CN105583010A - Alumina carrier and preparation method thereof - Google Patents
Alumina carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alumina carrier and a preparation method thereof. The alumina carrier includes, by weight, 2-5% of an additive on the basis of oxide, wherein the additive is one or two selected from silicon or zirconium. The mass percentage content of the silicon and/or zirconium in the alumina is gradually increased from the center to the external surface of an alumina carrier granule. The percentage content of the silicon and/or zirconium is 0.1-0.5 wt% at the position of 1/3R in the granule, is 0.5-1.5 wt% at the position of 2/3R in the granule, and is 1.5-3.5 wt% at the position of R in the granule,, wherein R refers to the radius of the carrier granule with center of the alumina as a start point. The alumina carrier is high in crystalline degree and has complete crystalline grains, and is concentrated in granular size distribution. The additive is distributed in the alumina carrier in a gradually increasing manner, so that the alumina carrier is suitable for preparing a hydrogenation catalyst which is high in desulfuration and denitrification and has strong stability.
Description
Technical field
The present invention relates to a kind of alumina support and preparation method thereof, specifically alumina support of a kind of auxiliary agent quality percentage composition distribution gradient and preparation method thereof.
Background technology
In crude oil and the distillate that obtains, contain sulphur, nitrogen, oxygen and metal impurities from crude oil. The existence of these impurity not only affects the stability of oil product, and in use also can discharge SOX、NOXDeng pernicious gas contaminated environment. In the secondary processing process of oil product, the existence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning. Therefore, removing above-mentioned impurity is the significant process in oil product processing. Distillate hydrogenation processing refers under uniform temperature and pressure, and feedstock oil contacts with catalyst with hydrogen, imurity-removal, and the process of aromatic saturation.
Aluminium oxide, as the carrier material of hydrotreating catalyst, is applied quite extensive. But the interaction force of the lip-deep active metal of pure alumina and carrier is larger, easily form the species (as formed nickel aluminate etc.) of non-activity, be difficult for complete cure and form the active phase with high hydrogenation activity. How to weaken the strong interaction of metal and carrier, become key prepared by high-activity hydrogenation catalyst. For improving the Activity and stabill of hydrotreating catalyst, often need to often carry out modification to alumina catalyst support, as add the auxiliary agents such as silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, the one, the acidity of modulation aluminium oxide, the 2nd, change the interaction of active component and aluminium oxide, and the heat endurance of raising aluminium oxide etc.
CN101491768A discloses a kind of preparation method of siliceous and zirconium hydrogenation catalyst, and the method is that bialuminate solution is reacted with the ammonia neutralization plastic of configuration by a certain percentage, reacts aging after a period of time; Then add acid silicon salting liquid, after aging a period of time, then add containing zirconium solution, continue aging after, washing, filters, the dry alumina dry glue that obtains required siliceous and zirconium, is then prepared into required hydrogenation catalyst. CN102309999A discloses a kind of catalyst carrier for hydrgenating and preparation method thereof, in the method related macroporous aluminium oxide dry glue powder adopt equally common in and plastic legal system standby, and the distribution of auxiliary agent in aluminium oxide is uniform.
Above method adopts the method for common neutralization, reaction environment heterogeneity, and the method is easy to form the inhomogenous nucleus of taking measurements greatly, thereby makes prepared aluminium oxide exist degree of crystallinity low, particle diameter distribution disperse, the incomplete phenomenon of crystal grain; Secondly the aluminium oxide that conventional method obtains, the auxiliary agent percentage composition on its particle distributes often comparatively even. The preparation method of the current aluminium oxide about auxiliary agent percentage composition distribution gradient reports less.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of alumina support and preparation method thereof. Alumina support degree of crystallinity of the present invention is high, and crystal grain is complete, and centralized particle diameter, and auxiliary agent increase distribution in gradient in aluminium oxide, be suitable for preparing high desulfurization, denitrogenation, the hydrotreating catalyst that stability is strong.
Alumina support of the present invention, taking carrying alumina body weight as benchmark, auxiliary agent accounts for 2% ~ 5% in oxide, wherein auxiliary agent is selected from one or both in silicon or zirconium, in aluminium oxide, the quality percentage composition of silicon and/or zirconium increases to outer surface gradually from carrier granular center, the percentage composition of particle 1/3R place's silicon and/or zirconium is 0.1wt%～0.5wt%, the percentage composition of 2/3R place silicon and/or zirconium is 0.5wt%～1.5wt%, the percentage composition of R place silicon and/or zirconium is 1.5%wt～3.5wt%, and wherein R is the radius of the carrier granular taking aluminium oxide center as initial point.
