LU87213A1 - INORGANIC MATERIAL AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

87 Ο ΤΊΐζ GRAND-DUCHÉ DE LUXEMBOURG - 'BL 4107 -

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~ * ~, *. **, ......................... Monsieur le Ministre », du______________11 May 1988 de l'Economie et des Classes Moyennes _. . . ,: ¾¾¾ Service de la Propriété Intellectuelle litre delivre ------------------------ egô LUXEMb0URG '

Demande de Brevet d'invention -----------------------------: -------- (1) · I. Requête ______ B.he.Ln.i.sch .-. Vy.estfâüs.ch.e..Ka.lkw.er] se.AktLeages, eJis.chatt ______________________ (2) _D „- ^ 5.6ÛQ ________________________.__ _représenté par: ET FREYL1NGER et E. MEYERS Ina. Cons. en PI_____. _____________________________________________46. rue du Cimetière LUXEMBOURG _______________________ (3) ____________________________________mandataires_____________________________________________ dépose (nt) ce ........ o.nz.e ... maL.mL] .... n.fiüf .. ^ ___________ (4) à heures, au Ministère de l'Economie et des Classes Moyennes, à Luxembourg: 1. la présente requête pour l'obtention d'un brevet d'invention concernant: _____ "Inorganic material and process for its production" ________ (5) 2. la description en langue _____ "allemande___________________de l'invention en trois exemplaires; 3.- ................................... planches de dessin, en trois exemplaires; 4. la quittance des taxes versées au Bureau de l’Enregistrement à Luxembourg, le .98.8 _________; 5. la délégation de pouvoir, datée de __________ Ey.BE®TÎ_? L _____________ le ._13 ._ ?. V_C..Ü 1,988 __________________; 6. le document d’ayant cause (authorization); déclarefnt) en assumant la responsabilité de cette déclaration, que l '(es) inventeurs) est (sont): (6) __________ Dr.Zran2 ... CJem.en.tî., ..... Emharislras.se..ll , ..... 8.Q.8.Q ... EMMERJ..N.G ___________________________ ______Dr Günter Achenbach, Neuenhöhe 80, 5632 WERMELSKIRCHEN 1_______________ _____ N.Qr.b..er..t .... Ä.J .sch.er .., -. Lan.gendo.rfer.slrasse .... lS, ._ 5.6Q3 ..- W.UELERÄlld ___________________ "........... Günter Fischedick. Württembergstrasse 11. 4030 RATINGEN 6_____________________ revendiuueCnt) pour la susdite demande de brevet la priorité d'une (des) demande (s) de (7) ________ br.evMJli.oy.aD.ti.QD ...: ____________________________________________ déposée (s) en (8) A11emagne FéHéng 1 a____ le (9) _________ 27 May 1987__________________________________________________________________________________________________________________________________________ sous le N ° (10) ________ P 37 17 848.2 _____________________________________________________________________ au nom de (11) ........... Rheinisch-Westfälische Kalkwerke Aktiengesellschaft___.

élit (élisent) domicile pour lui (elle) et, si désigné, pour son mandataire, à Luxembourg____ 46 »rue du Cimetière .... ................ ________ λ ___-___ ¢ 2) sollicitent) la délivrance d'un brevet d'invention pour l'objet décrit et représenté dans les annexes susmentionnées, avec ajournement de cette délivrance à __________________________________........____________________________ yüL ______.: ... 1_______________________________mois. (13)

Le déposant / mandatairei-j / ^. ... .. —.............................___________: .________________________________ (14) / d Π. Procès-verbal de Dépôt

La susdite demancßräe brevet d'invention a été déposée au Ministère de l'Économie et des Classes Moyennes, Service de la Propriété InteUpetflSIÎS'àiuxembourg, en date du: 11 Ma i -1988 (^ / ιίΗκ Pr. Le Ministre de l'Économie et des Classes Moyennes,

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à .......? ,, ±, E ........ heures / y / w d.

