WO2018073332A1 - Fcc catalysts as nh3 binders - Google Patents

Fcc catalysts as nh3 binders Download PDF

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Publication number
WO2018073332A1
WO2018073332A1 PCT/EP2017/076676 EP2017076676W WO2018073332A1 WO 2018073332 A1 WO2018073332 A1 WO 2018073332A1 EP 2017076676 W EP2017076676 W EP 2017076676W WO 2018073332 A1 WO2018073332 A1 WO 2018073332A1
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Prior art keywords
ammonia
catalyst material
binding
aluminum silicate
aluminum
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PCT/EP2017/076676
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German (de)
French (fr)
Inventor
Frank Schmidtgen
Hans-Peter Noack
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Prometimpex Gmbh
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Priority to EP17800392.7A priority Critical patent/EP3529208A1/en
Publication of WO2018073332A1 publication Critical patent/WO2018073332A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/003—Storage or handling of ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/58—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0266—Other waste gases from animal farms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32

Definitions

  • the invention relates to a process for the binding of ammonia (NH 3), wherein the binder is a prepared aluminum silicate catalyst material.
  • Ammonia (NH3) is the basic material for the synthesis of nearly all other nitrogen compounds and is synthesized on a large scale.
  • Ammonia is formed when aluminum melts in the air when at least part of the aluminum reacts with the air-nitrogen first to aluminum nitrite and then further to aluminum hydroxide and ammonia with water:
  • aluminum salt slag is processed stepwise. After mechanical comminution, the aluminum metal is first separated by sieving. Subsequently, the salt components remaining in the remaining slag are washed out with water, wherein the aluminum reacts with water to aluminum hydroxide and hydrogen:
  • ammonia is collected in a gas purification and processed into fertilizer (ammonium sulfate). However, part of the ammonia remains dissolved in the water of the treated salt slag.
  • the thus prepared aluminum salt slag is manufactured and sold as a synthetic aluminum raw material under the name SEROX on an industrial scale.
  • the processed aluminum salt slag (eg SEROX) has a moisture content of up to 35% at the end of the treatment and has a muddy consistency.
  • the residual moisture can be reduced to less than 25%, so that the now moist, treated aluminum salt slag (eg SEROX) reaches a free-flowing consistency.
  • ammonia is released, which is also noticeable in the product that is in storage and disappears only after complete drying.
  • Ammonia is also produced by the decomposition of animal excrements by microorganisms in (mass) animal husbandry and housing. This can be a problem, because in addition to the unpleasant odor, larger amounts of ammonia can be detrimental to health, especially on the lungs of animals and humans. Ammonia is also one of the main causes of particulate matter formation. In all these cases, the release of ammonia for health reasons as well as for reasons of odor nuisance is undesirable.
  • Another object of the invention is to provide a process for binding ammonia which can be used in as many different areas as possible.
  • the binder preferably contains a consumed as a cracking catalyst aluminum silicate catalyst material (FCC catalyst).
  • FCC catalyst cracking catalyst aluminum silicate catalyst material
  • powdered aluminum silicate catalyst material with high Al203 content is obtained in large quantities as waste in the chemical industry. These are mainly used cracking catalysts used in the production of gasoline from crude oil.
  • the aluminosilicate catalysts can be provided at low cost, optionally after a previous treatment. It Thus, large amounts of waste, which are usually to be disposed of as hazardous waste, fed to a meaningful use.
  • Typical aluminosilicate catalysts used in hydrocarbon cracking petrochemicals consist of approximately equal proportions of silica and alumina. Most of them contain at least 40% by weight of aluminum oxide and also at least 40% by weight of silicon oxide. The remaining ingredients commonly included in such materials do not interfere with the binding of NH3.
  • the aluminum silicate catalyst material used according to the invention is a synthetic zeolite powder.
  • the usual cracking catalysts are synthetic zeolites with a comparatively high Al 2 O 3 content and a very regular porous crystal structure.
  • the zeolite powders are highly hygroscopic and are usually present in hydrated form, which greatly favors the uptake of NH3.
  • the zeolite powder is expediently subjected to a pretreatment by calcination prior to the use according to the invention.
