CN103864123A - Water column forming method of spherical aluminum oxide - Google Patents
Water column forming method of spherical aluminum oxide Download PDFInfo
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- CN103864123A CN103864123A CN201410072563.1A CN201410072563A CN103864123A CN 103864123 A CN103864123 A CN 103864123A CN 201410072563 A CN201410072563 A CN 201410072563A CN 103864123 A CN103864123 A CN 103864123A
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- aluminium oxide
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- boehmite
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Abstract
The invention relates to a water-column forming method of spherical aluminum oxide. The water-column forming method is characterized by comprising the following steps: (1) preparing pseudo-boehmite and a soluble alginate water solution into suspended slurry, and dropwise adding the suspended slurry into a polyvalent metal cation water solution, so as to form pseudo-boehmite-alginic acid gel beads; (2) carrying out acid treatment, heat-moisture treatment and chemical chambering treatment on the gel beads; and (3) finally drying and baking, so as to prepare the spherical aluminum oxide. The water-column forming method has the advantages that the cost is low, the operational steps are simple and feasible, the industrial production is easy to implement, and the prepared spherical aluminum oxide has the advantages of large pore volume and aperture, high strength, concentration in distribution and the like.
Description
Technical field
The present invention is a kind of water column forming method of ball-aluminium oxide, is specifically related to a kind of water column forming method that utilizes the sol-gel character assistant formation of soluble alginate to prepare ball-aluminium oxide.
Technical background
The water column method of forming is prepared the ball-aluminium oxide preparation method that ball-aluminium oxide is a kind of novelty, compare with the method for forming in traditional rolling balling method and oil, this forming method has that shaping speed is fast, efficiency is high, preparation process is without advantages such as dust, and adopt aqueous systems normal temperature compacted under, be the ball-aluminium oxide preparation method of a kind of low cost, less energy-consumption, environmental protection.
Application number CN201210219122.0 discloses the method for a kind of Lalgine assistant formation legal system for ball-aluminium oxide, and this method is take pseudo-boehmite as raw material, and sodium alginate is the moulding of the auxiliary ball-aluminium oxide of forming agent.Concrete grammar is: sodium alginate-pseudo-boehmite suspension of preparation is splashed into moulding in the aqueous solution of aluminium, calcium, barium, copper, zinc, manganese or cobalt ion, after moulding or in moulding process, process the physical strength to increase product in the aqueous environment of pH1～4, drying, roasting afterwards makes ball-aluminium oxide.Ball-aluminium oxide prepared by this method have smooth surface, physical strength good, wear away the features such as low, specific surface area is large.
But aforesaid method exists following deficiency: 1. pore volume loss is large, shows that pseudo-boehmite can be transformed into amorphous gel under sour environment, and excessive acid also likely makes the excessive peptization of pseudo-boehmite, thereby reduce product pore volume; 2. intensity distribution inequality, is directly dried after acid treatment, and due to bead top layer moisture, to evaporate very fast acid concentration higher, causes the inside and outside peptization degree varies of bead to cause, and finally causes product strength skewness; 3. product sodium content is high, and the assistant formation agent that this method is used is sodium alginate, will introduce a large amount of sodium to product, and sodium is the solid acid that alkali metal can reduce product, unfavorable to a lot of catalytic reaction processes, if wash sodium, will expend a large amount of water resourcess again; 4. adaptability to raw material is poor, shows that acid-treated pH is at 1～4 o'clock, and the pseudo-boehmite lower to peptization index, cannot make high-intensity ball-aluminium oxide.
Summary of the invention
The present invention seeks to the shortcomings such as the loss of method pore volume described in technical solution background is large, intensity distribution is uneven, sodium content is high, adaptability to raw material is poor, the water column forming method of preparing ball-aluminium oxide of the damp and hot and chemical enlargement processing of a kind of process is provided, and ball-aluminium oxide obtained by this method.Ball-aluminium oxide prepared by the inventive method not only physical strength good, wear away low, specific surface area is large, and have that pore volume is large, foreign matter content is low, intensity is high and distribute and the advantage such as concentrate; And the inventive method to assistant formation, agent has multiple choices, when wherein ammonium alginate is forming agent, can not introduce sodium element to product; Acid treatment and chemical enlargement are processed and organically combined, hydrionic concentration range while having widened acid treatment, all can prepare the good ball-aluminium oxide of high strength and pore structure for the pseudo-boehmite of various peptization indexes, the adaptability of the raw material having improved.