Alumina support of the present invention, pore volume is 0.8～1.2mlg-1; Aperture is 150～200; Abrasion≤0.05%, preferably≤0.03%; Bulk density is 0.65～0.85g/ml; Degree of crystallinity >=85% of aluminium oxide, preferably 90%～95%.
The centralized particle diameter of alumina support of the present invention, particle diameter distributes as follows: < 120 μ m particle diameter proportions are 1%～2%, 120～150 μ m particle diameter proportions are that 10%～18%, >, 150 μ m particle diameter proportions are 80%～85%.
The preparation method of alumina support of the present invention, comprises following content:
(1) add reactant liquor and be heated to uniform temperature in impact flow reactor bottom, start ultrasonic generator;
(2) Acceleration of starting device is injected the bialuminate aqueous solution and the basic aluminate aqueous solution respectively by the accelerating tube (charging aperture I and II) on impact flow reactor top, the two is after pressure atomized fog jet atomization, carry out impinging stream reaction at L-L reactor I, generate nucleus, through entering into the L-L reactor II of bottom communicating pipe;
(3) after the reaction of L-L reactor I finishes, simultaneously from the charging aperture III at two ends, L-L reactor II bottom and IV respectively batch (-type) add acid metal saline solution and alkalinous metal saline solution, add after end at every turn, regulate pH value, neutralization and ageing process; Wherein said acid metal saline solution is selected from the one in the bialuminate aqueous solution or (bialuminate+acid zirconates) aqueous solution; Alkalinous metal saline solution is selected from the one in the basic aluminate aqueous solution or (basic aluminate+alkaline silicate) aqueous solution; Wherein in acid metal saline solution and alkalinous metal saline solution, bialuminate and basic aluminate be must contain simultaneously, but single bialuminate and basic aluminate contained when different; And the concentration of acid zirconates and/or alkaline silicate solution adds order step increase according to batch (-type);
(4) material of step (3) is carried out finally aging, in ageing process, drip containing the acid zirconates aqueous solution and/or alkaline silicate solution, then filter, wash, dry and roasting, obtain the alumina support of auxiliary agent percentage composition distribution gradient.
In the inventive method, the described heating-up temperature of step (1) is 45～100 DEG C, preferably 50～95 DEG C.
In the inventive method, the frequency of the described ultrasonic generator of step (1) is 20～100kHz, preferably 30～80kHz.
In the inventive method, described in step (2), bialuminate is AlCl3、Al2(SO4)3Or Al (NO)3In one or more, preferably Al2(SO4)3, the concentration of the bialuminate aqueous solution is with Al2O3Count 8～80g/100ml, preferably 8～70g/100ml.
In the inventive method, the basic aluminate described in step (2) is selected from NaAlO2Or KAlO2In one or both, preferably NaAlO2, the concentration of the basic aluminate aqueous solution is with Al2O3Count 8～80g/100ml, preferably 8～70g/100ml.
In the inventive method, the time of the liquid liquid impinging stream reaction described in step (2) is 20～50min, preferably 20～40min.
In the inventive method, the bialuminate described in step (3) is selected from AlCl3、Al2(SO4)3Or Al (NO)3In one or more, preferably Al2(SO4)3, the concentration of acid metal salt aqueous acid medium aluminate is with Al2O3Count 8～80g/100ml, preferably 8～70g/100ml. Described acid zirconates is selected from Zr (NO3)4、ZrCl4Or ZrOCl2In one or more, preferably ZrCl4, the concentration of acid metal salt aqueous acid medium zirconates is with ZrO2Count 3～30g/100ml, preferably 3～20g/100ml. Acid metal salt aqueous solution flow is 5～20L/h, preferably 5～10L/h.
In the inventive method, the described basic aluminate of step (3) is selected from NaAlO2Or KAlO2In one or both, preferably NaAlO2; The concentration of alkalinous metal saline solution neutral and alkali aluminate is with Al2O3Count 8～80g/100ml, preferably 8～70g/100ml; Described alkaline silicate is selected from Na2SiO3Or K2SiO3In one or both, preferably Na2SiO3, the concentration of alkalinous metal saline solution neutral and alkali silicate is with SiO2Meter 3～30g/100ml, preferably 3～20g/100ml. Alkaline metal salt aqueous solution flow is 5～20L/h, preferably 15～20L/h.
In the inventive method, the number of times that step (3) discontinuous formula adds can be adjusted according to actual needs, is generally preferably 3 ~ 4 times 2 ~ 5 times; The amplitude that the concentration gradient of acid zirconates and/or alkaline silicate solution increases is 3 ~ 12g/100ml, preferably 5 ~ 10g/100ml.
