CN105983443B - A kind of alumina supporter and preparation method thereof - Google Patents
A kind of alumina supporter and preparation method thereof Download PDFInfo
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- CN105983443B CN105983443B CN201510041288.1A CN201510041288A CN105983443B CN 105983443 B CN105983443 B CN 105983443B CN 201510041288 A CN201510041288 A CN 201510041288A CN 105983443 B CN105983443 B CN 105983443B
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Abstract
A kind of preparation method of alumina supporter, this method includes that hydrated alumina is mixed, is molded and roasted with adhesive, chemical enlargement agent and organic matter expanding agent, described adhesive is synthetic cellulose, the chemical enlargement agent is boron-containing compound, organic expanding agent is powdered high polymer, the calcination temperature is 500 1000 DEG C, and roasting time is 18 hours；The invention further relates to alumina supporters made from above method.
Description
Technical field
The present invention relates to a kind of alumina supports and preparation method thereof, are in particular about a kind of structure of double peak holes
Alumina support and preparation method thereof.
Background technology
Inferior heavy oil such as residual oil etc. contains the metal impurities such as higher Ni, V, it usually needs is taken off by hydrotreating
It removes, to pass through subsequent processing (such as catalytic cracking), produces the oil products such as clean vapour, diesel oil and industrial chemicals.Study table
Bright, metal impurities are primarily present in resin and asphalt in the inferior heavy oils such as residual oil, this moieties molecular weight is big, structure is multiple
It is miscellaneous, difficulty is spread, therefore it is required that catalyst has excellent pore passage structure, convenient for the diffusion of macromolecule reactant, reaction and is sunk
Product.Currently, residuum hydrogenating and metal-eliminating catalyst generally use structure of double peak holes aluminium oxide is as carrier.During the reaction, hole
Macropore of the diameter in 100nm or more provides channel for the diffusion of macromolecular reaction substance, promotes internal holes of the impurity to catalyst
Road is spread and deposition；And bore dia then provides reaction surface and depositional site in the ducts below 50nm for impurity.Two class ducts
Synergistic effect, to make catalyst that there is high metal removal activity and high appearance impurity ability.
CN1103009A discloses a kind of preparation method with double-hole alumina support, and this method is by two kinds of apertures point
The different aluminium oxide of cloth or its precursor and carbon powder, surfactant, peptizing agent and water mixed-forming are made through dry and roasting
At.When using carbon powder as expanding agent, reaming effect is poor, and support strength is relatively low, meanwhile, the addition of peptizing agent can drop
The Kong Rong of low carrier and aperture.
CN1120971 discloses a kind of preparation method of alumina supporter, and this method is by two kinds or two kinds
Boehmite dry glue prepared by the above different material route methods uniformly mixes, and then carries out peptization, molding, drying and roasting
It burns.But this method using oil ammonia column method carry out alumina support molding, low production efficiency and production process pollution it is larger,
Less use.
CN1647857A discloses a kind of preparation method of macropore alumina supporter, and this method is by the expanding agent containing organic matter
Boehmite composition is molded and is roasted, and the alumina support with structure of double peak holes is obtained.This method will need to first have
Machine expanding agent and boehmite are beaten and are spray-dried, and preparation process is complex.
In existing carrying alumina Antibody Production Techniques, it is both needed to that nitric acid, acetic acid, aluminum nitrate etc. is added when aluminium oxide is molded
Acidic materials are as peptizing agent, and the addition of acidic materials can destroy the particle structure of aluminium oxide, reduce Kong Rong and the hole of carrier
Diameter.It is to prepare a kind of effective technology route of macropore alumina supporter to alumina pore structural damage to reduce Aci-Jel solvent,
Peptization acid is carried out in part as certain ammonia is added in CN1154668 and CN1611578 during aluminium oxide kneading and compacting
With hold aperture to achieve the purpose that increase carrier hole, but such method cannot thoroughly eliminate acidic materials to carrier pore structure
Adverse effect, effect is limited.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide one kind there is structure of double peak holes, hole to hold, aperture is big, machine
Tool intensity is good, the preparation method of the simple alumina support of preparation process, and alumina support prepared by the method for the present invention can be used as
Catalyst carrier for hydrgenating especially residuum hydrogenating and metal-eliminating catalyst carrier uses.
Method provided by the invention include hydrated alumina is mixed with adhesive, chemical enlargement agent and organic expanding agent,
It is molded and roasts, described adhesive is synthetic cellulose, and the chemical enlargement agent is boron-containing compound, and organic expanding agent is
Powdered high polymer, calcination temperature are 500-1000 DEG C, and roasting time is 1-8 hours.
