US20110104494A1 - Adsorbent granulate and method for the manufacture thereof - Google Patents

Adsorbent granulate and method for the manufacture thereof Download PDF

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US20110104494A1
US20110104494A1 US12/920,742 US92074209A US2011104494A1 US 20110104494 A1 US20110104494 A1 US 20110104494A1 US 92074209 A US92074209 A US 92074209A US 2011104494 A1 US2011104494 A1 US 2011104494A1
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granulate
zeolite
solution
range
adsorption
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Alfons Brandt
Jens Schmeisser
Baldur Unger
Hartmut Tschritter
Uwe Henkel
Bálint Gojdár
Dietmar Gruhle
Georg Winterstein
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Chemiewerk Bad Kostritz GmbH
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    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • 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
    • B01D2253/108—Zeolites
    • 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
    • B01D2253/108—Zeolites
    • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
    • 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
    • B01D2253/11—Clays
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
    • 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
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/308—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention relates to an adsorbent granulate based on zeolite with a faujasite structure and to a method for the manufacture thereof.
  • the invention furthermore relates to using the granulate as an adsorption agent preferably for a selective separation, purification and drying of gases and liquids.
  • Adsorption agents based on zeolites with their specific properties like high chemical and thermal resistance, the existence of a homogenous channel pore system in the sub nanometer range and the development of specific interactions with adsorbed molecules based on a variable kation composition have an outstanding economic significance [“The Economics of Zeolites, Sixth Edition”: Roskill Inf. Serv. Ltd, London, UK, 2003].
  • faujasite-zeolite defines a class of crystalline alumosilicates which were originally discovered as a natural mineral, however, only the synthetic products with said faujasite structures have gained economic relevance.
  • LSX low silicon-X
  • MSX medium silicon X
  • SiO 2 /Al 2 O 3 ratio in the range >2.2 to approximately 2.45.
  • Y-type faujasite-zeolites are typically produced using a “pure” SiO 2 /Al 2 O 3 base component controlled, back feed of the base component from the “mother base” and possibly using a germination solution [e.g.: Costenoble u.a.: J/Chem.
  • LSX type faujasites-zeolites is generally performed in the presence of caustic potash solution besides the otherwise typical caustic soda solution [e.g. DE 2.731.010] or through the application of high pressures [U.S. Pat. No. 4,289,740].
  • the synthesis variants also differ significantly for a 13 ⁇ with a SiO 2 /Al 2 O 3 ratio of approximately 2.5 from the synthesis variants for the production of the MSX.
  • the “classic” 13X-type has the most significance based on volume. This relates to its use as an adsorption agent when processing raw air cryogenic air fractionizing devices for processing natural gas or also for non cryogenic oxygen enrichment through pressure change adsorption technology.
  • MSX-types are being used (preferably as materials including Li) for the non cryogenic oxygen enrichment through pressure change adsorption technology described supra [M.-T. Grandmougin, R. Le Bec, D. Plee: Ind. Appl: Zeol., Brugge, 2000, 93].
  • the present invention relates to the preceding paragraph and relates preferably to granulates for molecule sieves based on X-zeolites, in particular X-zeolites with a molar SiO 2 /Al 2 O 3 >2.1-2.5.
  • shaped bodies are required in order to be able to actually operate the processes in a dynamic manner. For known reasons these shaped bodies have to comply with particular minimum requirements with respect to their mechanical properties (dust, abrasion, pressure resistance, pouring weight).
  • shaped bodies are disadvantageous, since on the one hand side the active component is only provided in a thinned form in those formed bodies which include binder material and on the other hand the actually desired adsorption and desorption at the zeolite active component can be superimposed by the material transport processes in the formed bodies. Typically, the more mechanically stable the shaped body, the less disadvantageous are the material transport processes.
  • shaped bodies in spherical form are being used, which are typically produced through layered granulation using a natural clay binder or extruded shaped bodies (cylinders, hollow cylinders, wound strands), typically using clay or other silicate binder materials [e.g.: W. Pietsch: Aggl. Proc.: Phen., Techn., Equipmt.: Wiley-VCH, Weinheim, 2002].
  • All recited shaped bodies have in common that as a function of the size of the shaped bodies, which in turn is determined by the application process and/or the volume of the binder material used, more or less strong influences of the material transport processes recited supra have to be considered.
