CN102861616A - Preparation method of alumina supporter with concentrated hole distribution - Google Patents
Preparation method of alumina supporter with concentrated hole distribution Download PDFInfo
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- CN102861616A CN102861616A CN2011101884190A CN201110188419A CN102861616A CN 102861616 A CN102861616 A CN 102861616A CN 2011101884190 A CN2011101884190 A CN 2011101884190A CN 201110188419 A CN201110188419 A CN 201110188419A CN 102861616 A CN102861616 A CN 102861616A
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Abstract
The invention relates to a preparation method of an alumina supporter. The preparation method comprises the steps of weighing a certain quality of pseudo-boehmite dry glue powders, evenly mixing the pseudo-boehmite dry glue powders with a certain quality of aqueous solution of ammonia, placing mixing materials in a sealing container for hydro-thermal treatment, conducting molding, drying and roasting on the materials after the hydro-thermal treatment to prepare the alumina supporter. A mass concentration of the aqueous solution of ammonia is 1%-10%, and the adding quantity of the aqueous solution of ammonia is 50-100% of that of the pseudo-boehmite dry glue powder. The hydro-thermal treatment adopts forcing hydro-thermal type, the pressure of the hydro-thermal treatment is self-generated at a hydro-thermal treatment temperature, and the hydro-thermal treatment temperature is 100 DEG C-150 DEG C, a hydro-thermal treatment time is 1-5 hours. The alumina supporter prepared by the preparation method has a large hole volume and a large hole diameter, has concentrated hole distribution, has moderate mechanical strength, and the alumina supporter is applicable to the field preparation of heavy oil and residual oil hydrodemetallization catalyst and the like.
Description
Technical field
The present invention relates to a kind of carrying alumina preparation of pore distribution concentration, relate in particular to a kind of carrying alumina preparation that has than large pore volume aperture, suitable mechanical intensity and pore distribution concentration.
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 the feedstock oil, very easily form deposition, thereby the duct of blocking catalyst causes catalyst activity to descend rapidly, even inactivation, affect commercial Application.Have hold metal and hold the charcoal ability than the catalyst of large pore volume and larger bore dia strong, can slow down catalyst inactivation, prolonged the service cycle of catalyst.The pore structure of catalyst determines by the carrier that consists of catalyst, and therefore, it is preparation residual oil that preparation has carrier than large pore volume and larger bore dia, especially for the preparation of the key of the higher decompression residuum Hydrodemetalation catalyst of tenor.Aluminium oxide is class catalyst carrier commonly used, is widely used in the fields such as PETROLEUM PROCESSING, chemical industry, environmental protection.The bore dia that is generally used for preparing the aluminium oxide of hydrotreating catalyst and commercial alumina is less, can not satisfy the needs of preparation heavy oil, residuum hydrogenating and metal-eliminating and/or heavy oil hydrodesulfurization catalyst, therefore, must in the carrier preparation process, adopt the way of " reaming " to increase its aperture.
CN1160602A discloses a kind of large-pore alumina carrier and preparation method thereof.Its preparation process is in boehmite and water or aqueous solution kneading process, add simultaneously physics expanding agent such as carbon black and chemical enlargement agent such as phosphide, plastic that kneading becomes is extruded moulding on banded extruder, and is dry rear at 840 ℃ of-1000 ℃ of lower roasting 1-5 hours.The method can overcome the shortcoming of independent use physics expanding agent and chemical enlargement agent, but preparation process is complicated, and the hole content of 10nm-20nm is lower, is about about 60%-70%.In addition, the carrier mechanical strength is relatively poor, is 70N/cm-85N/cm.
CN1416955A discloses a kind of alumina support and preparation method thereof, and this pore size distribution of carrier is that bore dia is the 70%-98% that the pore volume in the hole of 10nm-20nm accounts for total pore volume.Its preparation method comprises article shaped under 90 ℃-300 ℃ temperature, in 35 minutes, finishes fast drying, and roasting at least 0.5 hour in 600 ℃-800 ℃ moisture vapor atmosphere.The aperture that the method adopts hydrothermal treatment consists really can improve carrier, but the hydrothermal treatment consists temperature is higher, and the pore volume of carrier is reduced greatly.
