one or more in nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickelous sulfate to the kind of described nickel compound containing, is preferably one or more in nickel nitrate, nickel acetate and basic nickel carbonate.
The present invention without specific (special) requirements, for example, can be one or more in cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobaltous sulfate to the kind of described cobalt compound, is preferably one or more in cobalt nitrate, cobalt acetate and basic cobaltous carbonate.
The present invention without specific (special) requirements, for example, can be the acid of chlorine palladium to the described kind containing palladium compound.
The present invention without specific (special) requirements, for example, can be chloroplatinic acid to the described kind containing platinum compounds.
The present invention without specific (special) requirements, is preferably the aqueous solution of group vib metallic compound to the described solution kind that contains group vib metallic compound, or ammonia spirit.
The present invention without specific (special) requirements, is preferably molybdate compound and/or Tungstenic compound to the kind of described group vib metallic compound.
The present invention to the kind of described molybdate compound without specific (special) requirements, for example can be for molybdic acid, molybdenum oxide, molybdate, paramolybdate, containing molybdenum heteropolyacid with containing one or more of molybdenum heteropolyacid salt, be preferably one or more in molybdic acid, molybdenum trioxide, ammonium molybdate, ammonium paramolybdate, phosphomolybdic acid and P-Mo-Wo acid.
The present invention to the kind of described Tungstenic compound without specific (special) requirements, can be for example one or more in wolframic acid, tungstates, metatungstate, ethyl metatungstate, heteropoly acid containing tungsten and heteropoly acid containing tungsten salt, be preferably one or more in wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate, phosphotungstic acid and P-Mo-Wo acid.
The present invention to the kind of described shaping carrier without specific (special) requirements, for example, the shaping carrier that described shaping carrier can obtain for one or more moulding in heat-resistant inorganic oxide, inorganic silicate and mesopore molecular sieve.Described shaping carrier is generally cylindrical pellet.
The present invention to the kind of described heat-resistant inorganic oxide without specific (special) requirements, can carry out with reference to prior art, it can be for example aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, aluminium oxide-magnesia, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, one or more in clay, wherein, be preferably aluminium oxide and/or silica.
The present invention without specific (special) requirements, can be the aluminium oxide of pure gamma phase structure to the structure of described aluminium oxide, can be also the aluminium oxide of transition state duplex grain structure (aluminium oxide of the mixed crystal of at least one in gamma and delta, theta).The present invention without specific (special) requirements, for example, can be to make through high-temperature roasting the preparation method of the aluminium oxide of described transition state duplex grain structure, and sintering temperature can be 600-1200 ℃, is preferably 600-900 ℃; Roasting time can be 0.5-12 hour, is preferably 4-8 hour.
The present invention without specific (special) requirements, can be one or more in zeolite or non-zeolitic molecular sieves to the kind of described mesopore molecular sieve.Described zeolite molecular sieve can be one or more in erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, L zeolite, y-type zeolite, X-type zeolite, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta zeolite and omega zeolite.Described non-zeolite molecular sieve can be one or more in phosphate aluminium molecular sieve, HTS and SAPO (as SAPO) molecular sieve.
The present invention, can carry out with reference to prior art without specific (special) requirements the condition of described dry, roasting.For example dry temperature is generally 40-120 ℃, is preferably 80-120 ℃, and the time is 30-120 minute, is preferably 60-90 minute; The temperature of roasting is generally 80-500 ℃, is preferably 200-450 ℃, and the time is 60-240 minute, is preferably 180-240 minute.
Catalyst of the present invention can be various fixed bed catalyst conventionally known to one of skill in the art, for example, can comprise hydrogenation catalyst, reforming catalyst, anthraquinone hydrogenation catalyst, catalyst for coal liquefaction and other all fixed bde catalysts.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
To the present invention, be described in further detail by the specific embodiment below.
