CN104549536A - Pretreating method of aluminum oxide carrier - Google Patents
Pretreating method of aluminum oxide carrier Download PDFInfo
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- CN104549536A CN104549536A CN201310499276.4A CN201310499276A CN104549536A CN 104549536 A CN104549536 A CN 104549536A CN 201310499276 A CN201310499276 A CN 201310499276A CN 104549536 A CN104549536 A CN 104549536A
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- microwave
- alumina support
- water solution
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Abstract
The invention discloses a pretreating method of an aluminum oxide carrier. The pretreating method comprises the following steps: firstly, impregnating the shaped aluminum oxide carrier by using an aqueous polyalcohol solution; secondly, transferring the mixture obtained in the step 1 to a closed container, and performing microwave treatment; finally, filtering, drying and roasting the aluminum oxide carrier obtained after the microwave treatment to obtain the final aluminum oxide carrier. By the pretreating method, a pore-enlarging effect is achieved, and other properties of the aluminum oxide carrier are effectively regulated; a heavy oil hydrodemetallization catalyst, prepared by using the pretreated aluminum oxide as the carrier, has high activity and stability.
Description
Technical field
The present invention relates to a kind of preprocess method of alumina support, relate in particular to a kind of preprocess method being suitable for alumina support as mink cell focus Hydrodemetalation catalyst.
Background technology
At present, in the production process of mink cell focus HDM, owing to containing the impurity such as a certain amount of vanadium, sulphur, arsenic, nickel in feedstock oil, very easily form deposition, thus the duct of blocking catalyst, cause catalyst activity to decline rapidly, even inactivation, affects commercial Application.Have and hold metal and hold coke formation strong compared with the catalyst of large pore volume and larger aperture, the inactivation of catalyst can be slowed down, the service cycle of catalyst is extended.The pore structure of catalyst is determined by the carrier forming catalyst, and therefore, it is the key prepared residual oil, especially prepare the higher decompression residuum Hydrodemetalation catalyst of tenor that preparation has compared with the carrier of large pore volume and larger aperture.
Aluminium oxide is the catalyst carrier that a class is commonly used, and is widely used in the fields such as PETROLEUM PROCESSING, chemical industry, environmental protection.The aperture being generally used for preparing the aluminium oxide of hydrotreating catalyst and commercial alumina is less, the needs preparing heavy oil, residuum hydrogenating and metal-eliminating and/or heavy oil hydrodesulfurization catalyst can not be met, therefore, must in carrier preparation process, the way of " reaming " be adopted to increase its aperture.
CN1416955A discloses a kind of alumina support and preparation method thereof, comprises article shaped at the temperature of 90 DEG C-300 DEG C, within 35 minutes, completes drying fast, and roasting at least 0.5 hour in the moisture vapor atmosphere of 600 DEG C-800 DEG C.The specific area of this carrier can be 100-250 rice
--
2/ gram, be preferably 110-200 rice
--
2/ gram, be more preferably 120-180 rice
--
2/ gram.Total pore volume can be 0.65-1.2 ml/g, is preferably 0.68-1 ml/g, is more preferably 0.68-0.9 ml/g.Can a few aperture be 12-24 nanometer, be preferably 13-20 nanometer, be more preferably 13-18 nanometer.
CN1087289A discloses a kind of method for preparing macropore alumina supporter.The moisture boehmite making to be under room temperature is placed in high-temperature atmosphere instantaneously, and high temperature range is 500 DEG C-650 DEG C, and constant temperature 2-4 hour at these elevated temperatures.The pore volume of gained carrier is 0.65-0.78 ml/g, and specific area is 230-270 rice
--
2/ gram, average pore diameter is 11-15 nanometer, and bore dia accounts for more than 85% of total pore volume at the pore volume of 5-15 nanometer range.
Divided by outside upper method, carrying out hydrothermal treatment consists to aluminium oxide or aluminium oxide precursor (boehmite) is also prepare a kind of conventional method of macropore alumina supporter.Aluminium oxide or aluminium oxide precursor (boehmite) degree of crystallinity increase under hydrothermal conditions, grain growth, thus reach the object increasing carrier aperture.
In the process of reaming, inevitably other performance of carrier is had an impact, as grain size, specific area, mechanical strength, carrier surface acid-base value etc.Although some carrier aperture, pore volume produce a desired effect, because other performance changing carrier in the process of reaming causes it can not become a kind of qualified carrier.Excellent catalyst carrier is the result of its various aspects of performance comprehensive function, can not attend to one thing and lose sight of another, and it finally will be embodied on the catalyst performance in actual application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preprocess method of alumina support.This preprocess method effectively have adjusted other performance of alumina support while playing reaming effect, and with pretreated aluminium oxide for carrier, the mink cell focus Hydrodemetalation catalyst prepared demonstrates high activity and stability.
A preprocess method for alumina support, comprises the steps: the alumina support after first adopting polyatomic alcohol water solution dip forming; Then said mixture material is proceeded in closed container and carry out microwave treatment; Alumina support after last microwave treatment after filtration, dry, roasting obtains final alumina support.