The present invention is a kind of water column forming method of ball-aluminium oxide, and its step comprises as follows:
1) batching: it is in the aqueous solution of 0.1～5% soluble alginate that pseudo-boehmite is added to massfraction, is fully mixed and made into suspendible slurry; Wherein the massfraction of pseudo-boehmite in suspendible slurry is not more than 30%(with Al
2o
3meter);
2) moulding: suspendible slurry is splashed in the multivalent metal cation salts solution that ion volumetric molar concentration is greater than 0.05mol/L, form gelled pill, then take out gelled pill, deionized water wash 3～4 times;
3) acid treatment: adopt the acidic solution that hydrogen ion volumetric molar concentration is 0.0001～5mol/L to carry out immersion treatment to gelled pill, the treatment time is no more than 8 hours;
4) wet heat treatment: the gelled pill after acid treatment is 40 ℃～99 ℃ in temperature, processes 0.5～10 hour in the heat and moisture preserving equipment that relative humidity is 50%～100%;
5) chemical enlargement: the gelled pill after wet heat treatment soaks and is no more than 8 hours in the weakly alkaline expanding agent aqueous solution;
6) dry, roasting: dry at 60 ℃～150 ℃, 400 ℃～800 ℃ roastings make ball-aluminium oxide.
According to water column forming method of the present invention, in described step 1), the soluble alginate aqueous solution is that massfraction is 0.5～3% the ammonium alginate aqueous solution.
According to water column forming method of the present invention, described step 2) in multivalent metal cation be calcium, aluminium, zinc, copper, iron, manganese, cobalt, nickel, lead or barium metallic cation, the volumetric molar concentration of multivalent metal cation is 0.2～1mol/L.
According to water column forming method of the present invention, in described step 3), acidic solution is that hydrogen ion volumetric molar concentration is nitric acid or the acetum of 0.01～4mol/L.
According to water column forming method of the present invention, in described step 4), wet heat treatment temperature is 65 ℃～85 ℃, and relative humidity is 75%～90%, and the treatment time is 2～5 hours.
According to water column forming method of the present invention, in described step 5), chemical enlargement expanding agent used is urea, vulkacit H, bicarbonate of ammonia, volatile salt or quadrol, and expanding agent aqueous solution pH is 7～9, and soak time is 5～60 minutes.
The present invention also provides a kind of ball-aluminium oxide that according to the present invention prepared by aforesaid method, it is characterized in that, the pore volume of ball-aluminium oxide is 0.3～1.8cm
3/ g, preferably 0.5～1.5cm
3/ g; Specific surface area is 150～350m
2/ g, preferably 190～300m
2/ g; Physical strength is 15～220N/, preferably 40～100N/; Aperture is adjustable, preferably 7～20nm.
Compared with prior art, its beneficial effect is the inventive method: 1. the bead of the present invention after to acid treatment carried out wet heat treatment, makes acid slowly diffusion in bead, reduce the inside and outside acid concentration gradient of bead, and acid is fully reacted with pseudo-boehmite, thus make product even, intensity distribution is concentrated; 2. increased chemical enlargement step, not only can neutralize excessive acid, and can make transformation forms under sour environment amorphous gel, aluminium glue under weakly alkaline environment, again be transformed into the pseudo-boehmite of low-crystallinity, thus reduce pore structure loss, increase the pore volume of product; 3. expanded the kind of forming agent, can select different soluble alginates according to practical use, preferably ammonium alginate, its ammonium radical ion can be decomposed and overflow with gas form in roasting process, can not bring additional impurities into product, make product sodium content low, purity is high; 4. acid treatment and reaming are processed and are organically combined, and have strengthened the adaptability of pseudo-boehmite raw material; 5. multivalent metal cation of the present invention has multiple choices, avoids bringing into detrimental impurity; 6. ball-aluminium oxide pore volume, the aperture of preparation are large, and intensity is high and distribute concentrated; 7. operation steps simple possible, easily realizes suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the water column method of forming of ball-aluminium oxide of the present invention is described further, but not thereby limiting the invention.