In the present invention, if shaping carrier (activated alumina) is strip, percentage of damage is defined as length and is less than the shaping carrier of 2 millimeters and the percentage of shaping carrier total amount.If shaping carrier (activated alumina) is spherical, percentage of damage is defined as the percentage of break bead and shaping carrier total amount.
In the present invention, the hydrogenation catalyst element composition obtaining adopts x-ray fluorescence spectrometry 500 ℃ of roastings after 4 hours by hydrogenation catalyst.
Embodiment 1
The present embodiment is for illustrating the preparation of hydrogenation catalyst provided by the invention.
Be prepared as follows impregnator as shown in Figure 1.
Described impregnator comprises cylinder 10, drive unit (not shown), feed arrangement 3, drawing mechanism 4 and the base 20 being obliquely installed, and described cylinder 10 is inclined on described base 20, and the angle of inclination of cylinder 10 is 11 degree.This cylinder 10 comprises rotating cylindrical shell 1 and spray equipment 2 and the feed arrangement 3 and the drawing mechanism 4 that are arranged on described cylindrical shell 1 one end, this feed arrangement 3 and drawing mechanism 4 are communicated with the inner space of described cylindrical shell 1 by the nozzle of described cylindrical shell 1 one end, and described feed arrangement 3 and described drawing mechanism 4 are tightly connected with described cylindrical shell 1 respectively, the internal diameter of cylindrical shell 1 is 1.5 meters, and length is 4.8 meters, on the inwall of described cylindrical shell 1, be provided with two helical blades, described spray equipment 2 is fixedly installed and extend in the inner space of described cylindrical shell 1, described spray equipment 2 comprises body 2 ' and nozzle, described body 2 ' extends to the other end through the nozzle of described cylindrical shell 1 from one end of described cylindrical shell 1, it is upper and towards the below of described body 2 ' that described nozzle is arranged on described body 2 ', described body 2 ' is along the longitudinal axis setting of described cylindrical shell 1, described nozzle comprises 10 groups of nozzles that arrange along the axially spaced-apart of described body 2 ', 0.1 meter, interval, described in every group, nozzle comprises circumferential spaced 5 nozzles along described body 2 ', in described every group of nozzle, the jeting area of described a plurality of nozzles is the sector region of 120 ° of described body (2 ') belows.
Take 1500 kg of hydrogen alumina powders (butt 70 % by weight, purchased from China Petrochemical Industry's catalyst Chang Ling branch company) use banded extruder (manufacturer: U.S. BONNOT company, model: 8 ") to be extruded into circumscribed circle diameter be the cloverleaf pattern bar of 1.6 millimeters; then 120 ℃ dry 4 hours; 550 ℃ of roastings 4 hours, obtain shaping carrier S1 (Al
2o
3content is 98.5 % by weight), the aluminium oxide characterizing in this carrier through X-ray diffraction is gama-alumina.
Start the motor of impregnator, drive cylindrical shell 1 to clockwise rotate (rotating speed is 8 revs/min) around central shaft, by above-mentioned, prepare 1047 kilograms of shaping carrier S1 and by feed arrangement 3, send in cylindrical shell 1 continuously, and vacuumize 30 minutes, making the relative pressure (gauge pressure) in cylindrical shell 1 is-0.02Mpa will contain 544 kilograms of (WO of ammonium metatungstate by described spray equipment 2
3content is 91 % by weight), 56 kilograms of (MoO of ammonium paramolybdate
3content is 81 % by weight) and 750 liters of the aqueous solution of basic nickel carbonate 103 kilograms (NiO content is 50 % by weight) under the effect of compress wind (blast (atomizing pressure) is 0.3MPa), at 25 ℃, body 2 ' and nozzle through spray equipment 2 spray into the shaping carrier S1 upper (flow of the described metallic compound aqueous solution is 100 liters/min) in cylindrical shell by the above-mentioned aqueous solution that is spray pattern, 8 minutes maceration extract joining days, then continue dipping 30 minutes.The wet feed obtaining after dipping is discharged to cylindrical shell 1 by drawing mechanism 4.