  • typical granulates deformed with clay minerals and including zeolite always show a comparatively high percentage of pores in the portion of the transport pores (measured through mercury high pressure porosimetry) wherein the pores have a diameter ⁇ 50 nm, (so called meso-pores), which are known to restrict the movability of the molecules when transported to and from the adsorption centers in the zeolites.
  • a transport pore system is desirable for technical adsorption agents, wherein the system only includes a negligible percentage of meso-pores and a mean pore diameter which is as large as possible [D. Bathen, M. Breitbach: “Adsorptionstechnik”, Springer-Verlag 2001, 13.].
  • the problem of the restricted movability of the molecules in the granulate of zeolite-containing molecular sieves deformed by clay binders can be alleviated by keeping the shaped bodies relatively small with respect to their dimensions (short transport paths), wherein in this case, however, the occurring pressure drop in an adsorption material compilation restricts the use of these small particles to low pouring heights or small devices. Large, but highly porous formed bodies can be used alternatively.
  • thermal (hydrothermal) treatment Unfortunately, the classic zeolite types (A and in particular faujasites), however, are more sensitive with respect to thermal (hydrothermal) treatment. Thus, the thermal breakdown of the pore forming agents has to be performed, so that said thermal/hydrothermal loading of the granulate is avoided which causes additional complexity.
  • the problem of thermal loading furthermore already relates to the binding of the typically used mineral binding agents (like e.g. Attapulgit) which have to go through a thermal treatment in the range of 500->600° C. [cf. e.g. U.S. Pat. No. 6,743,745].
  • 4,818,508 discloses a similar method; however the use of a mandatory pore forming agent is described herein in order to be able to assure the most complete transformation into zeolite material possible.
  • Another option to produce binder-free zeolite containing formed bodies is comprised in deforming a powder of a certain zeolite-type with a suitable binder material, possibly a mix of several products, and subsequently converting the binder portion into zeolite.
  • kaoline or meta-kaoline (a thermally activated kaoline) play an important role again [U.S. Pat. No. 3,119,659].
  • kaoline/meta-kaoline used as binding agent is converted into zeolite material through subsequent thermal-chemical treatment.
  • silica gel is used as a primary binding agent, wherein the silica gel is introduced into the system in different partially very complex ways. Mixtures of silica sol and magnesium oxide suspension or sodium silicate are described therein as gel forming systems. The silicate binder portion formed in this manner is then in turn converted into zeolite material in a subsequent step.
  • the object of the invention to provide a low cost mechanically stable granulate based on a zeolite with faujasite structure and with a SiO 2 /Al 2 O 3 ratio in a range of >2.1-2.5, wherein the granulate includes an optimum transport system with a negligibly small portion of meso-pores and the highest possible mean diameter of the transport pores and a maximum content of zeolite material with a faujasite structure and an SiO 2 /Al 2 O 3 ratio in a range of >2.1-2.5.
  • the granulate shall be usable as a highly efficient adsorption agent for technical adsorption processes.
  • the object is achieved by intensively mixing a powdery zeolite of the X-type with a molar SiO 2 /Al 2 O 3 ratio of >2.1-2.5 initially with a powdery thermally treated kaoline into this mix a solution including sodium hydroxide and sodium silicate is added and mixed intensively as well as the mixture thus produced is converted in a known manner with the addition of water into an evenly configured granulate.
  • the granulate is dried and hydrated after the drying and treated with a solution of sodium hydroxide and sodium aluminate subsequently separated from this solution, washed, dried and tempered.
  • the shaped bodies thus produced have the desirable properties described supra to be achieved as objects of the invention and the disadvantages of existing/described products known in the art were eliminated.
  • Particularly advantageous is the fact that the shaped bodies at least for water, carbon dioxide and nitrogen under comparable measurement conditions have the same weight adsorption capacities as the zeolite powder used as a base product (in activated condition). It is furthermore advantageous that the granulate does not have to be exposed to temperatures above 400° C. during its entire production process. This yields energy and thus cost savings and the zeolite structure is simultaneously treated gently.
  • Dried X-type zeolite powder is used as base material now with a molar SiO 2 /Al 2 O 3 of >2.1-2.5, preferably with a molar SiO 2 /Al 2 O 3 ratio of 2.25-2.45.
  • said X-type zeolite is also usable when configured as a filter cake or slurry, wherein the respective moisture content has to be considered accordingly when computing the granulation mix.
  • the thermally treated kaoline used as another base component is generated from commercially available raw kaoline. It is essential to select this raw kaoline based on the content of non-kaolinitic components (in particular silica and feldspar). The content of these extraneous components which cannot be converted into zeolite material through further processing should be ⁇ mass-% preferably ⁇ 1 mass-%.
