CN103861659B - A kind of preparation method of amorphous aluminum silicide ball type carrier - Google Patents
A kind of preparation method of amorphous aluminum silicide ball type carrier Download PDFInfo
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- CN103861659B CN103861659B CN201410072701.6A CN201410072701A CN103861659B CN 103861659 B CN103861659 B CN 103861659B CN 201410072701 A CN201410072701 A CN 201410072701A CN 103861659 B CN103861659 B CN 103861659B
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Abstract
The present invention relates to a kind of preparation method of amorphous aluminum silicide ball type carrier, be characterised in that: first employing neutralisation obtains the filter cake containing amorphous silicon aluminium composite oxide, add sodium alginate aqueous solution subsequently and obtain amorphous silicon aluminium composite oxide-sodium alginate suspension, sial composite oxides-sodium alginate suspension instillation is contained in the aqueous solution of certain density divalence or trivalent metal ion, gel-forming amorphous silicon aluminium composite oxide-alginate composite pellets, then obtains amorphous aluminum silicide ball type carrier through washing, drying, roasting.The present invention is directly shaping in the aqueous phase of gentleness by amorphous silicon aluminium composite oxide filter cake, and only obtain ball type carrier through primary drying, roasting, energy consumption is low, preparation process is pollution-free, and preparation process is simple, easy to operate, is easy to realize suitability for industrialized production.
Description
Technical field:
The invention belongs to field of inorganic material preparing technology, relate to a kind of preparation method of amorphous aluminum silicide ball type carrier, in particular, the present invention relates to a kind of filter cake amorphous silicon aluminium composite oxide being prepared by neutralisation, filter cake is fully mixed obtained suspension with sodium alginate aqueous solution, further instillation metal salt solution gel forming, drying, roasting obtain the method for amorphous aluminum silicide ball type carrier.
Background technology:
The progress of petrochemical catalyst technology often has benefited from the lifting of catalysis material performance, therefore always in widespread attention to the research of carrier technology of preparing.Along with the development of catalyst industry, the improvement of carrier property plays an increasingly important role in catalyst updating is regenerated.The performance of carrier is primarily of decisions such as chemical composition, pore structure, surface acidity, shapes.
Aluminium oxide is most widely used catalyst carrier, accounts for total use amount more than 70%.Research shows, in aluminium oxide, add appropriate silica can produce a very large impact aluminium oxide performance, adding of silicon, and carrier specific area, surface acidity all have and significantly improve, very favourable to a lot of hydrogenation reaction.When both occur to interact, according to the minimum principle of maximum system energy, first silica will act on the strong activated centre of alumina surface, thus slackened the effect in alumina surface activated centre, aluminium oxide and intermetallic interaction are comparatively relaxed, is conducive to the dispersion of metal and the performance of activity.But, the preparation method of traditional sial composite oxides is mechanical mixing or infusion process, due to the reason of preparation method, easily cause uneven dispersion between the silica of introducing system and alumina substrate and impurity ion content is higher, and then affect the physicochemical property, surface nature, pore structure etc. of carrier.
US4721696 adopts swing method to prepare the false colloidal sol of aluminium oxide by aluminum nitrate and sodium metaaluminate, adds sodium metasilicate subsequently, after washing, drying and roasting, forms amorphous aluminum silicide.This preparation process complicated operation, in product, sodium content is high and performance is difficult to stability contorting.
CN100431965C discloses a kind of preparation method of spherical silicon-containing alumina carrier, the employing of this method adds Ludox and obtains sial mixed sols in Alumina gel, adopt oil-drop method to obtain shaping bead again, obtain spherical silicon-containing alumina through the technique such as aging, washing, drying, roasting.
In in the mixed liquor that CN101239314B adopts carbonizatin method to be passed into by carbon dioxide containing sodium metaaluminate and sodium metasilicate and plastic, after washing, dry, roasting, add binding agent kneading, roll agglomerating, extruded moulding and obtain amorphous aluminum silicide.
