CN103861659A - Method for preparing spherical amorphous silicon aluminum carrier - Google Patents
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- CN103861659A CN103861659A CN201410072701.6A CN201410072701A CN103861659A CN 103861659 A CN103861659 A CN 103861659A CN 201410072701 A CN201410072701 A CN 201410072701A CN 103861659 A CN103861659 A CN 103861659A
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Abstract
The invention relates to a method for preparing a spherical amorphous silicon aluminum carrier. The method is characterized by comprising the following steps: firstly, preparing a filter cake containing an amorphous silicon aluminum composite oxide by using a neutralization method; secondly, adding a sodium alginate water solution to obtain an amorphous silicon aluminum composite oxide-sodium alginate suspension, dropwise adding the silicon aluminum composite oxide-sodium alginate suspension into a water solution containing divalent or trivalent metal ions with certain concentration, and gelling to form small amorphous silicon aluminum composite oxide-alginate composite balls; finally, washing, drying and roasting the small amorphous silicon aluminum composite oxide-alginate composite balls to obtain the spherical amorphous silicon aluminum carrier. According to the method, the spherical amorphous silicon aluminum carrier is prepared by directly molding the amorphous silicon aluminum composite oxide filter cake in a mild water phase, and only drying and roasting the filter cake once; the spherical amorphous silicon aluminum carrier is low in energy consumption, pollution-free and simple in preparation process, convenient to operate and easy to realize industrial 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 of being prepared by neutralisation to amorphous silicon aluminium composite oxide, filter cake is fully mixed and makes suspension with sodium alginate aqueous solution, further splash into metal salt solution gel forming, drying, roasting make 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 mainly by 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, adding appropriate silica can produce a very large impact aluminium oxide performance, and the adding of silicon, carrier specific area, surface acidity all have significantly and improve, very favourable to a lot of hydrogenation reactions.When both interact, according to the minimum principle of maximum system energy, first silica will act on the strong activated centre of alumina surface, thereby slackened the effect in alumina surface activated centre, aluminium oxide and intermetallic interaction are relaxed, be conducive to dispersion and the active performance of metal.But, the preparation method of traditional sial composite oxides is mechanical mixing or infusion process, due to preparation method's reason, between the silica of introducing system and alumina substrate, easily cause inhomogeneous dispersion and impurity ion content higher, and then affect physicochemical property, surface nature, pore structure of carrier etc.
US4721696 adopts swing method to prepare the false colloidal sol of aluminium oxide by aluminum nitrate and sodium metaaluminate, adds subsequently sodium metasilicate, after washing, dry and roasting, forms amorphous aluminum silicide.This preparation process complicated operation, in product, the high and performance of sodium content is difficult to stable control.
CN100431965C discloses a kind of preparation method of spherical silicon-containing alumina carrier, this method adopts and in aluminium colloidal sol, adds Ludox to obtain sial mixed sols, adopt again oil-drop method to obtain moulding bead, obtain spherical silicon-containing alumina through techniques such as aging, washing, dry, roastings.
CN101239314B adopt carbonizatin method carbon dioxide is passed in the mixed liquor that contains sodium metaaluminate and sodium metasilicate in and plastic, after washing, dry, roasting, add binding agent kneading, roll agglomerating, extruded moulding and obtain amorphous aluminum silicide.
CN1123383C will aluminum sulfate and weak aqua ammonia add waterglass, Ludox or organosilicon after mixing plastic, 50～70 DEG C aging 10～60 minutes, filter, washing, dry and pulverize after obtain amorphous aluminum silicide product.This product is powdery, can only serve as fluid catalyst or carrier, needs further processing in fixed bed while use.
CN1197650C discloses a kind of method that mechanical mixture is prepared silicon-containing alumina carrier.After aluminium-hydroxide powder or alumina powder are mixed by a certain percentage with peptizing agent, extrusion aid etc., become plastic, be extruded into bar on banded extruder, drying, roasting obtain porous silicon-containing alumina carrier.Because silicon adds with the form of SiO2 particle, can not reach molecular state and disperse, affect its serviceability as catalyst or catalyst carrier.