On band drier, be dried 240 minutes, the temperature that keeps dry is 60 ℃.Finally, by dried material, at mesh-belt kiln or turn kiln roasting 180 minutes, sintering temperature is 120 ℃, obtains 1590 kilograms of hydrogenation catalyst C1 (contents on dry basis is 97 % by weight).In oxide, catalyst C1 500 ℃ of roastings composition and the catalytic activity after 4 hours list in table 1.Detecting dipping process percentage of damage is 0.38%, and catalyst activity (removing total nitrogen rate) is 99.82% (feedstock oil: air-distillation three line diesel oil, total sulfur content 5361.2ng/ μ l, total nitrogen content 291.0ng/ μ l.Appreciation condition: 340 ℃ of reaction temperatures, reaction pressure 6.4MPa, hydrogen to oil volume ratio 500, liquid hourly space velocity (LHSV) 2.0h
-1).
Adopt existing double conical rotary vessel technology (in rotary drum, to add 0 kilogram of above-mentioned S1 carrier 30 as one kind, by 156 kilograms of (WO of ammonium metatungstate
3content is 91 % by weight), 16 kilograms of (MoO of ammonium paramolybdate
3content is 81 % by weight) and 215 liters of the aqueous solution of basic nickel carbonate 30 kilograms (NiO content is 50 % by weight) under the effect of compress wind (blast is 0.3MPa); at 25 ℃; on shaping carrier S1 in spray equipment sprays into rotary drum; 2 minutes maceration extract joining days; then continue dipping 30 minutes, shut down and discharge rotary drum.Dry, roasting condition is the same, obtaining 451 kilograms of hydrogenation catalyst C1 ' (contents on dry basis is 97 % by weight)) the hydrogenation catalyst dipping process percentage of damage produced is 1.94%, catalyst activity is 98.96% (feedstock oil: air-distillation three line diesel oil, total sulfur content 5361.2ng/ μ l, total nitrogen content 291.0ng/ μ l.Appreciation condition: 340 ℃ of reaction temperatures, reaction pressure 6.4MPa, hydrogen to oil volume ratio 500, liquid hourly space velocity (LHSV) 2.0h
-1).
Embodiment 2
The present embodiment is for illustrating the preparation of protective layer catalyst provided by the invention.
According to the method preparation of embodiment 1 impregnator as shown in Figure 1, and preparation and catalyst thereof, different, by Raschig ring active aluminum oxide carrier S2 (Al
2o
3content is 98.5 % by weight) (purchased from Yixing Chiba nonmetallic materials Co., Ltd) 1000kg sends in cylindrical shell 1 by feed arrangement 3 continuously, and vacuumize 30 minutes, making the relative pressure (gauge pressure) in cylindrical shell 1 is-0.02Mpa will contain 94 kilograms of (MoO of ammonium paramolybdate by described spray equipment 2
3content is 81 % by weight) and 870 liters of the aqueous solution of nickel nitrate 72.5 kilograms (NiO content is 25 % by weight) under the effect of compress wind (blast (atomizing pressure) is 0.5MPa), at 25 ℃, body 2 ' and nozzle through spray equipment 2 spray into the shaping carrier S2 upper (flow of the described metallic compound aqueous solution is 140 liters/min) in cylindrical shell by the above-mentioned aqueous solution that is spray pattern, 4 minutes maceration extract joining days, then continue dipping 30 minutes.The wet feed obtaining after dipping is discharged to cylindrical shell 1 by drawing mechanism 4.