  • a pretreatment is recommended to remove the hydrocarbon residues remaining in the material.
  • the zeolites pretreated in this way have virtually no ammonium in their cage structure, since this has been exchanged for lanthanum, hydrogen or sodium in the refinery during subsequent use and subsequent processing.
  • the zeolites are then again able to exchange ammonia as a cation in their cage structure. This succeeds above all with a sufficiently large concentration gradient to the ammonia.
  • the particle size there are practically no restrictions; it is possible to use the grain sizes of the FCC catalysts customarily used in the chemical industry.
  • the particle or granule size in the according to the invention a set zeolite powder, however, be easily adjusted in a range of 10 ⁇ to 1000 pm, if a special application should require. Accordingly, the material can be produced particularly easily also in the size that is needed for the best possible mixing with the other starting materials and thus for optimum NH3 bond.
  • the zeolite powder may be bound with a binder and water.
  • a binder and water any sizes and shapes can be realized, which can be easily adapted to the individual uses.
  • Suitable binders are conventional cement types, for example fast-binding Portland cement, but also ashes from the combustion of deinking residues of waste paper processing, which have a high mineral content.
  • zeolite powder is zeolite A, X, Y or ZSM
  • a particularly high proportion of alumina is ensured.
  • said zeolites in which the silicon to aluminum ratio is between 1 and 5, are used industrially in the chemical industry.
  • the following table shows the composition of an aluminum silicate catalyst material which is a cracking catalyst commonly used in the chemical industry:
  • An advantage of the method according to the invention is that the catalyst material after calcination as described can be easily further processed and fed to the respective use. It comes next to the pure NH3 bond to other benefits.
  • the processed aluminum salt slag (eg SEROX) is obtained as described by the treatment of salt slags from the secondary aluminum production.
  • the processed aluminum salt slag (eg SEROX) serves, among other things, as an aluminum raw material supplier for the production of cement, glass fibers (mineral wool) and on a trial basis also for glass.
  • the zeolites are added to the treated aluminum salt slag (eg SEROX) for the binding of ammonia in a proportion of 10% to 50%, preferably in a proportion of 20% to 40% and in particular in a proportion of 30%.
  • the treated aluminum salt slag eg SEROX
  • an increase in the rather low SiO 2 content of the processed aluminum salt slag eg SEROX (only about 10%) can be achieved (see Table 1). This may increase the attractiveness of such a mixture for other uses as well as enable a proportionately higher use in known uses.
  • Zeolites have long been known as porous minerals as aggregates for soils in agriculture or in the garden.
  • the addition of the zeolite powder according to the invention to fertilizers results in addition to the reduction of the ammonia odor in addition to the known advantages for the thus fertilized soils, such as a high water storage capacity.
  • Other substances can be easily added to a fertilizer produced in this way, the zeolites provide for its storage.
  • the zeolite powder according to the invention for reducing the ammonia odor as bedding in animal husbandry, for example in the stable or in the pet animal area, or as a filter material, for example in air filters the spent material may also be used as natural, low-odor nitrogen fertilizer without further treatment become.
  • the aforementioned uses are of course only preferred examples. In principle, the method according to the invention and its use are not limited thereto.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a method for binding ammonia (NH3) by means of a binder. The problem addressed by the invention is that of providing a method that can be used to bind ammonia such that an unpleasant odor and a risk to health are considerably reduced. This problem is solved according to the invention in that the binder contains a used aluminum silicate catalyst material (FCC catalyst).

Description

FCC-Katalysatoren als NH3-_Bindernittel Die Erfindung betrifft ein Verfahren zur Bindung von Ammoniak (NHa), wobei das Bindemittel ein aufbereitetes Aluminiumsilikat-Katalysatormaterial ist.  The invention relates to a process for the binding of ammonia (NH 3), wherein the binder is a prepared aluminum silicate catalyst material.
Ammoniak (NH3) ist der Grundstoff für die Synthese nahezu aller weiteren Stickstoffverbindungen und wird im großindustriellen Maßstab synthetisiert. Ammonia (NH3) is the basic material for the synthesis of nearly all other nitrogen compounds and is synthesized on a large scale.
