CN102861618B - Preparation method of alumina supporter - Google Patents
Preparation method of alumina supporter Download PDFInfo
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- CN102861618B CN102861618B CN201110188434.5A CN201110188434A CN102861618B CN 102861618 B CN102861618 B CN 102861618B CN 201110188434 A CN201110188434 A CN 201110188434A CN 102861618 B CN102861618 B CN 102861618B
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Abstract
The invention discloses a preparation method of an alumina supporter. The preparation method comprises the steps of a sol solidification process, a shaping process and a roasting process, a sugar solution with a concentration of 1-5mol/L is added in a sol system in the sol solidification process, and a molar ratio of sugar to aluminum in the sol system is 1-6. The alumina supporter prepared by the preparation method has a high hole volume and a high hole diameter, has concentrated hole distribution, has moderate mechanical strength, and is applicable to serving as a supporter of a heavy oil hydrotreating catalytic agent.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, relate in particular to the preparation method of the alumina support of a kind of large pore volume and aperture, pore distribution concentration.
Background technology
Along with the continuous aggravation of the continuous minimizing of petroleum resources and crude oil heaviness, in poor quality trend, mink cell focus deep process technology is subject to the worker's that refines oil great attention both at home and abroad always.Have hold metal and hold charcoal ability compared with the catalyst of large pore volume and larger bore dia strong, can slow down catalyst inactivation, extended the service cycle of catalyst.Aluminium oxide is the conventional catalyst carrier of a class, is widely used in the fields such as PETROLEUM PROCESSING, chemical industry, environmental protection.Be generally used for preparing the aluminium oxide of hydrotreating catalyst and the bore dia of commercial alumina is less, can not meet the needs of preparing heavy oil, residuum hydrogenating and metal-eliminating and/or heavy oil hydrodesulfurization catalyst, therefore, preparation have compared with the carrier of large pore volume and larger bore dia be prepare residual oil, especially for the preparation of the key of the higher decompression residuum Hydrodemetalation catalyst of tenor.
US4448896 proposes to adopt carbon black as expanding agent.Pulverous expanding agent and boehmite dry glue powder are mixed together, are mediated and extruded moulding, carrier after moulding is in roasting process, expanding agent is through oxidation, burning, finally be converted into gas and overflow, so just form larger " cavity " at carrier body in mutually, thereby generated macroporous aluminium oxide.
CN92112511.9 proposes to add Ludox can play reaming effect in the kneading of boehmite, extrusion process.In addition, in alumina support, add silicon and phosphorus compound also can play the reaming effect of reaming effect, particularly phosphorus compound more obvious simultaneously.This expanding agent and boehmite generation chemical action, therefore can be described as chemical enlargement agent.
CN1160602A discloses a kind of macropore alumina supporter that is suitable as Hydrodemetalation catalyst carrier and preparation method thereof.The preparation method of this macropore alumina supporter comprises boehmite dry glue powder and water or aqueous solution, be kneaded into plastic, the plastic obtaining is extruded into bar on banded extruder, dry and roasting obtains product, be characterized in, in said process, also added carbon powder as physics expanding agent and can with the chemical enlargement agent of phosphorous, the silicon of boehmite or aluminium oxide generation chemical action or boron compound.
In sum, the method that prior art is prepared macropore alumina supporter mostly adopts in alumina support forming process, by increase the aperture of carrier with physics expanding agent and/or chemical enlargement agent.While using physics expanding agent separately, in order to reach desirable often expanding agent large usage quantity of reaming effect, cause the bad mechanical strength of final carrier, pore size distribution disperse.While using chemical enlargement agent separately, due to chemical enlargement agent and boehmite generation chemical action, the pore volume of carrier, specific area are reduced.Use physics expanding agent and chemical enlargement agent simultaneously, can bring into play the synergy of two kinds of expanding agents, reduce its each plant demand, can overcome certain negative effect, but preparation process is more complicated, the pore distribution concentration of carrier needs further to improve.
CN200510003776.X discloses a kind of preparation method of mesoporous aluminas, take aluminium colloidal sol as precursor, add surfactant, high molecular polymer or carboxylic acid to make structure directing agent, add alkali regulation system pH value 8～11, Hydrothermal Synthesis at 80～100 ℃ forms in 500 ℃ of roastings after separating, wash, being dried; Or directly the mixture of aluminium colloidal sol and structure directing agent is dried in 30～100 ℃, then obtain mesoporous aluminas 500 ℃ of roastings.Although alumina support prepared by the method has larger specific area, its pore volume and aperture mechanical strength less and carrier is low.