In the inventive method, described shaping after alumina support can be self-control or any one alumina support bought.Alumina support after shaping first can carry out calcination process, and sintering temperature is generally 500-700 DEG C, and roasting time is 1-5h.
In the inventive method, described polyalcohol comprises one or more in glycerine, sorbierite, sweet mellow wine, arabite.The addition of polyatomic alcohol water solution be at least make shaping after the complete submergence of alumina support, dip time is 1-4 hour.Polyol amount in the polyatomic alcohol water solution added and shaping after the mass ratio of alumina support be 5%-25%.
In the inventive method, airtight container can directly be positioned in microwave reactor by microwave processing process, described airtight container material on microwave without impact; Also can directly process in the microwave reactor of sealing.
In the inventive method, carry out microwave treatment time in described closed container and be generally 2 ~ 10 hours, the volume ratio of microwave power and polyatomic alcohol water solution is 20 ~ 280 watts/L, microwave frequency 1000 ~ 3000MHz, preferred microwave treatment time is generally 4 ~ 8 hours, the volume ratio of microwave power and polyatomic alcohol water solution is 80 ~ 200 watts/L, microwave frequency 1500 ~ 2500MHz.
In the inventive method, described dry run is generally dry 1-10 hour at 100 DEG C-130 DEG C.Described roasting process refers at 550 DEG C-650 DEG C roasting 2-4 hour.
The inventive method adopts polyatomic alcohol water solution dip forming alumina support, in dipping process, polynary organic alcohols is optionally adsorbed onto in the particular crystal plane of alumina support by hydrogen bond action, then in the container of sealing, microwave hydrothermal process is carried out, the synergy of polyatomic alcohol water solution, shaped alumina alumina supporter and microwave, while raising aperture, significantly improve other performance of carrier, the hydrogenation catalyst prepared has obvious high-activity stable compared with the hydro-thermal reaming of routine.
Detailed description of the invention
Further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.
The preprocess method of alumina support of the present invention, concrete processing procedure is as follows: take appropriate shaping after alumina support, 600 DEG C of roasting time are that 3h is stand-by; The alumina support after above-mentioned roasting is flooded with appropriate polyatomic alcohol water solution; Said mixture material is proceeded in the autoclave of steel to seal and put it in microwave reactor and carries out microwave hydrothermal process; Aluminium oxide after process after filtration, dry, roasting obtains alumina support of the present invention.Adopt in embodiment shaping after alumina support there is following character: pore volume 0.68ml/g, specific area 180m
2/ g, the hole of most probable pore size 13nm, 10-20nm accounts for the 30%-40% of total pore volume.
Example 1
Take 10 grams shaping after alumina support be placed in beaker, contain the above-mentioned alumina support of aqueous impregnation 1 hour of 0.5 gram of sweet mellow wine with 0.5L; Proceeded in autoclave by said mixture material to seal and put it in microwave reactor and carry out microwave hydrothermal process, the volume ratio of microwave power and polyatomic alcohol water solution is 200 watts/L, microwave frequency 2000MHz, and the processing time is 8 hours; Aluminium oxide after process after filtration, at 120 DEG C dry 6 hours, 600 DEG C of roastings, 4 hours obtained carrier A 1 of the present invention.Take above-mentioned alumina support A1100 gram, with 230 milliliters containing MoO
376.2 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO12 grams per liter flood 2 hours, elimination redundant solution, 120 DEG C dry 2 hours, then at 550 DEG C roasting 5 hours obtained catalyst C1.Activity rating is carried out to catalyst C1.Residual oil character and evaluate process conditions in table 1 and table 2, evaluation result in table 3, the temperature rise running 5000h in the load of Table 4(following examples and comparative example catalyst activity component and raw material oil properties and appreciation condition with embodiment 1).
Example 2
With example 1, just with 2.5 grams of appropriate sorbitol aqueous solution oxide impregnation alumina supporters 4 hours, alumina support after dipping is through microwave treatment, microwave treatment conditions is the volume ratio of microwave power and polyatomic alcohol water solution is 20 watts/L, microwave frequency 1000MHz, processing time is 4 hours obtained catalyst C2 of the present invention, and evaluation result is in table 3, table 4.
Example 3
With example 1, just with 1 gram of appropriate arabite aqueous impregnation alumina support 2 hours, alumina support after dipping is through microwave treatment, microwave treatment conditions is the volume ratio of microwave power and polyatomic alcohol water solution is 150 watts/L, microwave frequency 2500MHz, processing time is 10 hours obtained catalyst C3 of the present invention, and evaluation result is in table 3, table 4.
Example 4
With example 1, just with 1.5 gram masses than be the appropriate sorbierite of 1:1:1, sweet mellow wine and arabite mixed aqueous solution oxide impregnation alumina supporter 3 little time, alumina support after dipping is through microwave treatment, microwave treatment conditions is the volume ratio of microwave power and polyatomic alcohol water solution is 280 watts/L, microwave frequency 3000MHz, processing time is 2 hours obtained catalyst C4 of the present invention, and evaluation result is in table 3, table 4.