Embodiment 1
Prepare ball-aluminium oxide by the inventive method step:
1. batching: 100g pseudo-boehmite, join 500g massfraction and be in 0.75% ammonium alginate solution, fully stir and form ammonium alginate-pseudo-boehmite suspension;
2. moulding: ammonium alginate-pseudo-boehmite suspension is splashed in the fluid column of ca nitrate soln of 0.3mol/L, drop forms alginate calcium-pseudo-boehmite plural gel bead in the moment that enters solution with regard to gelation, then take out gelled pill, deionized water wash 3～4 times;
3. acid treatment: by the salpeter solution immersion treatment of 0.15mol/L 15 minutes for gelled pill, then take out;
4. wet heat treatment: be to react 4 hours in 75 ℃, the relative humidity heat and moisture preserving case that is 82% in temperature;
5. chemical enlargement: the urea soln of 0.18mol/L for the bead after wet heat treatment soaks 10 minutes in 35 ℃ of water-baths;
6. dry, roasting: at 75 ℃ dry 5 hours, then 120 ℃ dry 10 hours, last 600 ℃ of roastings 4 hours, the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 2
Prepare γ-A by the step in embodiment 1
2o
3bead, what when different is batching, use is that 1200g massfraction is 0.75% ammonium alginate solution, the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 3
Prepare γ-A by the step in embodiment 1
2o
3bead, what acid treatment that different is was used is the acetum of 0.5mol/L, the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 4
Prepare γ-A by the step in embodiment 1
2o
3bead, what acid treatment that different is was used is the mixed acid solution that nitric acid and acetic acid are made into, and wherein concentration of nitric acid is 0.05mol/L, and acetate concentration is 0.4mol/L, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 5
Prepare γ-A by the step in embodiment 1
2o
3bead, different is that the metallic cation aqueous solution is 0.3mol/L aluminum nitrate solution, the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 6
Prepare γ-A by the step in embodiment 1
2o
3bead, different is that chemical enlargement expanding agent used is 0.1mol/L vulkacit H solution, the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 7
Prepare γ-A by the step in embodiment 1
2o
3bead, different is that concentration of nitric acid used is 3.5mol/L, and in 5 minutes treatment times, when chemical enlargement, expanding agent used is 3mol/L urea, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 8
Prepare γ-A by the step in embodiment 1
2o
3bead, what acid treatment that different is was used is the acetum of 0.4mol/L, and the treatment time is 2 hours, and when chemical enlargement, expanding agent used is the urea soln of 0.2mol/L, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 9
Prepare γ-A by the step in embodiment 1
2o
3bead, what acid treatment that different is was used is the acetum of 0.4mol/L, and when chemical enlargement, expanding agent used is the urea soln of 0.4mol/L, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 10
Prepare γ-A by the step in embodiment 5
2o
3bead, what acid treatment that different is was used is the acetum of 0.4mol/L, and when chemical enlargement, expanding agent used is the urea soln of 0.4mol/L, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 11
Prepare γ-A by the step in embodiment 5
2o
3bead, what acid treatment that different is was used is the acetum of 0.4mol/L, and when chemical enlargement, expanding agent used is the vulkacit H solution of 0.2mol/L, and the sample physical properties of preparation and foreign matter content are in table 1.
Embodiment 12
Prepare γ-A by the step in embodiment 5
2o
3bead, what acid treatment that different is was used is the acetum of 2mol/L, the sample physical properties of preparation and foreign matter content are in table 1.