~ tfiprppriété intellectuelle, A 68007 _; _ "_ / / __ ~ __ r ^ i, n EXPLICATIONS RELATIVES AU FORMUXÂR & BFîÆpÔT. = / \ / (Ow K (1) s'il ya lieu“ Demande de certificat d'âîdition au brevet principal , lia demande de brevet principal No ..... JL ·. ......... ”- (2) inscrire les nom, prénom, profession, / LJ '“ address du demandeur, lorsque celui-ci est unparticuHer ou les dénomination sociale, formme juridique, adresse du siège / s ^ al, Lorsque le demandeur est une personne morale - (3) inscrire les nom, prénom, adresse du mandataire agrée, conseil en propriété industrial, muni d'un pouvoir spécial , s'il ya lieur'représenté par ............ agissant en qualité de mandataire ”- (4) date de dépit en toutes lettres - (S) utrë de (invention - (6) - inscrire les noms, prénoms, adresses des inventeurs ou l'indication ”(voir) désignation séparée (suivra)”, lorsque la dési-enation se fait ou se fera dans un document séoaré. ou encore l'indication "ne oas mentionner”, lorsoue l'inventeur screens ou sienera un docum ent de non-mention à joindre ä une désienadon BL 4107 / ·

Revendication de la priorité de la demande de brevet déposée en Allemagne le 27 Mai 1987 No. P 37 17 848.2 Mémoire descriptif déposé à l'appui d'une demande de brevet d'invention pour: "Inorganic material and process for its production"

Rheinisch-Westfälische Kalkwerke Aktiengesellschaft D - 5600 - WUPPERTAL 11 - Dornap "*

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Rhenish-Westphalian R19l2vol2

Kalkwerke Aktiengesellschaft 5 5600 Wuppertal 11 - Dornap May 26, 1987 10 Inorganic material and process for its manufacture 15 Description

The invention relates to an inorganic material of high open porosity based on cement and / or lime and 20 SiÛ2-rich aggregate and at least one porosity agent and a method for its production.

The term "cement" includes any type of inorganic, at least latent hydraulic binder.

25 The term "SiO ^ -rich additive" denotes siliceous material that can be involved in a hydrothermal reaction.

Such inorganic materials are used to produce gas and foam concrete, which is understood to mean a fine-pored concrete loosened up by gas or foam or by other means, which is foamed from cement, building lime and quartz sand and / or silica-rich fly ash, mixed with water, and then 35 are cured hydrothermally, is produced.

- 2 - Further information can be found in the "Concrete Calendar 1985, Part I, pp. 86, 87".

The gas and foam concrete products are then used as heat-insulating building materials in building construction.

5

The high pore volume is therefore only used "passively" for thermal insulation.

A completely different field of application of inorganic materials such as limestone chippings are filters, where fine particles to be separated are held on the surface of the filter medium primarily by adhesive forces, and possibly also for a chemical reaction between the surface of the filter material and the passed medium can come.

However, the filter effect is very limited due to the small surface area of the limestone chippings, which are otherwise non-porous.

20 Within the scope of flue gas desulfurization are among others

Wet processes are known in which, using burnt lime or limestone as the absorbent, the gaseous pollutants, in particular SO2, are washed out of the flue gas and chemically bound. A high-purity gypsum is produced as the end product 25.

In the context of stricter requirements for environmental protection measures, the cleaning of polluted gases and liquids is also in the foreground.

30th

This is where the object of the invention is based, which is to provide a possibility for cleaning 35 - 3 -

Offer pollutant-laden gases and liquids that ensure the greatest possible intensive and extensive reduction of pollutants with a simple structure. The aim is to use filter or absorption materials that are as simple and inexpensive to manufacture as possible and to ensure simple process management. The aim of this is to also open up areas of application for emitting systems which, for example because of their size or age, only permit relatively simple cleaning measures for cost reasons.

The invention is based on the knowledge that, in principle, known bed fillers can be used, in order to avoid pressure losses to a large extent it is important to build up the bed layer from coarse-grained material, which to avoid dust emissions and subsequent blockage of the Filters should have a high strength. The invention is based on the further knowledge that, as such bulk material, an organic material with a carrier matrix known from the above-described gas concrete production is particularly suitable, provided that it corresponds to the respective area of application with a for absorbing and / or reacting with pollutants suitable additive is doped.

