CN103803616A - Preparation method for alumina dry gel - Google Patents
Preparation method for alumina dry gel Download PDFInfo
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- CN103803616A CN103803616A CN201210443030.0A CN201210443030A CN103803616A CN 103803616 A CN103803616 A CN 103803616A CN 201210443030 A CN201210443030 A CN 201210443030A CN 103803616 A CN103803616 A CN 103803616A
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Abstract
The invention discloses a preparation method for alumina dry gel. The method comprises the following steps: in the process of gel formation by concurrent flow of an alkaline solution containing aluminum and an acidic solution containing aluminum, adding an additive and an organic template agent in the manner of concurrent flow at the same time, controlling proper reaction conditions and carrying out gel formation, wherein the organic template agent is cellulose ethers; then adding an alkaline solution to adjust a pH value; and then carrying out filtering, washing and drying so as to obtain the alumina dry gel. The alumina dry gel prepared by using the method has the advantages of a large specific surface area, a great pore volume and a reasonable pore structure and is particularly applicable as a carrier component for a heavy oil hydrotreating catalyst, especially applicable as a carrier component for a residual oil hydrodesulfurization or hydro-conversion catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of alumina dry glue, in particular for the carrier component of heavy catalyst for hydrotreatment of residual oil.
Background technology
Aluminum oxide is one of the most frequently used industrial raw material, at field important roles such as catalyzer, pottery, refractory materialss.Because aluminum oxide has good physical strength, thermostability, Acidity and pore structure that can modulation, be therefore widely used in catalytic field as support of the catalyst.The world makes catalyzer market constantly increase the demand of hydrogenation catalyst to the attention of hydrogen addition technology at present.Current most widely used hydrogenation catalyst is generally loaded catalyst, and its carrier is generally aluminum oxide and by its derivative complex carrier, as TiO
2-Al
2o
3, SiO
2-Al
2o
3deng, or in alumina supporter, add some auxiliary agents and carry out modification, as phosphorus, boron, fluorine etc.Along with the further investigation of people to hydrogenation catalyst, the importance of the carrier property to catalyzer has also had new understanding, the not only dispersity important to active ingredient of pore structure (specific surface area, pore volume and pore size distribution) of carrier, and be directly connected to diffusion and mass transfer in reaction process, pore size and hole shape can affect the inner diffusing rate of reactant, product, thereby affect the activity and selectivity of catalyzer.Especially for residual hydrocracking reaction process, residual oil molecule is because molecular dimension is large, viscosity high, residual oil molecule is subject to inner diffusional limitation more serious in catalyzer duct, therefore, residual oil molecule can be spread effectively in duct, can react fully again, just need catalyzer to there is suitable pore structure.
γ-A1
2o
3duct mainly formed by several parts, comprise interlayer hole (intragranular hole), intergranular pore (mesopore), offspring hole and poly particle hole.Wherein intergranular pore is to provide the most important hole of catalyzer pore volume, aperture and specific surface area, and its size depends primarily on the factor such as size, shape and accumulation mode and the form of offspring of pseudo-boehmite primary particle.And offspring hole and poly particle hole are larger for the duct contribution of hundred nano-scale.There is substantial connection with the preparation condition (as reacted and aging temperature, pH value, stirring velocity, the residence time and washing and drying conditions) of pseudo-boehmite in these factors.The primary particle of pseudo-boehmite particle and form and the accumulation mode etc. of offspring greatly affect the pore structure of aluminum oxide prepared therefrom as can be seen here.
CN1257754A discloses a kind of preparation method of support of the catalyst, wherein adopts water glass and Tai-Ace S 150 to prepare the dry glue of sial, and the carrier pore volume of preparation is 0.45 ~ 0.75mL/g, and mean pore size is 5 ~ 10nm.Prepared by this one-tenth gluing method contains silicon carrier, and aperture is less, is not suitable for as heavy oil or catalyst for hydrotreatment of residual oil.
CN102039195A discloses a kind of carrying alumina preparation.The method is while adopting carborization to prepare alumina dry glue, to add organic expanding agent and defoamer.Although the alumina supporter that the method provides can reach 12 ~ 13nm in several apertures, its pore volume and specific surface area are all lower.When this carrier is used for catalyst for hydroprocessing of heavy oil, cannot provide more chain carrier.