CN1123383C adds waterglass, Ludox or organosilicon by after aluminum sulfate and weak aqua ammonia mixing plastic, aging 10 ~ 60 minutes at 50 ~ 70 DEG C, obtains amorphous aluminum silicide product after filtration, washing, drying and pulverizing.This product is powdery, as fluid catalyst or carrier, can only need processing further when using in fixed bed.
CN1197650C discloses a kind of method that mechanical mixture prepares silicon-containing alumina carrier.Become plastic after aluminium-hydroxide powder or alumina powder being mixed by a certain percentage with peptizing agent, extrusion aid etc., banded extruder is extruded into bar, drying, roasting obtain porous silicon-containing alumina carrier.Because silicon is with SiO
2the form of particle adds, and can not reach molecular state dispersion, have impact on its serviceability as catalyst or catalyst carrier.
In order to better play the performance of catalyst, except requiring that more excellent carrier physical and chemical indexes (needs larger specific surface, more large pore volume usually, aperture preferably and surface property, higher intensity etc.) outward, the shape of catalyst also embodies very important effect in through engineering approaches application aspect (heat transfer, mass transfer, pressure drop etc.).The shaping carrier of industrial fixed bed reactors application comprises bar shaped, column, cellular and spherical etc., when wherein ball type carrier is as catalyst or carrier, owing to contacting with each other with point between particle, pile up evenly, reduce bed resistance, substantially increase mass transfer and catalytic effect.Therefore, be applied widely in the processes such as the hydrogenation reaction in the hydrofinishing of ball type carrier in petrochemical industry, selective hydrogenation and fine chemistry industry.Conventional ball type carrier production method has: mist projection granulating, shaping, the shaping granulation of rolling, oil (ammonia) post are shaping.Wherein mist projection granulating preparing product particle diameter is less; Roll and be shapingly mainly used in hydraulicity material forming, adaptability to raw material is poor; Shaping granulation product particle diameter heterogeneity, sphericity are poor, and complex process, is not suitable for continuous seepage simultaneously, and preparation process dust is large, and material loss is high; Oil (ammonia) can obtain high performance ball type carrier although post is shaping, and the high cost of this technique limits its scope of application.
In existing sial ball type carrier technology of preparing, all there is Distribution of silicon and aluminium uneven, prepared by powder and carrier need through twice dry, roasting, powder is balling-up not easily, or high in cost of production shortcoming, need the technology of preparing of the amorphous aluminum silicide ball type carrier that exploitation is a kind ofly evenly distributed, silica alumina ratio can regulate, preparation process is simple, with low cost badly on a large scale.
Summary of the invention:
For the deficiencies in the prior art, the object of the invention is the preparation method providing a kind of amorphous aluminum silicide ball type carrier.Amorphous aluminum silicide ball type carrier prepared by the present invention had both had suitable specific surface, pore volume, there is again adjustable silica content, ensure acidity needed for chemical reaction, can be used as catalyst or the carrier course of reaction for petrochemical industry, fine chemistry industry and organic synthesis.The present invention is from industrial chemicals such as sodium aluminate solution, sodium silicate solution and aluminum sulfate, do not need obtained amorphous aluminum silicide powder, only the drying of need one step, roasting can obtain high-performance sial ball type carrier, simplify preparation process, reduce material consumption, energy consumption, significantly reduce production cost.
In order to the pore structure controlling amorphous aluminum silicide measure with acid, adopt sodium aluminate solution, sodium silicate solution and aluminum sulfate also to flow fixed pH method, not only process is easy to control, and product have can the character of modulation pore structure on a large scale.By sial filter cake and sodium alginate aqueous solution Homogeneous phase mixing, subsequently by the sol-gel performance of sodium alginate, suspension is instilled in salting liquid, rapid contraction is shaping, with after can obtain high performance amorphous aluminum silicide ball type carrier through primary drying, roasting, pore volume 0.6 ~ 1.5ml/g, specific surface 200 ~ 450m
2/ g, aperture 6 ~ 25nm is adjustable.
