EP2646367A2 - Mechanochemische herstellung von zeolithen - Google Patents

Mechanochemische herstellung von zeolithen

Info

Publication number
EP2646367A2
EP2646367A2 EP11788450.2A EP11788450A EP2646367A2 EP 2646367 A2 EP2646367 A2 EP 2646367A2 EP 11788450 A EP11788450 A EP 11788450A EP 2646367 A2 EP2646367 A2 EP 2646367A2
Authority
EP
European Patent Office
Prior art keywords
grinding
synthesis
mill
template
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11788450.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
Josef SCHÖNLINNER
Jürgen Ladebeck
Jürgen Koy
Stephan Wellach
Götz BURGFELS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie IP GmbH and Co KG
Original Assignee
Sued Chemie IP GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sued Chemie IP GmbH and Co KG filed Critical Sued Chemie IP GmbH and Co KG
Publication of EP2646367A2 publication Critical patent/EP2646367A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • the invention relates to a process for the preparation of zeolites, as well as zeolites obtainable by this process
  • Zeolite materials can be prepared by hydrothermal synthesis, that is, by synthesis in an aqueous medium under pressure and at elevated temperature.
  • the synthesis gels usually comprise a silicon source (e.g., silica), an aluminum source (e.g., sodium aluminate, aluminum hydroxide, aluminum sulfate, etc.), a template
  • hydrothermal synthesis is relatively long and the resulting zeolites often are not uniform substances, but mixtures.
  • the invention therefore an object of the invention to provide a method that makes it possible with a simple
  • this additional process step allows the reduction of the amount of template used without the
  • the invention relates to a method for the synthesis of
  • Zeolites comprising the following steps: a)
  • Aluminum source and optional template for generating a synthesis gel e) grinding the synthesis gel; f)
  • the present invention relates to zeolites obtainable by the process of the invention.
  • Preferred is the preparation of beta zeolite and MFI zeolite; more preferably of beta zeolite having a molar ratio Si: Al of 10 to 400, more preferably 20 to 50, of MFI zeolite having a molar ratio Si: Al of 12 to 800, more preferably 24 to 500, and particularly preferred from 75 to 250.
  • the present invention teaches the use of at least one grinding apparatus for treating a
  • Synthetic gels comprising a silicon source, an aluminum source, and optionally at least one template, prior to the generation of crystalline zeolite under hydrothermal conditions
  • the present invention teaches the use of the zeolites obtainable by the process according to the invention as catalysts or catalyst supports, in particular for acid-catalyzed reactions, oxidations, reductions and adsorptions.
  • catalysts or catalyst supports particularly for acid-catalyzed reactions, oxidations, reductions and adsorptions.
  • Particularly preferred is the use for catalytic cracking of hydrocarbons (cracking) and hydrogenating cracking of hydrocarbons (hydrocracking, mild hydrocracking and / or dewaxing); Alkylation of
  • Aromatics with olefins, alcohols or halogenated Aromatics with olefins, alcohols or halogenated
  • the invention relates generally to a method for
  • a synthesis gel is prepared. Generation of synthesis gel by mixing silicon source,
  • Aluminum source and optionally one or more
  • Template may be made in a manner known to those skilled in the art based on the teachings of the present invention.
  • Silicon source, aluminum source and the one or more templates can be mixed together as such or in the form of a fluid, for example as a solution, suspension or gel, or added to a solvent or solvent mixture.
  • a solvent or solvent mixture Preferably, the solvent used is water or an aqueous solvent mixture.
  • Aluminum source the optional template and / or the
  • Silicon source aluminum source and optionally one or more templates mixing or homogenizing. Particularly good results can be achieved if the silicon source is a silicon source selected from the group consisting of precipitated
  • the silicon source may comprise or consist of precipitated silica.
  • the aluminum source may be an aluminum source selected from the group consisting of aluminates (especially sodium aluminate), aluminum hydroxide, aluminum sulfate and mixtures thereof.
  • aluminates especially sodium aluminate
  • aluminum hydroxide especially aluminum sulfate
  • any template based on the general knowledge or teaching of the present invention may be used, preferably quaternary ammonium compounds which may serve as structure-directing agents are used as a template. Examples of templates that can be used are
  • Tetraalkylammonium salts Preference is given to the use of tetraalkylammonium hydroxides and / or
  • Alkyl groups preferably by the same or different, straight-chain or branched alkyl groups having one to ten
  • TEAOH tetrapropylammonium bromide
  • TPABr tetrapropylammonium bromide
  • Template or multiple templates can be used, preferred is the use of a template.
  • the synthesis gel can have a molar ratio of Al to Si
  • the synthesis gel comprises at least 10 moles of water per mole of S1O2, more preferably 18-30 moles of water.
  • the synthesis gel may have a molar ratio of Al to Si, for example, in the range of 0.0025: 1 to 0.1: 1, preferably in the range of
  • the synthesis gel comprises at least 5 moles of water per mole of S1O2, more preferably 10 to 50 moles of water.
  • synthesis gel in the context of the present invention comprises both synthesis gels, which are in the form of a gelatinous or gelatinous mass, as well as in fluid form,