Ammoniak entsteht beim Schmelzen von Aluminium an der Luft, wenn zumindest ein Teil des Aluminiums mit den Luft-Stickstoff zunächst zu Aluminiumnitrit und anschließend mit Wasser weiter zu Aluminiumhydroxid und Ammoniak reagiert: Ammonia is formed when aluminum melts in the air when at least part of the aluminum reacts with the air-nitrogen first to aluminum nitrite and then further to aluminum hydroxide and ammonia with water:
2AI + N2→ 2AIN 2AI + N2 → 2AIN
AIN + 3H20→ AI(OH)3 + NH3 Diese zweite Reaktion spielt eine wichtige Rolle bei der Aufbereitung von Aluminium-Salzschlacke, die in einem nicht unerheblichen Maß von bis zu 70 % beim Recycling von Aluminium-Schrott entsteht. AIN + 3H 2 0 → Al (OH) 3 + NH 3 This second reaction plays an important role in the treatment of aluminum salt slag, which is produced to a considerable extent by up to 70% in the recycling of aluminum scrap.
In einem vorbekannten Verfahren wird Aluminium-Salzschlacke stufenweise aufbereitet. Nach einer mechanischen Zerkleinerung wird zunächst das Aluminium-Metall durch Siebung abgetrennt. Anschließend werden die in der restlichen Schlacke verbliebenen Salzkomponenten mit Wasser ausgewaschen, wobei das Aluminium mit Wasser zu Aluminium-Hydroxid und Wasserstoff reagiert: In a previously known method, aluminum salt slag is processed stepwise. After mechanical comminution, the aluminum metal is first separated by sieving. Subsequently, the salt components remaining in the remaining slag are washed out with water, wherein the aluminum reacts with water to aluminum hydroxide and hydrogen:
2AI + 6H2O→ 2AI(OH)3 + 3H2 2Al + 6H2O → 2Al (OH) 3 + 3H 2
Ferner kommt es zu der zuvor beschriebenen Reaktion, bei der Aluminiumnitrit mit Wasser zu Aluminiumhydroxid und Ammoniak reagiert: Furthermore, there is the reaction described above, in which aluminum nitrite reacts with water to aluminum hydroxide and ammonia:
AIN + 3H20→ AI(OH)3 + NH3 AIN + 3H 2 0 → Al (OH) 3 + NH 3
Der Ammoniak wird dabei in einer Gasreinigung aufgefangen und zu Düngemittel (Ammoniumsulfat) weiterverarbeitet. Jedoch verbleibt ein Teil des Ammoniaks gelöst im Wasser der aufbereiteten Salzschlacke. Die so aufbereitete Aluminium-Salzschlacke wird als synthetischer Aluminium-Rohstoff unter dem Namen SEROX in industriellem Umfang hergestellt und vertrieben. The ammonia is collected in a gas purification and processed into fertilizer (ammonium sulfate). However, part of the ammonia remains dissolved in the water of the treated salt slag. The thus prepared aluminum salt slag is manufactured and sold as a synthetic aluminum raw material under the name SEROX on an industrial scale.
Die aufbereitete Aluminium-Salzschlacke (z. B. SEROX) weist zum Ende der Aufbereitung eine Feuchte von bis zu 35 % auf und hat eine schlammige Konsistenz. Durch Trocknung kann die Restfeuchte auf unter 25 % reduziert werden, wodurch die nun lagerfeuchte, aufbereitete Aluminium-Salzschlacke (z. B. SEROX) eine rieselfähige Konsistenz erreicht. Bei der Trocknung wird Ammoniak freigesetzt, der auch beim lagerfeuchten Produkt wahrnehmbar ist und erst nach vollständiger Trocknung verschwindet. The processed aluminum salt slag (eg SEROX) has a moisture content of up to 35% at the end of the treatment and has a muddy consistency. By drying, the residual moisture can be reduced to less than 25%, so that the now moist, treated aluminum salt slag (eg SEROX) reaches a free-flowing consistency. When drying, ammonia is released, which is also noticeable in the product that is in storage and disappears only after complete drying.
Auch von künstlichen und natürlichen Düngemitteln ist bekannt, dass der darin gebundene Ammoniak gasförmig freigesetzt wird. It is also known from artificial and natural fertilizers that the ammonia bound in it is released in gaseous form.