Accordingly, the invention proposes an inorganic material of high open porosity based on cement 30 and / or lime and Si02-rich aggregate and at least one porosity agent, with at least one additive firmly anchored on its free surface to absorb and / or react with pollutants from gases 35 and / or liquids brought into contact with the material.

- 4 -

The characteristic properties of gas / foam concrete, namely its high and fine porosity with thin-walled partitions, are used to incorporate one or more additives on the free surfaces, which are then used to absorb and / or react 5 with pollutants of a gas passed through and / or a liquid passed through it.

Basically, the "inert" surface of gas concrete is made "reactive" by appropriate additives.

The additive can be one with a high absorption capacity for organic, non-polar and / or acid components of an exhaust gas or waste water.

15

Examples of the first group are carbon, graphite and / or activated carbon, examples of the second group are calcium and / or magnesium carbonates and / or hydroxides.

20th

The substance can also be a reducing substance such as a metal powder or a powder of a metal alloy, for example based on iron or zinc.

25th

Conversely, depending on the area of application, an oxidizing substance such as a peroxide (for example a metal peroxide) can also be used.

30 Also catalytically active compounds such as oxides or hydroxides of, for example, iron, chromium, vanadium, titanium, manganese, copper, zinc and / or tin can be used as an additive. These serve, for example, as redox catalysts or catalysts for 35 alkylation and cracking reactions.

- 5 -

Depending on the field of application, one or the other additive, possibly also a combination of the different additives, will be used.

Exemplary applications are given in the execution examples.

Due to the special structure of the foam matrix-like carrier matrix, it is possible to arrange the additives largely superficially, but firmly connected to the carrier matrix, 10, so that on the one hand a stable "filter network" is available, but on the other hand an optimum reaction surface is also provided.

In principle, it is also conceivable to use any other inorganic carrier matrix with the same properties instead of the described inorganic carrier matrix made of cement, lime, SiOg-rich aggregate and foaming agent, whereby it is primarily due to the large surface area and the strength of the Scaffold of the carrier matrix arrives, 20 which is then again doped with inorganic or organic additives.

The use of Trä.germa.trix, which is known from gas concrete production, is preferred because it is based on an easy manufacturing process:

It is proposed according to the invention to mix the matrix constituents (cement, lime, SiO 2 -rich aggregate, porosity agent) with water and one of the additives mentioned until a suspension with a high pore content is established. This is then subjected to steam curing in an autoclave, if appropriate after being filled into an appropriate form. During this hydrothermal hardening, lime and silicic acid react - the cement is added to achieve sufficient

Stability of the primarily formed foam mass - with each other to form the solid support matrix - 6 -

Calcium silicate hydrate phases.

Surprisingly, the additives only take part in this hydrothermal reaction to a limited extent. Experiments have shown that the additives are homogeneously distributed even after the hydrothermal reaction and are very finely divided, bound to a certain extent by "framing" with the calcium silicate hydrate phase, in all surface areas.

10 Mixtures of 20 to 70 parts by mass in percent of the matrix material and 80 to 30 parts by mass in percent of the additive are preferred.

Within the framework of the matrix material, finely ground quartz sand, natural sand and / or ash, preferably a filter or fly ash, can be used as the additive. Aluminum powder and / or surfactants are preferably used as the porosity agent.

20 In order to optimize the distribution and readiness for reaction of the additive (s), it is further proposed to mix them in as homogeneously and in finely divided form as possible during the preparation. Then even after the hydrothermal hardening, a uniform and finely divided surface coating is ensured.

Depending on the raw materials used, the water / solid ratio is between 0.3 and 0.7, preferably between 0.4 and 0.6.

30th

The steam curing should preferably be between 6 and 16 bar, preferably between. 8 and 12 bar can be carried out, with residence times in the autoclave between 2 and 5 hours having proven to be optimal.

