CN1204964C - Oil ammonia column shaping method of spherical aluminium oxide - Google Patents
Oil ammonia column shaping method of spherical aluminium oxide Download PDFInfo
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- CN1204964C CN1204964C CN 02146394 CN02146394A CN1204964C CN 1204964 C CN1204964 C CN 1204964C CN 02146394 CN02146394 CN 02146394 CN 02146394 A CN02146394 A CN 02146394A CN 1204964 C CN1204964 C CN 1204964C
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Abstract
The present invention relates to an oil ammonia column shaping method of spherical aluminium oxide, which comprises the following steps: the aluminum oxide sol is dripped in the oil ammonia column to form spherical gel particles, wherein the oil ammonia column is composed of 0.1 to 4.5 millimeters of upper oil phases and 10 to 300 centimeters of lower electrolyte solution phases; then, the gel particles are aged in the electrolyte solution phases for 0.5 to 10 hours, dried and calcined. In method of the present invention, the oil phases have no surfactants, and the prepared spherical aluminium oxide has little impurity content.
Description
Technical field
The present invention is a kind of spherical solid particulate oil ammonia column forming method, specifically, is that a kind of employing oil ammonia column legal system is equipped with the spherical particulate method of aluminum oxide.
Background technology
The oil ammonia column method of forming is a kind of common method of beads such as preparation aluminum oxide, silicon oxide, sial.It is that colloidal sol is splashed in the oil ammonia column, makes sol particles balling-up in the oil phase on pillar upper strata, gelling in the ammoniacal liquor of lower floor.The aging back of agglomerative particle drying, roasting promptly obtain the spherical solid particle.Adopt the bead even structure of this method preparation, it is low to wear and tear, and the intensity height is widely used as fixed bed and movable bed catalyst, support of the catalyst and sorbent material etc.
USP4179408 discloses a kind of method for preparing ball-aluminium oxide, and this method makes topper that aluminium colloidal sol drop is made up of water-fast liquid and ammonia by air admission earlier mutually, enters lower floor's thing phase of ammoniacal liquor formation again.Aging formed particle, drying, roasting again in ammoniacal liquor then.Oil phase adopts viscosity bigger in this method, and the hydro carbons that flash-point is higher is as kerosene, toluene, petroleum naphtha, gas oil, lubricating oil or coal tar.The oil phase volume is bigger, accounts for three of oil ammonia column total amount/one or more.The ammonia that contains in the oil phase can make the colloidal sol drop external jellified that enters wherein, does not deform so that particle enters lower floor's thing phase time by fluid surface.
In the spherical particulate method of the disclosed preparation aluminum oxide of USP4542113, the urea that adds 1～10 heavy % in aluminium colloidal sol is as stablizer.And then it is splashed in the oil ammonia column be shaped.In the shaping column, ammoniacal liquor accounts for 50～90%, and concentration is 1～10%, and is preferred 8%, and oil phase accounts for 10～50%, adopts diesel oil, gas oil, kerosene etc.
USP4116882 discloses a kind of method for preparing the high-purity alpha-alumina bead.The high purity aluminium oxide preparation that the aluminium colloidal sol that this method is used adopts the aluminum alkoxide hydrolysis to get, its aluminum oxide solid content are 10～20 heavy %, and adopting acetate, formic acid or nitric acid is peptizing agent, and viscosity is 200～600 centipoises.
In the aforesaid method, for overcome oil phase and ammoniacal liquor mutually between bigger interfacial tension, make sol particles after the shaping smoothly by this interface.All need in ammoniacal liquor, to add tensio-active agent to reduce surface tension.Cause oil-water emulsion easily but introduce tensio-active agent, cause ammoniacal liquor phase, oil phase muddiness, oil phase character changes.The use anion surfactant is effective, but its metallic cation that contains is easily adsorbed by sol particles and makes gel particles contain impurity.
Summary of the invention
The purpose of this invention is to provide the method that a kind of easy easy-to-use employing oil ammonia column method of forming prepares ball-aluminium oxide.
The inventive method adopts the lower organism of viscosity as oil phase substance, and the oil phase height is all little than prior art, does not use tensio-active agent in oil phase, thereby can avoid using the ionic soil of tensio-active agent introducing, helps preparing highly purified aluminum oxide.