Ammoniak entsteht auch bei der Zersetzung von tierischen Exkrementen durch Mikroorganismen in der (Massen-) Tierhaltung und Stallhaltung. Dies kann zu einem Problem werden, denn neben dem unangenehmen Geruch können größere Mengen Ammoniak gesundheitsschädlich vor allem auf die Lungen der Tiere und Menschen wirken. Ammoniak ist in der Folge zudem eine der Hauptursachen für die Bildung von Feinstaubpartikeln. In all diesen Fällen ist die Freisetzung von Ammoniak aus gesundheitlichen wie auch aus Gründen der Geruchsbelästigung ungewünscht. Ammonia is also produced by the decomposition of animal excrements by microorganisms in (mass) animal husbandry and housing. This can be a problem, because in addition to the unpleasant odor, larger amounts of ammonia can be detrimental to health, especially on the lungs of animals and humans. Ammonia is also one of the main causes of particulate matter formation. In all these cases, the release of ammonia for health reasons as well as for reasons of odor nuisance is undesirable.
Es ist daher eine Aufgabe der Erfindung, ein Verfahren bereit zu stellen, dessen Einsatz Ammoniak insoweit zu binden vermag, dass eine Geruchsbelästigung und auch eine Gefährdung für die Gesundheit deutlich verringert wird. It is therefore an object of the invention to provide a method whose use ammonia is able to bind to the extent that an odor nuisance and also a risk to health is significantly reduced.
Eine weitere Aufgabe der Erfindung ist es, ein Verfahren zur Bindung von Ammoniak bereitzustellen, das in möglichst vielen verschiedenen Bereichen eingesetzt werden kann. Another object of the invention is to provide a process for binding ammonia which can be used in as many different areas as possible.
Nicht zuletzt ist es eine Aufgabe der Erfindung, ein Verfahren zur Bindung von Ammoniak bereitzustellen, dessen Verfahrensstoffe problemlos entweder recycelbar sind oder direkt einer weiteren Verwertung zugeführt werden können. Not least of all, it is an object of the invention to provide a process for binding ammonia, the process materials of which are either readily recyclable or can be fed directly to further utilization.
Gelöst wird diese Aufgabe durch ein Verfahren mit den Merkmalen des Anspruchs 1. Das Bindemittel enthält vorzugsweise ein als Cracking-Katalysator verbrauchtes Aluminiumsilikat-Katalysatormaterial (FCC-Katalysator). Zur Bindung von Ammoniak wird das Bindemittel verfahrensgemäß mit ammoniakhaltigen Ausgangsstoffen vermischt, um das Ammoniak aus diesen Ausgangstoffen zu binden. This object is achieved by a method having the features of claim 1. The binder preferably contains a consumed as a cracking catalyst aluminum silicate catalyst material (FCC catalyst). To bind ammonia, the binder is mixed according to the method with ammonia-containing starting materials in order to bind the ammonia from these starting materials.
Vorteilhafte Ausgestaltungen sind jeweils Gegenstand der abhängigen Ansprüche. Es ist darauf hinzuweisen, dass die in den Ansprüchen einzeln aufgeführten Merkmale auch in beliebiger und technologisch sinnvoller Weise miteinander kombiniert werden können und somit weitere Ausgestaltungen der Erfindung aufzeigen. Advantageous embodiments are the subject of the dependent claims. It should be noted that the features listed individually in the claims can also be combined with one another in any desired and technologically sensible manner and thus show further embodiments of the invention.
Ein im Sinne der Erfindung geeignetes pulverförmiges Aluminiumsilikat-Katalysatormaterial mit hohem Al203-Gehalt fällt in großen Mengen als Abfallstoff in der chemischen Industrie an. Es handelt sich hierbei vor allem um verbrauchte Cracking-Katalysatoren, die bei der Herstellung von Benzin aus Rohöl eingesetzt werden. Die Aluminiumsilikat-Katalysatoren können, gegebenenfalls nach einer vorherigen Aufbereitung, zu geringen Kosten bereitgestellt werden. Es werden also große Mengen von Abfallstoffen, die üblicherweise als Sondermüll zu entsorgen sind, einer sinnvollen Verwendung zugeführt. A suitable in the context of the invention powdered aluminum silicate catalyst material with high Al203 content is obtained in large quantities as waste in the chemical industry. These are mainly used cracking catalysts used in the production of gasoline from crude oil. The aluminosilicate catalysts can be provided at low cost, optionally after a previous treatment. It Thus, large amounts of waste, which are usually to be disposed of as hazardous waste, fed to a meaningful use.