CN102309998A discloses a kind of carrying alumina preparation.The method is to adopt at a lower temperature pH value swing method to carry out plastic, more aging for some time at high temperature.Although this one-tenth gluing method can be prepared the alumina supporter with larger aperture, it is less that it is less than pore distribution within the scope of 15nm.Be prepared into after catalyzer as catalyst for hydroprocessing of heavy oil carrier using this aluminum oxide, its pore structure may react favourable to demetalization, but is unfavorable for desulfurization and hydroconversion reactions.
CN1768948A discloses a kind of carrying alumina preparation, wherein take sodium metaaluminate and alum liquor as raw material, adopts cocurrent cooling operation to prepare alumina dry glue.Although alumina supporter mean pore size prepared by this one-tenth gluing method is large, specific surface area is little, is unfavorable for mink cell focus hydrogenating desulfurization and hydroconversion reactions using it as support of the catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of alumina dry glue.The aluminum oxide specific surface area of the method gained is large, pore volume is large, pore structure is reasonable, is especially suitable for use as the carrier component of catalyst for hydroprocessing of heavy oil, is particularly useful for the carrier component of residuum hydrodesulfurization or hydrogenation conversion catalyst.
The preparation method of alumina dry glue of the present invention, comprising:
(1) containing the basic solution of aluminium with containing the acidic solution of aluminium and flow in plastic process, simultaneously and stream add additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, temperature of reaction is 50 ~ 100 ℃, the reaction times is 30 ~ 120min; Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight, described organic formwork agent is ether of cellulose compounds, and add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight;
(2) in the product of step (1) gained, add basic solution, regulating pH value is 7.5 ~ 10.0, and temperature of reaction is 60 ℃ ~ 100 ℃, and the reaction times is 30 ~ 120min;
(3) slurries of step (2) gained are filtered, filter cake, through washing, obtains alumina dry glue after being dried.
In the inventive method, step (2) gained slurries are through aging step, described aging referring to makes solution keep the regular hour under stirring or stationary state, aging temperature is 60 ~ 100 ℃, preferably 80 ~ 95 ℃, more preferably 85 ~ 90 ℃, digestion time is 10 ~ 120min, preferably 15 ~ 60 min, more preferably 20 ~ 40min.
In step (1), contain the basic solution of aluminium, carry out and flow plastic reaction containing acidic solution, additive and the template of aluminium, regulate pH value to be preferably 6.5 ~ 8.0, control at least 50 ℃ of plastic temperature, preferably 50 ~ 95 ℃, the reaction times is preferably 40 ~ 100min, more preferably 60 ~ 80min.Wherein, additive and organic formwork agent can add separately respectively, after also both can being mixed, add, and also both can be added to containing the basic solution of aluminium or containing in the acidic solution of aluminium and add, and preferably will after additive and organic formwork agent mixing, add; Additive and organic formwork agent add separately respectively or both add fashionablely after mixing, and preferably add with the form of the aqueous solution, and in the aqueous solution, the concentration of additive is 0.5 ~ 60g/L, and the concentration of organic formwork agent is 0.5 ~ 60g/L.The described acidic solution containing aluminium, the solution of one or more of preferably sulfuric acid aluminium, aluminum nitrate, aluminum chloride etc., more preferably sulfuric acid aluminum solutions.The concentration that contains the acidic solution of aluminium is 20 ~ 80gAl
2o
3/ L.The described basic solution containing aluminium, the preferably solution of sodium metaaluminate, potassium metaaluminate or their mixture, more preferred sodium aluminate solution.The concentration that contains the basic solution of aluminium is 100 ~ 200gAl
2o
3/ L.Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, preferably sodium dodecyl sulfate.Described template is ether of cellulose compounds, comprise one or more in methylcellulose gum (MC), ethyl cellulose (EC), Walocel MT 20.000PV (HMC), Natvosol (HEC), hydroxypropylcellulose (HPC), ethylmethylcellulose (EMC), hydroxyethylmethyl-cellulose (HEMC), Vltra tears (HPMC), carboxymethyl Walocel MT 20.000PV (CMHMC), preferable methyl Mierocrystalline cellulose and Vltra tears.