Embodiment
The oil ammonia column forming method of ball-aluminium oxide provided by the invention, comprise alumina sol splashed in the oil ammonia column by lower floor's electrolyte solution phase composite of 0.1～4.5 millimeter upper oil phase and 10～300 centimetres and form spherical gel particles, make then gel particles electrolyte solution mutually in aging 0.5～15 hour, dry again, roasting.
The upper oil phase of oil ammonia column is thinner among the present invention, its highly preferred 0.1～2.0 millimeter.The existence of oil phase mainly is that the aluminium colloidal sol behind the formation drop is played moulding and provide protection.When aluminium colloidal sol drop can be out of shape because of the bump of liquid near the electrolyte solution phase time, if there is not oil phase, this distortion meeting keeps in mutually and does not change at electrolyte solution.When oil phase exists, the bump of liquid body and the aluminium sol particles balling-up again of being out of shape.The height of oil phase should not be too big, is beneficial to sol particles and keeps suitable speed to enter electrolyte solution smoothly forming gel particles mutually.
Described oil ammonia column lower floor is the electrolyte solution phase, i.e. water, its highly preferred 100～200 centimetres.Electrolyte solution is the aqueous solution of ammoniacal liquor, ammonium sulfate or ammonium chloride mutually, and wherein electrolyte concentration is 1～15 heavy %, preferred 5～10 heavy %.Preferred electrolyte solution is ammonia soln mutually.
Described oil phase is the organism with suitable viscosity, does not contain tensio-active agent.Organism viscosity is 0.3～2.2 centipoise, preferred 0.4～1.5 centipoise.The organism that is preferably used as oil phase is hexane, heptane, octane, nonane, toluene, gasoline, kerosene, sherwood oil or their mixture.
After aluminium colloidal sol drop splashes into oil phase from the top, promptly coated by one deck oil film, dependence speed enters the electrolyte solution phase.Therefore, aluminium colloidal sol should remain 1～7 centimetre apart from the distance of oil reservoir top when dripping ball, preferred 1.5～5.0 centimetres, distance is big more, and drop suffered resistance in air is big more, the speed that enters oil phase is fast more, be out of shape also greatly more, because it is big to enter the speed of oil phase, it is also many more to carry the oil mass that enters the electrolyte solution phase, sol particles will float, and easily form emulsion layer.Distance is too little, and it is too slow that aluminium colloidal sol drop enters the speed of oil phase, is difficult to pass through water-oil interface.
The formation of described emulsion layer is relevant with a ball speed of aluminium colloidal sol, and the excessive ball speed of dripping easily forms more emulsion droplet between two-phase, make profit have little time to separate and form emulsion layer.The complete displace oil phase time of emulsion layer, sol particles is globulate no longer, and shape is identical with the situation that sol particles directly splashes into water.Therefore, for improving the balling-up quality, oil phase is kept perfectly.Therefore, drip ball speed and should be controlled in the proper range, preferably dripping ball speed is 15～40 droplets/centimetre
2Minute.
The solid content of described aluminium colloidal sol is determining the viscosity of slurries, thereby also determines a ball speed of aluminium colloidal sol.Preferred aluminium colloidal sol solid content is 15～30 heavy %.Aluminium colloidal sol can be prepared by hydrated aluminum oxide, high-purity hydrated aluminum oxide preparation of preferably adopting the aluminum alkoxide hydrolysis to make.For making aluminium colloidal sol stable in dripping the ball process, should be to wherein adding an amount of urea, content of urea should be 0～15 heavy % in the aluminium colloidal sol, preferred 5～10 heavy %.
The aluminium sol particles forms gel particles and moulding by behind the oil phase at aqueous phase.Preferred 15～25 ℃ of water temperature, ionogen and oily volatilizations such as the too high meeting aggravation of temperature ammonia.Micelle after the moulding should wear out at aqueous phase, preferred 1～10 hour of digestion time.After the aged gel particles takes out from aqueous phase, need carry out drying and roasting, drying temperature is 60～120 ℃, maturing temperature is 450～750 ℃, preferred 550～650 ℃.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Get SB70 powder (pseudo-boehmite) 100 grams that German SASOL company produces, with 140 gram deionized water pulps, adding concentration is the nitric acid 60 gram peptizations of 5.0 heavy %, and adding 20 gram urea, to make solid content as viscosity stabilizer be that 23 to weigh the aluminium colloidal sol of % stand-by.