On band drier, be dried 60 minutes, the temperature that keeps dry is 120 ℃.Finally, by dried material, at mesh-belt kiln or turn kiln roasting 240 minutes, sintering temperature is 420 ℃, obtains 1090 kilograms of protective layer catalyst C2 (contents on dry basis is 97 % by weight).In oxide, catalyst C2 500 ℃ of roastings composition and the catalytic activity after 4 hours list in table 1.Detecting dipping process percentage of damage is 0.2%, and catalyst activity (deferrization rate) is 98.3% (feedstock oil: HVI150+30ppm iron naphthenate, concentration is in iron.Appreciation condition: 300 ℃ of reaction temperatures, reaction pressure 6.0MPa, hydrogen to oil volume ratio 300, liquid hourly space velocity (LHSV) 10.0h
-1).
Adopt existing double conical rotary vessel technology (in rotary drum, to add 200 kilograms, S2 carrier, by 19 kilograms of (MoO of ammonium paramolybdate
3content is 81 % by weight) and 174 liters of the aqueous solution of nickel nitrate 14.5 kilograms (NiO content is 25 % by weight) under the effect of compress wind (blast is 0.5MPa); at 25 ℃; on shaping carrier S2 in spray equipment sprays into rotary drum; 1 minute maceration extract joining day; then continue dipping 30 minutes, shut down and discharge rotary drum.Dry, roasting condition is the same; obtaining 216 kilograms of protective layer catalyst C2 ' (contents on dry basis is 97 % by weight)) the protective layer catalyst soakage process percentage of damage produced is 1.3%; catalyst activity (deferrization rate) is 97.8% (appreciation condition: feedstock oil: HVI150+30ppm iron naphthenate, concentration is in iron.300 ℃ of reaction temperatures, reaction pressure 6.0MPa, hydrogen to oil volume ratio 300, liquid hourly space velocity (LHSV) 10.0h
-1).
Embodiment 3
The present embodiment is for illustrating the preparation of anthraquinone hydrogenation catalyst provided by the invention.
According to the method preparation of embodiment 1 impregnator as shown in Figure 1, and preparation and catalyst thereof, different, by cylindric active aluminum oxide carrier S3 (Al
2o
3content is 98.5 % by weight) (purchased from China Petrochemical Industry's catalyst Chang Ling branch company) 1000kg sends in cylindrical shell 1 by feed arrangement 3 continuously, and vacuumize 30 minutes, make the relative pressure (gauge pressure) in cylindrical shell 1 be-0.02Mpa, by described spray equipment 2 by 800 liters of chlorine palladium aqueous acids that contains 2.2 kilograms of palladiums under the effect of compress wind (blast (atomizing pressure) is 0.4MPa), at 25 ℃, body 2 ' and nozzle through spray equipment 2 spray into the shaping carrier S3 upper (flow of the described metallic compound aqueous solution is 140 liters/min) in cylindrical shell by the above-mentioned aqueous solution that is spray pattern, 4 minutes maceration extract joining days, then continue dipping 60 minutes.The wet feed obtaining after dipping is discharged to cylindrical shell 1 by drawing mechanism 4.
On band drier, be dried 60 minutes, the temperature that keeps dry is 80 ℃.Finally, by dried material, at mesh-belt kiln or turn kiln roasting 240 minutes, sintering temperature is 430 ℃, obtains 998 kilograms of (contents on dry basis is 97 % by weight) anthraquinone hydrogenation catalyst C3.In oxide, catalyst C3 500 ℃ of roastings composition and the catalytic activity after 4 hours list in table 1.Detecting dipping process percentage of damage is 0.28%.
The working solution that evaluating catalyst is used is that anthraquinone is dissolved in the mixed solvent of aromatic hydrocarbons and trioctyl phosphate composition, consists of: 2-EAQ 37.68g/L, tetrahydrochysene 2-EAQ 79.45g/L, heavy aromatics 652g/L, trioctyl phosphate 199g/L.2mL catalyst is packed into
in the stainless steel reaction pipe of 10mm, quartz sand is all loaded in upper and lower part.First, by catalyst in 80 ℃ of logical hydrogen reducing 7h.Then, at 50 ℃, Hydrogen Vapor Pressure 0.3MPa, liquid hourly space velocity (LHSV) 18h
-1condition under evaluate, hydrogenation efficiency is 6.3-6.5gH
2o
2/ L.
