DE2826095A1 - Granulated activated alumina prepn. - by decomposition of alumina tri:hydrate using fluidised bed - Google Patents

Abstract

Granulated activated alumina is prepd. by (a) decomposing alumina trihydrate by contacting it with a fluidized bed at 350-600 degrees C for 0.05-0.5, esp 0.05-0.2, seconds to form amorphous hydroxide; (b) mixing the hydroxide with H2O to form an aq. suspension contg. 100-500g/litre calculated as Al oxide; (c) hydrating the hydroxide by heating at 20-100 degrees C and at pH 5-12 for 0.5-10 hours. This is followed by (d) treating with an acid which can form H2O sol. basic salts with Al at 20-150 degrees C; (e) granulating, drying at 20-150 degrees C and calcining the prod. at 400-600 degrees C. The activated prod. is used as an adsorbing material, a catalyst, or a support for active components in the chemical and petrochemical industry. Using a fluidised bed decreases the decompsn. temp. also the specified hydration conditions make it possible to modify within a wide range the pore structure of the end prod.

Description

PROCEDURE FOR H @ RS @ E @@ UNG OF GRANU @ I @ RTER

ACTIVE TONER @ E The present invention relates to a method for the production of aluminum oxide, in particular a process for the production of uranulated active clay, which is used as an adsorbent, @catalyst or Carrier for the active component in the chemical and petroleum processing industry Use @@ ndet.

@s is @@@ process for the production of @ranulated active alumina got ("Chemische l @ dustrie", @ r.7, 196 @, page 557, in Russian) through processing dispersed precipitates of aluminum hydroxide (shaping, annealing), which one in the @ Precipitation of crystalline aluminum orthohydroxide (hydrargillite) is obtained.

The reprecipitation of the hydrargillite is carried out by its dissolution in acid or alkali with subsequent treatment of the solutions with alkali or Acid through.

; the disadvantage of this method is that it is used up excessively from Acids and alkalis, as a result of which significant amounts of impurities are formed, @elche complicate the washing of the disperse sediment. The washing of this precipitate requires a significant amount of water for washing, which results in larger Amounts of waste water are produced that have to be recycled.

A method is also known (US Pat. No. 3,226,191, 3,223,483, 3222129) for the production of granulated active alumina by decomposing aluminum trihydroxide under Du @ chleiten dessel @ en by @@eißgas with a temperature of 700 to 7 @@ ° C until transition or amorphous aluminum oxide is obtained, which at least @ ens 95% Gemic @ t - # - contains Al2O3 and losses of 5 to 10% by weight during annealing has, mixing the decomposition product with water and then shaping to granules of the desired shape.

The granules obtained are placed in water at a temperature from 60 to 100 ° c. This leads to a transition of part of x - # - Al2O3 in aluminum hydroxide, which solidifies the formed granules.

After hydration, the granules contain the following components: Pseudobo with aluminum trihydroxide 42 to 27 percent by weight; Bayerite aluminum trihydroxide 7 to 2 percent by weight; X - # - Al2O3 rest.

The granules are then dried and glowed at a temperature of 200 to 450 ° C.

The product obtained by this process shows a total pore volume of 0.42 cm @ / g, a specific surface area of 365 m2 / g and a predominant pore radius of 4b X.

A disadvantage of this method is the complexity of the technological Design of the process as a result of the granulation of the moist powder of the transition alumina, which is a decomposition product of aluminum trihydroxide. It also makes it difficult Carrying out the hydration of the granulated decomposition product of the Aluminum trihydroxide a broad modification of the porous structure of the active Alumina as the end product. Carrying out the process of decomposition of aluminum trihydroxide up to the formation of transition aluminum oxides leads to an inexpedient expenditure of heat As a result of the removal <from the aluminum trihydroxide>, practically three water molecules are obtained n <> The purpose of the present invention is to address the disadvantages mentioned remove.

he invention is based on the specification. in a method of manufacture of granulated active alumina Conditions for carrying out the process the and decomposition to indicate the hydration of the acid treatment, which it is possible, to increase the yield of the finished product and the technological and apparatus-related Design to simplify the process.

This object is achieved in that in a method for Production of granulated active alumina, which decomposes aluminum trihydroxide under heating, Mixing the harvested decomposition product with Water, its hydration, forming granules, drying at a temperature of 20 to 150 ° C and annealing at a temperature of 400 to 600 ° C, according to the invention the decomposition of the aluminum trihydroxide when it comes into contact with the layer of a solid thermal carrier, which has a temperature of 3 @ 0 to 600 ° C, with a duration of contact from 0.05 to 0.5 seconds, a decomposition product in the form of amorphous Alumina obtained by mixing the decomposition product with water up to a concentration of 100 to 500 g / l, converted to aluminum oxide, after which hydration of the above decomposition product at a temperature from 2w to 1000C and a p @ value of 5 to 12 during @.5 to lu hours and prior to forming the granules, treating the hydrated decomposition product with a Acid capable of forming water-soluble basic aluminum salts at a temperature Treated from 20 to 15,000.