Compared with the conventional method, the method provided by the present invention does not use Aci-Jel solvent in carrier forming process, reduces
Destruction of the acid to hydrated alumina particle structure, thus carrier hole holds and aperture is larger；The addition of organic expanding agent is relatively low,
It advantageously reduces manufacturing cost and prevents roasting process from temperature runaway phenomenon occurs；And preparation process is simple, production efficiency is higher.
There is typical structure of double peak holes by alumina support prepared by the method provided by the present invention.For example, according to the present invention
Alumina support prepared by providing method roasts 3 hours through 800 DEG C, and 1.2 milliliters of Kong Rongwei/gram, it is received respectively in 25 nanometers and 250
There is characteristic peak at rice, bore dia accounts for holes of 40.5%, the Kong Rong of total pore volume at 100-2000 nanometers in 20-50 nanometers of Kong Rong
Appearance accounts for the 24.1% of total pore volume, and hole of the bore dia less than 20nm accounts for the 28.2% of total pore volume
Specific implementation mode
According to method provided by the present invention, the hydrated alumina is selected from gibbsite, boehmite, boehmite
With one or more kinds of mixtures among amorphous hydroted alumina.Preferably boehmite.They can be commercially available
Commodity can also be any one method preparation in the prior art.Boehmite is such as prepared using aluminum sulfate-sodium metaaluminate method.
Described adhesive is synthetic cellulose, can be methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose,
One or more of hydroxyethylmethylcellulose；Its 2% solution viscosity of the synthetic cellulose is not less than 100000mPa
s；The addition of the synthetic cellulose is the 1-5% of alumina weight.
The boron-containing compound is selected from one or more of boric acid, boron oxide, borate；It is described to contain in terms of pure boron
The addition of boron compound is the 1-4% of alumina weight.
Organic expanding agent is in pva powder, nitrile rubber powder, Polystyrene powder, lignocellulosic
One or more；The particle diameter of organic expanding agent is 75-180 μm；The addition of organic expanding agent is oxidation
The 2-8% of aluminium weight.
The present invention why boron-containing compound is used in combination with powdered high polymer, is primarily due to during the experiment
It was found that with obvious effects better than the two exclusive use, the duct sides 100nm or more especially in increasing carrier are used in combination in the two
Face.Mainly boron-containing compound is utilized to the facilitation of the organic expanding agent reaming effect of high polymer class, such as polyvinyl alcohol in this
" gelation " reaction can occur when encountering boron-containing compound, to form more macropore ducts.
The calcination temperature is preferably 700-900 DEG C, and roasting time is preferably 2-4 hours.
The forming method can be used common method and carry out, such as tabletting, spin and extrusion, preferably extrusion.Carrier
Shape can be changed as needed, such as cylinder, clover, bunge bedstraw herb.Suitable extrusion aid can be added in forming process
And water.
The alumina support that the method for the present invention is provided is had structure of double peak holes, is such as measured using mercury injection method, Kong Rongwei
0.9-1.6 mls/g, bore dia accounts for the 30-70% of total pore volume in 20-50 nanometers of Kong Rong, and Kong Rong is at 100-2000 nanometers
Kong Rong accounts for the 15-40% of total pore volume, and the ratio that hole of the bore dia less than 20nm accounts for total pore volume is less than 50%, and BET specific surface area is
100-300 meters squared per grams.
There is the alumina support that the method for the present invention provides big hole to hold aperture and structure of double peak holes, can be used as plus hydrogen is urged
Agent carrier especially residuum hydrogenating and metal-eliminating catalyst carrier uses.
The feature further illustrated the present invention below with embodiment and comparative example.
Embodiment 1
Weigh the macropore boehmite dry glue powder (contents on dry basis 71.5wt%) of Yantai Heng Hui Chemical Co., Ltd.s production
500g, addition viscosity are hydroxypropyl methyl cellulose 10.7g, the particle diameter of 150,000 mPas (viscosity for referring to 2% aqueous solution)
For 90-150 μm of pva powder 17.9g, it is uniformly mixed；40.9g boric acid is dissolved in 390g water purifications, before being slowly added to
It states in material, then kneading is extruded into the cloverleaf pattern of a diameter of 1.6mm at plastic on preceding crowded formula single-screw extruder.
120 DEG C of dryings 2.0 hours, then be placed in roaster obtained carrier A, physico-chemical property is listed in table 1 in 800 DEG C of constant temperature 3 hours
In.