  • the thermal treatment of this raw kaoline is preformed e.g. in a temperature range of 600° C. to 800° C., preferably in a range of 620° C. to 800° C.
  • the firing loss of the raw kaoline one hour, 950° C. is reduced from 14% to approximately 1%.
  • the thermally treated kaoline has to be run through a milling process before further processing, since it has proven advantageous to use material with a mean particle size of ⁇ 10 ⁇ m.
  • the thermally treated kaoline is mixed with the zeolite component at a mass ratio of 1:1 to 1:5, preferably at a mass ratio of 1:2 to 1:3.5 respectively with reference to the absolutely water free material of the two components.
  • a solution including sodium hydroxide and sodium silicate is added to the mix and intensively mixed.
  • the mixing can be performed in known devices, like e.g. drum mixers, cyclone mixers, plow share mixers. In any case intense mixing of the components has to be assured.
  • the mixture recited supra is transferred into an evenly formed granulate (preferably ball granulate) through known techniques.
  • granulate preferably ball granulate
  • mixing granulators, plate granulators or cyclone granulators can be used for equipment.
  • water is added to the mixer during the granulating process.
  • the finished granulate is dried at temperatures of 10° C. to 100° C., preferably 40° C. to 70° C.
  • the drying can be performed in a static ambient or inert gas atmosphere, however, it has proven advantageous that the granulate to be dried is flowed through by ambient air.
  • the dried granulate is subsequently hydrated with completely desalinated water in order to remove adhering dust particles and also to improve the accessibility of the transport pores for the zeolitization step.
  • This process can be performed in a suitable stirring vessel or also in a column continuously flowed through with flushing water and filled with granulate.
  • the ratio of water to granulate is preferably in a range of 5:1 to 40:1, preferably in the range of 8:1 to 20:1.
  • the temperature of the water used for flushing should be in a range of 15° C. to 40° C., preferably the watering is performed at ambient temperature.
  • the treatment time is 5 minutes to 120 minutes, preferably 15 minutes to 60 minutes.
  • the watered granulate is subsequently treated with a solution including thinned sodium hydroxide solution with an addition of sodium aluminate solution.
  • the treatment can be performed in a suitable stirring vessel or also in a column that is continuously flowed through by the solution and filled with the granulate.
  • the ratio of solution to granulate is typically in a range of 5:1 to 40:1, preferably in a range of 8:1 to 20:1.
  • the treatment temperature for this process step is in a range of e.g. 70° C. to 95° C., preferably in a range of 75° C. to 90° C.
  • the duration of the treatment is in a range of 8 to 24 hours and is determined in detail by the achieved degree of conversion of the previously non zeolite granulate portions into the desired zeolite material.
  • An “aging step” can be performed before this treatment using an alkaline solution with a similar composition or of the same solution, however at a lower temperature, preferably at ambient temperature over a time period of 0.5 to 24 hours, preferably 1 to 4 hours.
  • the granulate is separated from the treatment solution and is washed with completely desalinated water in the same basic manner as described supra until a ph-value ⁇ 12 is reached in the washing water.
  • the used treatment solution from the conversion can be reconditioned and can be used for a subsequent treatment step with new granulate.
  • the washed granulate is separated from the washing water, dried and tempered.
  • the recited thermal steps have to be performed under such conditions that a thermal/hydrothermal damaging of the material is excluded.
  • Preferably devices are being used in which the granulate is continuously flowed through by dry air or inert gas and where the temperature can be increased incrementally.
  • the duration of these thermal steps and the end temperature have to be selected, so that the material includes the required minimal humidity content (typically ⁇ 1% mass).
  • maximum temperatures ⁇ 450° C. are sufficient.
  • NaMSX powder manufactured through industrial production methods with subsequent properties was used as a base material:
  • SiO 2 /Al 2 O 3 approx. 2.35
  • the material described in this embodiment is a molecular sieve produced in a conventional manner through industrial production techniques based on a NaMSX zeolite powder with a SiO 2 /Al 2 O 3 ratio of approx. 2.35 (re. embodiment 1) in a typical kernel size range of 1.6-2.5 mm.
  • An Attapulgit (type Clarsol (Zeoclay) ATC NA, CECA) at a ratio of 17% mass with reference to the material in activated state was used as a binder material. The activation was performed in a conveyor belt oven with different temperature zones and a final temperature of 540° C.