Adopt existing double conical rotary vessel technology (in rotary drum, to add 150 kilograms, S3 carrier; by 120 liters of chlorine palladium aqueous acids that contains 0.33 kilogram of palladium under the effect of compress wind (blast is 0.4MPa); at 25 ℃; on shaping carrier S3 in spray equipment sprays into rotary drum; 1 minute maceration extract joining day; then continue dipping 60 minutes, shut down and discharge rotary drum.Dry, roasting condition is the same, obtains 148 kilograms of anthraquinone hydrogenation catalyst C3 ' (contents on dry basis is 97 % by weight)) the anthraquinone hydrogenation catalyst dipping process percentage of damage produced is 1.4%.
The working solution that evaluating catalyst is used is that anthraquinone is dissolved in the mixed solvent of aromatic hydrocarbons and trioctyl phosphate composition, consists of: 2-EAQ 37.68g/L, tetrahydrochysene 2-EAQ 79.45g/L, heavy aromatics 652g/L, trioctyl phosphate 199g/L.2mL catalyst is packed into
in the stainless steel reaction pipe of 10mm, quartz sand is all loaded in upper and lower part.First, by catalyst in 80 ℃ of logical hydrogen reducing 7h.Then, at 50 ℃, Hydrogen Vapor Pressure 0.3MPa, liquid hourly space velocity (LHSV) 18h
-1condition under evaluate, hydrogenation efficiency is 6.1-6.2gH
2o
2/ L.
Embodiment 4
The present embodiment is for illustrating the preparation of catalytic reforming catalyst provided by the invention.
According to the method preparation of embodiment 1 impregnator as shown in Figure 1, and preparation and catalyst thereof, different, by spherical active aluminum oxide carrier S4 (Al
2o
3content is 98.5 % by weight) (purchased from China Petrochemical Industry's catalyst Chang Ling branch company) 1000kg sends in cylindrical shell 1 by feed arrangement 3 continuously, and vacuumize 30 minutes, make the relative pressure (gauge pressure) in cylindrical shell 1 be-0.02Mpa, by described spray equipment 2 by 800 liters of chloroplatinic acid aqueous solutions that contains 2.2 kilograms, platinum under the effect of compress wind (blast (atomizing pressure) is 0.3MPa), at 25 ℃, body 2 ' and nozzle through spray equipment 2 spray into the shaping carrier S4 upper (flow of the described metallic compound aqueous solution is 140 liters/min) in cylindrical shell by the above-mentioned aqueous solution that is spray pattern, 4 minutes maceration extract joining days, then continue dipping 60 minutes.The wet feed obtaining after dipping is discharged to cylindrical shell 1 by drawing mechanism 4.
On band drier, be dried 60 minutes, the temperature that keeps dry is 100 ℃.Finally, by dried material, at mesh-belt kiln or turn kiln roasting 240 minutes, sintering temperature is 490 ℃, obtains 1002 kilograms of (contents on dry basis is 97 % by weight) catalytic reforming catalyst C4.In oxide, catalyst C4 500 ℃ of roastings composition and the catalytic activity after 4 hours list in table 1.Detecting dipping process percentage of damage is 0.1%, and catalyst activity is 118% (appreciation condition: 500 ℃ of reaction temperatures, reaction pressure 1.47MPa, hydrogen to oil volume ratio 1200, liquid hourly space velocity (LHSV) 2.0h
-1, feedstock oil is refining naphtha, described refining naphtha virtue potential content 38 % by weight).