Typische Aluminiumsilikat-Katalysatoren, die in der Petrochemie zum Cracken von Kohlenwasserstoff verwendet werden, bestehen zu etwa gleichen Teilen aus Siliziumoxid und Aluminiumoxid. Meist enthalten sie wenigstens 40 Gew.-% Aluminiumoxid und ebenfalls wenigstens 40 Gew.-% Siliziumoxid. Die übrigen Bestandteile, die in solchen Materialien üblicherweise enthalten sind, stören bei der Bindung von NH3 nicht. Typical aluminosilicate catalysts used in hydrocarbon cracking petrochemicals consist of approximately equal proportions of silica and alumina. Most of them contain at least 40% by weight of aluminum oxide and also at least 40% by weight of silicon oxide. The remaining ingredients commonly included in such materials do not interfere with the binding of NH3.
In der Regel handelt es sich bei dem gemäß der Erfindung verwendeten Aluminiumsilikat-Katalysatormaterial um ein synthetisches Zeolithpulver. Bei den üblichen Cracking-Katalysatoren handelt es sich nämlich um synthetische Zeolithe mit einem vergleichsweise hohen Al203-Gehalt und einer sehr regelmäßigen porösen Kristallstruktur. Die Zeolithpulver sind stark hygroskopisch und liegen üblicherweise in hydratisierter Form vor, was die Aufnahme von NH3 sehr begünstigt. As a rule, the aluminum silicate catalyst material used according to the invention is a synthetic zeolite powder. In fact, the usual cracking catalysts are synthetic zeolites with a comparatively high Al 2 O 3 content and a very regular porous crystal structure. The zeolite powders are highly hygroscopic and are usually present in hydrated form, which greatly favors the uptake of NH3.
Zweckmäßigerweise wird das Zeolithpulver vor dem erfindungsgemäßen Einsatz einer Vorbehandlung durch Kalzinierung unterzogen. Insbesondere wenn das Zeolithpulver als Abfall aus der Chemieindustrie stammt, ist eine derartige Vorbehandlung empfehlenswert, um die in dem Material verbliebenen Kohlenwasserstoffreste zu entfernen. The zeolite powder is expediently subjected to a pretreatment by calcination prior to the use according to the invention. In particular, if the zeolite powder originates as waste from the chemical industry, such a pretreatment is recommended to remove the hydrocarbon residues remaining in the material.
Die so vorbehandelten Zeolithe verfügen über nahezu kein Ammonium mehr in ihrer Käfigstruktur, da dieses im Laufe der Anwendung in der Raffinerie und der nachfolgenden Aufbereitung vor allem gegen Lanthan, Wasserstoff oder Natrium ausgetauscht wurde. Die Zeolithe sind im Anschluss erneut in der Lage, Ammoniak als Kation in ihre Käfigstruktur einzutauschen. Dies gelingt vor allem bei einem ausreichend großen Konzentrationsgefälle zum Ammoniak. The zeolites pretreated in this way have virtually no ammonium in their cage structure, since this has been exchanged for lanthanum, hydrogen or sodium in the refinery during subsequent use and subsequent processing. The zeolites are then again able to exchange ammonia as a cation in their cage structure. This succeeds above all with a sufficiently large concentration gradient to the ammonia.