Expediently, the decomposition of the aluminum trihydroxide is carried out in the @ i @ belschicht of a solid heat transfer medium with a contact time of @ .05 to 0.5 seconds.

One leads advantageously to the production of a hydrated decomposition product with a pseudoboehmite aluminum trihydroxide content of at least 50 percent by weight the hydration of the decomposition product at a temperature of 20 to 80 ° C and a pH of 5 to 10 for 5 to 8 Hours and for the Preparation of a hydrated decomposition product containing bayerite aluminum trihydroxide of at least 80 percent by weight at a temperature of 99 to 100 ° C and one pH from 10.5 to 11.0 for 8 one to 10 hours and for making one hydrated decomposition product containing nordstrandite aluminum trihydroxide of at least 80% at a temperature of 80 to 90 ° C and a pH value of 11 to 12 in the medium of 5% ethylenediamine for 8 to 10 hours.

For the production of granulated active alumina from the sodium admixtures is free, the hydrated decomposition product is filtered before the acid treatment and washes with water until it reaches a sodium content of at most 0.02 percent by weight, converted to Na2O.

The inventive method for the preparation of granulated active Alumina consists in the decomposition of the aluminum trihydroside on contact with it with the layer of a solid heat carrier, which has a temperature of 350 to 6000C has, with a contact time of 0.05 to 0.5 seconds.

e For example, metallic is used as a solid heat transfer medium ceramic particles of any shape, by such decomposition of aluminum trihydroxide one obtains a X-ray am @ rphes decomposition product with ignition losses of 10 to 16 Percentage by weight, which belongs to the amorphous aluminum trihydroxide, which in its Composition is close to the monohydrate of aluminum oxide. The term "glow losses means a standard weight loss obtained on eating the product at one temperature of 800 ° C for 2 hours.

The sedimentation analysis of the amorphous aluminum trihydroxide, the is a decomposition product of aluminum trihydroxide, and of @ usg @ ngs aluminum trihydroxide showed that the distribution of particles @ ac @ of size is the same. This means, that you @ c @ the decomposition to no destruction @ of particles of the starting aluminum trihydroxide, special @ only to whose plates u @@@ r elimination of two hydration water molecules comes. This increases the specific surface area of the decomposition product, which in some cases reaches a size of 400 m2 / g.

The product of decomposition of aluminum trihydroxide obtained is mixed one with water @is to obtain a suspension with a concentration of 100 up to 500 g / 1, converted to Al2O3 and hyuratised. depending on the dehydration conditions (the temperature and pH value of the medium) is the amorphous aluminum trihydroxide, which is a product of the decomposition of aluminum trihydroxide, capable of being converted into various @modifications of aluminum trihydroxide, namely in pseudoohmite-aluminum trihydroxide, Bayerite aluminum trihydroxide and @ordstrandite aluminum trihydroxide or mixture the same coated. To obtain pseudobönmit aluminum trihydroxide, one leads the hydration of the decomposition product in an aqueous medium with a pH value from 5 to 10 at a temperature of 2u to 80 ° C. It should be noted that both Mixing and upon further hydration of the amorphous aluminum trihydroxide, the is a product of the decomposition of aluminum trihydroxide, with water it becomes one Increase in the pH value of the medium to 10.5 to 11 through the excretion of the Sodium ions from the particles of the decomposition product come into the water. Des @ al @ are added to the mixture of the decomposition product to achieve a pH value of less than 11 and acid to the water in an amount of 1 to 8% acid per 1 kg of aluminum oxide.

@ei the hydration of the decomposition product of the aluminum tri-hydroxide for the formation of the bayerite or the north strandite aluminum trihydroxide it is not necessary to adjust the pH with acid. leads in this ball one is the hydration of the amorphous aluminum trihydroxide, which is a decomposition product of the aluminum trihydroxide, at a temperature of 90 to 100 ° C and a pH value from 10.5 to 11 for making bayerite aluminum trihydroxide respectively at a temperature of 80 to 90 ° C and a pH value of 11 @is 12 in the medium of 5 @ igem ethylenediamine for the production of north strandite aluminum trioxide.

@@ Recover active clay free from admixtures of sodium, filtered the hydrated decomposition product is added before the acid treatment is carried out of @luminium trihydroxide and washes with water, whereby after the filtration before the Purification of the residual amount of sodium additions from 0.05 to 17 Percent by weight, converted to Na2O. To get one, converted to sodium, To obtain purer active clay, the hydrated decomposition product is washed, the aluminum @rinydroxid, with distilled water for one Total consumption of 7 to 9 liters of water per 1 kg of aluminum oxide in the precipitate.

The hydrated decomposition products are modified further of the aluminum tri @ hydroxide with an acid, the water-soluble @asic aluminum salts able to form, for example with nitric acid, until plastic is achieved Masses of aluminum trihydroxide, which can be found at @eise zu Gr @@ ulat let shape.

The formed granules are dried at a temperature of 20 up to 150 ° C and glows at a temperature of 400 to 600 ° C in a stream of dry air or of inert gas when using air. of at least 1000 St-1.