Summary of the invention
For prior art deficiency, the invention provides and a kind ofly have compared with the preparation method of the alumina support of large pore volume and aperture, concentrated pore size distribution, moderate mechanical strength.
The preparation method of a kind of alumina support of the present invention, comprise sol-gel process, forming process and roasting process, it has added the sugar juice that concentration is 1～5mol/L in sol-gel process in sol system, and in sugar and sol system, the mol ratio of aluminium is 1～6.
Sugar juice concentration described in the inventive method is preferably 2～4mol/L, and in sugar and sol system, the mol ratio of aluminium is preferably 1～3.Described sugar juice is the sugared aqueous solution.
Sugar described in the inventive method is monose or disaccharide, the preferred glucose of monose or fructose, disaccharide preferably sucrose or maltose.
Sol-gel process described in the inventive method is as follows: take appropriate aluminum nitrate and be dissolved in the water, drip ammonia spirit, filter and washing leaching cake, to washing after filter cake in add suitable quantity of water stir after add appropriate salpeter solution, more than 70 ℃, continue to stir within least 2 hours, to obtain aluminium colloidal sol, in aluminium colloidal sol, add sugar juice, after stirring under room temperature aging 1～5 hour, gel was dry in 100～130 ℃ of baking ovens.
The mass concentration of the ammonia spirit described in the inventive method is 1%～5%, and addition is the pH>9.0 that makes system; The concentration of described salpeter solution is 0.5mol/L～2mol/L, and addition is for making H
+/ Al
3+=0.05～0.15.
Forming process described in the inventive method is that aluminium oxide dry powder is mixed with suitable quantity of water, peptizing agent, extrusion aid, the evenly rear extruded moulding of kneading, and shaping carrier is dried 2～4 hours in 100～130 ℃ of baking ovens.
In the inventive method carrier forming process, extrusion aid can be one or more mixing in starch, methylcellulose, sesbania powder; Peptizing agent can be one or more mixing in formic acid, acetic acid, citric acid, malonic acid, nitric acid.
Roasting process described in the inventive method, for dry support is proceeded in Muffle furnace, rises to 600～800 ℃ with the programming rate of 0.5～2 ℃/min, and constant temperature calcining obtains final alumina support for 2～4 hours.
Active aluminum oxide carrier is actually by the particulate cohesion than its little several order of magnitude and forms, and particulate is to form by than it, less primary particle is coalescent.The hole of active aluminum oxide carrier can be divided into three types: primary particle is piled up and the micropore differing in size or the mesopore of formation, i.e. the intercrystalline hole of primary particle; Particulate is piled up the macropore forming, i.e. particulate intercrystalline hole; And the defective hole forming when aluminium oxide moulding.Therefore interparticle space is exactly the source of alumina pore, and further the size in hole and shape depend on particle size, shape and accumulation mode completely.The aluminium colloidal sol that the present invention is evenly distributed using particle diameter is as aluminium source, and glucide is as structure directing agent Borolon carrier.In carbohydrate molecule structure, contain multiple hydroxyls, it is intermolecular can form aggregation with hydrogen bond action.These aggregations can be with inorganic species with hydrogen bond action, thereby guides the arrangement mode of inorganic species.The aluminium colloidal sol that particle diameter is evenly distributed is the accumulation of rule, arrangement centered by carbohydrate aggregation under hydrogen bond action, the accumulation of this rule, arranges and makes gained alumina support of the present invention have larger pore volume, concentrated pore-size distribution and higher specific area.
The preparation method of a kind of alumina support of the present invention has the following advantages:
(1) use glucide as structure directing agent, accumulation, the arrangement of aluminium colloidal sol rule under the effect of structure directing agent, make gained carrier have larger pore volume, aperture, concentrated pore size distribution and suitable mechanical strength;
(2) do not need to use physics expanding agent and or chemical enlargement agent make carrier there is higher specific area;
(3) raw materials used as carbohydrate, aluminum nitrate, cheap, environmental protection, pollution-free;
(4) preparation method simple, be suitable for commercial Application.
The specific embodiment
Further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.