In the inventive method, the pH value scope described in step (3) is 6～8, preferably 7.0～7.8. The time of described neutralization reaction is 5～20min, preferably 5～15min. Described ageing time is 5～30min, preferably 10～20min.
In the inventive method, preparation auxiliary agents of silicon increases the alumina support of distribution in gradient, in step (3), is added and is contained alkali aluminate soln that alkaline silicate concentration in gradient increases and bialuminate solution reaction and prepare auxiliary agents of silicon and increase in gradient the alumina support of distribution by batch (-type);
Preparing auxiliary agent zirconium increases the alumina support of distribution in gradient, in (3), is added and is contained bialuminate solution that acid zirconates concentration in gradient increases and alkali aluminate soln and react to prepare auxiliary agent zirconium and increase in gradient the aluminium oxide of distribution by batch (-type);
Preparation auxiliary agents of silicon and zirconium increase the alumina support of distribution in gradient, in step (3), are added and are contained the bialuminate aqueous solution that acid zirconates concentration in gradient increases and contain alkaline silicate concentration in gradient the alkali aluminate soln increasing and react to prepare auxiliary agents of silicon and zirconium and increase in gradient the aluminium oxide of distribution by batch (-type).
In the inventive method, in a step that can be in step (1), (2) or (3) or a few step, introduce other auxiliary agent, comprise the one in auxiliary agent F, P etc. Can in the end water of step (1), add, in one or more aqueous solution in also can the bialuminate aqueous solution, the acid zirconates aqueous solution, the basic aluminate aqueous solution or alkaline silicate solution in step (2) or (3), add other auxiliary agents.
In the inventive method, the acid zirconates that step (4) is described is identical with step (3) with the source of alkaline silicate, the concentration of the acid zirconates aqueous solution described in step (4) is 21～30g/100ml, the concentration of alkaline silicate solution is 21～30g/100ml, and the drop rate of solution is 1L/h～5L/h.
In the inventive method, the described aging pH value of step (4) is 8.0～10.0, preferably 9.0～9.5.
In the inventive method, the described aging temperature of step (4) is 80～150 DEG C, preferably 90～120 DEG C; Ageing time is 1～3 hour, preferably 2～3 hours.
In the inventive method, the described drying mode of step (4) adopts centrifugal spraying dry, and rotating speed is 10000～15000r/min, and electrical heating peak power is 10～100kW, and charging rate is 4～10L/h, and baking temperature is 40～200 DEG C, preferably 60～150 DEG C; Be 1～5 hour drying time, preferably 2～4 hours; Described sintering temperature is 350～800 DEG C, and preferably 500～700 DEG C, roasting time is 2～6 hours, preferably 2～4 hours.
Degree of crystallinity in the inventive method adopts XRD to measure, and particle diameter distributes and adopts laser particle analyzer to measure, and auxiliary agent distributes and adopts field emission scanning electron microscope to measure, and abrasion adopt abrasion instrument to measure, and minute is 1h.
Impact flow reactor of the present invention, from top to bottom comprises: L-L reactor I, communicating pipe and L-L reactor II, between L-L reactor I and L-L reactor II by being connected communicating pipe.
Wherein, described L-L reactor I housing is cylindrical shape, reactor bottom is turbination, in reactor, be provided with accelerating tube and pressure atomized fog jet, L-L reactor I top is provided with gas vent, and on the sidewall of both sides, horizontal symmetrical arranges accelerating tube, accelerating tube one end is as charging aperture (feed liquor body), the other end extend into L-L reactor I inside as discharging opening, and discharging opening (one end of inlet) is located setting pressure atomizer, by the atomization of liquid; The height of L-L reactor I is determined according to the quantity of the situation of top reactor and paired accelerating tube.
Described communicating pipe is cylindrical shape, the cross-section center of communicating pipe, L-L reactor I and L-L reactor II is on same central axis, communicating pipe cross-sectional area S1 is less than the cross-sectional area S2 of L-L reactor II, and preferably S1:S2 is between 1:3～1:4; Communicating pipe, Main Function was to carry out Separation of Solid and Liquid, avoided liquid liquid to clash into the impact on below L-L reactor II, and the solid generating under the effect of gravity by entering into L-L reactor II communicating pipe.