This gives granulated active clay with a specific Surface area of 200 to 400 m2 / g, a total pore volume of 0.45 to 0.90 cm3 / g and different porous structure.

Compared to the prototype mentioned above, the inventive Processes for the production of granulated active alumina are a number of essential ones Advantages.

Carrying out the process of decomposition of aluminum trihydroxide when it comes into contact with the fluidized bed of a solid heat transfer medium, to intensify the exchange of heat and substances in the decomposition zone, which in turn it allows to lower the decomposition temperature with a noticeable shortening of the Residence time of the aluminum trihydroxide particles in the zone with honer temperature.

Carrying out the decomposition of the aluminum trihydroxide up to Formation of transition aluminum oxides of type X -Al2O3 and # -Al2O3 with ignition losses 5 to 10 percent by weight is not absolutely necessary. After the invention In the process, an X-ray amorphous decomposition product is obtained with losses on ignition of 10 to 16 percent by weight, that is, amorphous Alum @ nium @ rihydroxid, which is in the composition is close to aluminum mono-hydroxide. The properties of such a decomposition product practically do not differ from the properties of the transition aluminum oxides of type X -Al2O3 and # -Al2O3. Carrying out the decomposition of the aluminum tri- @ ydroxids according to the process according to the invention makes it possible to determine the structure of the decomposition product a @ assermo @ ekül @ eizu @ e, which leads to a significant reduction in heat consumption for the decomposition, because the heat for the removal of the last, the third Water molecule (35.3 kcal / mol) the sum of the @ arms for the removal of the two first water molecules (30.3 kcal / @ ol) is practically the same.

In addition, it makes the change in the conditions of hydration (temperature, pH word of the medium and duration) of the decomposition product of the aluminum trihydroxide in water in the form of a suspension with a concentration of 100 to 500 g / 1, converted on Al2O3, or the change in the conditions of acid treatment of the hydrated Decomposition product possible, a broad modification of the porous structure of the End product, the granulated active clay.

The acid treatment of the hydrated decomposition products makes it is possible to obtain plastic masses of aluminum trihydroxides according to any known processes can be formed into granules.

For a better understanding of the present invention, the following are made Examples of their implementation are given.

Example 1. A mixture consisting of aluminum trihydroxide with a Particle size of at most 200 µm / and air is passed through an reactor Fluidized bed of a solid heat carrier in the form of cylindrical aluminum granules of 4mm diameter and 4 @@ length. The fluidized bed of the solid @ ärmetrager has a temperature of 500 ° C and a height in the steady state of 60 mm. the Average contact duration of aluminum trihydroxide particles with the hot solid carrier @ is 0.1 seconds. During this time, the aluminum trihydroxide decomposes under @@ ldung amorphous @ aluminum trihydroxide with a specific @ surface area of 250 m2 / g and green losses of 14 percent by weight. The x-ray analysis of this The decomposition product shows that the decomposition product is X-ray amorphous.

1 kg of the decomposition product is mixed with 3 liters of distilled water iiasser by converting a suspension with a concentration of 215 g / 1 on Al2O3, eats. To create a medium with pn = one gives the suspension 4,3 g of nitric acid. The hydration of the decomposition product leads one at a temperature of 70 ° C for @ hours with constant stirring. This gives @an a hydrated decomposition product with a moisture in the pressed state of 6o. The specific surface area of the at a temperature of hydrated product dried at 1100C is 240 m2 / g. The X-ray phase analysis results in the following composition: 75 percent by weight of pseudobönmit aluminum trihydroxide, 3 @ weight percent bayerite aluminum trihydroxide.

After hydration, the hydrated decomposition product is filtered off and washes off the sodium additions when using distilled water for washing 7 liters of H2O per 1 kg of Al2O3 in the precipitate, with a residual content of the sodium precipitate of 0.02 percent by weight, converted to @ a2O, achieved.

2.1 kg of the hydrated decomposition product is mixed with 2.2 liters of distilled water to obtain a suspension with one concentration of 250 g / 1 converted to, Al2O3, and treated with nitric acid in an amount of 0.15 mol @@@@ per 1 @ol Al2O3. The treatment is carried out at a temperature of 130 ° C performed for 4 hours with constant ruffling, whereby a plastic, sicn non-segregating @ass obtained from aluminum trihydroxide.

The mass of aluminum trihydroxide obtained by the acid treatment one shaped into spherical granules, which one da @ n Dei Cilier temperature of 10500 dries and in an oven at a 'i' temperature of 55000 for 4 hours an air consumption of 1000 St-1 anneals.

The end product, granulated active clay, is spherical Granules of 2.5 # 0.5 mm in diameter with the following characteristics: specific surface area 350 m2 / g, total pore volume 0.71 cm3 / g, predominant pore radius 60 Å, compressive strength 95 kp / cm2.