  • zeolite NaMSX with a molar SiO 2 /Al 2 O 3 ratio of 2.35 and a firing loss of 21.4% (cf. embodiment 1) are mixed in a MTI-mixer with 223 g of a kaoline of the KS brand (vendor DVS Co. Limited/Ukraine composition cf. Table 1) pretreated at 700° C. for 1 hour in a muffle furnace with a firing loss of 1% dry material.
  • the obtained granulate is dried in a ventilated drying chest for 20 hours at 60° C. (layer thickness, approx. 2 cm) and subsequently sieved into 2 fractions.
  • the zeolitization In order to perform the zeolitization, 30 g of the 1.6-2.5 mm fraction of the granulate are hydrated 3 times with 200 ml of de-ionized water in order to remove all adhering dust particles. Subsequently the granulate is left for another 30 minutes under 300 ml of de-ionized water. The water is mostly poured out after this time period and replaced with the reaction mix for the zeolitization.
  • the zeolitization is performed by adding 1.75 g of technical sodium aluminate hydroxide with a content of 19.5% each of Na 2 O and Al 2 O 3 in order to produce 320 g of 3% sodium hydroxide.
  • this solution is added to hydrated humid base granulate and the mix made from granulate and reactive solution is aged for a period of 4 hr. at ambient temperature. During this time period the vessel is shaken lightly from time to time in order to limit in homogeneities in the composition of aging solution to a minimum.
  • the reaction vessel After the completion of the aging process the reaction vessel is placed in a water bath and heated to a temperature of 83° C. Thus, the vessel is closed, so that evaporation of the liquid is essentially excluded. Subsequently the zeolitization reaction is performed at this temperature over a time period of 16 hr.
  • reaction vessel is removed from the water bath and the superfluous mother hydroxide is poured out after cooling down to 50° C. and discarded. Subsequently washing with approx. 200 ml deionized water is performed and the washing water is respectively removed by decanting. Subsequently the granulate is left under 300 ml of water for 5-10 min., thereafter sucked out with a BUECHNER funnel and washed again two times with 200 ml of de-ionized water each, evacuated hard and subsequently dried under an infrared lamp at approx. 60° C. for approx. 30 minutes.
  • the x-ray crystallinity and the extraneous phase content 0.8 grams of the dried granulate are milled over for 10 minutes in a ball mill. The obtained powder is then placed on a sample carrier and checked for the crystallinity of the obtained zeolite type-X phase and for the non presence of crystalline extraneous phases using a defractometer type “D4 ENDEAVOR” made by Bruker-AXS GmbH, Düsseldorf using the software package “DIFFRACplus”. For the granulate produced according to this embodiment this yields and x-ray crystallinity of 90% and a lack of crystalline extraneous phases.
  • 1.2 g of the dry granulate is milled for a time period of approximately 20 min. in a ball mill and subsequently pressed to form a pressed spar-component according to SCHRAMM using 6 g of crystalline boric acid.
  • the composition of this sample is then determined at an x-ray spectrometer of the type “S4 explorer” made by Fa. Bruker-AXS GmbH, Düsseldorf using the “SPEC plus” software package.
  • the molar ratio of SiO 2 /Al 2 O 3 and Na 2 O/Al 2 O 3 is determined using a respective calibration while the content of other elements is obtained as a measurement without standard using the line library of the software package.
  • the SiO 2 /Al 2 O 3 ratio thus determined (“module”) is 2.34 and thus corresponds almost exactly to the module of the NaMSX powder used for producing the base granulate.
  • the granulate includes 0.2% TiO 2 , 0.2% Fe 2 O 3 and respectively close to 0.1% CaO and K 2 O.
  • the pressure resistance determined at the dried granulate was approximately 31 N/ball.
  • adsorption capacity for nitrogen and carbon dioxide 0.4 g of the dry granulate is activated in a test tube in a sample preparation station type “VacPrep 061” made by the Micrometrics Company (USA) under vacuum for a period of 3 hrs. at 400° C. and subsequently measured at 25.0° C. in an adsorption measurement device type “Gemini 2370” made by the Micrometrics Company (USA) with the respective measurement gas as an adsorptive.
  • the obtained adsorption values are included in Table 2 and within the measurement precision correspond to the values determined for the NaMSX powder used for producing the base granulate.