In order better to bring into play the performance of catalyst, except requiring more excellent carrier physical and chemical indexes (conventionally to need larger specific surface, large pore volume more, aperture preferably and surface property, higher intensity etc.) outside, 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 being in contact with one another with point between particle, pile up evenly, reduce bed resistance, greatly improved mass transfer and catalytic effect.Therefore, in the process such as hydrogenation reaction in hydrofinishing, selective hydrogenation and the fine chemistry industry of ball type carrier in petrochemical industry, be applied widely.Conventional ball type carrier production method has: mist projection granulating, rolling moulding, shaping granulation, the moulding of oil (ammonia) post etc.Wherein mist projection granulating preparing product particle diameter is less; Rolling moulding is mainly used in hydraulicity material forming, and adaptability to raw material is poor; Shaping granulation product particle diameter heterogeneity, sphericity are poor, and complex process, is not suitable for continuous production simultaneously, and preparation process dust is large, and material loss is high; Oil (ammonia) although post moulding can make high performance ball type carrier, expensive its scope of application that limited of this technique.
In existing sial ball type carrier technology of preparing, all exist Distribution of silicon and aluminium inhomogeneous, powder and carrier preparation need be through twice dry, roastings, powder is difficult for balling-up, 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 to provide a kind of preparation method 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 the required acidity of 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 to make amorphous aluminum silicide powder, need one step is dry, roasting can make high-performance sial ball type carrier, simplifies preparation process, reduce material consumption, energy consumption, significantly reduced production cost.
In order to control the pore structure and acid amount of amorphous aluminum silicide, adopt sodium aluminate solution, sodium silicate solution and aluminum sulfate and flow fixed pH method, not only process is easy to control, and product has the character of modulation pore structure on a large scale.Sial filter cake is evenly mixed with sodium alginate aqueous solution, subsequently by the sol-gel performance of sodium alginate, suspension is splashed in salting liquid, shrink rapidly moulding, with after can make 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) prepare respectively sodium aluminate solution, sodium silicate solution and aluminum sulfate solution; The concentration of described sodium aluminate solution is 100～200g Al
2o
3/ L, the concentration of sodium silicate solution is 50～150g SiO
2/ L, aluminum sulfate solution is 100～200g Al
2o
3/ L;
2) sodium aluminate solution, sodium silicate solution and aluminum sulfate solution stream are joined in the reaction vessel that adds a certain amount of deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 20～45% amorphous silicon aluminium composite oxide filter cake after suction filtration;
3) by a certain amount of step 2) filter cake to add mass fraction be, in 1.0～4.5% sodium alginate aqueous solution, to be fully uniformly mixed in batches, obtaining dynamic viscosity is the suspension of 50～500 milli pascal seconds;
4) it is in the divalence of 0.5～2mol/L or the aqueous solution of trivalent metal ion that suspension step 3) being made splashes into concentration, gel 1～20min, form amorphous silicon aluminium composite oxide-alginate gelled pill, further wash by deionized water, 80～150 DEG C of dry, 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, magnesium 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, join in the reaction vessel that adds a certain amount of deionized water with aluminum sulfate solution stream, keeping reaction temperature is 30～40 DEG C, pH value is 7.0～8.5, in 0.5～2.0 hour, add, be heated to subsequently 75～85 DEG C aging 1.0～2.0 hours, Separation of Solid and Liquid, with the deionized water washing of fully pulling an oar, after suction filtration, obtain solid content and be 25～40% amorphous silicon aluminium composite oxide filter cake;
Step 3) is: by a certain amount of step 2) filter cake to add mass fraction be, in 1.5～4.0% sodium alginate aqueous solution, to be fully uniformly mixed in batches, obtaining dynamic viscosity is the suspension of 100～450 milli pascal seconds.