Example 2. A mixture consisting of aluminum trihydroxide with a Particle size of at most 200 µm and air is passed through a reactor Fluidized bed of a solid heat carrier in the form of ceramic balls from 2 to 3 mm you @ chmesser. The fluidized bed of the solid heat carrier has a temperature of 350 ° C and a height in the stationary state of 100 mm. The mean contact time the aluminum trihydroxide particle with the hot solid thermal carrier is 0.2%. During this time, the aluminum tri-hydroxide decomposes to form amorphous ones Aluminum @ rihydroxide with a specific surface area of 200 m2 / g and ignition losses by 1 @ Gewic @@ percent. The X-ray phase analysis of this decomposition product shows that there @ decomposition product x-ray @ amorphous with @opures of residual aluminum tri @ ydroxide is.

1 kg of decomposition product is mixed with 1.4 liters of distilled @asser by adding a suspension with a concentration of 350 g / 1, converted on Al2O3. To maintain a pH value of 9.5 in the medium, the Suspension to 2.5 6 nitric acid. The hydration of the decomposition product leads one durcn at a temperature of 8 ° C. for 5 hours with constant stirring, whereby a hydrated decomposition product with a moisture in pressed State of 48 percent by weight er @ eld. The specific surface area of the at a temperature hydrated product dried at 110 ° C is 220 m2 / g. The X-ray phase analysis gives the following composition: 60 percent by weight of pseudobönmit aluminum trihydroxide and 40 weight percent bayerite aluminum trihydroxide.

The suspension of the hydrated decomposition product is further treated with a concentration of 35O g / 1, converted to Al2O3, with hydrochloric acid in one Amount of 0.20 @ol HCl per 1 @ol Al2O3. The treatment is carried out at a temperature carried out of 150 ° C for 6 hours with constant stirring, one plastic mass of aluminum trihydroxide according to The ones through the acid treatment The mass obtained is shaped into cylindrical granules and dried at one temperature of 20 ° C for 24 hours and then at a temperature of 150 ° C for 1 hour and glows in a furnace at a temperature of 400 ° C for 6 hours in a stream of air the end.

The final product, granulated active clay, is cylindrical Granules of 4 mm in diameter and 4 to 6 mm in length with the following nominal values: specific surface 300 m2 / g, total pore volume 0.45 cm3 / g, predominant pore radius 50 Å, forehead compressive strength 140 kp / cm2.

Example 3. A mixture consisting of aluminum trihydroxide with a Particle size of at most 200 µm and air is passed through a reactor with a fluidized bed a solid heat carrier in the form of copper cylinders 2 mm in diameter and 2 min length. The fluidized bed of the solid heat transfer medium has a temperature of 6 @ 0 ° C and a height in the stationary state of 40 mm. The mean contact time the fraction of the aluminum tri-hydroxide with the hot heat transfer medium is 0.05 seconds during which there is decomposition of the tri-hydroxide up to the formation of an X-ray amorphous Decomposition product with a specific surface area of 380 m2 / g and ignition losses comes from 15 percent by weight.

1 kg of the decomposition product of the aluminum trihydroxide mixed one with 7.5 liters of distilled water, whereby one is a suspension with a concentration of 10 @ g / 1, converted to Al2O3, is obtained. To maintain a medium with pH = 10 0.85 g of nitric acid are added to the suspension. The hydration of the decomposition product is carried out at a temperature of whereby solid 50 ° C. is placed under for @ hours constant stirring, hydrated decomposition product with a moisture obtained in the pressed state of 55 percent by weight. The specific surface of the The hydrated product dried at a temperature of 110 ° C is 300 m2 / g. The X-ray phase analysis gives the following composition: 60 percent by weight Pseudobönmit aluminum tri-hydroxide, 40 weight percent bayerite aluminum tri-hydroxide.

The suspension of the hydrated decomposition product is then treated with a concentration of 100 g / 1, converted to Al2O3, with nitric acid in an amount of 0.1 mol of HNO3 per 1 mol of Al2O3. The treatment is carried out at one temperature of 110 ° C for 6 hours with constant stirring. The through the The mass of aluminum trihydroxide obtained by acid treatment forms it is dried to granules of the "spherical" type) at a temperature of 1000C and glows at a tempe temperature of 400 ° C for 4 hours in a stream of air.

The harvested granulated active clay constitutes spherical granules from 0.1 to 2 mm in diameter with the following characteristics: specific surface 380 m2 / g, total pore volume 0.65 cm3 / g, predominant pore radii 150 Å and 1000 Å.

Example 4. A mixture consisting of aluminum trihydroxide with a Particle size of at most 200 µm and air is passed through a reactor Fluidized bed with a solid heat carrier consisting of annular granules of 1 mm inside diameter and 3 @@@ outside diameter. @ Not the solid heat carrier has a temperature of 450 ° C and a no @ e of 5 @@ mm. The residence time of the Aluminum trihydroxide particles in the layer of the Neisse heat transfer medium is 0.5 Seconds. During this time, the aluminum hydroxide decomposes up to the formation of an X-ray amorphous product with a specific surface of 400 m2 / g and green losses of 10 percent by weight.