In the oil ammonia column of 1.5 meters of length, 70 millimeters of diameters, 20 ℃ add normal heptane down is oil phase, and high 1 millimeter, normal heptane viscosity (20 ℃) is 0.41 centipoise, and the ammoniacal liquor of adding 8% is water, highly is 149.5 centimetres.Adopt pump or U-shaped pipe communicating vessels control level height steady.Pour aluminium colloidal sol into be positioned at the oil ammonia column top a ball device, drip ball device bottom pin hole apart from 2 centimetres of pastas.With 22 droplets/centimetre
2Minute the ball speed of dripping aluminium colloidal sol is splashed in the oil ammonia column, sol particles is in the oil phase balling-up, smoothly by oily ammonia interface, enter ammoniacal liquor mutually and gelling become solid.
With gelling particle in ammoniacal liquor aging 10 hours, take out, 60 ℃ of dryings 10 hours, 120 ℃ of dryings 3 hours, 550 ℃ of roastings were prepared into the γ-Al of smooth in appearance in 3 hours
2O
3Alumina globule.Bead physical properties and foreign matter content see Table 1.
Ammoniacal liquor used 4 months, and muddiness takes place, and can continue to use.For guaranteeing ammonia concn 8%, need to add a small amount of 25% ammoniacal liquor.
Example 2
Method by example 1 prepares γ-Al
2O
3Bead, different is that the oil phase normal heptane is high 2 millimeters, drips ball device bottom pin hole apart from 3 centimetres of pastas, and the bead outward appearance that makes is identical with example 1, and its physical properties and foreign matter content see Table 1.
Example 3
Method by example 1 prepares γ-Al
2O
3Bead, different is that oil phase is an octane, and viscosity (20 ℃) is 0.55 centipoise, drips ball device bottom pin hole apart from 2.2 centimetres of pastas, and the bead outward appearance that makes is identical with example 1, and its physical properties and foreign matter content see Table 1.
Example 4
Method by example 1 prepares γ-Al
2O
3Bead, different is that oil phase is an aviation kerosene, and viscosity (20 ℃) is 2.0 centipoises, drips ball device bottom pin hole apart from 6 centimetres of pastas, and dripping ball speed is 15 droplets/centimetre
2Minute, the bead outward appearance that makes is with example 1, and its physical properties and foreign matter content see Table 1.
Example 5
Method by example 1 prepares γ-Al
2O
3Bead, different is that oil phase is positive nonane, highly is 2 millimeters, and viscosity (20 ℃) is 0.72 centipoise, and dripping ball speed is 20 droplets/centimetre
2Minute, form emulsion layer during moulding, replace the part oil phase, sol particles is moulding smoothly in oil ammonia column, and the bead outward appearance that makes is with example 1, and its physical properties and foreign matter content see Table 1.
Example 6
Method by example 1 prepares γ-Al
2O
3Bead, different is that the normal heptane height is 2 millimeters, dripping ball speed is 27 droplets/centimetre
2Minute, form emulsion layer during moulding, replace the part oil phase, sol particles is moulding smoothly in oil ammonia column, and the bead outward appearance that makes is with example 1, and its physical properties and foreign matter content see Table 1.
Example 7
Method by example 1 prepares γ-Al
2O
3Bead, different is that the normal heptane height is 3 millimeters, dripping ball speed is 37 droplets/centimetre
2Minute, form emulsion layer during moulding, replace the part oil phase, sol particles is moulding smoothly in oil ammonia column, and the bead outward appearance that makes is with example 1, and its physical properties and foreign matter content see Table 1.
Example 8
Method by example 1 prepares γ-Al
2O
3Bead, different is the ammonium chloride solution replacement of ammoniacal liquor by 10m%, sol particles has remaining colloidal sol to be retained on the pasta by oil phase the time.The bead smooth in appearance, its physical properties and foreign matter content see Table 1.
Example 9
Get SB70 powder (pseudo-boehmite) 100 grams that German SASOL company produces, 120 ℃ of dryings 3 hours, with 140 gram deionized water pulps, adding concentration is the nitric acid 60 gram peptizations of 5.0 heavy %, makes solid content and is 25 and weigh the aluminium colloidal sol of %.Prepare γ-Al by example 1 described oil ammonia column forming method then
2O
3Bead, the bead smooth in appearance that makes, its physical properties and foreign matter content see Table 1.
Comparative Examples 1
By prior art for preparing γ-Al
2O
3Bead.
