CN102861616B - 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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- CN102861616B CN102861616B CN201110188419.0A CN201110188419A CN102861616B CN 102861616 B CN102861616 B CN 102861616B CN 201110188419 A CN201110188419 A CN 201110188419A CN 102861616 B CN102861616 B CN 102861616B
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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 having compared with 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 feedstock oil, very easily form deposition, thereby the duct of blocking catalyst causes catalyst activity to decline rapidly, even inactivation, affects commercial Application.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.The pore structure of catalyst determines by the carrier that forms 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.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, must in 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 physics expanding agent if carbon black and chemical enlargement agent are as phosphide simultaneously, plastic that kneading becomes is extruded moulding on banded extruder, dry after at 840 ℃-1000 ℃ roasting 1-5 hour.The method can overcome the shortcoming of independent use physics expanding agent and chemical enlargement agent, but preparation process is more complicated, and the hole content of 10nm-20nm is lower, is about 60%-70% left and right.In addition, carrier mechanical strength is poor, is 70N/cm-85N/cm.
CN1416955A discloses a kind of alumina support and preparation method thereof, and the pore size distribution of this 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 at the temperature of 90 ℃-300 ℃, in 35 minutes, complete fast dry, and roasting at least 0.5 hour in the moisture vapor atmosphere of 600 ℃-800 ℃.The aperture that the method adopts hydrothermal treatment consists really can improve carrier, but 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 under room temperature be placed in 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: at high temperature rapid evaporation of the moisture content that boehmite itself contains, play the effect same with hydrothermal treatment consists, and make aperture become macropore.But alumina support average pore size prepared by the method is lower, be about 11nm left and right, in addition, the shortcoming that exists equally high-temperature water heat treatment to cause the pore volume of carrier to reduce.
Summary of the invention
For prior art deficiency, the invention provides one and do not use expanding agent, adopt gentle hydrothermal treatment consists mode to prepare the method for macropore alumina supporter.Alumina support prepared by the inventive method has compared with 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 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 hydrothermal treatment consists makes alumina support through moulding, dry, 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 pressurized thermal water processing, and hydrothermal treatment consists pressure is the self-generated pressure at hydrothermal treatment consists temperature, and 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 to prepare.
Moulding described in the inventive method refers to boehmite and appropriate peptizing agent, the even extruded moulding of extrusion aid kneading.Described extrusion aid can be sesbania powder, starch, methylcellulose, preferably sesbania powder.Described peptizing agent can be one or more mixing in formic acid, acetic acid, citric acid, nitric acid.
Dry run described in the inventive method is generally at 100 ℃-130 ℃ and is dried 1 ~ 10 hour.Described roasting process refers to 600 ℃ of-750 ℃ of roastings 2 ~ 4 hours.
Research shows, in alumina support preparation process, the physical property such as the aperture of presoma boehmite grain size to carrier, pore volume, specific area, mechanical strength has considerable influence.The present invention is placed in the mixed material of boehmite and ammonia spirit in airtight container, under alkaline atmosphere and self-generated pressure thereof, carry out gentle hydrothermal treatment consists (ammoniacal liquor and water in mixed material are subject to thermal evaporation), can make presoma boehmite particle crystallization more complete, degree of crystallinity increases, grain growth, thus reach the object that increases carrier aperture.In addition, due to hydrothermal treatment consists mild condition, when making carrier there is larger aperture, also there is larger pore volume, specific area, mechanical strength and concentrated pore size distribution.
Compared with prior art, preparation method's tool of a kind of alumina support of the present invention has the following advantages:
(1) in the inventive method, boehmite, under alkaline atmosphere, carries out gentle pressurized thermal water processing, can make in carrier aperture carrier have larger pore volume, higher specific area, concentrated pore size distribution and moderate mechanical strength improving;
(2) in the inventive method, do not use expanding agent, greatly reduce production cost, the method is simple to operate, without the preparation technology of existing aluminium oxide is carried out to large change, is suitable for industrial production and 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 macropore alumina supporter of the present invention, concrete preparation process is as follows: take a certain amount of boehmite dry glue powder, with appropriate amounts of ammonia aqueous solution, mixed material proceeds in autoclave, and sealing autoclave is in being heated to 100 ℃ of-150 ℃ of constant temperature 1-5 hour; Boehmite after hydrothermal treatment consists and appropriate sesbania powder, peptizing agent kneading are even, form plasticity material; By banded extruder extrusion molding; Strip wet feed after moulding is dry 1-3 hour at 100 ℃-130 ℃; Dried article shaped is made to alumina support in 600 ℃ of-750 ℃ of roasting 2-4 hour.
Example 1
Take boehmite dry glue powder (Shenyang Catalyst Plant's production of 100g, aluminium oxide butt content 65%), adding mass concentration is that 1% ammonia spirit mixes, the addition of ammonia spirit is 100% of boehmite dry glue powder weight, mixed material is proceeded in autoclave, and sealing autoclave is heated to 120 ℃ of constant temperature 2 hours; Boehmite after hydrothermal treatment consists and 2g sesbania powder, appropriate to contain 3g nitre aqueous acid kneading even, forms plasticity material; By banded extruder extrusion molding; Strip wet feed after moulding is dried 3 hours at 120 ℃; Dried article shaped is made to alumina support B1 provided by the invention for 3 hours in 700 ℃ of roastings.