In step (2), described basic solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, volatile salt, bicarbonate of ammonia, potassium hydroxide, ammoniacal liquor, preferably sodium carbonate solution.It is 7.5 ~ 10.0 that step (2) regulates pH value, and temperature of reaction is 60 ℃ ~ 100 ℃, pH value preferably 8.0 ~ 9.0, more preferably 8.2 ~ 8.8, preferably 70 ~ 95 ℃ of temperature of reaction, more preferably 80 ~ 90 ℃, reaction times is 30 ~ 120min, preferably 50 ~ 90min, more preferably 60 ~ 80min.
In step (3), described washing generally adopts deionized water wash to neutral, described drying conditions: 100 ~ 150 ℃ are dried 2 ~ 6 hours, and preferably 110 ~ 130 ℃, dry 4 ~ 6 hours.
Alumina dry glue prepared by the inventive method obtains aluminum oxide for 2 ~ 6 hours through 500 ~ 950 ℃ of roastings, and its character is as follows: pore volume is 0.75 ~ 1.10mL/g, and specific surface area is 200 ~ 400m
2/ g, pore distribution is as follows: the pore volume in the hole of bore dia < 8nm accounts for below 15% of total pore volume, bore dia be the pore volume in the hole of 8 ~ 15nm account for total pore volume 40% ~ 60%, the pore volume in the hole of bore dia > 15nm accounts for the more than 30% of total pore volume, be generally 30% ~ 45%, the pore volume in the hole of its median pore diameter > 100 nm accounts for 5% ~ 20% of total pore volume.
The inventive method preferably adopts continuous process to prepare alumina dry glue, and wherein step (1) and step (2) are preferably in two reactors separately and carry out.
The inventive method adds suitable appropriate additive and template at the basic solution containing aluminium with containing in aluminium acidic solution plastic reaction process, and control plastic reaction conditions, by improving plastic temperature of reaction, solution degree of supersaturation declines, molecular motion speed is accelerated, accelerate dissolution-crystallization process, be conducive to the growth of crystal grain.The additive adding can match with template, the hydrophobic part of strengthening in template molecule and the effect of water molecules, cause template gelling temp rising and can be in more stable state in reaction system.Under the cooperatively interacting of additive and organic formwork agent, pseudo-boehmite crystal grain in reaction system is mainly grown along a certain fixed-direction in further growth process, and radial growth is very slow, therefore can promote the grain formation particle shape with certain length-to-diameter ratio of pseudo-boehmite, as bar-shaped or chain pattern, make the connectivity in formed duct good, be conducive to the diffusion of reactant, and improving the utilization ratio in duct, settling is not easy to deposit in duct, the work-ing life of extending catalyst.The inventive method is by effectively controlling the process of growth of pseudo-boehmite crystal grain, and the alumina dry glue grain size, the accumulation mode that obtain are even.The aluminum oxide of preparation has the feature of large pore volume, high-ratio surface and reasonable pore distribution thus, thereby be conducive to the diffusion of macromolecular reaction thing in catalyzer duct in mink cell focus or residual oil, be conducive to again especially the carrying out of desulfurization and denitrification reaction of macromolecular reaction thing removing impurities matter.Therefore, alumina supporter prepared by the inventive method, just can meet Production requirement without the extra expanding agent that adds.
Aluminum oxide prepared by the inventive method is suitable for the carrier component of heavy oil or residuum hydrodesulfurization or hydrogenation conversion catalyst, and catalyzer prepared therefrom is more stable in the mink cell focus hydrogenation process of height reaction severity.
The inventive method technological process is simple, there is no the discharge of pollutent, non-environmental-pollution, and cost is low, is especially suitable for industrial continuous production alumina dry glue.
Central hole structure of the present invention and specific surface area adopt mercury penetration method analysis.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares aluminum oxide;
Fig. 2 is the scanning electron microscope (SEM) photograph that comparative example 1 is prepared aluminum oxide.
Embodiment
Below by further statement technical characterictic of the present invention of embodiment, but be not limited to embodiment.
Embodiment 1
Preparation sodium aluminate solution concentration is 140gAl
2o
3/ L, amounts to 2.5L; Alum liquor concentration is 40gAl
2o
3/ L amounts to 5.0L; In sodium lauryl sulphate and Vltra tears (HPMC) mixing solutions, sodium lauryl sulphate concentration is 1.0g/L, and HPMC concentration is 1.0g/L, amounts to 1.0L.