Example 5
With example 1, just with 2 gram masses than be the appropriate sorbierite of 1:1, sweet mellow wine mixed aqueous solution oxide impregnation alumina supporter 3 little time, alumina support after dipping is through microwave treatment, microwave treatment conditions is the volume ratio of microwave power and polyatomic alcohol water solution is 100 watts/L, microwave frequency 1500MHz, processing time is 6 hours obtained catalyst C5 of the present invention, and evaluation result is in table 3, table 4.
Comparative example 1
With embodiment 1, just do not adopt microwave hydrothermal process, adopt conventional electric heating control hydrothermal treatment consists temperature to make the heat treated temperature of itself and Microwave Water identical.Obtained catalyst is C6, and evaluation result is in table 3, table 4.
Comparative example 2
With embodiment 1, just do not add polyalcohol in the aqueous solution.Obtained catalyst is C7, and evaluation result is in table 3, table 4.
Comparative example 3
With embodiment 1, just do not adopt in microwave hydrothermal process and the aqueous solution and do not add polyalcohol, hydrothermal treatment consists adopts electrical heating, and control treatment temperature makes the heat treated temperature of itself and Microwave Water identical.Obtained catalyst is C8, and evaluation result is in table 3, table 4.
Table 1 residual oil character
Industrial condition evaluated by table 2
Table 3 catalyst hydrogenation performance comparison
Table 4 reaction temperature lift-off value
As can be seen from table 3 data, compared with comparative catalyst, catalyst provided by the invention has higher HDM activity and hydrodesulfurization activity.Find out from the result of table 4, react after 5000 hours, adopt Hydrodemetalation catalyst provided by the invention, in order to keep high demetallization per, desired reaction temperature increase rate is far smaller than comparative catalyst, and this illustrates that Hydrodemetalation catalyst provided by the invention has higher activity stability.
Claims (10)
1. a preprocess method for alumina support, is characterized in that: comprise the steps: the alumina support after first adopting polyatomic alcohol water solution dip forming; Then said mixture material is proceeded in closed container and carry out microwave treatment; Alumina support after last microwave treatment after filtration, dry, roasting obtains final alumina support.
2. method according to claim 1, is characterized in that: described shaping after alumina support use before carry out calcination process, sintering temperature is 500-700 DEG C, and roasting time is 1-5h.
3. method according to claim 1, is characterized in that: described polyalcohol comprises one or more in glycerine, sorbierite, sweet mellow wine, arabite.
4. method according to claim 1, is characterized in that: the addition of polyatomic alcohol water solution be at least make shaping after the complete submergence of alumina support, dip time is 1-4 hour.
5. method according to claim 1, is characterized in that: the polyol amount in the polyatomic alcohol water solution added and shaping after the mass ratio of alumina support be 5%-25%.
6. method according to claim 1, is characterized in that: airtight container is directly positioned in microwave reactor or directly and processes in the microwave reactor of sealing by microwave processing process.
7. method according to claim 1, is characterized in that: carrying out microwave treatment time in closed container is 2 ~ 10 hours, and the volume ratio of microwave power and polyatomic alcohol water solution is 20 ~ 280 watts/L, microwave frequency 1000 ~ 3000MHz.
8. the method according to claim 1 or 7, is characterized in that: microwave treatment time is 4 ~ 8 hours, and the volume ratio of microwave power and polyatomic alcohol water solution is 80 ~ 200 watts/L, microwave frequency 1500 ~ 2500MHz.
9. method according to claim 1, is characterized in that: described dry run is dry 1-10 hour at 100 DEG C-130 DEG C.
10. method according to claim 1, is characterized in that: described roasting process is at 550 DEG C-650 DEG C roasting 2-4 hour.
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Citations (5)
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| US4271042A (en) * | 1977-12-20 | 1981-06-02 | Mobil Oil Corporation | Process for demetalation and desulfurization of petroleum oils |
| CN1579618A (en) * | 2003-08-06 | 2005-02-16 | 中国科学院大连化学物理研究所 | Carrying-type metal catalyst and its preparation method |
| CN102041042A (en) * | 2009-10-22 | 2011-05-04 | 中国石油天然气股份有限公司 | Method for hydrotreating inferior coker gatch |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
| CN102441399A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst |
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2013
- 2013-10-23 CN CN201310499276.4A patent/CN104549536B/en active Active
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| US4271042A (en) * | 1977-12-20 | 1981-06-02 | Mobil Oil Corporation | Process for demetalation and desulfurization of petroleum oils |
| CN1579618A (en) * | 2003-08-06 | 2005-02-16 | 中国科学院大连化学物理研究所 | Carrying-type metal catalyst and its preparation method |
| CN102041042A (en) * | 2009-10-22 | 2011-05-04 | 中国石油天然气股份有限公司 | Method for hydrotreating inferior coker gatch |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
| CN102441399A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst |
Non-Patent Citations (3)
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| 孙发民等: "《微波技术在催化材料制备领域的研究进展》", 《工业催化》 * |
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