Bezüglich der Partikelgröße gibt es praktisch keine Einschränkungen, es können die üblicherweise in der chemischen Industrie anfallenden Körnungen der dort verwendeten FCC-Katalysatoren eingesetzt werden. Vorteilhafterweise kann die Partikel- beziehungsweise Granulatgröße bei dem gemäß der Erfindung ein- gesetzten Zeolithpulver jedoch problemlos in einem Bereich von 10 μιη bis 1000 pm eingestellt werden, sofern eine spezielle Anwendung dies erfordern sollte. Entsprechend lässt sich das Material besonders leicht auch in der Größe herstellen, die für eine bestmögliche Vermischung mit den übrigen Ausgangsstoffen und somit für eine optimale NH3-Bindung benötigt wird. With regard to the particle size, there are practically no restrictions; it is possible to use the grain sizes of the FCC catalysts customarily used in the chemical industry. Advantageously, the particle or granule size in the according to the invention a set zeolite powder, however, be easily adjusted in a range of 10 μιη to 1000 pm, if a special application should require. Accordingly, the material can be produced particularly easily also in the size that is needed for the best possible mixing with the other starting materials and thus for optimum NH3 bond.
Beispielsweise kann das Zeolithpulver mit einem Bindemittel und Wasser gebunden werden. Hierbei sind beliebige Größen und Formen realisierbar, die den einzelnen Verwendungszwecken problemlos angepasst werden können. Als Bindemittel kommen übliche Zementsorten in Frage, beispielsweise schnellbindender Portlandzement, aber auch Asche aus der Verbrennung von Deinking-Rückständen der Altpapieraufbereitung, die einen hohen Mineralstoffgehalt haben. For example, the zeolite powder may be bound with a binder and water. Here, any sizes and shapes can be realized, which can be easily adapted to the individual uses. Suitable binders are conventional cement types, for example fast-binding Portland cement, but also ashes from the combustion of deinking residues of waste paper processing, which have a high mineral content.
Wenn es sich bei dem Zeolithpulver um Zeolith A, X, Y oder ZSM handelt, ist ein besonders hoher Anteil von Aluminiumoxid sichergestellt. Vorzugsweise werden die genannten Zeolithe, bei denen das Silizium-zu-Aluminium-Verhältnis zwischen 1 und 5 liegt, großtechnisch in der chemischen Industrie eingesetzt. When the zeolite powder is zeolite A, X, Y or ZSM, a particularly high proportion of alumina is ensured. Preferably, said zeolites, in which the silicon to aluminum ratio is between 1 and 5, are used industrially in the chemical industry.
Als Ausführungsbeispiel der Erfindung ist in der folgenden Tabelle die Zusammensetzung eines Aluminiumsilikat-Katalysatormaterials angegeben, bei dem es sich um einen Cracking-Katalysator handelt, wie er üblicherweise in der chemischen Industrie zum Einsatz kommt: As an embodiment of the invention, the following table shows the composition of an aluminum silicate catalyst material which is a cracking catalyst commonly used in the chemical industry:
Tabelle 1 Table 1
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000006_0001
Figure imgf000007_0001
Vorteilhaft an dem erfindungsgemäßen Verfahren ist, dass das Katalysatormaterial nach Kalzinierung wie beschrieben einfach weiterverarbeitet und der jeweiligen Verwendung zugeführt werden kann. Dabei kommt es neben der reinen NH3-Bindung zu weiteren Vorteilen. An advantage of the method according to the invention is that the catalyst material after calcination as described can be easily further processed and fed to the respective use. It comes next to the pure NH3 bond to other benefits.
Die aufbereitete Aluminium-Salzschlacke (z. B. SEROX) wird wie beschrieben durch die Aufbereitung von Salzschlacken aus der sekundären Aluminium- Gewinnung erhalten. Dabei dient die aufbereitete Aluminium-Salzschlacke (z. B. SEROX) unter anderem als Aluminium-Rohstofflieferant für die Produktion von Zement, Glasfasern (Mineralwolle) und versuchsweise auch für Glas. The processed aluminum salt slag (eg SEROX) is obtained as described by the treatment of salt slags from the secondary aluminum production. The processed aluminum salt slag (eg SEROX) serves, among other things, as an aluminum raw material supplier for the production of cement, glass fibers (mineral wool) and on a trial basis also for glass.