Example 2
With example 1, just adding mass concentration is 3% ammonia spirit, and the addition of ammonia spirit is 80% of boehmite dry glue powder weight, and 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 adding mass concentration is 10% ammonia spirit, and the addition of ammonia spirit is 50% of boehmite dry glue powder weight, and 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 adding mass concentration is 5% ammonia spirit, and the addition of ammonia spirit is 70% of boehmite dry glue powder weight, and 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 adding mass concentration is 6% ammonia spirit, and the addition of ammonia spirit is 80% of boehmite dry glue powder weight, and 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 adding mass concentration is 8% ammonia spirit, and the addition of ammonia spirit is 60% of boehmite dry glue powder weight, and sealing autoclave is heated to 130 ℃ of constant temperature 3 hours; Make alumina support B6 provided by the invention.
Comparative example 1
This comparative example is the alumina support of preparing by the method for describing in CN1087289A.
Take the boehmite dry glue powder 300g that Chinese Qilu Petroleum Chemical Corporation Institute prepares with carbon dioxide neutralisation, add the salpeter solution 240ml of 3.5w%, kneading becomes plastic, on banded extruder, be extruded into diameter and be little of 1.5mm, extrude little at 70 ℃ dry 50 minutes, dry after the moisture 35w% of material, be then directly placed in temperature and be the roaster of 550 ℃, constant temperature 3 hours, obtains contrasting alumina support B7.
Comparative example 2
This comparative example is the alumina support of preparing by the method for describing in CN1416955A.
Take boehmite prepared by 300gCN1247772A example 1, the nitric acid, 3 g sesbania powder and the 120 g deionized waters that are 65 heavy % with 3.9 g concentration mix, and are extruded into diameter and are the trilobal bar of 1.8 millimeters on banded extruder.Forced air drying at 110 ℃, within 25 minutes, aftershaping thing is all dry complete.Dried article shaped is passed at the temperature of 650 ℃ to 100% water vapour, flow is the water vapour of every gram of catalyst 1.5g per hour, and roasting 5 hours, obtains contrasting alumina support B8.
Above-mentioned example and comparative example gained support are in table 1.
Table 1 support.
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | Comparative example 1 | Comparative example 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 carrier accounts for the percentage of total pore volume.
The result of table 1 shows, alumina support prepared by existing hydro-thermal treatment method is because hydrothermal treatment consists excess Temperature causes carrier pore volume lower.And embodiment 1 ~ 6, the alumina support that adopts the inventive method to prepare, has larger pore volume when having larger aperture, concentrated pore size distribution, preferably mechanical strength.Alumina support prepared by this method is applicable to the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.
Claims (7)
1. the preparation method of an alumina support, it is characterized in that: comprise following content: take 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, material after hydrothermal treatment consists is through moulding, dry, roasting makes alumina support, described ammonia spirit mass concentration is 1%-10%, the addition of ammonia spirit is the 50%-100% of boehmite weight, described hydrothermal treatment consists is pressurized thermal water processing, hydrothermal treatment consists pressure is the self-generated pressure at hydrothermal treatment consists temperature, hydrothermal treatment consists temperature is 100 ℃-150 ℃, the hydrothermal treatment consists time is 1-5 hour.
2. 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 to prepare.
3. method according to claim 1, is characterized in that: described moulding refers to boehmite and appropriate peptizing agent, the evenly rear extruded moulding of extrusion aid kneading that hydrothermal treatment consists is crossed.
4. method according to claim 3, is characterized in that: described extrusion aid is the one in sesbania powder, starch or methylcellulose.
5. method according to claim 3, is characterized in that: described peptizing agent is one or more mixing in formic acid, acetic acid, citric acid, nitric acid.
6. method according to claim 1, is characterized in that: described dry run for being dried 1 ~ 10 hour at 100 ℃-130 ℃.
7. method according to claim 1, is characterized in that: described roasting process refers to 600 ℃ of-750 ℃ of roastings 2 ~ 4 hours.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104556162B (en) * | 2013-10-22 | 2016-04-13 | 中国石油化工股份有限公司 | Sheet polycrystalline gama-alumina 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 |
| 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 |
| 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 |
| 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 |
| CN113461408B (en) * | 2021-07-22 | 2022-11-01 | 杭州智华杰科技有限公司 | Method for improving strength of activated alumina balls |
Citations (1)
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 (2)
| Title |
|---|
| Kiyoshi Okada et al..Relationship between Formation Conditions, Properties, and Crystallite Size of Boehmite.《Journal of Colloid and Interface Science》.2002,pp. 308–314,实验部分. |
| Relationship between Formation Conditions, Properties, and Crystallite Size of Boehmite;Kiyoshi Okada et al.;《Journal of Colloid and Interface Science》;20020827;pp. 308–314,实验部分 * |
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