Described L-L reactor II housing is cuboid or square, reactor head is conical, the cross-sectional area S3 of L-L reactor II, S3 is greater than communicating pipe cross-sectional area S1, preferably S1:S3 is between 1:6～1:10, in reactor, be provided with guide shell and ultrasonic generator, L-L reactor II both sides sidewall arranges charging aperture III and charging aperture IV, charging aperture communicates with guide shell respectively, material enters into reactor by guide shell, guide shell is symmetrical arranged at L-L reactor two middle side parts, in guide shell, be provided with paddle, L-L reactor II bottom is provided with ultrasonic generator, this reactor bottom is provided with discharge port.
In impact flow reactor of the present invention, accelerating tube is 1 ~ 5 pair, arranges according to the needs of reaction; Accelerating tube is connected with the accelerator of impact flow reactor outside.
In impact flow reactor of the present invention, charging aperture I, II, III and IV communicate with raw material through feedstock pump.
In impact flow reactor of the present invention, between L-L reactor I and L-L reactor II, by being connected communicating pipe, the size of two reactors is determined according to actual conditions. When L-L reactor II reacts, add reactant liquor (being generally water) at reactor, reactant liquor need not have guide shell, the wicket shutoff of the discharge port of reactor bottom.
In impact flow reactor of the present invention, the frequency of ultrasonic generator is between 20～80kHz, preferably 20～50kHz, and power is between 600～1200W, preferably 600～1000W.
Compared with prior art, the preparation method of catalyst carrier for hydrgenating provided by the invention has the following advantages:
1, in L-L reactor I, adopt transmission characteristic between atomization impinging stream reaction district hardening constituent, the process of being undertaken reacting rapidly by quick shock after the atomization of liquid is not subject to mass transfer limit, can generate fast a large amount of tiny nucleus; Secondly after the atomization of liquid, react to each other, increased contact area, make reactive liquid solution more abundant; A large amount of tiny nucleus have higher degree of supersaturation at impingement region after entering bottom L-L reactor II, degree of supersaturation in impingement region is even, impel alumina dry glue growth fraction slower, the aluminium hydroxide particle diameter narrow distribution generating within the shorter reaction time, degree of crystallinity is high, and average grain diameter is uniformly dispersed. Therefore the seed crystal of aluminium hydroxide crystallization purity generating is high, and granularity is less, centralized particle diameter, and also pH in L-L reactor II is stable, can play good guide effect;
2, the prepared alumina crystal degree of this method is high, crystal grain is complete, particle diameter is evenly distributed, and auxiliary agent percentage composition increases and distributes in gradient in aluminium oxide, can effectively improve catalyst surface acidity, the deactivation rate that has slowed down catalyst in mink cell focus hydrotreatment process, is well suited for preparing high desulfurization, denitrogenation, the hydrotreating catalyst that stability is strong.
Brief description of the drawings
Fig. 1 is the structural representation of the impact flow reactor in the present invention.
Wherein 1-L-L reactor I; 2-accelerating tube; 3-pressure atomized fog jet I; 4-gas vent; 5-pressure atomized fog jet II; 6-liquid liquid impingement region; 7-charging aperture I; 8-charging aperture II; 9-communicating pipe; 10-contacts liquid level; 11-L-L reactor II; 12-charging aperture III; 13-charging aperture IV; 14-guide shell; 15-discharge port; 16-ultrasonic generator.
Detailed description of the invention
Below by specific embodiment, the preparation method of catalyst carrier for hydrgenating of the present invention is described in more detail. Embodiment is illustrating of the detailed description of the invention to the inventive method just, do not form the restriction of protection domain of the present invention, and the mode that adds of the auxiliary agents such as silicon, zirconium is one or more in multiple introducing mode.
In the embodiment of the present invention and comparative example, the aluminum sulfate, the sodium metaaluminate that use, zirconium chloride, sodium metasilicate is all purchased from Yantai Heng Hui Chemical Co., Ltd.. In the inventive method, degree of crystallinity adopts XRD to measure; Particle diameter distributes and adopts laser particle analyzer to measure; Auxiliary agent particle diameter distributes and adopts field scan Electronic Speculum to measure; Abrasion adopt abrasion instrument to measure, minute 1h.
Embodiment 1
The present embodiment is introduced the compound method of Mo, Ni, P original solution. The present embodiment is only prepared Mo, Ni, the P original solution of a kind of concentration and ratio, can, according to introduced method, prepare the solution of other ratios and concentration.