Adding aviation kerosene in oil ammonia column is oil phase, high 20 centimetres, makes to drip ball device bottom pin hole apart from 2.5 centimetres of pastas.Constantly drip permeate agent in dripping the ball process, this permeate agent is that concentration is the aqueous solution of the sulfo-succinic acid monooctyl ester sodium of 0.4 heavy %, and all the other conditions are with example 1.Sol particles is moulding smoothly in oil ammonia column.The bead smooth in appearance that makes, its physical properties and foreign matter content see Table 1.
Ammoniacal liquor uses and becomes muddy after one month, and aviation kerosene is by the colourless redness that becomes.
By table 1 data as can be known, the bead foreign matter content is higher, and this is owing to sol particles adsorption surface promoting agent in the moulding process causes.
Comparative Examples 2
Press the method preparation preparation γ-Al of example 1
2O
3Bead, different is that oil phase is a normal heptane, high 5 millimeters, drips ball device bottom pin hole apart from 3 centimetres of pastas, sol particles stops the several seconds on oily ammonia interface.Retention period is because sol particles gel not, can collide to assemble or be sticked together, and finally causes gel ball not of uniform size.
Table 1
| Instance number | Diameter, millimeter | Specific surface, rice 2/ gram | Crushing strength, newton/grain | Pore volume, milliliter/gram | Bulk density, grams per milliliter | Sodium content, ppm |
| 1 | 1～2 | 239 | 151 | 0.44 | 0.68 | 21 |
| 2 | 1～2 | 238 | 158 | 0.43 | 0.68 | 23 |
| 3 | 1～2 | 235 | 150 | 0.45 | 0.67 | 21 |
| 4 | 1～2 | 236 | 152 | 0.45 | 0.67 | 21 |
| 5 | 1～2 | 237 | 155 | 0.44 | 0.67 | 21 |
| 6 | 1～2 | 235 | 153 | 0.45 | 0.67 | 22 |
| 7 | 1～2 | 236 | 155 | 0.45 | 0.67 | 21 |
| 8 | 1～2 | 233 | 156 | 0.46 | 0.67 | 20 |
| 9 | 1～2 | 255 | 210 | 0.41 | 0.72 | 21 |
| Comparative Examples 1 | 1～2 | 238 | 150 | 0.45 | 0.67 | 53 |
Claims (9)
1, a kind of oil ammonia column forming method of ball-aluminium oxide, comprise alumina sol splashed in the oil ammonia column by lower floor's electrolyte solution phase composite of 0.1～4.5 millimeter upper oil phase and 10～300 centimetres and form spherical gel particles, make then gel particles electrolyte solution mutually in aging 0.5～15 hour, dry again, roasting after the taking-up, the viscosity of described oil phase is 0.3～2.2 centipoise.
2, in accordance with the method for claim 1, it is characterized in that the oil ammonia column upper oil phase is high 0.1～2.0 millimeter, lower floor's electrolyte solution is mutually high 100～200 centimetres.
3, in accordance with the method for claim 1, the viscosity that it is characterized in that oil phase is 0.4～1.5 centipoise.
4, in accordance with the method for claim 1, it is characterized in that oil phase is hexane, heptane, octane, nonane, toluene, gasoline, kerosene, sherwood oil or their mixture.
5, according to claim 1 or 2 described methods, it is characterized in that described electrolyte solution is the aqueous solution of ammoniacal liquor, ammonium sulfate or ammonium chloride mutually, wherein electrolyte concentration is 1～15 heavy %.
6, according to claim 1 or 2 described methods, the solid content that it is characterized in that alumina sol is 15～30 heavy %.The urea that contains 0～15 heavy % in the aluminium colloidal sol.
7, in accordance with the method for claim 6, it is characterized in that high-purity hydrated aluminum oxide preparation that described alumina sol is made by the aluminum alkoxide hydrolysis.
8, according to claim 1 or 2 described methods, alumina sol is 1～7 centimetre apart from the distance of oil reservoir top when it is characterized in that dripping ball, and dripping ball speed is 15～40 droplets/centimetre
2Minute.
9, according to claim 1 or 2 described methods, the digestion time that it is characterized in that gel particles is 1～10 hour, and drying temperature is 60～120 ℃, and maturing temperature is 450～750 ℃.
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| CN 02146394 CN1204964C (en) | 2002-10-30 | 2002-10-30 | Oil ammonia column shaping method of spherical aluminium oxide |
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