Embodiment 2
Aforementioned boehmite 500g is weighed, addition viscosity is the hydroxypropyl of 150,000 mPas (viscosity for referring to 2% aqueous solution)
The pva powder 18.6g and particle diameter that ylmethyl cellulose 3.6g, particle diameter are 90-150 μm are 80-160 μm
Lignocellulosic 10.0g is uniformly mixed；20.5 grams of boric acid are dissolved in 390g water purifications, according to preceding method carry out molding and
It is dry, with 900 DEG C of constant temperature 2 hours in roaster, carrier B is obtained, physico-chemical property is listed in Table 1 below.
Embodiment 3
Aforementioned boehmite 500g is weighed, addition viscosity is the hydroxyl second of 100,000 mPas (viscosity for referring to 2% aqueous solution)
Ylmethyl cellulose 17.9g, nitrile rubber powder 17.9g, the boron oxide 28.6g that particle diameter is 75-140 μm are uniformly mixed；
31.0 grams of boric acid are dissolved in 390g water purifications, is molded and is dried according to preceding method, with 700 DEG C of constant temperature in roaster
4 hours, support C is obtained, physico-chemical property is listed in Table 1 below.
Embodiment 4
Aforementioned boehmite 500g is weighed, addition viscosity is the hydroxypropyl of 150,000 mPas (viscosity for referring to 2% aqueous solution)
Ylmethyl cellulose 6.7g and methylcellulose 4.0g, particle that viscosity is 100,000 mPas (viscosity for referring to 2% aqueous solution) are straight
Polystyrene powder 7.2 gram, boron oxide 28.6g of the diameter for 106-180 μm, are uniformly mixed；Water purification 390g is added, according to aforementioned side
Method is molded and is dried, and with 850 DEG C of constant temperature 3 hours in roaster, obtains carrier D, physico-chemical property is listed in Table 1 below.
Embodiment 5
Aforementioned boehmite 500g is weighed, addition viscosity is the hydroxypropyl of 150,000 mPas (viscosity for referring to 2% aqueous solution)
The pva powder 12.9g and particle diameter that ylmethyl cellulose 10.7g, particle diameter are 90-150 μm are 106-180 μm
Polystyrene powder 5.0g, be uniformly mixed；20.0g boric acid and 13.5g ammonium borates are dissolved in 390g water purifications, according to aforementioned
Method is molded and is dried, and with 850 DEG C of constant temperature 3 hours in roaster, obtains carrier E, physico-chemical property is listed in Table 1 below.
The alumina supporter that comparative example 1-2 illustrates existing method and prepared by existing method.
Comparative example 1
This comparative example is to prepare alumina support according to method described in CN1103009A.
By hydrogen made from 34.1g aluminum hydroxide solid elastomers powder (salic 75% alkyl aluminum hydrolysis product) and aluminum sulfate method
Be added after alumina powder 39.3g mixing high wear-resistant carbon black 4.7g and surfactant SA-203.5g and 2.1g aluminum nitrate, 66 milliliters
Water fully grinds mixed, 1.8 millimeters of cloverleaf patterns of diameter is extruded on banded extruder, 120 DEG C of drying, 600 DEG C roast 4 hours, are carried
Body F, physico-chemical property are listed in Table 1 below.
Comparative example 2
This comparative example is to prepare alumina support according to method described in CN1647857A.
Reacted with aluminium hydroxide using aluminium hydroxide prepare a concentration of 200g aluminium oxide/liter NaAlO2Solution, this is molten
Liquid and a concentration of 90g aluminium oxide/liter aluminum sulfate solution be added to simultaneously in manner of cocurrent flow in one 2 liters of plastic cans, tank
In be placed in advance in 1.5 liters of water, sodium metaaluminate flow is 1.1 ls/h, adjusts the flow of aluminum sulfate solution, makes the plastic pH value be
8, gelling temperature is 50 DEG C, and the slurries that plastic generates are collected in an ageing can.It collects and carbonic acid is added in the ageing can finished
Sodium adjusts pH value to 10, and aging 50 minutes is filtered and washed, and boehmite wet cake is made.Take 6.5 kilograms of the wet cake with
Sesbania powder 20.5g mixing, is added mashing, is spray-dried under conditions of 600 DEG C of inlet temperature, 145 DEG C of outlet temperature later, will
Dry resulting composition extruded moulding on banded extruder, and it is dry at 120 DEG C, it is roasted 3.5 hours at 800 DEG C, obtains carrier
G, physico-chemical property are listed in Table 1 below.
Comparative example 3
Weigh the macropore boehmite dry glue powder (contents on dry basis 71.5wt%) of Yantai Heng Hui Chemical Co., Ltd.s production
500g, addition viscosity be 150,000 mPas (viscosity for referring to 2% aqueous solution) hydroxypropyl methyl cellulose 10.7g, be uniformly mixed；
58.8g boric acid is dissolved in 390g water purifications, is slowly added in afore-mentioned materials, kneading is at plastic, then in preceding crowded formula list spiral shell
The cloverleaf pattern of a diameter of 1.6mm is extruded on bar banded extruder.It is 2.0 hours dry at 120 DEG C, then be placed in roaster, in 800 DEG C
Constant temperature 3 hours, obtains carrier H, and physico-chemical property is listed in Table 1 below.