  • a meta kaoline powder is used for producing larger amounts of the base granulate for zeolitization, wherein the meta kaoline powder is obtained by calcinating the kaoline with the brand “Super Standard Porcelain” made by the IMERYS Co. in a rotating tube kiln at a maximum product temperature of approx. 720° C. and a dwelling time of approx. 1 hr. with subsequently milling in a jet mill to a defined mean particle size.
  • the composition of the base kaoline is included in Table 1.
  • the material is almost silica free, it apparently includes significant amounts of potassium feldspar. This can be derived from the relatively high K 2 O content and also from the presence of the respective reflexes in the x-ray diffractogram.
  • the last of the produced 40 kg batches of the premix is left in the EIRICH mixer and the granulate formation is initiated by slowly adding water.
  • a dusting with the premix and a humidification with water is performed in an alternating manner until the desired granulate spectrum of approx. 1.5-3.0 mm is reached.
  • the completely granulated mixture is then separated in a sifting device into a usable kernel fraction, a under size kernel fraction and an oversize kernel fraction.
  • the oversize kernel fraction is then subsequently crushed in an EIRICH mixer and fed back into the granulation process together with the under size kernel fraction as reclaimed material.
  • the subsequent granulation process is then performed respectively using premix and reclaimed material.
  • the usable kernel fraction of the obtained fresh granulate is then dried in a chamber dryer with air circulation in a layer thickness of approx. 2 over the course of 24-36 hours and used as a base granulate for the subsequent zeolitization.
  • 8.5 kg of dry granulate are placed into a flow through reactor with a remove able insert with approximately 15 cm interior diameter and approx. 70 cm useable height and watered for 30 min. with de-ionized water in a flow cycle.
  • a reactive solution is prepared in a separate storage container, wherein the solution includes 200 liters 3% sodium hydroxide and 1.1 kg of a technical sodium aluminate hydroxide with a content of 19.5% Na 2 O and Al 2 O 3 respectively.
  • This reactive solution is then pumped over the pre-washed granulate with a temperature of 23° C. and a flow through velocity of 200 l/h for 2 hours.
  • the reactive solution is heated to 83° C. with vapor through a bypass heat exchanger and the zeolitization is performed over a period of 16 hours.
  • the mother base is drained and the granulate is washed with three portions of 200 liters of de-ionized water each.
  • the humid granulate is then removed from the reactor together with the insert and dried for approx. 8 hrs. in an air flow at a maximum temperature of 50° C. After the drying an incremental activation up to 380° C. is performed.
  • the granulate obtained has a residual water content of ⁇ 1.0%.
  • the modulus of the granulate determined through x-ray florescent analysis is 2.37 and thus approx. corresponds to the value for the NaMSX powder which was used to produce the base granulate.
  • the data regarding the adsorption properties and the pressure resistance and regarding the granulate obtained are included in Table 2.
  • the obtained adsorption properties correspond approximately to the adsorption properties of the NaMSX powder used for producing the base granulate.
  • the slightly lower adsorption capacity for carbon dioxide compared to embodiment 1 can be explained by the detectable content of the potassium feldspar in the meta-kaoline used. Apparently, this potassium feldspar is not converted into the zeolite phase or not sufficiently converted.
  • composition for the kaolines in delivered form as used for producing the base granulates Content (in % m/m) of: Kaoline SiO 2 Al 2 O 3 Na 2 O K 2 O TiO 2 Fe 2 O 3 H 2 O KS 45.1 38.1 0.1 0.3 0.7 0.7 14.5 Super 47.8 36.0 0.2 1.4 0.02 0.5 13.4 Standard Porcelain
  • FIGS. 1 through 5 illustrate pore radius distributions of the products according to embodiments 2-4 measured through mercury porosimetry.
  • the measurements were performed with the equipment combination PASCAL P140, P440 made by the Porotec Co. Initially interfering gases were removed from the sample surface in a vacuum. Thereafter an incremental pressure increase up to 400 kPa was performed in the low pressure porosimeter P140. Thereafter the sample is put into the high pressure station at ambient pressure and the pressure is increased up to 400 mPa.
  • PASCAL the pressure change gradients are varied as a function of the pressure range and as a function of the mercury adsorption by the probe. The mercury volume penetrating the probe is registered and a pore size distribution is determined.
  • the products according to the invention only include a negligibly small percentage of undesirable transport pores with a diameter ⁇ 50 nm (Mesopores).
  • the properties are already formed during the production of the base granulate (fresh granulate cf. FIG. 3 ):
  • the subsequent process steps watering, zeolitization, washing, drying and tempering, cf. FIGS. 4 and 5 ) lead to movement of the transport pore spectrum to larger diameters and/or to an elimination of still existing meso-pores through e.g. crystallization processes.