Adopt existing double conical rotary vessel technology (in rotary drum, to add 150 kilograms, S4 carrier; by 120 liters of chloroplatinic acid aqueous solutions that contains 0.33 kilogram, platinum under the effect of compress wind (blast is 0.3MPa); at 25 ℃; on shaping carrier S4 in spray equipment sprays into rotary drum; 1 minute maceration extract joining day; then continue dipping 60 minutes, shut down and discharge rotary drum.Dry, roasting condition is the same, obtaining 150 kilograms of catalytic reforming catalyst C4 ' (contents on dry basis is 97 % by weight)) the catalytic reforming catalyst dipping process percentage of damage produced is 0.8%, catalyst activity is 117% (appreciation condition: 500 ℃ of reaction temperatures, reaction pressure 1.47MPa, hydrogen to oil volume ratio 1200, liquid hourly space velocity (LHSV) 2.0h
-1, feedstock oil is refining naphtha, described refining naphtha virtue potential content is 38 % by weight).
Table 1
Result by embodiment 1-4 and upper table 1 can find out, compares with catalyst prepared by the method that adopts prior art, adopts the percentage of damage of the catalyst that method of the present invention prepares lower, and the activity of catalyst is higher simultaneously.
Claims (21)
1. the preparation method of catalyst for fixed bed, is characterized in that, the method comprises shaping carrier metallizing thing solution is contacted in impregnator, the dry and roasting by the shaping carrier after contact; Described impregnator comprises the cylinder (10) being obliquely installed, the angle of inclination of described cylinder (10) is 10-14 degree, this cylinder (10) comprises rotating cylindrical shell (1) and spray equipment (2), on the inwall of described cylindrical shell (1), be provided with helical blade, described spray equipment (2) is fixedly installed and extend in the inner space of described cylindrical shell (1); The method comprises shaping carrier is sent in described cylindrical shell (1), by described spray equipment (2), described metal compound solution is sprayed onto on shaping carrier.
2. preparation method according to claim 1, wherein, described cylinder (10) comprises feed arrangement (3) and the drawing mechanism (4) that is arranged on described cylindrical shell (1) one end, and this feed arrangement (3) and drawing mechanism (4) are communicated with the inner space of described cylindrical shell (1) by the nozzle of described cylindrical shell (1) one end; Described shaping carrier is sent in described cylindrical shell (1) by described feed arrangement (3), and the fixed bed obtaining after dipping is discharged from cylindrical shell (1) is inner by described drawing mechanism (4) with catalyst.
3. preparation method according to claim 2, wherein, described feed arrangement (3) and described drawing mechanism (4) are tightly connected with described cylindrical shell (1) respectively.
4. preparation method according to claim 1, wherein, described spray equipment (2) comprises body (2 ') and nozzle, described body (2 ') extends to the other end through the nozzle of described cylindrical shell (1) from one end of described cylindrical shell (1), and it is upper and towards the below of described body (2 ') that described nozzle is arranged on described body (2 ').
5. preparation method according to claim 4, wherein, described body (2 ') is along the longitudinal axis setting of described cylindrical shell (1).
6. preparation method according to claim 5, wherein, described nozzle comprises the many groups nozzle arranging along the axially spaced-apart of described body (2 ').
7. preparation method according to claim 6, wherein, described in every group, nozzle comprises the circumferential spaced a plurality of nozzles along described body (2 ').
8. preparation method according to claim 7, wherein, in described every group of nozzle, the jeting area of described a plurality of nozzles is the sector region of 60 °-180 ° of described body (2 ') belows.
9. preparation method according to claim 1, wherein, is provided with at least one helical blade on the inwall of described cylindrical shell (1).
10. preparation method according to claim 1, wherein, described impregnator also comprises drive unit, and utilizes described drive unit to drive the rotation of cylindrical shell (1).
11. preparation methods according to claim 10, wherein, described drive unit can drive described cylindrical shell (1) axial rotation.
12. according to the preparation method described in claim 10 or 11, and wherein, described drive unit can drive described cylindrical shell (1) axially forward and reverse alternate rotation.
13. preparation methods according to claim 1, wherein, described impregnator also comprises base (20), described cylinder (10) is inclined on described base (20).