The present invention is a kind of preparation method of amorphous aluminum silicide ball type carrier, it is characterized in that: carry out according to the following steps:
1) sodium aluminate solution, sodium silicate solution and aluminum sulfate solution is prepared respectively; The concentration of described sodium aluminate solution is 100 ~ 200gAl
2o
3/ L, the concentration of sodium silicate solution is 50 ~ 150gSiO
2/ L, aluminum sulfate solution is 100 ~ 200gAl
2o
3/ L;
2) by sodium aluminate solution, sodium silicate solution and aluminum sulfate solution and stream joins in the reaction vessel adding a certain amount of deionized water, reaction temperature is kept to be 20 ~ 50 DEG C, pH value is 6.5 ~ 9.5, react 0.5 ~ 2.5 hour, be heated to subsequently 60 ~ 90 DEG C aging 0.5 ~ 3 hour, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake that solid content is 20 ~ 45% after suction filtration;
3) by a certain amount of step 2) filter cake to add mass fraction be in the sodium alginate aqueous solution of 1.0 ~ 4.5% in batches, be fully uniformly mixed, obtain the suspension that dynamic viscosity is 50 ~ 500 milli pascal seconds;
4) by step 3) obtained suspension instillation concentration is in the divalence of 0.5 ~ 2mol/L or the aqueous solution of trivalent metal ion, gel 1 ~ 20min, form amorphous silicon aluminium composite oxide-alginate bead, spend deionized water further, 80 ~ 150 DEG C of dryings, 500 ~ 650 DEG C of roastings obtain amorphous aluminum silicide bead, and wherein the metal ion of divalence or trivalent is selected from calcium ion, zinc ion, aluminium ion or iron ion.
According to preparation method of the present invention, it is characterized in that:
Step 2) be: after sodium aluminate solution mixes with sodium silicate solution, with aluminum sulfate solution and stream joins in the reaction vessel adding a certain amount of deionized water, reaction temperature is kept to be 30 ~ 40 DEG C, pH value is 7.0 ~ 8.5, added in 0.5 ~ 2.0 hour, be heated to subsequently 75 ~ 85 DEG C aging 1.0 ~ 2.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, after suction filtration, obtain the amorphous silicon aluminium composite oxide filter cake that solid content is 25 ~ 40%;
Step 3) be: by a certain amount of step 2) filter cake to add mass fraction be in the sodium alginate aqueous solution of 1.5 ~ 4.0% in batches, be fully uniformly mixed, obtain the suspension that dynamic viscosity is 100 ~ 450 milli pascal seconds.
Step 4) be: by step 3) obtained suspension instillation concentration is in the divalence of 0.8 ~ 1.6mol/L or the aqueous solution of trivalent metal ion, gel 4 ~ 16min, form amorphous silicon aluminium composite oxide-alginate bead, spend deionized water further, 100 ~ 130 DEG C of dryings, 550 ~ 600 DEG C of roastings obtain amorphous aluminum silicide bead, and wherein the metal ion of divalence or trivalent is selected from calcium ion, zinc ion.
According to preparation method of the present invention, it is characterized in that: the amorphous aluminum silicide bead of described preparation method's gained, its character is as follows: intensity is 20 ~ 100N/, and specific surface is 200 ~ 450m
2/ g, pore volume is 0.6 ~ 1.5ml/g.