  • the products according to the invention have significant advantages in their application in dynamic adsorption processes based on the transport pore system over conventional products, in particular for adsorption processes with a quick change between adsorption and desorption.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
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WO2013192435A1 (en) 2012-06-22 2013-12-27 Praxair Technology, Inc. Novel adsorbent compositions
FR3013236A1 (fr) * 2013-11-20 2015-05-22 Ceca Sa Materiau granulaire zeolithique a structure connexe
US9533280B2 (en) 2012-06-22 2017-01-03 Praxair Technology, Inc. High rate compositions
FR3045413A1 (fr) * 2015-12-18 2017-06-23 Air Liquide Adsorbant structure monolithique autosupporte comprenant du silicate de sodium
US20200023341A1 (en) * 2017-11-03 2020-01-23 Uop Llc Adsorbent for contaminant removal from c4 hydrocarbons
EP2906341B1 (de) 2012-10-15 2021-06-16 Chemiewerk Bad Köstritz GmbH Bindemittelfreie kompakte zeolithische formkörper und verfahren zu deren herstellung
EP2527296B1 (de) 2011-05-25 2021-07-07 Chemiewerk Bad Köstritz GmbH Bindemittelfreies zeolithisches Granulat mit Faujasitstruktur und Verfahren zur Herstellung eines derartigen bindemittelfreien zeolithischen Granulats nebst Verwendung
US20220402779A1 (en) * 2021-06-17 2022-12-22 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Composite and method for removing dissolved organic matter from water
US11583799B2 (en) * 2018-10-26 2023-02-21 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for conditioning a container comprising a granular material
WO2023126595A1 (fr) * 2021-12-30 2023-07-06 Arkema France Solide dessicant résistant aux hydroxydes alcalins

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DE102011104006A1 (de) 2010-12-10 2012-06-14 Süd-Chemie AG Granulierte Zeolithe mit hoher Adsorptionskapazität zur Adsorption von organischen Molekülen
FR3028431B1 (fr) 2014-11-13 2016-11-18 Ceca Sa Adsorbants zeolithiques a base de zeolithe x a faible taux de liant et a faible surface externe, leur procede de preparation et leurs utilisations
RU2712540C2 (ru) 2015-03-23 2020-01-29 Басф Корпорейшн Сорбенты диоксида углерода для контроля качества воздуха в помещении
JP2016221428A (ja) * 2015-05-28 2016-12-28 宇部興産株式会社 ガスの処理装置及びガスの処理カートリッジ
TW201741022A (zh) 2016-02-12 2017-12-01 巴斯夫公司 用於空氣品質控制的二氧化碳吸附劑
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FR3117379A1 (fr) 2020-12-15 2022-06-17 IFP Energies Nouvelles Procede de preparation d'un materiau microporeux zeolithique contenant plus de 95% de zeolithe x et ayant une bonne resistance mecanique

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EP2527296B1 (de) 2011-05-25 2021-07-07 Chemiewerk Bad Köstritz GmbH Bindemittelfreies zeolithisches Granulat mit Faujasitstruktur und Verfahren zur Herstellung eines derartigen bindemittelfreien zeolithischen Granulats nebst Verwendung
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US20200023341A1 (en) * 2017-11-03 2020-01-23 Uop Llc Adsorbent for contaminant removal from c4 hydrocarbons
US10744492B2 (en) * 2017-11-03 2020-08-18 Uop Llc Adsorbent for contaminant removal from C4 hydrocarbons
US11583799B2 (en) * 2018-10-26 2023-02-21 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for conditioning a container comprising a granular material
US20220402779A1 (en) * 2021-06-17 2022-12-22 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Composite and method for removing dissolved organic matter from water
WO2023126595A1 (fr) * 2021-12-30 2023-07-06 Arkema France Solide dessicant résistant aux hydroxydes alcalins
FR3131545A1 (fr) * 2021-12-30 2023-07-07 Arkema France Solide dessicant résistant aux hydroxydes alcalins

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JP5372023B2 (ja) 2013-12-18
EP2249961B1 (de) 2015-04-08
PL2249961T3 (pl) 2015-11-30
US9682361B2 (en) 2017-06-20
DE102008046155A1 (de) 2009-09-10
US20140086817A1 (en) 2014-03-27
WO2009109529A1 (de) 2009-09-11

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