Get 386g molybdenum oxide, 123g basic nickel carbonate is put into many mouthfuls of flasks, add after a certain amount of deionized water, stir until vial matter is pulpous state, then slowly add 86g phosphoric acid, wait initial action slowly heating more later, keeping 90～110 DEG C of times of solution temperature is 1～3 hour, stop after heating, while hot to gained solution filter, obtain the bottle green original solution of clarification. Solution composition is MoO3：69.27g/100ml；NiO：12.49g/100ml；P：4.10g/100ml。
Embodiment 2
Add end water to impact flow reactor bottom, and be heated to 90 DEG C; Start impact flow reactor, adjust the frequency of ultrasonic generator for being 20kHz. Regulate the crash direction of two accelerating tubes to be lateral impact, the AlCl that Acceleration of starting device is 30g/100mL by concentration3Solution injects from charging aperture I with 15L/h flow, and by pressure atomized fog jet by the NaAlO that is 35g/100mL through pressure atomized fog jet ejection by the concentration of 20L/h flow injection with the accelerating tube at the charging aperture II place of its level after the atomization of liquid2Solution phase knock against each other hits, and reaction 30min, stops filling liquid and bottom ultrasonic generator; Add respectively and contain NaAlO simultaneously with 15L/h at charging aperture III and the IV at L-L reactor II two ends simultaneously2(concentration is 20g/100ml) and Na2SiO3Mixed solution and the AlCl of (concentration is 3g/100ml)3Solution (concentration is 30g/100ml), regulating pH value is 7.5, after neutralization reaction 15min, stops the aging 10min of charging; Then add continuously NaAlO at charging aperture III and the IV at L-L reactor II two ends with 15L/h simultaneously2(solution concentration is 20g/100ml) and Na2SiO3Mixed solution and the AlCl of solution (concentration is 10g/100ml)3Solution (concentration is 30g/100ml), regulating pH value is 7.5, neutralizes after anti-10min, stops the aging 15min of charging; Then add continuously NaAlO at charging aperture III and the IV at L-L reactor II two ends with 15L/h simultaneously2Solution (concentration is 20g/100ml) and Na2SiO3Mixed solution and the AlCl of solution (concentration is 20g/100ml)3Solution (concentration is 30g/100ml), regulating pH value is 7.5, after neutralization reaction 10min, stops throat-fed; By bottom temp be elevated to carry out at 100 DEG C aging, regulate pH be 9.5, aging 2h, drips 30g/100mlNa in ageing process2SiO3Solution, after aging end filters aluminium oxide, and regulating the rotating speed of centrifugal spray dryer is 10000r/min, and baking temperature is 120 DEG C, and after dry 5h, roasting 3h under 600 DEG C of conditions, obtains required aluminum oxide micro-sphere, is numbered WQ-1, and character is in table 1.
Embodiment 3
Add end water to impact flow reactor bottom, and be heated to 90 DEG C; Start impact flow reactor, adjusting ultrasonic generator frequency is 30kHz. Regulate the crash direction of two accelerating tubes to be lateral impact, the AlCl that Acceleration of starting device is 30g/100mL by concentration3Solution injects from charging aperture I with 25L/h flow, and by pressure atomized fog jet by the NaAlO that is 35g/100mL through pressure atomized fog jet ejection by the concentration of 20L/h flow injection with the accelerating tube at the charging aperture II place of its level after the atomization of liquid2Solution phase knock against each other hits, and reaction 25min, stops filling liquid and bottom stirrer; Add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 16L/h simultaneously simultaneously2Solution (concentration is 35g/100mL) and AlCl3(concentration is 5g/100mlZrCl for solution (concentration is 30g/100mL) and solution4) mixed solution, regulating pH value is 7.0, after neutralization reaction 5min, stops the aging 10min of charging; Then add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 16L/h simultaneously2Solution (concentration is 35g/100mL) and AlCl3Solution (concentration is 30g/100mL) and ZrCl4The mixed solution of solution (concentration is 15g/100ml), regulating pH value is 7.0, after neutralization reaction 5min, stops the aging 15min of charging; Then add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 16L/h simultaneously2Solution (concentration is 35g/100mL) and AlCl3Solution (concentration is 30g/100mL) and ZrCl4The mixed solution of solution (concentration is 20g/100ml), regulating pH value is 7.0, after neutralization reaction 15min, stops throat-fed; By bottom temp be elevated to carry out at 120 DEG C aging, regulate pH be 9.0; Aging 1.5h, drips ZrCl in ageing process4Solution (concentration is 25g/100ml), after aging end filters aluminium oxide, and regulating the rotating speed of centrifugal spray dryer is 12000r/min, baking temperature is 100 DEG C, after dry 5h, and roasting 3h under 650 DEG C of conditions, obtain required aluminum oxide micro-sphere, be numbered WQ-2, character is in table 1.