In retort, the pre-end water that adds, arranges 75 ℃ by retort temperature, opens and stirs.The sodium aluminate solution preparing and alum liquor are added in retort process according to certain flow rate stream, simultaneously and stream add sodium lauryl sulphate and Vltra tears (HPMC) mixing solutions, adjusting pH value is 6.5.After material adds, in the product of gained, add basic solution, regulating pH value is 8.8, and temperature of reaction is 90 ℃, and the reaction times is 30min.After reaction finishes, enter the aging step, temperature of reaction is 90 ℃, and digestion time is 20min.The slurries of gained are filtered, and filter cake, through washing, obtains alumina dry glue after being dried.650 ℃ of roastings obtain aluminum oxide A for 3 hours.
Embodiment 2
Other condition, with embodiment 1, just replaces with sodium stearyl sulfate sodium lauryl sulphate, and the sodium stearyl sulfate concentration of preparation changes 30g/L into, and HPMC replaces with MC, and the MC concentration of preparation changes 20g/L into, prepares aluminum oxide B.
Embodiment 3
Other condition, with embodiment 1, just changes sodium lauryl sulphate concentration as 50g/L into, and HPMC concentration changes 50g/L into, prepares aluminum oxide C.
Embodiment 4
Other condition, with embodiment 1, is just set to 80 ℃ retort temperature setting, prepares aluminum oxide D.
Embodiment 5
Other condition is with embodiment 1, and just digestion time is set as 40min, prepares aluminum oxide E.
Embodiment 6
Other condition is with embodiment 1, and just the sodium aluminate solution concentration of preparation is 180gAl
2o
3/ L, alum liquor concentration is 60gAl
2o
3/ L, prepares aluminum oxide F.
Comparative example 1
Other condition, with embodiment 1, does not just add additive and template, prepares alumina G.
The physico-chemical property of the aluminum oxide that obtained is above listed in to table 1.
Table 1 aluminum oxide physico-chemical property
| Numbering | A | B | C | D | E | F | G |
| Specific surface area/m 2·g -1 | 368 | 360 | 371 | 337 | 361 | 334 | 309 |
| Pore volume/cm 3·g -1 | 1.03 | 1.02 | 1.04 | 1.06 | 1.04 | 1.05 | 1.00 |
| Pore distribution/% | ? | ? | ? | ? | ? | ? | ? |
| <8nm | 10.1 | 9.2 | 10.3 | 9.1 | 9.0 | 7.9 | 6.6 |
| 8~15nm | 50.7 | 56.3 | 49.1 | 50.0 | 51.9 | 49.8 | 32.3 |
| 15~100nm | 21.1 | 17.8 | 22.4 | 23.7 | 23.4 | 31.8 | 59.3 |
| >100nm | 18.1 | 16.7 | 18.2 | 17.2 | 15.7 | 10.5 | 1.8 |
From table 1, data can be found out: in the time adding tensio-active agent and template in plastic reaction process, under higher temperature of reaction, prepared aluminum oxide pore volume and specific surface area still have higher level, and increase after sodium metaaluminate and Tai-Ace S 150 concentration, specific surface area reduces slightly, and pore volume does not reduce, the existence of pattern of descriptive parts agent can be grown the pseudo-boehmite crystal grain generating under higher temperature in slewing.And while not adding additive and template, higher plastic temperature of reaction causes pseudo-boehmite grain growing too fast, grain size is inhomogeneous also causes that specific surface area declines.
In Fig. 1 and Fig. 2, the scanning electron microscope image of two kinds of aluminum oxide shows, in embodiment 1, evenly, the particle of state of aggregation around exists with " bar-shaped " or " chain " particle shape and piles up each other alumina grain size, thereby can form the duct of hundred nano-scale.And aluminium oxide particles size in comparative example 1 is inhomogeneous, between state of aggregation particle, exists mainly with " sheet " particle shape.Therefore the alumina supporter that, adopts the inventive method to provide is applicable to being used as the carrier component of the catalyzer such as residuum hydrogenating and metal-eliminating, hydrogenating desulfurization and hydrocracking.
