CN104402028B - A kind of profit post forming method of ball-aluminium oxide - Google Patents
A kind of profit post forming method of ball-aluminium oxide Download PDFInfo
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- CN104402028B CN104402028B CN201410645915.8A CN201410645915A CN104402028B CN 104402028 B CN104402028 B CN 104402028B CN 201410645915 A CN201410645915 A CN 201410645915A CN 104402028 B CN104402028 B CN 104402028B
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Abstract
The present invention relates to a kind of profit post forming method of ball-aluminium oxide, be characterised in that: pseudo-boehmite is joined in alginate solution, stir and form Lalgine-pseudo-boehmite suspendible slurry; Suspendible slurry is added dropwise in the profit post by upper oil phase and lower floor's multivalent metal cation salts solution phase composite and forms composite spherical gel particle; Take out gel particle, carry out acid treatment, drier, roasting obtains ball-aluminium oxide product.This method has that shaping speed is fast, efficiency is high, and product strength is large, good sphericity, and the advantages such as preparation process is pollution-free, and operation steps simple possible, easily realize suitability for industrialized production.
Description
Technical field
The present invention relates to support of the catalyst technical field, be specially a kind of profit post forming method of ball-aluminium oxide, especially a kind ofly utilize the sol-gel performance of Lalgine and adopt profit post legal system for the forming method of Spherical alumina particles.
Background technology
Oil ammonia column method prepares the conventional method of ball-aluminium oxide, silicon-dioxide and complex carrier.It is added dropwise in oil ammonia column by colloidal sol, and sol particles shrinks balling-up in upper oil phase, gel solidification in lower floor's ammoniacal liquor, and gel particle obtains spherical solid particles through aging, dry, roasting.Ball-aluminium oxide good sphericity, even particle size, intensity prepared by this method are high, are widely used as fixed bed and movable bed catalyst carrier.
Lalgine is a kind of natural biologic material, has collosol and gel performance, is widely used in the preparation of the material such as microcapsule, hydrogel.Lalgine assistant formation legal system just proposes recently for the method for Spherical alumina particles, the embeddability properties that tridimensional network when it utilizes the fast sol gellifying property of Lalgine and forms gel has, the preparation of spheroidal particle is carried out in water column, compare with the method for forming in oil with traditional rolling balling method, this forming method has the advantages such as shaping speed is fast, efficiency is high, cost is low, preparation process is pollution-free.
USP4542113 discloses a kind of preparation method of Spherical alumina particles, and this method adds 1 ~ 10 heavy % urea in Alumina gel, and be then added dropwise in oil ammonia column shaping, oil ammonia column is oil phase 10 ~ 50% at the middle and upper levels, lower floor's ammoniacal liquor phase 50 ~ 90%.
CN1204964C discloses a kind of oil ammonia column forming method of ball-aluminium oxide, alumina sol is added dropwise to and forms spherical gel particles by the oil ammonia column of lower floor's electrolyte solution phase composite of the upper oil phase of 0.1 ~ 4.5mm and 10 ~ 300cm by this method, then aging 0.5 ~ 10 hour, drier, roasting obtains product.
CN103011213A discloses a kind of method using oil ammonia column to prepare ball-aluminium oxide, and Alumina gel and nonionogenic tenside are instilled balling-up in oil ammonia column by this method simultaneously.
CN102718241A discloses the method for a kind of Lalgine assistant formation legal system for ball-aluminium oxide, sodium alginate-pseudo-boehmite suspension is added dropwise in the aqueous solution of aluminium, calcium, barium, copper, zinc, manganese or cobalt ion shaping by this method, in the aqueous solution of pH1 ~ 4, process 10 ~ 120 minutes to increase the physical strength of product after shaping or in moulding process, drying, roasting afterwards obtains ball-aluminium oxide.
The aqueous phase of above-mentioned oil ammonia column method is ammoniacal liquor, utilizes the acidity of ammonia neutralization Alumina gel, thus makes Alumina gel gelation.But ammoniacal liquor in use can volatilize and cause environmental pollution, and the intensity that sol solutions drops in ammoniacal liquor after gelation is very low, just can carry out the process such as next step drying after also needing long burin-in process to increase its state of cure, cause preparation time long, efficiency is low.
Above-mentioned Lalgine assistant formation method is a kind of water column forming method, and this method shaping efficiency is high, cost is low.But due to Lalgine and the cationic combination of different metal different, and the surface tension of ion salt solution is also different, and the sphericity of gel particle when causing shaping has very big difference.Wherein, time shaping in calcium, zine ion solution, product sphericity is better, but can introduce more foreign ion, is unfavorable for preparing high purity aluminium oxide; Time shaping in aluminum ion solution, additional impurities ion can not be introduced, but product sphericity is lower.Therefore, this method is adopted cannot to take into account purity and the sphericity of product.
Summary of the invention
The object of the invention is to provide the method for a kind of profit post legal system for ball-aluminium oxide,, the problem such as efficiency low, environmental pollution long with the digestion time of oil ammonia column method described in technical solution background, and the problem that described Lalgine assistant formation method product purity and sphericity cannot be taken into account.
The present invention is a kind of profit post forming method of ball-aluminium oxide, it is characterized in that: join in alginate solution by pseudo-boehmite, expanding agent, stirs and makes Lalgine-pseudo-boehmite suspendible slurry; Suspendible slurry is added dropwise in the profit post by upper oil phase and lower floor's multivalent metal cation salts solution phase composite and forms composite spherical gel particle; Take out gel particle, use acidic solution process; Final drying, roasting obtain ball-aluminium oxide product;
Wherein: described expanding agent is urea, urotropine, Mierocrystalline cellulose or gac, expanding agent add-on is 0 ~ 10% of pseudo-boehmite quality;
Described alginates is one or more in sodium alginate, potassium alginate, Lalgine magnesium, ammonium alginate, and the concentration of alginates is 0.3 ~ 5 heavy %;
The quality of described pseudo-boehmite is 5 ~ 30% of Lalgine solution quality;
Described multivalent metal cation salts solution is the salts solution of the aluminium of 0.1mol/L ~ saturation concentration, zinc, calcium, copper, iron, ferrous iron, cobalt, manganese or nickel ion, preferably the salts solution of the aluminium of 0.2 ~ 1mol/L, zinc, calcium, copper or cobalt ion;
One or more in the preferred kerosene of described oil phase, diesel oil, lubricating oil, heptane, octane, whiteruss, oil phase height 0.1mm ~ 20cm;
Described acidic solution hydrogen ion concentration is 0.0001 ~ 2mol/L, and the treatment time is 1 ~ 120 minute, preferably the salpeter solution of 0.01 ~ 1mol/L, and the treatment time is 5 ~ 30 minutes.
Drying temperature described in technique scheme preferably 80 ~ 120 DEG C, maturing temperature preferably 450 ~ 800 DEG C.
Compared with prior art, its beneficial effect is the inventive method:
1. the present invention is in conjunction with the advantage of both oil ammonia column method and Lalgine auxiliary law, has that shaping speed is fast, efficiency is high, and product strength is large, good sphericity, can prepare the advantages such as the large and preparation process of particle size range is pollution-free;
2. operation steps simple possible, easily realizes suitability for industrialized production.
Embodiment
Be described further below in conjunction with the profit post method of forming of specific embodiment to ball-aluminium oxide of the present invention, but not thereby limiting the invention.
In embodiment, particle sphericity Zingg index is expressed, and Zingg index definition is the length degree of particle and the ratio of flatness.Wherein length degree is the ratio of the line of apsides, and flatness is minor axis and the ratio of thickness.
Embodiment 1
Ball-aluminium oxide is prepared by the inventive method step:
Sasol company of 100g Germany produces SB powder (pseudo-boehmite), joins the sodium alginate soln that 300g concentration is 3 heavy %, fully stirs and form Lalgine-pseudo-boehmite suspension, for subsequent use.
In the profit post of high 1.2m, diameter 30cm, upper oil phase is lubricating oil, high 1mm, and lower floor's aqueous phase is the aluminum nitrate solution of 0.5mol/L, high 119cm.Pump is adopted to control oil level steady.
Instilled above profit post by dripping ball device by Lalgine-pseudo-boehmite suspendible slurry, drip drip nozzle distance pasta 2cm bottom ball device, drip nozzle pore size is 2.0mm, and it is 2 drops/sec that single mouth drips speed.Suspension drops in oil phase and shrinks balling-up, and enters aqueous phase by water-oil interface smoothly, and in aqueous phase, drop gel becomes solid, and discharges from pillar lower part outlet along liquid stream.
By the salpeter solution process 10 minutes of gel particle 0.01mol/L, take out, 80 DEG C of dryings 10 hours, 120 DEG C of dryings 4 hours, 550 DEG C of roastings, 4 hours obtained smooth in appearance, the γ-A that sphericity is good
2o
3bead, its essential property is in table 1.
Embodiment 2
γ-A is prepared by the step in embodiment 1
2o
3bead, unlike: add the sodium alginate soln that 500g concentration is 2 heavy % during batching, fully stir and form Lalgine-pseudo-boehmite suspension; Profit post at the middle and upper levels oil phase height is 15cm, and lower floor's aqueous phase height is 104cm; Drip ball time drip nozzle pore size used be 3.0mm, obtained bead character is in table 1.
Embodiment 3
γ-A is prepared by the step in embodiment 1
2o
3bead, unlike: add the sodium alginate soln that 700g concentration is 0.5 heavy % during batching, fully stir and form Lalgine-pseudo-boehmite suspension, adopt the drip nozzle of 1mm when dripping ball, obtained bead character is in table 1.
Embodiment 4
γ-A is prepared by the step in embodiment 1
2o
3bead, unlike profit post at the middle and upper levels oil phase be kerosene, the acid treatment time is 50 minutes, and obtained bead character is in table 1.
Embodiment 5
γ-A is prepared by the step in embodiment 1
2o
3bead, unlike profit post at the middle and upper levels oil phase be diesel oil, obtained bead character is in table 1.
Embodiment 6
γ-A is prepared by the step in embodiment 1
2o
3bead, unlike profit post at the middle and upper levels oil phase be whiteruss, obtained bead character is in table 1.
Embodiment 7
γ-A is prepared by the step in embodiment 1
2o
3bead, be the zinc nitrate solution of 0.6mol/L unlike profit Zhu Zhong lower floor aqueous phase, obtained bead character is in table 1.
Embodiment 8
γ-A is prepared by the step in embodiment 1
2o
3bead, be the ca nitrate soln of 0.3mol/L unlike profit Zhu Zhong lower floor aqueous phase, obtained bead character is in table 1.
Embodiment 9
γ-A is prepared by the step in embodiment 1
2o
3bead, also adds 5g urea unlike in feed liquid, and obtained bead character is in table 1.
Embodiment 10
γ-A is prepared by the step in embodiment 1
2o
3bead, also adds 10g urea unlike in feed liquid, and obtained bead character is in table 1.
Embodiment 11
γ-A is prepared by the step in embodiment 1
2o
3bead, also adds 5g gac unlike in feed liquid, and obtained bead character is in table 1.
Comparative example 1
γ-A is prepared by the step in embodiment 1
2o
3bead is highly the aluminum nitrate solution of 119cm unlike only having in the pillar that 1.2m is high
Comparative example 2
γ-A is prepared by the step in embodiment 1
2o
3bead is highly the ca nitrate soln of 119cm unlike only having in the pillar that 1.2m is high.
Table 1
Claims (5)
1. a profit post forming method for ball-aluminium oxide, is characterized in that: join in alginate solution by pseudo-boehmite, expanding agent, stirs and makes Lalgine-pseudo-boehmite suspendible slurry; Suspendible slurry is added dropwise in the profit post by upper oil phase and lower floor's multivalent metal cation salts solution phase composite and forms composite spherical gel particle; Take out gel particle, use acidic solution process; Final drying, roasting obtain ball-aluminium oxide product;
Wherein: described expanding agent is urea, urotropine, Mierocrystalline cellulose or gac, expanding agent add-on is 0 ~ 10% of pseudo-boehmite quality;
Described alginates is one or more in sodium alginate, potassium alginate, Lalgine magnesium, ammonium alginate, and the concentration of alginates is 0.3 ~ 5 % by weight;
The quality of described pseudo-boehmite is 5 ~ 30% of alginate solution quality;
Described multivalent metal cation salts solution is the salts solution of the aluminium of 0.1mol/L ~ saturation concentration, zinc, calcium, copper, iron, ferrous iron, cobalt, manganese or nickel ion;
Described acidic solution hydrogen ion concentration is 0.0001 ~ 2mol/L, and the treatment time is 1 ~ 120 minute.
2., according to method described in claim 1, it is characterized in that described multivalent metal cation salts solution is the aluminium of 0.2 ~ 1mol/L, zinc, calcium, copper or cobalt ion salts solution.
3., according to method described in claim 1, it is characterized in that described oil phase is one or more in kerosene, diesel oil, lubricating oil, heptane, octane, whiteruss, oil phase height 0.1mm ~ 20cm.
4., according to method described in claim 1, it is characterized in that described acidic solution is the salpeter solution of 0.01 ~ 1mol/L, the treatment time is 5 ~ 30 minutes.
5., according to method described in claim 1, it is characterized in that described drying temperature is 80 ~ 120 DEG C, maturing temperature is 450 ~ 800 DEG C.
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| CN104891539B (en) * | 2015-05-22 | 2017-01-04 | 中国海洋石油总公司 | A kind of expanding method of Spherical alumina particles |
| CN105384182B (en) * | 2015-10-12 | 2017-04-26 | 中海油天津化工研究设计院有限公司 | Preparation method for alumina microsphere |
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| CN106167270B (en) * | 2016-06-14 | 2018-03-30 | 淄博众森石化工程技术有限公司 | A kind of preparation method of mesoporous θ aluminum oxide ball type carrier |
| CN106745125B (en) * | 2016-11-15 | 2018-02-16 | 中国海洋石油总公司 | A kind of preparation method of ball-aluminium oxide |
| CN106475023B (en) * | 2016-11-15 | 2019-05-28 | 中国海洋石油集团有限公司 | A kind of macropore holds the preparation method of aluminum oxide micro-sphere |
| CN108298959B (en) * | 2017-12-19 | 2021-01-29 | 江苏金石研磨有限公司 | Liquid forming method of ceramic grinding ball |
| CN112718015B (en) * | 2019-10-14 | 2024-07-12 | 中国石油化工股份有限公司 | Electrostatic oil-ammonia suction forming equipment and electrostatic oil-ammonia suction forming method |
| CN113289595B (en) * | 2021-05-31 | 2022-10-14 | 淄博开迈新材料科技有限公司 | Spherical aluminum-based catalyst carrier based on composite hydrogel molding and preparation method thereof |
| CN114042443B (en) * | 2021-11-26 | 2023-11-14 | 武亚梅 | Forming method of spherical alumina |
| CN115178298A (en) * | 2022-06-17 | 2022-10-14 | 中海油天津化工研究设计院有限公司 | Water column forming method of MOFs material |
| CN117105250B (en) * | 2023-10-19 | 2023-12-26 | 淄博宏豪晶体材料有限公司 | Preparation method of high-strength active alumina balls |
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| US4542113A (en) * | 1982-04-02 | 1985-09-17 | Condea Chemie Gmbh | Method for preparing spheroidal alumina |
| CN1493524A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Oil ammonia column shaping method of spherical aluminium oxide |
| CN103011213A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing spherical alumina by virtue of oil ammonia column |
| CN103864123A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Water column forming method of spherical aluminum oxide |
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2014
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|---|---|---|---|---|
| US4542113A (en) * | 1982-04-02 | 1985-09-17 | Condea Chemie Gmbh | Method for preparing spheroidal alumina |
| CN1493524A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Oil ammonia column shaping method of spherical aluminium oxide |
| CN103011213A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing spherical alumina by virtue of oil ammonia column |
| CN103864123A (en) * | 2014-02-28 | 2014-06-18 | 中国海洋石油总公司 | Water column forming method of spherical aluminum oxide |
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