Embodiment 4
Add end water to impact flow reactor bottom, and be heated to 90 DEG C; Start impact flow reactor, adjusting ultrasonic generator frequency is 50kHZ. Regulate the crash direction of two accelerating tubes to be lateral impact, the AlCl that Acceleration of starting device is 30g/100mL by concentration3Solution injects from charging aperture I with 25L/h flow, and will after the atomization of liquid, spray the NaAlO that is 30g/100mL by 20L/h flow implantation concentration with the accelerating tube at the charging aperture II place of its level through pressure atomized fog jet by pressure atomized fog jet2Solution phase knock against each other hits, and after reaction 30min, stops filling liquid and bottom stirrer; Add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 20L/h simultaneously simultaneously2Solution (concentration is 30g/100ml) and Na2SiO3Mixed solution and the AlCl of solution (concentration is 5g/100ml)3Solution (concentration is 35g/100ml) and ZrCl4The mixed solution of solution (concentration is 5g/100ml), regulating pH value is 7.0, after neutralization reaction 15min, stops the aging 10min of charging; Then add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 20L/h simultaneously2Solution (concentration is 30g/100ml) and Na2SiO3Mixed solution and the AlCl of solution (concentration is 13g/100ml)3Solution (concentration is 35g/100ml) and ZrCl4The mixed solution of solution (12g/100ml), regulating pH value is 7.0, after neutralization reaction 5min, stops the aging 10min of charging; Then add continuously NaAlO at charging aperture III and the IV at two ends, impact flow reactor bottom with 20L/h simultaneously2Solution (concentration is 30g/100ml) and Na2SiO3Mixed solution and the body AlCl of solution (concentration is 20g/100ml)3Solution (concentration is 35g/100ml) and ZrCl4The mixed solution of solution (18g/100ml), regulating pH value is 7.0, after neutralization reaction 15min, stops throat-fed; By bottom temp be elevated to carry out at 120 DEG C aging, regulate pH be 9.2; Aging 1.5h, adds Na in ageing process2SiO3Solution (concentration is 25g/100ml) and ZrCl4The mixed solution of solution (concentration is 25g/100ml), after aging end, aluminium oxide is filtered, regulating the rotating speed of centrifugal spray dryer is 15000r/min, baking temperature is 120 DEG C, after dry 5h, roasting 3h under 700 DEG C of conditions, obtains required aluminum oxide micro-sphere, be numbered WQ-3, character is in table 1.
Comparative example 1
The method that adopts CN200810010260.1 adds 1L deionized water in container, is warmed up to 62 DEG C, adds 3L to contain Al simultaneously2O3For the AlCl of 20g/100ml3The aqueous solution and containing NH3For the ammonia spirit of 50g/100ml precipitates, controlling pH is 8.0, and having added the time is 80min. After stopping feeding in raw material, system is pressed aging 50min at said temperature and pH condition, adds SiO2Content is the solution of sodium metasilicate through 100ml of 10g, continue aging 10min, then adding Zr content is the zirconyl chloride solution 120ml of 8g, and 10min adds, and after reinforced end, material pH value is 6.5, continue aging 60min, then wash 4 times, filter cake, after 100 DEG C of dry 15h, is obtained to siliceous and aluminum oxide micro-sphere zirconium at 800 DEG C after roasting 4h after being pulverized, numbering WQ-4, character is listed in table 1.
Properties of Alumina prepared by table 1 embodiment and comparative example.
| WQ-1 | WQ-2 | WQ-3 | WQ-4 | |
| Bulk density, g/ml | 0.70 | 0.71 | 0.72 | 0.58 |
| Pore volume, ml/g | 1.02 | 1.01 | 1.00 | 0.72 |
| Specific area, m2/g | 300 | 297 | 298 | 254 |
| Degree of crystallinity/% | 91 | 90 | 92 | 80 |
| SiO2，% | 2.2 | 0 | 1.2 | 1.1 |
| ZrO2，% | 0 | 2.1 | 1.0 | 1.0 |
| Particle diameter distribution/% | ||||
| ＞150μm | 82.6 | 82.5 | 83.5 | 24.2 |
| 120～150μm | 16.3 | 15.9 | 15.5 | 38.0 |
| ＜120μm | 1.1 | 1.6 | 1.0 | 37.8 |
| Auxiliary agent percentage composition, wt% | ||||
| 1/3R place | 0.45 | 0.50 | 0.48 | 2.01 |
| 2/3R place | 1.25 | 1.36 | 1.42 | 1.98 |
| R place | 2.25 | 2.31 | 2.19 | 2.11 |
Data by table 1 can be found out, prepared its bulk density of aluminium oxide of the inventive method is higher, pore volume, aperture are larger, degree of crystallinity is high, crystal grain distributes and concentrates, and the percentage composition of auxiliary agent Si and/or Zr distribution gradient in aluminium oxide, is well suited for the preparation for the hydrotreating catalyst of heavy inferior raw material.