The preparation method of a kind of alumina support of the present invention, concrete preparation process is as follows:
Take appropriate Al (NO
3)
3be dissolved in deionized water, the ammonia spirit that dropping mass concentration is 2.5% is to system pH>9.0, the sediment obtaining is carried out to suction filtration, Washing of Filter Cake is transferred in beaker to neutrality by deionized water, add appropriate amount of deionized water to stir after 0.5 hour and drip appropriate salpeter solution, more than 70 ℃, continue stirring and within least 2 hours, obtain aluminium colloidal sol; The aqueous solution of proper amount of sugar is added in gained aluminium colloidal sol, stir after 0.5 hour under room temperature aging 3 hours, gel in 120 ℃ of baking ovens dry 3 hours; By even to gained dry powder and suitable quantity of water, peptizing agent, extrusion aid kneading, extruded moulding, shaping carrier is dry 2-4 hour in 120 ℃ of baking ovens; Dry support proceeds in Muffle furnace, rises to 700 ℃ with the programming rate of 1 ℃/min, within constant temperature calcining 2-4 hour, obtains final alumina support.
Example 1
Take 375gAl (NO
3)
39H
2o is dissolved in deionized water, the ammonia spirit that dropping mass fraction is 2.5% is to system pH>9.0, the precipitation suction filtration obtaining is separated, extremely neutral with deionized water washing, the filter cake obtaining is transferred in beaker, add appropriate amount of deionized water to stir the salpeter solution 100ml that drips 1mol/L after 0.5 hour, under 70 ℃ of conditions, continue to stir within 2 hours, to obtain aluminium colloidal sol, adding 1L concentration is that 1mol/L glucose is in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and sol system is 1:1, stir after 0.5 hour under room temperature aging 3 hours, gel is dried 3 hours in 120 ℃ of baking ovens, by even to gained dry powder and suitable quantity of water, nitric acid, sesbania powder kneading, extruded moulding, shaping carrier is dry 2-4 hour in 120 ℃ of baking ovens, dry support proceeds in Muffle furnace, rises to 700 ℃ with the programming rate of 1 ℃/min, within constant temperature calcining 2-4 hour, obtains final alumina support B1.
Example 2
With example 1, just add 1L concentration be the mixed solution (sucrose and glucose mol ratio are 1:1) of 3mol/L sucrose and glucose in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and sol system is 1:3, obtains alumina support B2 provided by the invention.
Example 3
With example 1, just add 1L concentration be 5mol/L sucrose solution in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and sol system is 1:5, obtains alumina support B3 provided by the invention.
Example 4
With example 1, just add 2L concentration be the mixed solution of 3mol/L maltose and fructose in gained aluminium colloidal sol, making the mol ratio of aluminium in sugar and sol system is 1:6, obtains alumina support B4 provided by the invention.
Comparative example 1
This comparative example is the alumina support of preparing by the method for describing in CN1160602A.
Take Chinese Qilu Petroleum Chemical Corporation Institute and prepare boehmite dry glue powder 300g (moisture 78g), take again granular size and be carbon black 18 g and extrusion aid sesbania powder 10 g of 30 microns, mix, add the solution being made into by 2.0 g phosphoric acid and 400 g water, kneading becomes plastic, and the cloverleaf pattern bar of be extruded on banded extruder=1.8mm is dried 4 hours at 120 ℃, then roasting 2 hours at 900 ℃, obtains alumina support B5.
Comparative example 2
This comparative example is the alumina support of preparing by the method for describing in CN200510003776.X.
Get 13.67g boehmite powder (Al
2o
3mass content is 74.6%) be dispersed in 200ml water, at 80 ℃, add the nitric acid 14ml of 1M, keep temperature to continue to stir 6 hours, stablized, the 1M boehmite sol of high dispersive, at 30 ℃, 3.64g CTAB (CTAB), 3.6g urea (or ammoniacal liquor of 60ml2M) are joined in the boehmite sol of 40ml 1M, after dissolving completely, continue to stir 12 hours, proceed to 100 ℃ of hydrothermal treatment consists 24 hours, go out the pH=9.0 of mixture after still, within 3 hours, make alumina support B6 in 500 ℃ of roastings after dry through separating, at washing, 30 ℃.
Above-mentioned example and comparative example gained support are in table 1.