Die Zeolithe werden der aufbereiteten Aluminium-Salzschlacke (z.B. SEROX) zur Bindung von Ammoniak mit einem Anteil von 10 % bis 50 %, bevorzugt mit einem Anteil von 20 % bis 40 % und insbesondere mit einem Anteil von 30 % beigemengt. Zudem kann durch die Beimengung des erfindungsgemäßen Zeolith-Pulvers neben der Verringerung des Ammoniak-Geruchs weiterhin eine Erhöhung des recht niedrigen Si02-Gehaltes der aufbereiteten Aluminium-Salzschlacke (z.B. SEROX) (nur etwa 10 %) erreicht werden (siehe Tabelle 1). Dies kann die Attraktivität eines solchen Gemisches für weitere Verwendungen erhöhen als auch einen anteilsmäßig höheren Einsatz in bekannten Verwendungen ermöglichen. The zeolites are added to the treated aluminum salt slag (eg SEROX) for the binding of ammonia in a proportion of 10% to 50%, preferably in a proportion of 20% to 40% and in particular in a proportion of 30%. In addition, by adding the zeolite powder according to the invention, in addition to the reduction of the ammonia odor, an increase in the rather low SiO 2 content of the processed aluminum salt slag (eg SEROX) (only about 10%) can be achieved (see Table 1). This may increase the attractiveness of such a mixture for other uses as well as enable a proportionately higher use in known uses.
Zeolithe sind als poröse Mineralien seit langem als Zuschlagsstoffe für Böden in der Landwirtschaft oder auch im Garten bekannt. Das Zusetzen des erfindungsgemäßen Zeolith-Pulvers zu Düngemitteln führt neben der Verringerung des Ammoniak-Geruchs zusätzlich zu den bekannten Vorteilen für die so gedüngten Böden, wie beispielsweise eine hohe Wasserspeicherkapazität. Weitere Stoffe können einem so hergestellten Dünger problemlos beigemischt werden, die Zeolithe sorgen für seine Speicherung. Bei der Verwendung des erfindungsgemäßen Zeolith-Pulvers zur Verringerung des Ammoniak-Geruchs als Einstreu in der Tierhaltung, beispielweise im Stall oder im Heimtierbereich, oder als Filtermaterial, beispielsweise in Luftfiltern, kann das verbrauchte Material gegebenenfalls auch ohne weitere Aufbereitung als natürlicher, geruchsarmer Stickstoffdünger verwendet werden. Die genannten Verwendungsmöglichkeiten sind selbstverständlich nur bevorzugte Beispiele. Grundsätzlich ist das erfindungsgemäße Verfahren und seine Verwendung nicht hierauf beschränkt. Zeolites have long been known as porous minerals as aggregates for soils in agriculture or in the garden. The addition of the zeolite powder according to the invention to fertilizers results in addition to the reduction of the ammonia odor in addition to the known advantages for the thus fertilized soils, such as a high water storage capacity. Other substances can be easily added to a fertilizer produced in this way, the zeolites provide for its storage. When using the zeolite powder according to the invention for reducing the ammonia odor as bedding in animal husbandry, for example in the stable or in the pet animal area, or as a filter material, for example in air filters, the spent material may also be used as natural, low-odor nitrogen fertilizer without further treatment become. The aforementioned uses are of course only preferred examples. In principle, the method according to the invention and its use are not limited thereto.

Claims

Patentanspüche Patentanspüche
1. Verfahren zur Bindung von Ammoniak (NH3) unter Verwendung eines Bindemittels, 1. A method for binding ammonia (NH3) using a binder,
d a d u r c h g e k e n n z e i c h n e t, dass das Bindemittel ein verbrauchtes Aluminiumsilikat-Katalysatormaterial (FCC-Katalysator) enthält. The binder contains a spent aluminum silicate catalyst material (FCC catalyst).