Embodiment 5
The saturated dipping of solution that WQ-1～WQ-4 is adopted to embodiment 1, the catalyst obtaining is numbered CT-1～CT-4, and catalyst and feedstock oil character are in table 2 and table 3, and CT-1～CT-4 catalyst carries out active appraisal experiment, and evaluation result is in table 4.
Catalyst activity evaluation experimental carries out on 50mL small hydrogenation device, before activity rating, catalyst is carried out to presulfurization. Catalyst is at reaction stagnation pressure 8.0MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 700:1, reaction temperature is 380 DEG C, has carried out the running evaluation of 2000h, and the catalyst after evaluating is dissected.
Catalyst property prepared by table 2 embodiment and comparative example.
| Physical property | CT-1 | CT-2 | CT-3 | CT-4 |
| Tenor, % | ||||
| MoO3 | 18.3 | 18.0 | 18.2 | 18.2 |
| NiO | 3.5 | 3.3 | 3.5 | 3.3 |
| P | 0.5 | 0.6 | 0.6 | 0.6 |
Table 3 feedstock oil character.
| Feedstock oil | Iran VGO |
| Density (20 DEG C), gcm-3 | 0.9010 |
| Carbon residue, % | 0.5 |
| Boiling range, DEG C | |
| IBP/EBP | 336/532 |
| S，wt% | 1.51 |
| N，μg·g-1 | 1281 |
Table 4 catalyst activity evaluation result.
| Catalyst | CT-1 | CT-2 | CT-3 | CT-4 |
| Denitrification activity relatively, % | 119 | 122 | 123 | 100 |
| Relatively desulphurizing activated, % | 120 | 121 | 124 | 100 |
Data by table 2 and table 4 can find out, the prepared catalyst of the inventive method, under same process condition, because auxiliary agent percentage composition increases and distributes in gradient in catalyst, can improve the hydrogenation activity of catalyst effectively.
Table 5 turn round rear catalyst dissect result.
| Catalyst | CT-1 | CT-2 | CT-3 | CT-4 |
| Carbon content, % | 3.2 | 2.9 | 3.1 | 5.2 |
Data by table 5 can be found out, the catalyst that the inventive method is prepared and reference agent are the in the situation that of running same time, because catalyst promoter percentage composition of the present invention increases and distributes in gradient in catalyst, can effectively improve catalyst surface acidity, thereby slow down the coking rate of catalyst, thereby improved the Activity and stabill of catalyst.
Claims (16)
1. an alumina support, it is characterized in that: taking carrying alumina body weight as benchmark, auxiliary agent accounts for 2% ~ 5% in oxide, wherein auxiliary agent is selected from one or both in silicon or zirconium, in aluminium oxide, the quality percentage composition of silicon and/or zirconium increases to outer surface gradually from carrier granular center, the percentage composition of particle 1/3R place's silicon and/or zirconium is 0.1wt%～0.5wt%, the percentage composition of 2/3R place silicon and/or zirconium is 0.5wt%～1.5wt%, the percentage composition of R place silicon and/or zirconium is 1.5%wt～3.5wt%, and wherein R is the radius of the carrier granular taking aluminium oxide center as initial point.
2. according to alumina support claimed in claim 1, it is characterized in that: the pore volume of alumina support is 0.8～1.2mlg-1, aperture is 150～200, abrasion≤0.05%, and bulk density is 0.65～0.85g/ml, degree of crystallinity >=85% of aluminium oxide.
3. according to the alumina support described in claim 1 or 2, it is characterized in that: the particle diameter of alumina support distributes as follows: < 120 μ m particle diameter proportions are 1%～2%, 120～150 μ m particle diameter proportions are that 10%～18%, >, 150 μ m particle diameter proportions are 80%～85%.