Comparative example 4
Weigh the macropore boehmite dry glue powder (contents on dry basis 71.5wt%) of Yantai Heng Hui Chemical Co., Ltd.s production
500g, addition viscosity are hydroxypropyl methyl cellulose 10.7g, the particle diameter of 150,000 mPas (viscosity for referring to 2% aqueous solution)
For 90-150 μm of pva powder 58.8g, it is uniformly mixed；390g water purifications are slowly added in afore-mentioned materials, kneading is at can
Then plastomer is extruded into the cloverleaf pattern of a diameter of 1.6mm on preceding crowded formula single-screw extruder.It is 2.0 hours dry at 120 DEG C,
It is placed in roaster again, in 800 DEG C of constant temperature 3 hours, obtains carrier I, physico-chemical property is listed in Table 1 below.
1 carrier physico-chemical property of table
Table 1 the result shows that, compared with comparative example, alumina support prepared by the method for the present invention has apparent bimodal
Pore structure, and large pore volume, aperture is big, 100nm or more macropores are relatively high, support strength is high；From comparative example 3,4 and embodiment 1
It can also be seen that powdered high polymer class organic compound and boron-containing compound are expanding agent, the effect that the two is used in combination is bright
It is aobvious to be used alone better than the two, especially in increasing carrier in terms of the ducts 100nm or more.Mainly boracic chemical combination is utilized in this
Object is to the facilitation of the organic expanding agent reaming effect of high polymer class, as polyvinyl alcohol can occur when encountering boron-containing compound
" gelation " is reacted, to form more macropore ducts.
Claims (6)
1. a kind of preparation method of alumina supporter, which is characterized in that this method include by hydrated alumina with
Adhesive, chemical enlargement agent and the mixing of organic matter expanding agent are molded and roast, and described adhesive is synthetic cellulose, describedization
Expanding agent is boron-containing compound, and organic expanding agent is powdered high polymer, and the calcination temperature is 500-1000 DEG C, roasting
It is 1-8 hours to burn the time；
The boron-containing compound is selected from one or more of boric acid, boron oxide, borate；
Organic expanding agent in pva powder, nitrile rubber powder, Polystyrene powder, lignocellulosic one
Kind is several, and the particle diameter of organic expanding agent is 75-180 μm；
In terms of pure boron, the addition of the boron-containing compound is the 1-4% of alumina weight；The addition of organic expanding agent
Amount is the 2-8% of alumina weight.
2. the preparation method of alumina supporter according to claim 1, which is characterized in that the synthesis is fine
The one kind or several of dimension element in methylcellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethylmethylcellulose
Kind.
3. the preparation method of alumina supporter according to claim 2, which is characterized in that the synthesis is fine
Its plain 2% solution viscosity of dimension is not less than 100000mPas.
4. according to the preparation method of claims 1 to 3 any one of them alumina supporter, which is characterized in that
The addition of the synthetic cellulose is the 1-5% of alumina weight.
5. the preparation method of alumina supporter according to claim 1, which is characterized in that the roasting temperature
Degree is 700-900 DEG C, and roasting time is 2-4 hours.
6. a kind of alumina supporter is the system of any one of Claims 1 to 5 alumina supporter
Alumina support made from Preparation Method.
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| CN107913691B (en) * | 2016-10-10 | 2020-06-09 | 中国石油天然气股份有限公司 | Alumina carrier containing macropores and preparation method thereof |
| CN108236939B (en) * | 2016-12-27 | 2020-05-08 | 中国石油天然气股份有限公司 | Alumina carrier containing mesopores/macropores and preparation method thereof |
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| CN109897663B (en) * | 2017-12-07 | 2021-07-02 | 中国石油天然气股份有限公司 | FCC gasoline desulfurization treatment method |
| CN111420710B (en) * | 2020-04-29 | 2022-12-06 | 煤炭科学技术研究院有限公司 | Alumina carrier with double-peak pore structure and preparation method thereof |
| CN111604074B (en) * | 2020-06-29 | 2022-12-13 | 煤炭科学技术研究院有限公司 | Coal tar double-peak pore structure hydrogenation pretreatment catalyst and preparation method thereof |
| CN115475610B (en) * | 2021-06-15 | 2024-03-29 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method thereof, silver catalyst and olefin epoxidation method |
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