Table 1 support.
| Example number | 1 | 2 | 3 | 4 | Comparative example 1 | Comparative example 2 |
| Bearer number | B1 | B2 | B3 | B4 | B5 | B6 |
| Specific area, m 2/g | 264 | 270 | 249 | 266 | 162 | 335.6 |
| Pore volume, ml/g | 0.98 | 0.99 | 1.03 | 1.05 | 1.00 | 0.66 |
| Can a few aperture nm | 15 | 16 | 17 | 16 | 17 | 6.1 |
| Pore size distribution, v% < 10nm | 5 | 7 | 6 | 8 | 13 | 36 |
| 10~20nm | 83 | 84 | 84 | 85 | 60 | 31 |
| >20nm | 12 | 9 | 10 | 7 | 27 | 33 |
| Intensity N/cm | 153 | 149 | 139 | 142 | 76 | 98 |
Pore size distribution refers to that the pore volume of certain diameter range endoporus in carrier accounts for the percentage of total pore volume.
The result of table 1 shows, the alumina support that prior art is prepared, and the hole content of bore dia between 10 ~ 20nm is lower, pore size distribution disperse, mechanical strength is low.And embodiment 1 ~ 4, the alumina support that adopts the inventive method to prepare, specific area is larger, aperture is larger, can a few aperture >15nm, and also pore size distribution is relatively concentrated, the pore volume of bore dia between 10 ~ 20nm accounts for 84% left and right of whole pore volumes, and mechanical strength is large.Alumina support of the present invention is particularly suitable for preparing heavy, residuum hydrogenating and metal-eliminating catalyst.
Claims (6)
1. the preparation method of an alumina support, comprise sol-gel process, forming process and roasting process, it is characterized in that: sol-gel process is dissolved in the water for taking appropriate aluminum nitrate, the ammonia spirit that dropping mass concentration is 1%～5%, addition is the pH>9.0 that makes system, filter and washing leaching cake, to washing after filter cake in add suitable quantity of water stir after add appropriate salpeter solution, the concentration of salpeter solution is 0.5mol/L～2mol/L, and addition is for making H
+/ Al
3+=0.05-0.15 continues to stir within least 2 hours, to obtain aluminium colloidal sol more than 70 ℃, in aluminium colloidal sol, adds sugar juice, sugar juice concentration is the sugar juice of 1 ~ 5mol/L, in sugar and sol system, the mol ratio of aluminium is 1 ~ 6, after stirring under room temperature aging 1-5 hour, dry at 100-130 ℃; Forming process is that aluminium oxide dry powder is mixed with suitable quantity of water, peptizing agent, extrusion aid, the evenly rear extruded moulding of kneading, and shaping carrier is dry 2-4 hour at 100-130 ℃; Roasting process is for to be warming up to 600-800 ℃ with 0.5-2 ℃/min, constant temperature calcining 2-4h.
2. method according to claim 1, is characterized in that: described sugar juice concentration is 2 ~ 4mol/L, and in sugar and sol system, the mol ratio of aluminium is 1 ~ 3.
3. method according to claim 1, is characterized in that: described sugar juice is the sugared aqueous solution.
4. method according to claim 1, is characterized in that: described sugar is monose or disaccharide.
5. method according to claim 4, is characterized in that: described monose is glucose or fructose, and disaccharide is sucrose or maltose.
6. method according to claim 1, is characterized in that: described extrusion aid is one or more mixing in starch, methylcellulose, sesbania powder; Peptizing agent is one or more mixing in formic acid, acetic acid, citric acid, malonic acid, nitric acid.
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| CN107999117B (en) * | 2016-10-31 | 2020-07-28 | 中国石油化工股份有限公司 | Hydrated alumina composition containing Y-type molecular sieve, formed body, preparation method and application of hydrated alumina composition, catalyst and preparation method of catalyst |
| CN107999122B (en) * | 2016-10-31 | 2020-07-28 | 中国石油化工股份有限公司 | Hydrated alumina composition containing molecular sieve, molded body, preparation method and application of hydrated alumina composition and molded body, catalyst and preparation method of catalyst |
| CN109569676B (en) * | 2017-09-29 | 2021-11-12 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN109319813A (en) * | 2018-11-09 | 2019-02-12 | 中山大学 | A kind of preparation method of two dimensional oxidation aluminium powder |
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2011
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Patent Citations (4)
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| CN1160747A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Preparation of reforming platinum-rhenium catalyst |
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