4. a preparation method for the alumina support described in claim 1 or 2, is characterized in that comprising following content: (1) adds reactant liquor and is heated to uniform temperature in impact flow reactor bottom, starts ultrasonic generator; (2) Acceleration of starting device is injected the bialuminate aqueous solution and the basic aluminate aqueous solution respectively by the accelerating tube (charging aperture I and II) on impact flow reactor top, the two is after pressure atomized fog jet atomization, carry out impinging stream reaction at L-L reactor I, generate nucleus, through entering into the L-L reactor II of bottom communicating pipe; (3) after the reaction of L-L reactor I finishes, simultaneously from the charging aperture III at two ends, L-L reactor II bottom and IV respectively batch (-type) add acid metal saline solution and alkalinous metal saline solution, add after end at every turn, regulate pH value, neutralization and ageing process; Wherein said acid metal saline solution is selected from the one in the bialuminate aqueous solution or (bialuminate+acid zirconates) aqueous solution; Alkalinous metal saline solution is selected from the one in the basic aluminate aqueous solution or (basic aluminate+alkaline silicate) aqueous solution; Wherein in acid metal saline solution and alkalinous metal saline solution, bialuminate and basic aluminate be must contain simultaneously, but single bialuminate and basic aluminate contained when different; And the concentration of acid zirconates and/or alkaline silicate solution adds order step increase according to batch (-type); (4) material of step (3) is carried out finally aging, in ageing process, drip containing the acid zirconates aqueous solution and/or alkaline silicate solution, then filter, wash, dry and roasting, obtain the alumina support of auxiliary agent percentage composition distribution gradient.
5. it is characterized in that in accordance with the method for claim 4: the described heating-up temperature of step (1) is 45～100 DEG C.
6. it is characterized in that in accordance with the method for claim 4: the frequency of the ultrasonic generator described in step (1) is 20～100kHz.
7. it is characterized in that in accordance with the method for claim 4: described in step (2), bialuminate is AlCl3、Al2(SO4)3Or Al (NO)3In one or more, the concentration of the bialuminate aqueous solution is with Al2O3Count 8～80g/100ml.
8. it is characterized in that in accordance with the method for claim 4: the basic aluminate described in step (2) is selected from NaAlO2Or KAlO2In one or both, the concentration of the basic aluminate aqueous solution is with Al2O3Count 8～80g/100ml.
9. it is characterized in that in accordance with the method for claim 4: the time of the liquid liquid impinging stream reaction described in step (2) is 20～50min.
10. it is characterized in that in accordance with the method for claim 4: the bialuminate described in step (3) is AlCl3、Al2(SO4)3Or Al (NO)3In one or more, the concentration of acid metal salt aqueous acid medium aluminate is with Al2O3Count 8～80g/100ml; Described acid zirconates is selected from Zr (NO3)4、ZrCl4Or ZrOCl2In one or more, the concentration of acid metal salt aqueous acid medium zirconates is with ZrO2Count 3～30g/100ml; Acid metal salt aqueous solution flow is 5～20L/h.
11. in accordance with the method for claim 4, it is characterized in that: the described basic aluminate of step (3) is selected from NaAlO2Or KAlO2In one or both, the concentration of alkalinous metal saline solution neutral and alkali aluminate is with Al2O3Count 8～80g/100ml; Described alkaline silicate is selected from Na2SiO3Or K2SiO3In one or both, the concentration of alkalinous metal saline solution neutral and alkali silicate is with SiO2Meter 3～30g/100ml; Alkaline metal salt aqueous solution flow is 5～20L/h.
12. in accordance with the method for claim 4, it is characterized in that: the number of times that step (3) discontinuous formula adds is 2 ~ 5 times; The amplitude that the concentration gradient of acid zirconates and/or alkaline silicate solution increases is 3 ~ 12g/100ml.
13. in accordance with the method for claim 4, it is characterized in that: the pH value scope described in step (3) is 6～8; The time of described neutralization reaction is 5～20min; Described ageing time is 5～30min.
14. in accordance with the method for claim 4, it is characterized in that: the acid zirconates that step (4) is described is identical with step (3) with the source of alkaline silicate, the concentration of the acid zirconates aqueous solution described in step (4) is 21～30g/100ml, the concentration of alkaline silicate solution is 21～30g/100ml, and the drop rate of solution is 1～5L/h.
15. in accordance with the method for claim 4, it is characterized in that: the described aging pH value of step (4) is 8.0～10.0; Aging temperature is 80～150 DEG C, and ageing time is 1～3 hour.
16. in accordance with the method for claim 4, it is characterized in that: the described drying mode of step (4) adopts centrifugal spraying dry, rotating speed is 10000～15000r/min, electrical heating peak power is 10～100kW, charging rate is 4～10L/h, baking temperature is 40～200 DEG C, and be 1～5 hour drying time.
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| RU2103059C1 (en) * | 1996-09-05 | 1998-01-27 | Научно-производственная фирма "Химтэк" | Method of preparing aluminum oxide carrier for catalysts |
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