Step 4) is: it is in the divalence of 0.8～1.6mol/L or the aqueous solution of trivalent metal ion that the suspension that step 3) is made splashes into concentration, gel 4～16min, form amorphous silicon aluminium composite oxide-alginate gelled pill, further wash by deionized water, 100～130 DEG C of dry, 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, magnesium 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 100g Al
2o
3/ L sodium aluminate solution 180ml, 70g SiO
2/ L sodium silicate solution 190ml and 100gAl
2o
3/ L aluminum sulfate solution 140ml stream join in the reaction vessel that adds 200ml deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 33% amorphous silicon aluminium composite oxide filter cake 138g after suction filtration.It is in 2.5% sodium alginate aqueous solution 150ml that above-mentioned filter cake is added to mass fraction in batches, is fully uniformly mixed, and obtaining dynamic viscosity is the suspension of 260 milli pascal seconds.Subsequently suspension is splashed in the aluminum nitrate aqueous solution of 0.5mol/L, gel 5min, form sial composite oxides-sodium alginate gel bead, further wash by deionized water, 120 DEG C are dried 6 hours, 550 DEG C of roastings obtain amorphous aluminum silicide bead for 4 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 2
By 200g Al
2o
3/ L sodium aluminate solution 150ml, 100g SiO
2/ L sodium silicate solution 200ml and 200gAl
2o
3/ L aluminum sulfate solution 110ml stream join in the reaction vessel that adds 200ml deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 36% amorphous silicon aluminium composite oxide filter cake 200g after suction filtration.It is in 1.5% sodium alginate aqueous solution 260ml that above-mentioned filter cake is added to mass fraction in batches, is fully uniformly mixed, and obtaining dynamic viscosity is the suspension of 150 milli pascal seconds.Subsequently suspension is splashed in the calcium nitrate aqueous solution of 2.0mol/L, gel 1min, form sial composite oxides-sodium alginate gel bead, further wash by deionized water, 80 DEG C are dried 12 hours, 500 DEG C of roastings obtain amorphous aluminum silicide bead for 5 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 3
By 150g Al
2o
3/ L sodium aluminate solution 180ml, 150g SiO
2/ L sodium silicate solution 100ml and 180gAl
2o
3/ L aluminum sulfate solution 103ml stream join in the reaction vessel that adds 300ml deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 40% amorphous silicon aluminium composite oxide filter cake 152g after suction filtration.It is in 4.0% sodium alginate aqueous solution 260ml that above-mentioned filter cake is added to mass fraction in batches, is fully uniformly mixed, and obtaining dynamic viscosity is the suspension of 450 milli pascal seconds.Subsequently suspension is splashed in the iron nitrate aqueous solution of 2mol/L, gel 1min, form sial composite oxides-sodium alginate gel bead, further wash by deionized water, 150 DEG C are dried 2 hours, 650 DEG C of roastings obtain amorphous aluminum silicide bead for 3 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 4
By 200g Al
2o
3/ L sodium aluminate solution 100ml, 50g SiO
2/ L sodium silicate solution 300ml and 150gAl
2o
3/ L aluminum sulfate solution 95ml stream join in the reaction vessel that adds 200ml deionized water, keeping reaction temperature is 30～35 DEG C, pH value is 8.0～8.5, within 1.0 hours, add, be heated to subsequently 75 DEG C aging 2.0 hours, Separation of Solid and Liquid, with the deionized water washing of fully pulling an oar, obtains solid content and is 31% amorphous silicon aluminium composite oxide filter cake 160g after suction filtration.It is in 4.0% sodium alginate aqueous solution 180ml that above-mentioned filter cake is added to mass fraction in batches, is fully uniformly mixed, and obtaining dynamic viscosity is the suspension of 420 milli pascal seconds.Subsequently suspension is splashed in the magnesium nitrate aqueous solution of 0.5mol/L, gel 15min, form sial composite oxides-sodium alginate gel bead, further wash by deionized water, 120 DEG C are dried 4 hours, 550 DEG C of roastings obtain amorphous aluminum silicide bead for 5 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
Embodiment 5
By 100g Al
2o
3/ L sodium aluminate solution 100ml, 150g SiO
2/ L sodium silicate solution 100ml and 100gAl
2o
3/ L aluminum sulfate solution 90ml stream join in the reaction vessel that adds 200ml deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 25% amorphous silicon aluminium composite oxide filter cake 135g after suction filtration.It is in 3.5% sodium alginate aqueous solution 160ml that above-mentioned filter cake is added to mass fraction in batches, is fully uniformly mixed, and obtaining dynamic viscosity is the suspension of 320 milli pascal seconds.Subsequently suspension is splashed in the zinc nitrate aqueous solution of 1.0mol/L, gel 10min, form sial composite oxides-sodium alginate gel bead, further wash by deionized water, 120 DEG C are dried 4 hours, 550 DEG C of roastings obtain amorphous aluminum silicide bead for 5 hours, and its intensity, specific surface, pore volume, dioxide-containing silica are in table 1.