The performance of the different embodiment products obtained therefroms of table 1
Comparative example 1
Prepare as follows ball-aluminium oxide:
1. batching: 100g pseudo-boehmite, join 500g massfraction and be in 0.75% sodium alginate soln, fully stir and form sodium alginate-pseudo-boehmite suspension;
2. moulding: sodium alginate-pseudo-boehmite suspension is splashed in the fluid column of 0.3mol/L ca nitrate soln, drop forms alginate calcium-pseudo-boehmite plural gel bead in the moment that enters solution with regard to gelation, then take out gelled pill, deionized water wash 3～4 times;
3. acid treatment: by the salpeter solution immersion treatment of 0.15mol/L 15 minutes for washed gelled pill, then take out;
4. dry, roasting: at 75 ℃ dry 5 hours, then 120 ℃ dry 10 hours, last 600 ℃ of roastings 4 hours, the sample physical properties of preparation and foreign matter content are in table 2.
Comparative example 2
Prepare γ-A by the step in comparative example 1
2o
3bead, what acid treatment that different is was used is the acetum of 0.5mol/L, the physical properties of the sample of preparation and foreign matter content are in table 2.
Comparative example 3
Prepare γ-A by the step in comparative example 1
2o
3bead, the different aluminum nitrate solutions that the multivalent metal cation aqueous solution used is 0.3mol/L while being moulding, the physical properties of the sample of preparation and foreign matter content are in table 2.
Comparative example 4
Prepare γ-A by the step in comparative example 1
2o
3bead, different is is 2 hours the acid treatment time, the physical properties of the sample of preparation and foreign matter content are in table 2.
Comparative example 5
Prepare γ-A by the step in comparative example 1
2o
3bead, what acid treatment that different is was used is the salpeter solution of 3.5mol/L, the physical properties of the sample of preparation and foreign matter content are in table 2.
The performance of the different comparative example products obtained therefroms of table 2
Claims (9)
1. a water column forming method for ball-aluminium oxide, is characterized in that, comprises the steps:
1) batching: pseudo-boehmite is added in the aqueous solution that massfraction is 0.1～5% soluble alginate, is fully mixed and made into suspendible slurry, wherein the massfraction of pseudo-boehmite in suspendible slurry is not more than 30%, with Al
2o
3meter;
2) moulding: suspendible slurry is splashed in the multivalent metal cation salts solution that ion volumetric molar concentration is greater than 0.05mol/L, form gelled pill, then take out gelled pill, deionized water wash 3～4 times;
3) acid treatment: adopt the acidic solution that hydrogen ion volumetric molar concentration is 0.0001～5mol/L to carry out immersion treatment to gelled pill, the treatment time is no more than 8 hours;
4) wet heat treatment: the gelled pill after acid treatment is 40 ℃～99 ℃ in temperature, processes 0.5～10 hour in the heat and moisture preserving equipment that relative humidity is 50%～100%;
5) chemical enlargement: the gelled pill after wet heat treatment soaks and is no more than 8 hours in the weakly alkaline expanding agent aqueous solution;
6) dry, roasting: dry at 60 ℃～150 ℃, 400 ℃～800 ℃ roastings make ball-aluminium oxide.
2. method according to claim 1, is characterized in that, in described step 1), the soluble alginate aqueous solution is that massfraction is 0.5～3% the ammonium alginate aqueous solution.
3. method according to claim 1, is characterized in that, described step 2) in multivalent metal cation be calcium, aluminium, zinc, copper, iron, manganese, cobalt, nickel, lead or barium metallic cation, the volumetric molar concentration of multivalent metal cation is 0.2～1mol/L.
4. method according to claim 1, is characterized in that, in described step 3), acidic solution is that hydrogen ion volumetric molar concentration is nitric acid or the acetum of 0.01～4mol/L.
5. method according to claim 1, is characterized in that, in described step 4), wet heat treatment temperature is 65 ℃～85 ℃, and relative humidity is 75%～90%, and the treatment time is 2～5 hours.
6. according to the method described in claim 1-5 any one, it is characterized in that, expanding agent described in described step 5) is urea, vulkacit H, bicarbonate of ammonia, volatile salt or quadrol, and expanding agent aqueous solution pH is 7～9, and soak time is 5～60 minutes.