35 - 7 -

The autoclaving can be further optimized if the autoclave is vented with tensioned steam before loading. The venting can be carried out, for example, by flushing with water vapor (preferably at atmospheric pressure) or by previous evacuation, for example by means of a vacuum pump. In the former variant, the water vapor pushes the air out between the individual particles of the material being fed. In the second variant, the air is sucked in between the solid particles ab-10.

In a third variant, the procedure is such that the autoclave is first charged with steam under a pressure of X bar. The air between the particles is compressed and does not initially escape. By subsequently relaxing (lowering the pressure) it is possible to pull out the air between the particles, which is removed at the same time. The greater the pressure drop (maximum to atmospheric pressure), the more vigorous the venting takes place. Experiments have shown that a relaxation of 1 to 2 bar is sufficient to achieve an almost complete venting. After venting, the pressure is raised to the desired final pressure.

25th

Experiments have further shown that it is usually sufficient to carry out the evacuation up to about 70% in order to draw off so much air that sufficient pore space is subsequently available to guide the subsequently released 30 steam completely and uniformly into the cavities to be able to bring about the hydrothermal reaction.

35. - 8th -

The inorganic material produced in this way can be used as a filter either in the design in which it is taken from a mold, for example in block form. In a particularly advantageous embodiment, it is proposed to subsequently shred or classify the material 5 by cutting, breaking, sieving or air sifting, in order then to assemble it in a grain size adapted to the use.

10 When used, the material according to the invention proves to be particularly advantageous because the additives stored superficially for absorption or reaction with the pollutants of the gas or the liquid are arranged there particularly firmly due to the hydrothermal pretreatment, so that the bulk material can also be used over a longer period of time Reaction medium is available.

The material is simple and inexpensive to manufacture and can thus be used in previously unexplored areas of application in gas and wastewater treatment.

Further features of the invention result from the subclaims and the other application documents.

Various exemplary embodiments are listed below for further explanation.

In all examples, the autoclave treatment with saturated steam takes place over 4 hours at 12 bar. The 30 starting materials are all in a grain fraction <100 pm.

v 35 - 9 -

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example 1

Carrier matrix: finely ground quartz: 16 HA m%

White fine lime: 8 MA in%

Cement (PZ 45): 6 MA in%

5 aluminum powder: 0.1 HA in SS

Additive: limestone powder: 6 9, 9 MA in% 10 Water was added to the total dry mixture with the setting of a water / solids value of 0.4 and the suspension thus formed, which rose to the primary foam mass, was subjected to the autoclave treatment and then broken down to a grain size of 10 to 20 mm.

15

The material obtained in this way has a high absorption capacity against acidic exhaust gas components (for example SO ^, HF, HCL et cetera) and the specific surface area (BET) of this grain fraction was approximately 20-10 m ^ / g.

Example 2

Compared to Example 1, white lime hydrate was used as an additive and the water / solids value was corrected to 0.5 (due to the higher water requirement of the white lime hydrate, which is more finely divided in comparison to limestone powder). The other parameters remained unchanged.

30 With again high absorption capacity against acid

The specific surface area 2 (BET) of a particle fraction 10 to 20 mm was approximately 13 m / g of exhaust gas constituents.

35 - 10 -

Example 3

Carrier matrix: finely ground quartz: 24 MA in% 5 fine white lime: 12 MA in%

Cement (PZ 45): 9 employees in%

Aluminum powder: 0t2 MA in%

Additive: activated carbon: 54.8 MA in% 20 With otherwise the same parameters, a water / solids ratio of 0.5 was set and finally the material was broken down to a grain size of 15 to 30 mm. The material showed a high adsorption capacity for organic constituents of exhaust gases and waste water.

15

The term "uptake of and / or reactions with pollutants" also includes other reaction partners.

Example 4 20

Carrier matrix: finely ground quartz: 20 MA in%

White fine lime: 10 MA in%

Cement: 7.5 MA in%

Aluminum powder: 0.2 MA in% 25 Additive: Iron powder: 62.3 MA in%

With a slightly reduced water / solids value (0.45) compared to Example 3, an inorganic material was obtained after the hydrothermal hardening, which had outstanding reducing properties with regard to oxidizing constituents of gases and liquids.