Detailed description of the invention:
Embodiment 1
By 100gAl
2o
3/ L sodium aluminate solution 180ml, 70gSiO
2/ L sodium silicate solution 190ml and 100gAl
2o
3/ L aluminum sulfate solution 140ml stream joins in the reaction vessel adding 200ml deionized water, reaction temperature is kept to be 35 ~ 40 DEG C, pH value is 8.0 ~ 8.5, within 1.0 hours, add, be heated to subsequently 80 DEG C aging 2.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake 138g that solid content is 33% after suction filtration.Above-mentioned filter cake being added in batches mass fraction is in the sodium alginate aqueous solution 150ml of 2.5%, is fully uniformly mixed, and obtains the suspension that dynamic viscosity is 260 milli pascal seconds.Subsequently suspension is instilled in the aluminum nitrate aqueous solution of 0.5mol/L, gel 5min, form sial composite oxides-sodium alginate gel bead, spend deionized water further, 120 DEG C of dryings 6 hours, 550 DEG C of roastings obtain amorphous aluminum silicide bead in 4 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 2
By 200gAl
2o
3/ L sodium aluminate solution 150ml, 100gSiO
2/ L sodium silicate solution 200ml and 200gAl
2o
3/ L aluminum sulfate solution 110ml stream joins in the reaction vessel adding 200ml deionized water, reaction temperature is kept to be 30 ~ 35 DEG C, pH value is 7.5 ~ 8.0, within 2.0 hours, add, be heated to subsequently 85 DEG C aging 1.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake 200g that solid content is 36% after suction filtration.Above-mentioned filter cake being added in batches mass fraction is in the sodium alginate aqueous solution 260ml of 1.5%, is fully uniformly mixed, and obtains the suspension that dynamic viscosity is 150 milli pascal seconds.Subsequently suspension is instilled in the calcium nitrate aqueous solution of 2.0mol/L, gel 1min, form sial composite oxides-sodium alginate gel bead, spend deionized water further, 80 DEG C of dryings 12 hours, 500 DEG C of roastings obtain amorphous aluminum silicide bead in 5 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 3
By 150gAl
2o
3/ L sodium aluminate solution 180ml, 150gSiO
2/ L sodium silicate solution 100ml and 180gAl
2o
3/ L aluminum sulfate solution 103ml stream joins in the reaction vessel adding 300ml deionized water, reaction temperature is kept to be 35 ~ 40 DEG C, pH value is 7.0 ~ 7.5, within 0.5 hour, add, be heated to subsequently 75 DEG C aging 2.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake 152g that solid content is 40% after suction filtration.Above-mentioned filter cake being added in batches mass fraction is in the sodium alginate aqueous solution 260ml of 4.0%, is fully uniformly mixed, and obtains the suspension that dynamic viscosity is 450 milli pascal seconds.Subsequently suspension is instilled in the iron nitrate aqueous solution of 2mol/L, gel 1min, form sial composite oxides-sodium alginate gel bead, spend deionized water further, 150 DEG C of dryings 2 hours, 650 DEG C of roastings obtain amorphous aluminum silicide bead in 3 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 4
By 100gAl
2o
3/ L sodium aluminate solution 100ml, 150gSiO
2/ L sodium silicate solution 100ml and 100gAl
2o
3/ L aluminum sulfate solution 90ml stream joins in the reaction vessel adding 200ml deionized water, reaction temperature is kept to be 30 ~ 35 DEG C, pH value is 7.5 ~ 8.0, within 1.5 hours, add, be heated to subsequently 85 DEG C aging 2.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake 135g that solid content is 25% after suction filtration.Above-mentioned filter cake being added in batches mass fraction is in the sodium alginate aqueous solution 160ml of 3.5%, is fully uniformly mixed, and obtains the suspension that dynamic viscosity is 320 milli pascal seconds.Subsequently suspension is instilled in the zinc nitrate aqueous solution of 1.0mol/L, gel 10min, form sial composite oxides-sodium alginate gel bead, spend deionized water further, 120 DEG C of dryings 4 hours, 550 DEG C of roastings obtain amorphous aluminum silicide bead in 5 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Table 1 different embodiment products obtained therefrom performance indications