1 kg of the decomposition product is mixed with 0.8 liters of distilled Water, converting a suspension with a concentration of 500 g / l on Al2O3. To generate a medium with pH = 8, add the suspension 4.5 @ nitric acid too. The hydration of the decomposition product is at a Temperature of 69 ° C carried out for 8 hours with constant stirring, wherein get a hydrated Decomposition product with a moisture in the pressed state of 43 percent by weight. The specific surface of the hydrated product dried at a temperature of 110 ° C is 230 m2 / g. The X-ray phase analysis reveals the following composition: 80 percent by weight Pseudob @@ with aluminum trihydroxide, 20 percent by weight bayerite aluminum trihydroxide.

After hydration, the suspension is filtered and the harvested one Precipitation of the sodium additions when water is used for laundry of 7 liters of H2O per 1 kg of Al2O3 in precipitation, leaving a residual sodium with a deposit of 0.015 percent by weight, converted to @ a2O.

1. @ kg of the washed precipitate is mixed with 2 liters of distilled Water until a suspension with a concentration of 350 g / 1 is obtained on Al2O3, and treated analogously to Example 2 with acid. The acid treatment The mass of aluminum trihydroxide obtained is shaped into ring-shaped granules and dried at a temperature of 100 ° C and anneals at a temperature of 550 ° C during 4 hours in the fragrance stream with a consumption of 1000 St-1.

The harvested granulated active clay forms ring-shaped granules of 4 mm outside diameter, 2 mm inside diameter and 4 to 8 mm length with the following Characteristic values: specific surface 270 m2 / g, total pore volume 0.5 cm3 / g, predominant pore radius 100 Å, face compressive strength 40 kp / cm2.

Example 5. A plastic mass obtained analogously to Example 3 of the aluminum trihydroxide is formed into micro-spherical granules after the acid treatment, dries at a temperature of 100 ° C and glows at a temperature of 400 ° C for 4 hours in a stream of air.

The harvested granulated active clay constitutes spherical granules from 20 to 100 µm in diameter with the following parameters: specific surface area 330 m2 / g, total pore volume 0.6 cm3 / g, predominant pore radii 100 Å and 700 Å to 1000 Å Example 6. A suspension of the hydrated solution obtained analogously to Example 2 The decomposition product is treated with nitric acid in an amount of 0.05 mol HNO3 per 1 mole of Al2O3, the treatment will take place at a temperature of 70 ° C 3 hours carried out with constant stirring. The one obtained by the acid treatment The dimensions of the aluminum trihydroxide are shaped into cylindrical granules 1 mm in diameter and 3 to 5 mm in length, dries at a temperature of 100 ° C and anneals at a Temperature of 500 ° C for 5 hours in an air stream with a consumption of 1000 St-1 off.

The obtained granulated active clay has the following characteristics on: specific surface 300 m2 / g, total pore volume 0.55 cm3 / g, predominant Pore radii 50 Å, 1000 Å and 10000 Å, face compressive strength 90 kp / cm2.

Example 7. 2.1 kg of washed hydrated decomposition product, obtained analogously to Example 1, mixed with 0.3 liters of distilled water and treated with nitric acid in the amount of 0.08 mol of HNO3 1 mole of Al2O each. The treatment is carried out at a temperature of 20 ° C for 1.5 hours carried out with constant stirring. The plastic obtained by the acid treatment The mass of the aluminum trihydroxide is shaped into cylindrical granules 5 mm in diameter and 6 to 10 mm in length, dried at a temperature of 100 ° C and annealed Dei Temperature of 550 ° C for 3 hours in a stream of air oe a consumption of 1000 St-1 off.

The granulated active clay obtained has the following characteristics on: specific surface 350 m2 / g, total pore volume 0.75 cm3 / g, predominant Pore radii 100 Å and 10000 Å, face compressive strength 80 kp / cm2.

Example 8. 2.1 kg of washed hydrated decomposition product, er @ alten analogous to example 1, mixed with 0.9 liters of distilled water and treated with nitric acid in an amount of 0.02 mol HNO3 per 1 mol Al2O3. The treatment is at a temperature of 90 ° C for 1 hour under constant Stirring carried out. The plastic mass of the Aluminum tri-hydroxide is formed into cylindrical granules 3 mm in diameter and 4 to @ mm in length, dries at a temperature of 100 ° C and anneals at a @ Temperature of 550 ° C for 5 hours in the air flow with a consumption of 1000 St-1 off.

The harvested granulated active clay has the following values on: specific surface 340 m2 / g, total pore volume 0.5 cm3 / g, predominant Pore radii 50 Å and 500 Å, pressure resistance 180 kp / cm2.

Example 9. 1 kg of the decomposition product of aluminum trihydroxide, Follow the same procedure as in Example 1, mix with 7.6 liters of distilled water and hydrated at a temperature of 90 ° C for 10 hours under constant Stir.

It becomes a medium with pH = 11 through the excretion of sodium ions de @ @particles of the decomposition product are @produced into the water. @an ernalt thereby a hydrated decomposition product with a moisture in the compressed state of 45 weight percent. The specific surface of the at a temperature of 110 ° C dried hydrated product is @@ m2 / g. The X-ray phase analysis gives the following composition: 90 percent by weight bayerite aluminum trihydroxide and 10 weight percent pseudobönmit aluminum trihydroxide.

The hydrated decomposition product is filtered out and washed of the Na @ rium admixtures with a consumption of washing water of 9 liters per 1 kg Al2O3 in the precipitate, whereby a residual sodium content in the precipitate of 0.02 Percentage by weight, converted to Na2O, is obtained.

1. @ kg of the washed hydrated decomposition product mixed one with 1.4 liters of distilled water and treated with @alpitric acid in one Amount of 0.05 mol of NHO3 per 1 mol of Al2O3. The change takes place at a temperature carried out at 90 ° C for 4 hours with constant stirring. The one through the acid treatment The resulting plastic mass of aluminum tri-hydroxide is shaped into cylindrical granules 5 mm in diameter and 4 to 5 in length, dries at a temperature of 1000C and glows at a temperature of 450 ° C for 5 Hours in the air stream with a consumption of 1000 St-1.

The harvested granulated active clay has the following characteristics: specific surface area 380 m2 / g, total pore volume 0.90 cm3 / g, predominant pore radii less than 40 Å and 300 Å, face compressive strength 50 kp / cm2.

Example 10. 1 kg of the decomposition product of aluminum trihydroxide, If prepared analogously to Example 3, it is mixed with 7.5 liters of distilled water and hydrated at a temperature of 90 ° C for 8 hours under constant Rünren.

L5 becomes a medium with a pH value of 11, with deia the hydra ion of the decomposition product is going on, through the excretion of sodium ions Erzcut the particles of the decomposition product into the water. This gives you a hydrated decomposition product with a moisture in the compressed state of 5v weight percent. The specific surface area of the at a temperature of 110 ° C dried hydrated product is 80 m2 / g. The X-ray nasal analysis gives the following composition: 80 percent by weight bayerite aluminum trihydroxide and 20 weight percent pseudobönmit aluminum trihydroxide.

The further treatment of the named hydrated decomposition product (Filtration, washing, acid treatment, shaping of the granules, drying, annealing) is performed analogously to example 9 du @ ch.

The final product, granulated active clay, is cylindrical Represent granules of 3 mm diameter and 4 to 5 mm length with the following characteristics: specific surface 350 m2 / g, total pore volume 0.85 cm3 / g, predominantly pore size 40 Å and 300 Å, compressive strength 60 kp / cm2.

Example 11. 1 kg of the decomposition product obtained analogously to Example 4 of aluminum trihydroxide is mixed with 8 liters of distilled water and hydrated at a temperature of 100 ° C for 10 hours with constant stirring.

The pH value is determined by the separation of the sodium ions from the decomposition product set to 10.5 in the water. A hydrated decomposition product is thereby obtained with a moisture in the pressed state of 40 percent by weight.

The specific surface area was dried at a temperature of 110 ° C hydrated product is 90 m2 / g.

The X-ray phase analysis shows the following composition: 70 percent by weight Bayerite aluminum trihydroxide and 2u weight percent nordstrandite aluminum trihydroxide. and 10 weight percent pseudoboehmite aluminum trihydroxide.

The hydrated decomposition product is made up of the sodium impurities Washed analogously to Example 9.

1.5 kg of the washed hydrated decomposition product of aluminum trihydroxide Mix it with 1.2 liters of distilled water and treat it with nitric acid in an amount of 0.1 mol of HNO3 per 1 mol of Al2O3. The treatment is at one temperature carried out at 1100C for 6 hours with constant stirring. Further processing the plastic mass obtained by the acid treatment is analogous to example 9 carried out.

granulated active alumina is obtained with the following characteristics: specific surface 390 m2 / g, total pore volume 0.8 cm3 / g, predominant pore radii 50 Å and 10000 Å, face compressive strength 50 kp / cm2.

Example 12. 1 kg of the replacement product obtained analogously to Example 3 of aluminum trihydroxide is mixed with 7.5 liters of 5 iger aqueous ethylenediamine solution, , the pH of the mixture reaching 12. The hydration of the decomposition product is carried out at a temperature of 90 ° G for 8 hours with constant stirring, being a hydrated decomposition product with a moisture in pressed Condition of 45 percent by weight. The specific surface area of a Temperature of 110 ° C dried hydrated product is 60 m2 / g. the X-ray phase analysis gives the following composition: 90 percent by weight of Nordstrandite aluminum trihydroxide and 10 percent by weight of pseudo @ ohmite aluminum trihydroxide. Further treatment the hydrated decomposition product obtained is carried out analogously to Example 9, t by holding granulated active clay with fol6en- @ en Ke @@ values: Specific Surface 350 m2 / g, total pore volume 0.75 cm3 / g, predominant pore radii 50 Å and 5000 Å, face compressive strength 60 kp / cm2.

Example 13. The production of the granulated active alumina leads one analogous to Example 12 by with the difference, however, that the hydration at carried out at a temperature of 80 ° C for 10 hours with constant stirring will.

A hydrated product with a moisture is thereby obtained of 50 percent by weight, a specific surface area of @@ m2 / g, which is 80 percent by weight North strandite aluminum trihydroxide and 20 weight percent pseudoboehmite aluminum trihydroxide contains.

Example 14. A mixture consisting of aluminum trihydroxide with a particle size of at most 200 μm and air, is passed through a reactor with a fluidized bed of a solid heat carrier, the ring-shaped granules with an inner diameter of 2 mm and 4 mm outside diameter. The layer of the solid heat carrier has a Temperature of 550 ° C and a height of 2 @@ mm. The residence time of the aluminum trihydroxide particles in the Schic @ t of the hot heat transfer medium is 0.35 seconds.

During this time, the aluminum trihydroxide decomposes ois to the formation of an X-ray amorphous product with a specific surface of 300 m2 / g and ignition losses of 12 percent by weight.

1 kg of the decomposition product is mixed with 7.8 liters of distilled @ Water by converting a suspension with a @ onz @ n @ ration of 100 g / 1 on Al2O3, @ r. To create a medium with pH = 5, add the suspension 7 g Salpe-Lersäuje too. i) The hydration of the decomposition product is carried out in a Temperature of 20 ° C for 8 hours with constant stirring, whereby one hydrated decomposition product with a compression indentation of 55 percent by weight received. The specific surface area of a temperature hydrated product dried from 110 ° C is 210 m2 / g. The X-ray phase analysis results in the following composition: 70 percent by weight of pseudo @ önmit aluminum trihydroxide, 30% of the non-percent bayerite-Aluminiuntr ihydroxid and 18% by weight hydrargillite.

The further processing of the hydrated decomposition product and the properties of the end product are analogous to those described in Example 3.

Example 15. A mixture consisting of aluminum trihydroxide with a particle size of at most 200 µm and air, is passed through a reactor with the fluidized bed of a solid heat transfer medium in the form of cylindrical granules Made of aluminum with a diameter of 2 mm and a length of 3 mm. The fluidized bed of the solid The heat transfer medium has a temperature of 450 ° C and a level in the stationary layer of vi) mm. The mean time of contact of the aluminum trihydroxide particles with the hot solid heat carrier is 0.08 seconds. During this time, @s for the decomposition of the aluminum trihydroxide up to the formation of amorphous aluminum trihydroxide with a specific surface area of 210 m2 / g and ignition losses of 16 percent by weight.

1 kg of the amorphous aluminum trihydroxide, which is a decomposition product is mixed with 2 liters of distilled water and 5 g of nitric acid. The hydration is carried out at a temperature of 80 ° C and a pH of 7 for @ hours with constant stirring, a hydrated decomposition product being used with a moisture in pressed Condition of 62 percent by weight receives. The X-ray phase analysis gives the following composition: 75 percent by weight Pseudobönmit aluminum trihydroxide, 25 weight percent bayerite aluminum trihydroxide.

The further processing of the hydrated decomposition product is carried out carried out analogously to Example 1. The end product, the active clay, is spherical Granules with a diameter of 2.5 mm and 0.5 mm with the following characteristics: specific surface area 300 m2 / g, total pore volume 0.65 cm3 / g, predominant pore radii 100 Å and 1000 Å, compressive strength 70 kp / cm2.

Example 16. 1 kg of the decomposition product, obtained analogously to example 1, mix with 2.5 liters of distilled water by making a suspension with a concentration of 240 g / 1, converted to Al2O3. To create a Medium with pH = 5.8 is added to the suspension 6.5 g of nitric acid. The hydration the decomposition product is carried out at a temperature of 20 ° C. for 0.5 hours with constant intensive stirring. This gives a hydrated decomposition product with a moisture content in the pressed state of 60 @. The specific surface of the hydrated decomposition product dried at a temperature of 110 ° C petroleum 320 m2 / g. The X-ray phase analysis gives the following composition: 70 @ Pseudobönmit aluminum trihydroxide and 30 weight percent amorphous aluminum trihydroxide (Decomposition product of aluminum trihydroxide).

After hydration, the hydrated one is filtered Decomposition product and washes from @atrium with a water consumption for washing of 7.5 liters per 1 kg Al2O3 in the precipitate, with a residual sodium content in the precipitate of 0.02 percent by weight, converted to Na2O, is obtained.

2.1 kg of the hydrated decomposition product are mixed in 2 liters of distilled water until a suspension with one concentration is obtained of 260 g / 1, converted to Al2O3, and treated with nitric acid in an amount of 0.1 mol of HNO3 per 1 mol of Al2O3. The treatment will be at a tempe.

temperature of 130 ° C carried out for 4 hours with constant stirring, thereby a plastic case of aluminum trihydroxide is obtained.

The mass of aluminum @ riny @ roxide obtained by the acid treatment it is shaped into spherical granules, which are then dried at 100 ° C and at 500 ° C are annealed for 4 hours with an air consumption of 1000 St-1.