14. methods according to claim 1, wherein, the consumption of described metal compound solution and the condition of contact make, the described fixed bed of take is benchmark by the gross weight of catalyst, the content of described shaping carrier is 60-99.8 % by weight, in oxide, the content of described metallic compound is 0.2-40 % by weight.
15. according to the method described in claim 1 or 14, wherein, described metal compound solution is the solution that contains group VIB metallic compound or the solution that contains group VIII metal compound, or the mixed solution that contains group VIB metallic compound and group VIII metal compound.
16. methods according to claim 15, wherein, take the group VIB metallic compound of oxide and the weight ratio of shaping carrier that described in, contain in the solution of group VIB metallic compound or in the mixed solution that contains group VIB metallic compound and group VIII metal compound are 0.05-0.6:1; Take the group VIII metal compound of oxide and the weight ratio of shaping carrier in the described solution that contains group VIII metal compound or in the mixed solution that contains group VIB metallic compound and group VIII metal compound are 0.001-0.1:1.
17. methods according to claim 16, wherein, described group VIB metallic compound is molybdate compound and/or Tungstenic compound, and described group VIII metal compound is nickel compound containing, cobalt compound, containing palladium compound with containing one or more in platinum compounds.
18. according to the method described in claim 1 or 3, and wherein, described contact is carried out under vacuum condition, and the condition of described contact comprises: relative pressure is-0.03MPa to 0MPa, and the temperature of contact is 20-50 ℃, and the time of contact is 20-40 minute; The velocity of rotation of described cylindrical shell (1) is 0-10 rev/min.
19. according to the method described in claim 1 or 8, wherein, it is spray pattern that the spraying condition of described spray equipment (2) makes the metal compound solution spraying, and atomizing pressure is 0.3-0.8MPa, and the flow of described metal compound solution is 80-160 liter/min.
20. according to the method described in claim 1 or 14, and wherein, one or more moulding in heat-resistant inorganic oxide, inorganic silicate and mesopore molecular sieve of described shaping carrier obtain.
21. 1 kinds of fixed bed catalyst, is characterized in that, this fixed bed catalyst is to prepare by the method described in any one in claim 1-20.
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| CN104338564B (en) * | 2013-07-26 | 2017-03-29 | 中国石油化工股份有限公司 | Catalyst impregnating equipment and catalyst dipping method |
| CN104588126B (en) * | 2013-11-03 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of immersion system and the method for preparing catalyst |
| CN105268489A (en) * | 2014-06-10 | 2016-01-27 | 中国石油化工股份有限公司 | Dipping rotary drum and catalyst production equipment |
| CN106311359B (en) * | 2015-06-16 | 2019-07-26 | 中国石油化工股份有限公司 | A kind of molecular sieve catalyst and preparation method thereof |
| FR3051685B1 (en) * | 2016-05-30 | 2018-06-08 | IFP Energies Nouvelles | PROCESS FOR PREPARING A SELECTIVE HYDROGENATION CATALYST |
| CN106732564B (en) * | 2016-12-03 | 2019-06-14 | 西安凯立新材料股份有限公司 | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application |
| CN106582757B (en) * | 2016-12-03 | 2019-06-14 | 西安凯立新材料股份有限公司 | Dehydroepiandros-sterone adds hydrogen palladium/calcium carbonate catalyst preparation method and application |
| JPWO2021060419A1 (en) * | 2019-09-27 | 2021-04-01 | ||
| CN112717923B (en) * | 2019-10-28 | 2024-05-31 | 中国石油化工股份有限公司 | Catalyst for producing hydrogen peroxide by anthraquinone process and preparation method and application thereof |
| CN110845166B (en) * | 2019-12-14 | 2023-11-24 | 长安大学 | Device for soaking recycled aggregate |
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| CN87204630U (en) * | 1987-09-24 | 1988-07-27 | 中国石油化工总公司长岭炼油厂 | Spray impregnator for industrial use |
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