7. method according to claim 1, is characterized in that, comprises the steps:
1) batching: it is in 0.5～3% the ammonium alginate aqueous solution that pseudo-boehmite is added to massfraction, is fully mixed and made into suspendible slurry, and wherein the massfraction of pseudo-boehmite in suspendible slurry is not more than 30%, with Al
2o
3meter;
2) moulding: suspendible slurry is splashed in the multivalent metal cation salts solution that ion volumetric molar concentration is greater than 0.2～1mol/L, form gelled pill, then take out gelled pill, deionized water wash 3～4 times;
3) acid treatment: adopt nitric acid or the acetum that hydrogen ion volumetric molar concentration is 0.01～4mol/L to carry out immersion treatment to gelled pill, the treatment time is no more than 8 hours;
4) wet heat treatment: the gelled pill after acid treatment is 65 ℃～85 ℃ in temperature, processes 2～5 hours in the heat and moisture preserving equipment that relative humidity is 75%～90%;
5) chemical enlargement: soak 5～60 minutes in the weakly alkaline expanding agent aqueous solution that the gelled pill after wet heat treatment is 7～9 at pH;
6) dry, roasting: dry at 60 ℃～150 ℃, 400 ℃～800 ℃ roastings make ball-aluminium oxide;
Wherein said multivalent metal cation is calcium, aluminium, zinc, copper, iron, manganese, cobalt, nickel, lead or barium metallic cation, and described expanding agent is urea, vulkacit H, bicarbonate of ammonia, volatile salt or quadrol.
8. the ball-aluminium oxide that method prepares according to claim 1, is characterized in that, described ball-aluminium oxide pore volume is 0.3～1.8cm
3/ g, specific surface area is 150～350m
2/ g, physical strength is 15～220N/.
9. ball-aluminium oxide according to claim 8, is characterized in that, described ball-aluminium oxide pore volume is 0.5～1.5cm
3/ g, specific surface area is 190～300m
2/ g, physical strength is 40～100N/, aperture 7～20nm.
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| CN104477953A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Spherical alumina shaping method |
| CN105502447A (en) * | 2014-10-16 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of alumina pellets through hot oil column moulding |
| CN105727917A (en) * | 2014-12-12 | 2016-07-06 | 天津大学 | Preparation method of supported spherical aluminum oxide granules |
| CN107999048A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | Titaniferous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
| CN107999049A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | Siliceous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
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| CN109052599A (en) * | 2018-10-31 | 2018-12-21 | 张家界贵友环保材料科技有限公司 | A kind of polyaluminium chloride efficient water-purifying agent |
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| CN105502447A (en) * | 2014-10-16 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of alumina pellets through hot oil column moulding |
| CN105502447B (en) * | 2014-10-16 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method that hot forming oil column prepares alumina globule |
| CN104383967A (en) * | 2014-11-12 | 2015-03-04 | 中国海洋石油总公司 | Water column forming method of spherical molecular sieve |
| CN104402028A (en) * | 2014-11-12 | 2015-03-11 | 中国海洋石油总公司 | Forming method for spherical aluminium oxide through oil-water column process |
| CN104477953A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Spherical alumina shaping method |
| CN104402028B (en) * | 2014-11-12 | 2016-04-20 | 中国海洋石油总公司 | A kind of profit post forming method of ball-aluminium oxide |
| CN105727917A (en) * | 2014-12-12 | 2016-07-06 | 天津大学 | Preparation method of supported spherical aluminum oxide granules |
| CN105727917B (en) * | 2014-12-12 | 2018-08-10 | 天津大学 | A kind of preparation method of support type Spherical alumina particles |
| CN107999049A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | Siliceous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
| CN108014823A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | The composition of hydrated alumina containing halogen and formed body and preparation method and catalyst and preparation method thereof |
| CN107999048A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | Titaniferous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
| CN109052599A (en) * | 2018-10-31 | 2018-12-21 | 张家界贵友环保材料科技有限公司 | A kind of polyaluminium chloride efficient water-purifying agent |
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