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Aluminiumsilikat-Katalysatormaterial wenigstens 35 Gew.-% Aluminiumoxid und wenigstens 35 Gew.-% Siliziumoxid enthält. 2. The method according to claim 1, characterized in that the aluminum silicate catalyst material contains at least 35 wt .-% alumina and at least 35 wt .-% silica.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das3. The method according to claim 1, characterized in that the
Aluminiumsilikat-Katalysatormaterial bis zu 5 Gew.-% Magnesiumoxid enthält. Aluminum silicate catalyst material contains up to 5 wt .-% magnesium oxide.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Aluminiumsilikat-Katalysatormaterial bis zu 1 Gew.-% Titanoxid enthält. 4. The method according to claim 1, characterized in that the aluminum silicate catalyst material contains up to 1 wt .-% titanium oxide.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Aluminiumsilikat-Katalysatormaterial bis zu 5 Gew.-% Natrium- und/oder5. The method according to claim 1, characterized in that the aluminum silicate catalyst material up to 5 wt .-% sodium and / or
Kaliumoxid enthält. Contains potassium oxide.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Aluminiumsilikat-Katalysatormaterial bis zu 5 Gew.-% Selten-Erd-Oxide, insbesondere Lanthanoxid enthält. 6. The method according to claim 1, characterized in that the aluminum silicate catalyst material contains up to 5 wt .-% rare earth oxides, in particular lanthanum oxide.
7. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei dem Aluminiumsilikat-Katalysatormaterial um ein synthetisches Zeolithpulver handelt. 7. The method according to claim 1, characterized in that it is the aluminosilicate catalyst material is a synthetic zeolite powder.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Zeolithpulver vor Verwendung einer Vorbehandlung durch Kalzinierung unterzogen wird. 8. The method according to claim 7, characterized in that the zeolite powder is subjected before use of a pretreatment by calcination.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Zeolithpulver Zeolith A, X, Y oder ZSM enthält. 9. The method according to claim 7, characterized in that the zeolite powder contains zeolite A, X, Y or ZSM.
10. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das Zeolithpulver eine Partikelgröße zwischen 1 pm und10. The method according to any one of the preceding claims, characterized in that the zeolite powder has a particle size between 1 pm and
1000 pm aufweist. 1000 pm.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die Partikel zu Granulaten, Pellets oder sonstigen Körpern verarbeitet werden. 11. The method according to claim 10, characterized in that the particles are processed into granules, pellets or other bodies.
12. Verwendung von pulverförmigem oder granuliertem Cracking- Katalysator mit einem Aluminiumoxid-Gehalt von wenigstens 35 Gew.-% für die12. Use of powdered or granulated cracking catalyst having an alumina content of at least 35 wt .-% for the
Bindung von Ammoniak (NH3) gemäß einem der Ansprüche 1 bis 11. Binding of ammonia (NH 3) according to one of claims 1 to 11.
13. Verwendung nach Anspruch 12, wobei der Cracking-Katalysator mit einer aufbereiteten Aluminium-Salzschlacke vermengt wird, um die Freisetzung von Ammoniak aus der aufbereiteten Aluminium-Salzschlacke zu reduzieren. 13. Use according to claim 12, wherein the cracking catalyst is mixed with a treated aluminum salt slag to reduce the release of ammonia from the processed aluminum salt slag.
14. Verwendung nach Anspruch 13, wobei der Cracking-Katalysator der aufbereiteten Aluminium-Salzschlacke mit einem Anteil von 10 % bis 50 %, bevorzugt mit einem Anteil von 20 % bis 40 % und insbesondere mit einem Anteil von 30 % beigemengt wird. 14. Use according to claim 13, wherein the cracking catalyst is added to the treated aluminum salt slag in a proportion of 10% to 50%, preferably in a proportion of 20% to 40% and in particular in a proportion of 30%.
15. Verwendung nach Anspruch 12 für die Bindung von Ammoniak in15. Use according to claim 12 for the binding of ammonia in
Luftfiltern. Air filters.
16. Verwendung nach Anspruch 12 für die Bindung von Ammoniak in Dünger, wobei der Cracking-Katalysator mit dem Dünger vermengt wird. 16. Use according to claim 12 for the binding of ammonia in fertilizer, wherein the cracking catalyst is mixed with the fertilizer.
17. Verwendung von pulverförmigem Cracking-Katalysator mit einem Aluminiumoxid-Gehalt von wenigstens 35 Gew.-% als Einstreu in der Tierhaltung zur Bindung von Ammoniak (NH3) gemäß einem der Ansprüche 1 bis 11. 17. Use of pulverulent cracking catalyst having an alumina content of at least 35 wt .-% as bedding in the animal husbandry for binding of ammonia (NH 3) according to one of claims 1 to 11.
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