The different embodiment products obtained therefrom of table 1 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) prepare respectively sodium aluminate solution, sodium silicate solution and aluminum sulfate solution; The concentration of described sodium aluminate solution is 100～200g Al
2o
3/ L, the concentration of sodium silicate solution is 50～150g SiO
2/ L, aluminum sulfate solution is 100～200gAl
2o
3/ L;
2) sodium aluminate solution, sodium silicate solution and aluminum sulfate solution stream are joined in the reaction vessel that adds a certain amount of deionized water, keeping reaction temperature is 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, with the deionized water washing of fully pulling an oar, obtains solid content and is 20～45% amorphous silicon aluminium composite oxide filter cake after suction filtration;
3) by a certain amount of step 2) filter cake to add mass fraction be, in 1.0～4.5% sodium alginate aqueous solution, to be fully uniformly mixed in batches, obtaining dynamic viscosity is the suspension of 50～500 milli pascal seconds;
4) it is in the divalence of 0.5～2mol/L or the aqueous solution of trivalent metal ion that suspension step 3) being made splashes into concentration, gel 1～20min, form amorphous silicon aluminium composite oxide-alginate gelled pill, further wash by deionized water, 80～150 DEG C of dry, 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, magnesium ion, zinc ion, aluminium ion or iron ion.
2. according to preparation method claimed in claim 1, it is characterized in that:
Step 2) be: after sodium aluminate solution mixes with sodium silicate solution, join in the reaction vessel that adds a certain amount of deionized water with aluminum sulfate solution stream, keeping reaction temperature is 30～40 DEG C, pH value is 7.0～8.5, in 0.5～2.0 hour, add, be heated to subsequently 75～85 DEG C aging 1.0～2.0 hours, Separation of Solid and Liquid, with the deionized water washing of fully pulling an oar, after suction filtration, obtain solid content and be 25～40% amorphous silicon aluminium composite oxide filter cake;
Step 3) is: by a certain amount of step 2) filter cake to add mass fraction be, in 1.5～4.0% sodium alginate aqueous solution, to be fully uniformly mixed in batches, obtaining dynamic viscosity is the suspension of 100～450 milli pascal seconds;
Step 4) is: it is in the divalence of 0.8～1.6mol/L or the aqueous solution of trivalent metal ion that the suspension that step 3) is made splashes into concentration, gel 4～16min, form amorphous silicon aluminium composite oxide-alginate gelled pill, further wash by deionized water, 100～130 DEG C of dry, 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, magnesium ion, zinc ion.
3. according to the preparation method described in claim 1 and 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377467A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| CN102309994A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102489335A (en) * | 2011-12-20 | 2012-06-13 | 淄博齐创化工科技开发有限公司 | Preparation method of high-solid-content amorphous silicon aluminium |
| CN102718241A (en) * | 2012-06-28 | 2012-10-10 | 天津大学 | Method for preparing spherical alumina particles by alginic acid auxiliary forming method |
-
2014
- 2014-02-28 CN CN201410072701.6A patent/CN103861659B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| CN102309994A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102489335A (en) * | 2011-12-20 | 2012-06-13 | 淄博齐创化工科技开发有限公司 | Preparation method of high-solid-content amorphous silicon aluminium |
| CN102718241A (en) * | 2012-06-28 | 2012-10-10 | 天津大学 | Method for preparing spherical alumina particles by alginic acid auxiliary forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377467A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Alumina and preparation method thereof |
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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. |