Claims (3)
1. a preparation method for amorphous aluminum silicide ball type carrier, is characterized in that: carry out according to the following steps:
1) sodium aluminate solution, sodium silicate solution and aluminum sulfate solution is prepared respectively; The concentration of described sodium aluminate solution is 100 ~ 200gAl
2o
3/ L, the concentration of sodium silicate solution is 50 ~ 150gSiO
2/ L, aluminum sulfate solution is 100 ~ 200gAl
2o
3/ L;
2) by sodium aluminate solution, sodium silicate solution and aluminum sulfate solution and stream joins in the reaction vessel adding a certain amount of deionized water, reaction temperature is kept to be 20 ~ 50 DEG C, pH value is 6.5 ~ 9.5, react 0.5 ~ 2.5 hour, be heated to subsequently 60 ~ 90 DEG C aging 0.5 ~ 3 hour, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, obtains the amorphous silicon aluminium composite oxide filter cake that solid content is 20 ~ 45% after suction filtration;
3) by a certain amount of step 2) filter cake to add mass fraction be in the sodium alginate aqueous solution of 1.0 ~ 4.5% in batches, be fully uniformly mixed, obtain the suspension that dynamic viscosity is 50 ~ 500 milli pascal seconds;
4) by step 3) obtained suspension instillation concentration is in the divalence of 0.5 ~ 2mol/L or the aqueous solution of trivalent metal ion, gel 1 ~ 20min, form amorphous silicon aluminium composite oxide-alginate bead, spend deionized water further, 80 ~ 150 DEG C of dryings, 500 ~ 650 DEG C of roastings obtain amorphous aluminum silicide bead, and wherein the metal ion of divalence or trivalent is selected from calcium ion, zinc ion, aluminium ion or iron ion.
2., according to preparation method according to claim 1, it is characterized in that:
Step 2) be: after sodium aluminate solution mixes with sodium silicate solution, with aluminum sulfate solution and stream joins in the reaction vessel adding a certain amount of deionized water, reaction temperature is kept to be 30 ~ 40 DEG C, pH value is 7.0 ~ 8.5, added in 0.5 ~ 2.0 hour, be heated to subsequently 75 ~ 85 DEG C aging 1.0 ~ 2.0 hours, Separation of Solid and Liquid, fully to pull an oar washing by deionized water, after suction filtration, obtain the amorphous silicon aluminium composite oxide filter cake that solid content is 25 ~ 40%;
Step 3) be: by a certain amount of step 2) filter cake to add mass fraction be in the sodium alginate aqueous solution of 1.5 ~ 4.0% in batches, be fully uniformly mixed, obtain the suspension that dynamic viscosity is 100 ~ 450 milli pascal seconds;
Step 4) be: by step 3) obtained suspension instillation concentration is in the divalence of 0.8 ~ 1.6mol/L or the aqueous solution of trivalent metal ion, gel 4 ~ 16min, form amorphous silicon aluminium composite oxide-alginate bead, spend deionized water further, 100 ~ 130 DEG C of dryings, 550 ~ 600 DEG C of roastings obtain amorphous aluminum silicide bead, and wherein the metal ion of divalence or trivalent is selected from calcium ion, zinc ion.
3. according to the preparation method described in claim 1 or 2, it is characterized in that: the amorphous aluminum silicide bead of described preparation method's gained, its character is as follows: intensity is 20 ~ 100N/, and specific surface is 200 ~ 450m
2/ g, pore volume is 0.6 ~ 1.5ml/g.
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| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| CN102309994B (en) * | 2010-07-07 | 2013-04-10 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102489335B (en) * | 2011-12-20 | 2013-07-17 | 淄博齐创化工科技开发有限公司 | Preparation method of high-solid-content amorphous silicon aluminium |
| CN102718241B (en) * | 2012-06-28 | 2014-07-02 | 天津大学 | Method for preparing spherical alumina particles by alginic acid auxiliary forming method |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161008 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |