KR100839312B1 - In situ formed anionic clay-containing bodies - Google Patents

Abstract

The present invention relates to a method for producing crystalline anionic clay-containing bodies from sources comprising a trivalent metal source and a divalent metal source,

a) preparing a precursor mixture comprising a liquid, a divalent metal source and / or a trivalent metal source, at least one of which is insoluble in the liquid;

b) shaping the precursor mixture to obtain shaped bodies;

c) heat treatment of the formed body optionally carried out; And,

d) aging the shaped body to obtain a crystalline anionic clay-containing shaped body, and if there is no divalent or trivalent metal source present in the precursor mixture of step a), Then subject to addition to the shaped body prior to aging step d); And an additional condition that excludes the combination of an aluminum source as a trivalent metal source and a magnesium source as a divalent metal source. The essence of the invention is that the main part of the final amount of the anion clay is formed after molding, ie in situ of the shaped body. This becomes a friction resistor without the need to add a binder material.

Description

IN SITU FORMED ANIONIC CLAY-CONTAINING BODIES}

The present invention relates to a process for producing shaped crystalline anionic clay-containing shaped bodies. Examples of crystalline anionic clays include hydrotalcite, meixnerite, sjoegrenite, pyroaurite, stitchtite, reevesite, and hydrates. eardleyite, manassite and barbertonite. Crystalline anionic clays have several uses as absorbents in the field of catalysts. In most commercial applications, crystalline anionic clays are formed into shaped bodies, such as spheres. In all applications where the molded body is exposed to harsh process conditions and environments, such as oil refining applications, separation, refining and adsorption processes, it is of utmost importance that the integrity of the crystalline anionic clay-containing molded body remains intact to prevent wear.

In the prior art, crystalline anionic clays are generally combined with a binder or matrix material to obtain friction resistant shaped bodies. Mainly used binder or matrix materials are alumina and silica. Frequently used alumina precursors are aluminum chlorohydrol, soluble aluminum salts and acid dispersed pseudo-boehmite; Common silica precursors are silica sol, silicate, silica-alumina co-gel and combinations thereof.

EP-0 278 535 describes FCC additives or catalyst particles prepared using hydrotalcite and optionally zeolites in silica, silica-alumina or alumina matrices. As a result, hydrotalcite is slurried into a matrix precursor dispersion containing other catalyst components or precursors thereof, followed by spray-drying.

However, when crystalline anion clay is used in the matrix, the amount of active crystalline anion clay contained in the final formed body is relatively small. For performance reasons, it is a preferred embodiment that the shaped body consists mainly of active crystalline anionic clay. In addition, the addition of crystalline anion clay to the matrix material will adversely affect the physical properties of the crystalline anion clay, such as specific surface area, pore size distribution, and the like. Another disadvantage of using a matrix to obtain a friction resistant molded body is that the matrix / binder material most commonly used has some chemical activity which in some embodiments can cause undesirable side reactions. For example, one of the binder materials mainly used in FCC catalysts and additives is silica or silica based materials. This form of binder is not suitable for use in sulfur oxide removal additives as it has a detrimental effect on sulfur removal.

The present invention provides crystalline anionic clay-containing shaped bodies that are friction resistant without the presence and / or added amounts of binder. Indeed, it is provided that the crystalline anionic clay-containing shaped body is free of binder. The crystalline anion clay distribution in the crystalline anion clay-containing molded body of the present invention can be easily controlled as further described in the detailed description. As used herein, the term "crystalline anion clay" means a clay having an X-ray diffraction pattern that includes a particular X-ray diffraction pattern that has the properties of a particular type of anion clay.

The present invention describes a process for the preparation of crystalline anion clay-containing shaped bodies from a source comprising a trivalent metal source and a divalent metal source, comprising the following steps:

a) preparing a precursor mixture comprising a liquid, a divalent metal source and / or a trivalent metal source, at least one of which is insoluble in the liquid;

b) shaping the precursor mixture to obtain a shaped body;

c) heat treatment of the formed body optionally carried out; And

d) aging of the shaped bodies to obtain crystalline anionic clay-containing shaped bodies;

If a divalent or trivalent metal source is not present in the precursor mixture of step a), the source is subject to addition to the molding after forming step b) and before aging step d);

As an additional condition, the use of a combination of an aluminum source as a trivalent metal source and a magnesium source as a divalent metal source is excluded.

The essence of the present invention is that crystalline anionic clays are formed, i.e., after molding in situ. This results in a very good friction resistant molded body without the need to add binder material. In order to obtain a shaped body, a solid precursor must be present in the precursor mixture and at least one of the metal sources is preferably oxide, hydroxide, carbonate or hydroxy carbonate.

Molded bodies can be produced in a variety of ways. In a preferred embodiment of the method the trivalent metal source and the divalent metal source are combined into a slurry to form a precursor mixture. The precursor mixture is then shaped. The final shaped bodies are aged after optional heat treatment in the liquid to obtain crystalline anionic clay-containing shaped bodies.

Optionally, the precursor mixture is pre-aged before the forming step. The nuclei during the pre-aging step will be advantageous because it will be formed by enhancing the formation of crystalline anion clay during the aging step d). A precursor mixture is prepared from only one source, such as an oxide, hydroxide, or carbonate of a trivalent metal source or a divalent metal source, molded it, and then one or more other sources are added to the shaped body in the next process step. It is also possible to add. During the aging step, various sources react to produce crystalline anionic clay-containing shaped bodies. For example: an anion clay-containing, adding a trivalent metal source and a divalent metal source to form a precursor mixture, shaping to form a shaped body, and then comprising a large amount of said additive metal outside of the shaped body. It is also possible to use a combination of the two production routes described above for aging the shaped body in a liquid containing an additional metal source to form the shaped body.

Suitable trivalent metals include aluminum, gallium, indium, iron, chromium, vanadium, cobalt, manganese, cerium, niobium, lanthanum.

Aluminum sources include aluminum alkoxides, aluminum oxides and hydroxides such as transitional alumina, aluminum trihydrate (gibbsite, bayerite) and their heat treated forms [flash-calcined Alumina-containing clays such as alumina sol, amorphous alumina, (pseudo) bomite, kaolin, sepiolite and metakaolin, aluminum nitrate, aluminum chloride, aluminum chlorohydrate, sodium alumina Aluminum salts such as nate and aluminum sulphate. The coarse grades of aluminum trihydrate, such as Bauxite Ore Concentrate (BOC) or Bauxite, may also be used in the production process according to the invention.

When using clay as an aluminum source, it will be necessary to activate the alumina in the clay in acid treatment—eg, acid treatment bentonite—, base treatment, heat treatment, hydrothermal treatment, or a combination thereof. Acid treatments include acid treatments such as nitric acid, acetic acid, phosphoric acid, sulfuric acid and hydrochloric acid. The heat treatment is generally carried out at a temperature of 30 to 1000 ° C., preferably 200 to 800 ° C. for several minutes to 24 hours, preferably 1-10 hours.

Suitable gallium, indium, iron, chromium, vanadium, cobalt, cerium, niobium, lanthanum and manganese sources are oxides, hydroxides, carbonates, nitrates, chlorides, chlorohydrates and alkoxides, respectively.

Also mixtures of the trivalent metal sources mentioned above can be used, or doped trivalent metal sources can be used. The doped metal source is prepared by treatment of a trivalent metal source when additives are present. An example of a doped trivalent metal source is doped boehmite.

If more than one trivalent metal source is used, the metal sources may be bound to the precursor mixture in a particular order.

It is also possible to add trivalent metal sources after the forming step. In this case, the precursor mixture will already or will not contain a trivalent metal source. If a trivalent metal source is added after the forming step, it is preferably a liquid when in contact with the shaped body. This can be done by adding it to the shaped body and dissolving or dispersing the trivalent metal source.

Also other sources of trivalent metal than clay, for example aluminum trihydrate, will be pre-treated before contacting it with the moldings or before addition to the precursor mixture. The pre-treatments all relate to acid treatments, base treatments, heat and / or hydrothermal treatments, optionally when seeds are present.

Not all trivalent metal sources need to be converted to crystalline anionic clays. For example, the excess amount of aluminum source will be converted to alumina (typically in the form of transition alumina such as γ-alumina or (crystalline) boehmite) during the aging step. The compound will improve the binding to the shaped body and give the shaped body further desired functionality. For example, alumina provides an acid position for catalytic cracking, and (crystalline) boehmite also improves the nickel encapsulation ability of the shaped body. Formation of (crystalline) boehmite will be facilitated by adding seeds to the precursor mixture, to an aluminum source or during aging.

Suitable divalent metal sources include magnesium, zinc, nickel, copper, iron, cobalt, manganese, calcium and barium.

Suitable magnesium sources are oxides or hydroxides such as MgO and Mg (OH) ₂ , hydromagnesite, magnesium acetate, magnesium formate, magnesium hydroxy acetate, magnesium carbonate, magnesium hydroxy carbonate, magnesium bicarbonate, magnesium nitrate , Magnesium salts such as magnesium chloride, magnesium containing clays such as dolomite, saponite and sepiolite. Suitable zinc, nickel, copper, iron, cobalt, manganese, calcium and barium sources are oxides, hydroxides, carbonates, nitrates and chlorides, respectively.

Mixtures of the divalent metal sources mentioned above may also be used or doped divalent metal sources may be used. The doped metal source is made by treatment of a suitable dopant and divalent metal source. An example of a doped divalent metal source is doped brucite.

If more than one bivalent metal source is used, they may be bound to the precursor mixture in any process step in turn and / or after the shaping step. If a bivalent metal source is added after the forming step, a liquid is preferred when in contact with the shaped body. This can be done by dispersing or dissolving the divalent metal source and adding it to the shaped body.

The divalent metal source will be pre-treated before addition to the precursor mixture and / or before addition to the shaped body. All of the above pre-treatments will optionally include heat and / or hydrothermal treatment, acid treatment, base treatment in the presence of a seed.

Not all divalent metal sources need to be converted to crystalline anionic clays. For example, excess amounts of magnesium compounds will generally be converted to hydrated stone or magnesia. Certainly, the excess amount of the magnesium compound in the shaped particles will be referred to herein as magnesia. The presence of magnesia in the molded article will provide the desired functionality for the shaped article, for example metal trap capacity. The presence of magnesia provides a base position that makes the shaped body suitable for treating a strong acid stream of gas or liquid to remove or neutralize undesirable acid components.

Molded bodies comprising anionic clays, anionic clays and magnesia or anionic clays and aluminas may be used to purify and / or separate organic compounds in hydrocarbon streams, for example S-compounds and / or N- in gasoline and diesel fractions in FCC and hydrogenation processes. It will be used in methods involving the removal of compounds. The shaped bodies will also be used in water treatment for the removal of organic and inorganic compounds for the purpose of purifying, purifying and separating undesired compounds from the water stream including ion-exchange methods. The shaped body can also be treated in an industrial process to remove undesirable gas compounds such as chlorine, hydrochloric acid, sulfur compounds (eg SOx), nitrogen compounds (eg NOx, ammonia) and phosphorus compounds. Will be used.

Various process steps will be described in detail below.

Preparation of Precursor Mixtures

In this step, the precursor mixture is prepared from a trivalent metal source and / or a divalent metal source in the liquid. All liquids are suitable so long as they do not harmfully interfere with the various sources. Suitable liquids are water, ethanol and propanol. The amount of liquid is obtained with a mixture having a milky substance, and a mixture having a high viscosity such as, for example, a dough can be suitably selected. If more than one source is used as the precursor mixture, the source may be added as a solid, but may be added to the liquid except for a mixture of aluminum and magnesium sources. Various sources may be added in turn.

The preparation of the precursor mixture can be carried out at room or elevated temperature with or without stirring. Optionally, the precursor mixture and / or the individual sources are homogenized, for example by grinding, sonication or high shear mixing. The treatment will also reduce the particle size of the metal source (s) and / or increase the reactivity.

Any conversion to crystalline anionic clays will occur upon combining the various sources. At least 5% by weight of the final total amount of the anionic clay is already formed, but in the present invention it is also basic that the conversion is carried out after the shaping step. Generally at least 25% by weight, preferably at least 50% by weight, more preferably at least 75% by weight and most preferably 80-95% by weight of the final amount of anionic clay in the shaped body is formed after molding, and then This is because a molded article having a high physical strength at is obtained.

The molar ratio of divalent to trivalent metal in the anion clay can vary from 1 to 10, preferably from 1 to 6, most preferably from 2 to 4.

If desired, organic or inorganic acids and salts may be added to the precursor mixture, for example for pH control, or added to either the trivalent metal source and / or the divalent metal source before they are added to the precursor mixture. will be. Examples of preferred modifiers are ammonium bases because no harmful anions remain in the anion clay upon drying.

As mentioned above, the precursor mixture will be pre-aged before the forming step. The pre-aging temperature will be in the range of 30 ° C. to 500 ° C., and will be carried out at elevated temperatures or in an environment such as self-generated pressure at temperatures above 100 ° C. Aging time can vary from 1 minute to several days, for example 7 days.

The presence of interlayer-charge balanced anions will be controlled by the addition of specific anions to any of the precursor mixtures and / or trivalent and / or divalent metal sources. In general, the pH should be adjusted to represent the desired form of interlayer charge balanced anions (many charge balanced anions are pH dependent). Examples of suitable anions are carbonate, bicarbonate, nitrate, chloride, sulfate, bisulfate, vanadate, tungstate, borate, ^{_{phosphate, HVO 4 -, V 2 O}} 7 4-, HV 2 O 12 4-, V 3 ^{_{O 9 3-, V 10 O 28}} -6, Mo 7 O 24 6-, PW 12 O 40 3-, B (OH) 4 -, [B 3 O 3 (OH) 4] -, [B 3 O 3 (OH) ₅ ] ^2- , B ₄ O ₅ (OH) ₄ ^2- , HBO ₄ ^2- , HGaO ₃ ^2- , CrO ₄ ^2- and pillaring anions such as keggin-ions, Mate, acetate, and mixtures thereof. The presence of certain anions, such as carbonates, bicarbonates, sulfates and nitrates, affects the formation of byproducts such as hydrated stones. In addition, the addition of ammonium hydroxide promotes the formation of myxelite, while the addition of ammonium carbonate promotes the formation of hydrotalcite. In the case where it is desired that a particular anion be within the anion clay, the reaction conditions in further preparation steps should be adjusted to avoid the exchange of anions by other less preferred anions.

Molding

Suitable molding methods include spray-drying, pelletizing, granulating, extruding, beading (optionally combining kneading) or any other conventional molding method used in the field of catalyst and absorbent or combinations thereof. Include. The amount of liquid present in the precursor mixture must be adjusted to the particular molding step performed. The liquid used in the precursor mixture at the end will have to be partially removed and / or add additional or other liquids and / or change the pH of the precursor mixture to gel the precursor mixture and thus make it suitable for molding. Will be. Various additives mainly used in various molding methods such as extrusion additives will be added to the precursor mixture used for molding.

Heat treatment

After molding the molded body will optionally undergo a heat treatment. The treatment increases the physical strength of the particles. The heat treatment will be carried out in an inert environment or in an oxygen-containing environment, a hydrogen-containing environment at steam, at a range of temperatures from 30 ° C. to 900 ° C. for a few minutes to 24 hours. For example, heat treatment is inherently related, as in spray-drying, and no further heat treatment will be necessary.

Aging

In this step, the shaped body is immersed in a protic liquid or a protic gas medium. Crystallization of the crystalline anion clay is performed during the aging step. Suitable protic liquid or gaseous media are those in which the shaped body is not soluble in water, ethanol, methanol, propanol, steam, gas water and gas ethanol. Increasing the temperature and / or pressure may reduce the aging time. Aging can be performed under autogenous conditions. Aging temperature will range from 30 ° C to 500 ° C. Aging time can vary from one minute to several days, for example seven days. For some purpose, it is advantageous to carry out several aging steps, optionally with an intermediate drying step, after which the optional calcination step is carried out. For example, the aging step at a temperature below 100 ° C. may be carried out after the hydrothermal aging step is carried out under a self-generated pressure at a temperature above 100 ° C., and vice versa.

As will be described in further detail below, the additives may be added during, before, or after aging. By the addition of specific anions to the aging medium at controlled pH, the presence of interlayer-charge balanced anions can be controlled. Examples of suitable anions are carbonate, bicarbonate, nitrate, chloride, sulfate, bisulfate, vanadate, tungstate, borate, ^{_{phosphate, HVO 4 -, V 2 O}} 7 4-, HV 2 O 12 4-, V 3 ^{_{O 9 3-, V 10 O 28}} -6, Mo 7 O 24 6-, PW 12 O 40 3-, B (OH) 4 -, [B 3 O 3 (OH) 4] -, [B 3 O 3 (OH) ₅ ] ^2- , B ₄ O ₅ (OH) ₄ ^2- , HBO ₄ ^2- , HGaO ₃ ^2- , columnar anions such as CrO ₄ ^2- and keggin-ions, formate, acetate, and their Mixture. It is also believed that the presence of certain anions, such as carbonates, bicarbonates, sulfates, and / or nitrates, affects the formation of byproducts such as hydrated stones. In addition, the addition of ammonium hydroxide promotes the formation of quinnerite clay and the addition of ammonium carbonate promotes hydrotalcite clay formation.

In some embodiments, it is desirable to have additives present in and / or in the shaped bodies according to the invention. Suitable additives include rare earth metals (especially Ce and La), Si, P, B, Bi, group VI metals, group VIII metals, precious metals such as Pt and Pd, alkaline earth metals (eg Ca and Ba), and / or transitions Compounds of metals (eg Mn, Fe, Ti, V, W, Zr, Cu, Ni, Zn, Mo, Sn). Additives or precursors thereof may be added to the mixture in any of the manufacturing steps of the present invention or separately. For example, it may be deposited on the molded body before, during or after aging, or may be added to any and / or precursor mixture of the trivalent metal or divalent metal source. Suitable sources of metal compounds and non-metal compounds are oxides, halides such as chlorides, sulfates, nitrates and phosphates. As mentioned above, the additive will be added at any stage of manufacture. It is particularly advantageous for controlling the distribution of additives in shaped bodies. ^{_{HVO 4 -, V 2 O 7}} 4-, HV 2 O 12 4-, V 3 O 9 3-, V 10 O 28 -6, Mo 7 O 24 6-, PW 12 O 40 3-, B (OH) ^{_{4 -, [B 3 O 3}} (OH) 4] -, [B 3 O 3 (OH) 5] 2-, B 4 O 5 (OH) 4 2-, HBO 4 2-, HGaO 3 2-, CrO Calcination and rehydration of the shaped body is possible when an anion such as ₄ ^2- , keggin-ion, formate, acetate, and mixtures thereof are present. It is also possible to reduce the metals during and / or after production, hydrogenation or sulfiding. With the aid of the additive the shaped body will be provided with the desired functionality or the desired functionality will be increased by the addition of the additive. The suitability of anionic clay-containing shaped bodies for the removal of SOx and / or NOx compounds in the FCC will be improved with the addition of Ce and / or V. The presence of V, W, Mo and / or Zn improves the suitability for the removal of S-compounds in gasoline and diesel fractions of the FCC. The presence of Zn and / or Mn improves metal trapping. As mentioned above, the functionality will also be increased with the excess and use of trivalent and / or divalent metal sources. The combination of these measures increases the effect.

Crystalline anionic clay-containing shaped bodies can be prepared from matrix or filler materials (e.g. kaolin clay, phosphorylated kaolin, titanium oxide, zirconia, alumina, silica, silica-alumina and bentonite) and molecular sieves (e.g. zeolite Y , Conventional catalyst components such as USY zeolite, ion-exchanged zeolite, ZSM-5, beta-zeolite and ST-5). The conventional catalyst component will be added before the forming step. Since the anion clay is formed in place, the resulting body will have a homogeneous distribution of the anion clay and the catalyst component. In the process according to the invention multiple-functional bodies will be prepared which can be used as catalysts or catalyst additives.

The process according to the invention may be carried out in batch or continuous mode, optionally in continuous multi-step operation. The method may also be carried out in partial batches and partially continuous.

If desired, the crystalline anion clay-containing shaped body produced by the present invention will perform ion-exchange where the interlayer charge-balancing anion of clay is replaced with another anion. The other anions are mainly located in the anionic ^{_{clay, HVO 4 -, V 2 O}} 7 4-, HV 2 O 12 4-, V 3 O 9 3-, V 10 O 28 6-, Mo 7 O 24 6-, PW ^{_{12 O 40 3-, B (OH}} ) 4 -, [B 3 O 3 (OH) 4] -, [B 3 O 3 (OH) 5] 2-, B 4 O 5 (OH) 4 2-, HBO Columnar anions such as ₄ ^2- , HGaO ₃ ^2- , CrO ₄ ^2-, and kegin-ions. Examples of suitable columnar anions are shown in US 4,774,212 which is incorporated by reference for this purpose. The ion-exchange can be carried out as soon as the crystalline anion clay is formed.

The invention further deals with crystalline anionic clay-containing shaped bodies obtainable by the process according to the invention. As mentioned above, the shaped bodies are compared to clay-containing shaped bodies prepared by dispersing clay in a matrix or binder material and then molding a clay-containing composition which is not yet present in the matrix or binder material to be added to the crystalline anionic clay. It has high mechanical strength and friction resistance. The process according to the present invention is characterized in that the crystalline anionic clay-containing molded body is at least 25% by weight, preferably at least 50% by weight, more preferably at least 70% by weight, more preferably at least 90% by weight of crystalline anion clay. It can be prepared to contain. Although the binder material may be present in the shaped crystalline anionic clay-containing shaped bodies according to the invention as a result of, for example, more aluminum sources present in the precursor mixture, any binder present in the shaped bodies according to the invention is shown schematically in FIG. It will exist as a discontinuous phase, as shown. This is different from clay-containing molded bodies produced by conventional methods by embedding clay in a matrix or binder material, for example, as shown in FIG. 2, in which the binder material in the molded body is in continuous phase. It is of course possible to incorporate crystalline anionic clay-containing shaped bodies into the matrix. In this case, it is obtained that the composite particles are included in the binder material as shown schematically in FIG. 3 and include a crystalline anion clay-containing molded body selectively having the binder material on the discontinuous phase.

1 is a schematic view of a molded article according to the present invention.

2 is a schematic view of a molded article according to the prior art.

3 is a schematic view of a composite particle comprising a molded article according to the present invention.

In FIG. 1, the schematic shows a molded crystalline anion clay-containing molded body 1 according to the invention comprising a binder material 3 and a crystalline anion clay 2 in a discontinuous phase.

In FIG. 2, the schematic diagram shows a molded crystalline anion clay-containing molded body 1 according to the prior invention comprising a binder material 3 and a crystalline anion clay 2 in a continuous phase.

In FIG. 3, the schematic diagram shows a composite particle comprising a crystalline anion clay-containing shaped body 1 comprising a binder material 3 and a crystalline anion clay 2 in a discontinuous phase embedded in the binder material 3 ′ in a continuous phase. Indicates.

During or before being used for catalyst application, anionic clays are often heat treated to obtain so-called solid solutions or spinels. The present invention also deals with composite particles and shaped bodies containing anionic clays which have been heat treated.

The invention is illustrated by the following examples.

Example 1

The instant calcined gibbsite, Cp grades were slurried in water with zinc carbonate. The Zn: Al atomic ratio is two. The slurry was homogenized by shear mixing. The slurry was filtered and the filter cake was granulated to form a shaped body. The molded body was calcined at 250 ° C. for 4 hours. The calcined shaped body was slurried in water and aged at 65 ° C. for 6 hours. The pH of the slurry was titrated to 6.5 with nitric acid. XRD analysis shows the presence of Zn-Al hydrotalcite and some ZnO in the shaped body.

Example 2

Instant-calcined Gibbsite, Cp grades were slurried in water containing iron (II) nitrate. The slurry was homogenized by shear mixing. The slurry was filtered and the filter cake granulated to form a shaped body. The molded body was calcined at 250 ° C. for 4 hours. The calcined shaped body was slurried in water and aged at 65 ° C. for 18 hours. XRD analysis shows the presence of Fe-Al hydrotalcite in the shaped body.

Example 3

Gallium nitrate was added to the aqueous slurry containing magnesium oxide. The slurry was shear mixed to homogenize and spray-dried to form a shaped body. The molded body was calcined at 250 ° C. for 4 hours. The calcined shaped body was slurried in water and aged at 65 ° C. for 18 hours. The pH of the slurry was titrated to 9.5 with ammonium hydroxide. XRD analysis shows the presence of Mg-Ga hydrotalcite in the shaped body.

Example 4

Aluminum trihydrate (46.5) was slurried in 466 g demineralized water containing 389.6 g Fe (NO ₃ ) ₂ 6H ₂ O. The total amount of slurry is 976 g and has a solids content of 13% by weight. The final slurry was aged and the final product granulated. The granules were aged hydrothermally at 175 ° C. for 2 hours. The product was dried at 110 ° C. overnight. XRD analysis shows the formation of Fe-Al anion clay.

Example 5

Example 1 was repeated except that cobalt nitrate was used instead of zinc carbonate. The process conditions are the same. The PXRD pattern of the final product shows the formation of Co-Al anion clays.

Example 6

Ferric hydroxide was prepared by precipitation from the ferric nitrate solution. The ferric hydroxide was precipitated from the ferric nitrate solution by adding ammonium hydroxide in an inert environment of nitrogen. The two precipitates were combined and shear mixed. Half of the mixture was aged at 85 ° C. for 8 hours in a sealed vessel. The other half was aged at 150 ° C. for 30 minutes. The two mixtures were filtered and the filter cake granulated into shaped bodies. The shaped bodies were calcined at 200 ° C. for 4 hours and then rehydrated in water at 65 ° C. for 6 hours. The product was dried at 110 ° C. PXRD shows the formation of Fe ³⁺ Fe ²⁺ -anion clay in two products.

Claims (23)

A process for producing crystalline anionic clay-containing bodies from sources comprising a trivalent metal source and a divalent metal source, a) preparing a precursor mixture comprising a liquid, a divalent metal source and / or a trivalent metal source, at least one of which is insoluble in the liquid; b) shaping the precursor mixture to obtain shaped bodies; c) heat treatment of the formed body optionally carried out; And d) aging of the shaped bodies to obtain crystalline anionic clay-containing shaped bodies, If a divalent or trivalent metal source is not present in the precursor mixture of step a), the source is subject to addition to the molding after forming step b) and before aging step d); A method for producing a crystalline anion clay-containing molded article, characterized by further comprising except that a combination of an aluminum source as a trivalent metal source and a magnesium source as a divalent metal source is used. The method of claim 1, Wherein said precursor mixture comprises a divalent metal source and a trivalent metal source. The method of claim 1, Wherein said precursor mixture is pre-aged prior to forming step b). The method of claim 2 or 3, In step a), a trivalent metal source and a magnesium source are combined to obtain a precursor mixture. The method according to any one of claims 1 to 3, The trivalent metal source is present in the precursor mixture; A divalent metal source is added after forming step b); The trivalent metal source is selected from the group consisting of oxides, hydroxides, carbonates, hydroxy carbonates, and mixtures thereof. The method according to any one of claims 1 to 3, The divalent metal source is present in the precursor mixture, the trivalent metal source is added after the forming step b) and the divalent metal source is a group consisting of oxides, hydroxides, carbonates, hydroxy carbonates and mixtures thereof A process for the preparation of crystalline anionic clay-containing shaped bodies, characterized in that it is selected from The method according to any one of claims 1 to 3, Wherein said trivalent metal source is selected from aluminum trihydrate, its heat treated form or boehmite. The method according to any one of claims 1 to 3, The trivalent metal source may include kaolin, phosphated kaolin, bentonite, metakaolin, and / or bauxite. Manufacturing method. The method according to any one of claims 1 to 3, And said divalent metal source comprises magnesium oxide. The method according to any one of claims 1 to 3, Wherein at least one aging step is carried out, optionally a drying step is carried out in the middle, and then a calcination step is optionally carried out. The method according to any one of claims 1 to 3, An additive is added in step a), wherein the crystalline anionic clay-containing molded body is produced. The method according to any one of claims 1 to 3, A method for producing a crystalline anionic clay-containing molded body, wherein the additive is added after the molding step b). The method according to any one of claims 1 to 3, A method for producing a crystalline anionic clay-containing molded body, wherein the additive is added at any one of the aging steps. delete delete delete delete delete delete delete delete delete delete

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