35

Claims (29)

1. Inorganic material of high open porosity based on 2q of cement and / or lime and SiOg-rich aggregate and at least one porosity agent, characterized by at least one additive firmly anchored on its free surface to absorb and / or react with pollutants from the 25 material brought into contact with gases and / or liquids. 2. Inorganic material according to claim 1, characterized in that the additive is one with 2Q high absorption capacity for organic, non-polar components of an exhaust gas or waste water, 35 4 - 2 - 3. Inorganic material according to claim 2, characterized in that the additive is carbon, graphite and / or activated carbon. 4. Inorganic material according to one of claims 1 5 to 3, characterized in that the additive is one with a high absorption capacity for acidic components of an exhaust gas or waste water. 5. Inorganic material according to claim 4, character- 10 indicates that the additive is a calcium and / or magnesium carbonate and / or hydroxide. 6. Inorganic material according to one of claims 1 to 5, characterized in that the additive 15 is a reducing substance. 7. Inorganic material according to claim 6, characterized in that the additive is a pure metal, for example iron or zinc and / or a metal alloy in powder form. 8. Inorganic material according to one of claims 1 to 7, characterized in that the additive is an oxidizing substance, such as a peroxide, preferably a metal peroxide. 9. Inorganic material according to one of claims 1 to 8, characterized in that the additive comprises a catalytically active substance. 30th 10. Inorganic material according to claim 9, characterized in that the catalytically active substance is an oxide or hydroxide of iron, chromium, vanadium, titanium, manganese, copper, zinc and / or tin. 35 m Μ 1 4 - 3 - 11. Inorganic material according to one of claims 1 to 10, characterized in that the additive is uniformly distributed and is present in finely divided form on the surface of the matrix material. 12. Inorganic material according to one of claims 1 to 11, characterized in that the additive is a finely ground quartz sand, natural sand and / or an ash, preferably a filter or fly ash. 13. Inorganic material according to one of claims 1 to 12, characterized in that the porosity agent is an aluminum powder and / or surfactant. 14. Inorganic material according to one of claims 1 15 to 13, consisting of 20 to 70 parts by mass in percent of the matrix material of cement, lime, SiO 2 ~ rich additive and porosity agent with 80 to 30 parts by mass in percent of the additive. 15. Inorganic material according to one of claims 1 to 14, made up in granular form, 16. Inorganic material according to one of claims 1 to 14, assembled in block form. 25th 17. A method for producing an inorganic material of high open porosity based on cement and / or lime and SiO ^ -rich aggregate and at least one porosity agent (matrix components), wherein 30 the matrix components with the addition of water and at least one additive according to one of claims 2 to 10 mixed, foamed and then subjected to steam curing in an autoclave and after 35 > * m * - ’- 4 - * if necessary take from the autoclave to the desired grain size fraction and / or be classified. 18. The method according to claim 17 with adjustment of a 5 water / solids value of the suspension between 0.3 and 0.7, preferably 0.4 and 0.6. 19. The method according to claim 17 or 18, characterized in that the steam curing is carried out at 6 to 16 bar, preferably 10 to 8 bar and a residence time in the autoclave between 2 and 5 hours. 20. The method according to any one of claims 17 to 19, characterized in that the material is broken after removal from the 15 autoclave to a grain fraction between 10 to 30 mm, preferably 10 to 20 mm. 21. The method according to any one of claims 17 to 20, characterized in that the autoclave is vented with charged steam before the feed 20. 22. The method according to claim 20, wherein for venting the autoclave it is rinsed with steam. 23. The method according to claim 22, wherein the rinsing with steam takes place at atmospheric pressure. 24. The method according to claim 21, wherein the autoclave is evacuated to vent. 30th 25. The method according to claim 24, wherein the evacuation is carried out by means of a vacuum pump. 26. The method of claim 21, wherein venting the 35 autoclaves are carried out by the following, briefly successive - 5 - i folgende * i following sub-steps: a) loading the autoclave with water vapor while setting a pressure b) lowering the pressure by approximately 1 to 2 bar. 5