CN1087289A discloses a kind of method for preparing macropore alumina supporter.Alumina support expanding method main points of the present invention are: make the moisture boehmite moment that is under the room temperature place high-temperature atmosphere, high temperature range is 500 ℃-65 ℃, and under this high temperature constant temperature 2-4 hour.The principle of this expanding method is: the moisture content that boehmite itself contains is rapid evaporation at high temperature, plays the effect same with hydrothermal treatment consists, makes aperture become macropore.But the alumina support average pore size of the method preparation is lower, is about about 11nm, in addition, and the shortcoming that exists equally high-temperature water heat treatment to cause the pore volume of carrier to reduce.
Summary of the invention
Not enough for prior art, the invention provides a kind of expanding agent that do not use, adopt gentle hydrothermal treatment consists mode to prepare the method for macropore alumina supporter.The alumina support of the inventive method preparation has than large pore volume and aperture, concentrated pore size distribution, moderate mechanical strength, and this alumina support is applicable to the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.
A kind of preparation method of alumina support, comprise following content: take by weighing a certain amount of boehmite dry glue powder, mix with proper ammonia solution, mixed material is put into airtight container and is carried out hydrothermal treatment consists, and the material after the hydrothermal treatment consists makes alumina support through moulding, drying, roasting.
Ammonia spirit mass concentration described in the inventive method is 1%-10%, and the addition of ammonia spirit is the 50%-100% of boehmite weight.
Hydrothermal treatment consists described in the inventive method is that pressurized thermal water is processed, and hydrothermal treatment consists pressure is the self-generated pressure under the hydrothermal treatment consists temperature, and the hydrothermal treatment consists temperature is 100 ℃-150 ℃, and the hydrothermal treatment consists time is 1-5 hour.
Boehmite dry glue powder described in the inventive method can be the boehmite dry glue powder that adopts any one method preparation.
Moulding described in the inventive method refers to boehmite and an amount of peptizing agent, the even extruded moulding of extrusion aid kneading.Described extrusion aid can be sesbania powder, starch, methylcellulose, preferably the sesbania powder.Described peptizing agent can be one or more mixing in formic acid, acetic acid, citric acid, the nitric acid.
Dry run described in the inventive method is generally at 100 ℃-130 ℃ lower dry 1 ~ 10 hour.Described roasting process refers to 600 ℃ of-750 ℃ of roastings 2 ~ 4 hours.
Studies show that, in the alumina support preparation process, presoma boehmite grain size has considerable influence to physical property such as the aperture of carrier, pore volume, specific area, mechanical strengths.The present invention places the mixed material of boehmite and ammonia spirit in the airtight container, under alkaline atmosphere and self-generated pressure thereof, carry out gentle hydrothermal treatment consists (ammoniacal liquor and water in the mixed material are subjected to thermal evaporation), can make presoma boehmite particle crystallization more complete, degree of crystallinity increases, grain growth, thus reach the purpose that increases carrier aperture.In addition, since the hydrothermal treatment consists mild condition, the pore size distribution that also has larger pore volume, specific area, mechanical strength when making carrier have larger aperture and concentrate.
Compared with prior art, the preparation method of a kind of alumina support of the present invention has following advantage:
(1) boehmite carries out gentle pressurized thermal water and processes under alkaline atmosphere in the inventive method, can make carrier have larger pore volume, higher specific area, concentrated pore size distribution and moderate mechanical strength when improving carrier aperture;
(2) do not use expanding agent in the inventive method, greatly reduce production cost, the method is simple to operate, need not the preparation technology of existing aluminium oxide is carried out large change, is suitable for industrial production and application.
The specific embodiment
Further specify 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 macropore alumina supporter of the present invention, concrete preparation process is as follows: take by weighing a certain amount of boehmite dry glue powder, with the appropriate amounts of ammonia aqueous solution, mixed material changes in the autoclave, sealing autoclave in be heated to 100 ℃-150 ℃ constant temperature 1-5 hour; Boehmite after the hydrothermal treatment consists and an amount of sesbania powder, peptizing agent kneading are even, form the plasticity material; By the banded extruder extrusion molding; Strip wet feed after the moulding descended dry 1-3 hour through 100 ℃-130 ℃; Dried article shaped was made alumina support in roasting 2-4 hour in 600 ℃-750 ℃.
Example 1
Take by weighing boehmite dry glue powder (Shenyang Catalyst Plant's production of 100g, aluminium oxide butt content 65%), adding mass concentration and be 1% ammonia spirit mixes, the addition of ammonia spirit is 100% of boehmite dry glue powder weight, mixed material is changed in the autoclave, and sealing autoclave is heated to 120 ℃ of constant temperature 2 hours; Boehmite after the hydrothermal treatment consists and 2g sesbania powder, an amount of aqueous solution kneading that contains 3g nitric acid are even, form the plasticity material; By the banded extruder extrusion molding; Strip wet feed after the moulding is lower dry 3 hours through 120 ℃; Dried article shaped was made alumina support B1 provided by the invention in 3 hours in 700 ℃ of roastings.
Example 2
With example 1, just add mass concentration and be 3% ammonia spirit, the addition of ammonia spirit is 80% of boehmite dry glue powder weight, sealing autoclave is heated to 130 ℃ of constant temperature 3 hours; Make alumina support B2 provided by the invention.
Example 3
With example 1, just add mass concentration and be 10% ammonia spirit, the addition of ammonia spirit is 50% of boehmite dry glue powder weight, sealing autoclave is heated to 140 ℃ of constant temperature 5 hours; Make alumina support B3 provided by the invention.
Example 4
With example 1, just add mass concentration and be 5% ammonia spirit, the addition of ammonia spirit is 70% of boehmite dry glue powder weight, sealing autoclave is heated to 150 ℃ of constant temperature 4 hours; Make alumina support B4 provided by the invention.
Example 5
With example 1, just add mass concentration and be 6% ammonia spirit, the addition of ammonia spirit is 80% of boehmite dry glue powder weight, sealing autoclave is heated to 150 ℃ of constant temperature 2 hours; Make alumina support B5 provided by the invention.
Example 6
With example 1, just add mass concentration and be 8% ammonia spirit, the addition of ammonia spirit is 60% of boehmite dry glue powder weight, sealing autoclave is heated to 130 ℃ of constant temperature 3 hours; Make alumina support B6 provided by the invention.
Comparative Examples 1
This Comparative Examples is the alumina support by the method preparation of describing among the CN1087289A.
Take by weighing Chinese Qilu Petroleum Chemical Corporation Institute with the boehmite dry glue powder 300g of carbon dioxide neutralisation preparation, the salpeter solution 240ml that adds 3.5w%, kneading becomes plastic, being extruded into diameter at banded extruder is little of 1.5mm, extrude little 70 ℃ lower dry 50 minutes, dry after the moisture 35w% of material, then directly placing temperature is 550 ℃ roaster, constant temperature 3 hours obtains contrasting alumina support B7.
Comparative Examples 2
This Comparative Examples is the alumina support by the method preparation of describing among the CN1416955A.
Take by weighing the boehmite of 300gCN1247772A example 1 preparation, with 3.9 g concentration be that nitric acid, 3 g sesbania powder and the 120 g deionized waters of 65 heavy % mix, being extruded into diameter at banded extruder is 1.8 millimeters trilobal bar.110 ℃ of lower forced air dryings, the aftershaping thing was all dry complete in 25 minutes.Dried article shaped is passed into 100% water vapour under 650 ℃ temperature, flow is the per hour water vapour of 1.5g of every gram catalyst, and roasting 5 hours obtains contrasting alumina support B8.
Above-mentioned example and Comparative Examples gained support see Table 1.
Table 1 support.
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | Comparative Examples 1 | Comparative Examples 2 |
| Bearer number | B1 | B2 | B3 | B4 | B5 | B6 | B7 | B8 |
| Specific area, m 2/g | 226 | 220 | 230 | 218 | 240 | 245 | 262 | 145 |
| Pore volume, mL/g | 1.06 | 1.08 | 1.03 | 1.05 | 1.09 | 1.1 | 0.72 | 0.71 |
| Can a few aperture nm | 17 | 17 | 16 | 16 | 16 | 15 | 11.0 | 14.6 |
| Pore size distribution, v%＜10nm | 6 | 8 | 6 | 7 | 9 | 5 | 10 | 8 |
| 10~20nm | 87 | 84 | 83 | 85 | 86 | 90 | 75 | 82 |
| >20nm | 7 | 8 | 11 | 8 | 5 | 5 | 15 | 10 |
| Intensity N/cm | 137 | 130 | 133 | 136 | 129 | 125 | 118 | 110 |
Pore size distribution refers to that the pore volume of certain diameter range endoporus in the carrier accounts for the percentage of total pore volume.
The result of table 1 shows, has the alumina support of hydro-thermal treatment method preparation now because the hydrothermal treatment consists excess Temperature causes the carrier pore volume lower.And embodiment 1 ~ 6, the alumina support that namely adopts the inventive method to prepare has larger pore volume, concentrated pore size distribution, preferably mechanical strength when having larger aperture.The alumina support of this method preparation is applicable to the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.
Claims (9)
1. the preparation method of an alumina support, it is characterized in that: comprise following content: take by weighing a certain amount of boehmite dry glue powder, mix with proper ammonia solution, mixed material is put into airtight container and is carried out hydrothermal treatment consists, and the material after the hydrothermal treatment consists makes alumina support through moulding, drying, roasting.
2. method according to claim 1, it is characterized in that: described ammonia spirit mass concentration is 1%-10%, the addition of ammonia spirit is the 50%-100% of boehmite weight.
3. method according to claim 1 is characterized in that: described hydrothermal treatment consists is that pressurized thermal water is processed, and hydrothermal treatment consists pressure is the self-generated pressure under the hydrothermal treatment consists temperature, and the hydrothermal treatment consists temperature is 100 ℃-150 ℃, and the hydrothermal treatment consists time is 1-5 hour.
4. method according to claim 1 is characterized in that: described boehmite dry glue powder can be the boehmite dry glue powder that adopts any one method preparation.
5. method according to claim 1 is characterized in that: described moulding refers to extruded moulding after boehmite that hydrothermal treatment consists is crossed and an amount of peptizing agent, extrusion aid kneading are evenly.
6. method according to claim 5 is characterized in that: described extrusion aid is a kind of in sesbania powder, starch or the methylcellulose.
7. method according to claim 5, it is characterized in that: described peptizing agent is one or more mixing in formic acid, acetic acid, citric acid, the nitric acid.
8. method according to claim 1 is characterized in that: described dry run is for lower dry 1 ~ 10 hour at 100 ℃-130 ℃.
9. method according to claim 1, it is characterized in that: described roasting process refers to 600 ℃ of-750 ℃ of roastings 2 ~ 4 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111304A (en) * | 2013-01-31 | 2013-05-22 | 厦门大学 | Unsupported hydrodemetallization catalyst and preparation method thereof |
| CN104118894A (en) * | 2014-08-15 | 2014-10-29 | 福州大学 | Preparation method of aluminum oxide centralized in pore diameter distribution |
| CN104556162A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Flaky polycrystal gamma-aluminum oxide and preparation method thereof |
| CN106747591A (en) * | 2016-11-15 | 2017-05-31 | 中国海洋石油总公司 | A kind of preparation method of big pore volume alumina support |
| CN109277095A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and its preparation method and application |
| CN109277108A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Siliceous Hydrodemetalation catalyst and its preparation method and application |
| CN113461408A (en) * | 2021-07-22 | 2021-10-01 | 杭州智华杰科技有限公司 | Method for improving strength of activated alumina balls |
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| CN101293208A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Reforming catalyst and preparation method thereof |
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| CN101293208A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Reforming catalyst and preparation method thereof |
Non-Patent Citations (1)
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| KIYOSHI OKADA ET AL.: "Relationship between Formation Conditions, Properties, and Crystallite Size of Boehmite", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111304A (en) * | 2013-01-31 | 2013-05-22 | 厦门大学 | Unsupported hydrodemetallization catalyst and preparation method thereof |
| CN103111304B (en) * | 2013-01-31 | 2015-09-02 | 厦门大学 | A kind of non-supported hydrogenation catalyst for demetalation and preparation method thereof |
| CN104556162A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Flaky polycrystal gamma-aluminum oxide and preparation method thereof |
| CN104118894A (en) * | 2014-08-15 | 2014-10-29 | 福州大学 | Preparation method of aluminum oxide centralized in pore diameter distribution |
| CN106747591A (en) * | 2016-11-15 | 2017-05-31 | 中国海洋石油总公司 | A kind of preparation method of big pore volume alumina support |
| CN106747591B (en) * | 2016-11-15 | 2019-07-19 | 中国海洋石油集团有限公司 | A kind of macropore holds the preparation method of alumina support |
| CN109277095A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and its preparation method and application |
| CN109277108A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Siliceous Hydrodemetalation catalyst and its preparation method and application |
| CN109277108B (en) * | 2017-07-20 | 2021-07-27 | 中国石油化工股份有限公司 | Silicon-containing hydrodemetallization catalyst and preparation method and application thereof |
| CN109277095B (en) * | 2017-07-20 | 2021-07-30 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and preparation method and application thereof |
| CN113461408A (en) * | 2021-07-22 | 2021-10-01 | 杭州智华杰科技有限公司 | Method for improving strength of activated alumina balls |
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