The final product, the granulated active clay, represents spherical ones Granules of 2.5 # 0.5 diameter with the following characteristics @ar: specific surface 320 m2 / g, total pore volume 0.55 cm3 / g, predominant pore radii 50 Å compressive strength 100 kp / cm2.

Example 17. 1 kg of the decomposition product, obtained analogously to example 14, mix with 2.5 liters of distilled water by making a suspension with a concentration of 250 g / 1, converted to Al2O3. To the generation of a medium with pH = 6, 6.3 g of nitric acid are added to the suspension. Di hydration of the decomposition product is carried out at a temperature of 20 ° C for 3 hours with constant stirring. This will give you a hydrated Decomposition product with a compressed moisture content of 55%. The specific Oper area of the hydrated decomposition product dried at a temperature of 110 ° C amounts to 370 m2 / g. The X-ray phase analysis results in the following composition: 60% Pseudobönmit aluminum trihydroxide and 40% amorphous aluminum trihydroxide (decomposition product).

During the hydration, the hydrated decomposition product is filtered off, washes from the sodium additions with a water consumption for washing of 7.5 Liters per 1 kg of Al2O3 in the precipitate, with a residual sodium content in the Reduction of 0.02 percent by weight, converted to Na2O, is obtained.

1.9 @ kg of the hydrated decomposition product is mixed with 1. @ liters of distilled water @is to achieve a suspension with one concentration of 2 @ 0 g / 1, converted to Al2O3, and treated with nitric acid in an amount of 0.1 mol of HNO3 per 1 mol of Al2O3. The treatment is carried out at 130 ° C for 5 hours carried out with constant stirring, thereby creating a plastic mass of Aluminum trihydroxide is obtained.

The mass of aluminum trihydroxide obtained by the acid treatment they are shaped into spherical granules, which are then dried at 100 ° C and at 550 ° C are annealed for 4 hours with an air consumption of 1000 St-1.

The En @ product, the gra @ ulized active clay represents spherical Granules of 2.5 t 0.5 mm in diameter with the following Characteristic values represents: spherical surface 360 m2 / g, total pore volume 0.5 cm @ / g, predominant Pore radii 40 Å, compressive strength 120 kp / cm2.

Claims (1)

PATENT CLAIMS: 1. Verf @@ ren for @ making granulated active Ton- @ r @ e, welc @ es decomposition of the aluminum trinydroxide under er- @ itzen, ver @ ischen of the old decomposition product with water, @a @@@ ration, @forms of granules, Drying at a temperature of 2 @ to 150 ° C and @ us @ annealing at one temperature encompasses from 4 @@ to @@ 0 ° C, which means that it is not possible to use the Decomposition of the aluminum trihydroxide when it comes into contact with a layer of a f @ sten @@armetragers, which has a temperature of 350 to 6 @@ ° C, and a @contact duration from 0.05 to 0.5 seconds @ urc @ leads, with a decomposition product in @orm amorphous @ en Aluminum tri @ ydroxyds obtained by mixing the said decomposition product with water up to a concentration of 100 to 500 g / 1, based on aluminum oxide, durd @ leads, after which the @hydratation of @decomposition @sproduktes at a temperature from 20 to 100 ° C and a pH value of 5 to 12 for 0.5 to 10 hours before @ immt and before the granules are formed, the hydrated decomposition product at a Temperature from 2 @ to 150 ° C with an acid, the water-soluble @ basic aluminum salts able to form, treated, 2. Method according to claim 1, d a d u r c h g e k e n n-Z e i c h n e t that the decomposition of the aluminum trihydroxi @ -in the fluidized bed of a solid heat transfer medium with a contact time of 0.05 to 0.5 seconds. @. Procedure according to claim 1, d a d u r c h, e k e n nz e i c h n e t that the hydration of the decomposition product at a temperature of 20 to 80 ° C and a pH value of 5 to 10 for 0.5 to @ hours, being a hydrated decomposition product containing pseudoboehmite-aluminum @ rihydroxide of at least 50 percent by weight. 4. The method of claim 1, d a d u r c n g e k e n nz e i c n n t, the times the hydration of the decomposition product at a temperature of 90 up to 100 ° C and a pH of 10.5 to 11 for @ up to 10 hours, wherein a hydrated decomposition product containing @ ayerite aluminum trihydroxide of at least 80 percent by weight. 5. The method of claim 1, d a a d u r c h g ek e n n z e i c Not that the hydration of the decomposition product takes place at a temperature of bQ up to 90 ° G and a pH @ert from 11 to IL in the @edium of 5% @ ethylenediamine during Carries out 8 to 10 hours, with a hydrated decomposition product having a content of an @ ordstrandit aluminum tri @ ydroxide of at least 8% by weight receives. 6. The method according to claim 1, d a d u r c h U e k e n n and z e i c h n e t that after the hydration before the acid treatment, the hydrated Separate decomposition product from the water and with water until a sodium content is achieved iii this Vun at most 0.02 percent by weight, not counting on Na2O, washes.