Claims (12)
1. a preparation method for alumina dry glue, comprising:
(1) containing the basic solution of aluminium with containing the acidic solution of aluminium and flow in plastic process, simultaneously and stream add additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, temperature of reaction is 50 ~ 100 ℃, the reaction times is 30 ~ 120min; Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight, described organic formwork agent is ether of cellulose compounds, and add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight;
(2) in the product of step (1) gained, add basic solution, regulating pH value is 7.5 ~ 10.0, and temperature of reaction is 60 ℃ ~ 100 ℃, and the reaction times is 30 ~ 120min;
(3) slurries of step (2) gained are filtered, filter cake, through washing, obtains alumina dry glue after being dried.
2. in accordance with the method for claim 1, it is characterized in that step (2) gained slurries are through aging step, aging temperature is 60 ~ 100 ℃, and digestion time is 10 ~ 120min.
3. in accordance with the method for claim 1, it is characterized in that in step (1), contain the basic solution of aluminium, carry out and flow plastic reaction containing acidic solution, additive and the template of aluminium, regulating pH value is 6.5 ~ 8.0, controlling plastic temperature is 50 ~ 95 ℃, and the reaction times is 40 ~ 100min.
4. in accordance with the method for claim 1, it is characterized in that described additive and organic formwork agent add separately respectively, or add after both are mixed, or both are added to containing the basic solution of aluminium or containing in the acidic solution of aluminium and are added.
5. in accordance with the method for claim 1, it is characterized in that adding with the form of the aqueous solution and adding after described additive and organic formwork agent mix, in the aqueous solution, the concentration of additive is 0.5 ~ 60g/L, and the concentration of organic formwork agent is 0.5 ~ 60g/L.
6. in accordance with the method for claim 1, the solution of one or more that it is characterized in that the described acidic solution containing aluminium is Tai-Ace S 150, aluminum nitrate, aluminum chloride etc., is 20 ~ 80gAl containing the concentration of the acidic solution of aluminium
2o
3/ L; The described basic solution containing aluminium is the solution of sodium metaaluminate, potassium metaaluminate or their mixture, and the concentration that contains the basic solution of aluminium is 100 ~ 200gAl
2o
3/ L.
7. in accordance with the method for claim 1, it is characterized in that described template is that ether of cellulose compounds is one or more in methylcellulose gum, ethyl cellulose, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, ethylmethylcellulose, hydroxyethylmethyl-cellulose, Vltra tears, carboxymethyl Walocel MT 20.000PV.
8. in accordance with the method for claim 1, it is characterized in that described template is that ether of cellulose compounds is methylcellulose gum and/or Vltra tears.
9. in accordance with the method for claim 1, it is characterized in that in step (2), described basic solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, volatile salt, bicarbonate of ammonia, potassium hydroxide, ammoniacal liquor.
10. in accordance with the method for claim 1, it is characterized in that it is 8.0 ~ 9.0 that step (2) regulates pH value, temperature of reaction is 80 ~ 90 ℃, and the reaction times is for being 50 ~ 90min.
11. in accordance with the method for claim 1, it is characterized in that described drying conditions: 100 ~ 150 ℃ are dried 2 ~ 6 hours, and preferably 110 ~ 130 ℃, dry 4 ~ 6 hours.
12. 1 kinds of aluminum oxide, is characterized in that the arbitrary described alumina dry glue of claim 1 ~ 11 obtains aluminum oxide for 2 ~ 6 hours through 500 ~ 950 ℃ of roastings.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106673032A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | High-acidity low-crystallinity alumina dry glue and preparation method thereof |
| CN106669645A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof |
| CN107055580A (en) * | 2017-04-13 | 2017-08-18 | 山东公泉化工股份有限公司 | The preparation method of alumina dry glue |
| CN111099646A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673032A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | High-acidity low-crystallinity alumina dry glue and preparation method thereof |
| CN106669645A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof |
| CN106669645B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof |
| CN107055580A (en) * | 2017-04-13 | 2017-08-18 | 山东公泉化工股份有限公司 | The preparation method of alumina dry glue |
| CN111099646A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
| CN111099646B (en) * | 2018-10-26 | 2022-11-22 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
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