  • the ground synthesis gel is then transferred under hydrothermal conditions in the crystalline zeolite, whereupon the crystalline zeolite can be separated from the aqueous phase and optionally dried and calcined.
  • Zeolites preferably have a phase purity of more than 80%, preferably more than 90%, preferably more than 95%, in particular more than 98%.
  • the phase purity is determined by measuring an X-ray diffractogram and based on a 100% pure sample. The grinding of the synthesis gel before treatment under
  • hydrothermal conditions can lead to an increase in the dispersion of the silicon source used, e.g. a precipitated silica, which in turn accelerates the
  • Crystallization process can lead. Surprisingly, moreover, the formation of foreign phases can be inhibited or
  • the colloidal silicic acids can be formed on the basis of the
  • those zeolites can be achieved, in their preparation as a raw material usually colloidal silica sources are used. Furthermore, preferably none
  • Zeolite seed crystals in particular the production of beta-zeolite, which can also reduce the production costs.
  • mother liquors can be used instead of high-purity starting materials in the preparation of the synthesis gel.
  • mother liquors the first filtrate after the
  • Filtrate still contains raw materials during the
  • a grinding is preferably carried out such that the
  • average particle size ds o of the synthesis gel after completion of the grinding by at least 10%, more
  • the grinding can be done generally with any suitable
  • a high amount of energy (for example about 0.5 to 10 kW / liter, preferably about 1 to 10 kW / liter) is introduced into the system via the mechanical energy.
  • a high amount of energy for example about 0.5 to 10 kW / liter, preferably about 1 to 10 kW / liter
  • the amount of energy can be reduced, for example to 2 to 5 kW / liter.
  • Synthetic gel after completion of grinding for example, at least 10%, preferably at least 15%, more
  • the silicon source and / or the aluminum source are subjected to grinding.
  • Synthesis gel preferably under a pressure of not more than 2.4 bar, more preferably under a pressure of not more than 1.9 bar, more preferably under a pressure of not more than 1.5 bar, most preferably under a pressure of not more set as 1.1 bar and / or preferably to a Temperature of not more than 128 ° C, more preferably not more than 110 ° C, even more preferably not more than 100 ° C, most preferably not more than 70 ° C, and most preferably not more than 35 ° C heated.
  • the grinding is preferably at a temperature
  • synthesis gel is pumped, for example, by a grinding chamber filled with grinding chamber.
  • the grinding is carried out in a mill comprising a grinding chamber filled with grinding balls, for example in a ball mill, in an annular gap mill, a bead mill, a Manton-Gaulin mill or in a grinding device combination comprising one or more comprising these grinding devices.
  • a multi-stage grinding apparatus for example a multi-stage ball or annular gap mill, may be used in which the coarse fractions from the last stage are returned to the first stage.
  • the one or more milling devices may comprise at least one grinding device selected from the group consisting of mills comprising a grinding chamber filled with grinding balls, in particular selected from ball mills, annular gap mills, bead mills, Manton-Gaulin mills and
  • a Manton Gaulin mill is
  • Grinding devices are used sequentially or simultaneously. Higher temperatures, ie more than 100 ° C may also be possible if the grinding process is carried out at overpressure. In this case, the inlet and outlet of the synthesis gel must be regulated in or out of the grinding chamber.
  • the pH of the synthesis gel is adjusted according to the synthesis ⁇ conditions and is generally about 9 to 14.
  • the milling at a pH in the range of about 9 to 14, preferably from about 10 to 13 are performed.
  • Adjustment of the pH can be carried out according to a procedure known to the person skilled in the art, for example by addition of acids, bases and / or buffer salt mixtures.
  • Reaction mixture can be conveyed through the grinding chamber in several passes or with a longer residence time.
  • the synthesis gel or the reaction mixture formed therefrom may additionally contain zeolite precursors as crystallization nuclei and may then be subjected to a hydrothermal aftertreatment, the resulting product optionally being separated from the reaction mixture, dried and
  • the grinding is carried out twice or more frequently, eg. B. twice, three times or four times.
  • Crystallization nuclei formed are the course of the hydrothermal zeolite synthesis in terms of synthesis time, flexibility in the selection of the reactants, yield,
  • Reaction mixture can be pumped through the grinding chamber.
  • Crystallization seeds are then further processed according to an imple mentation in a conventional manner under hydrothermal conditions and worked up the finished product. After a possible implementation form become
  • the raw materials (a silicon source, an aluminum source and an alkali source) are stirred together with a template and demineralized water to form a suspension.
  • Suspension is passed through one or more milling devices as indicated herein.
  • the mechanically activated fines act as
  • the drying can at a
  • Temperature of about 60 to 200 ° C, preferably from about 80 to 150 ° C, for z. B. 0.5 to 10 hours, and the
  • Calcination if provided, at about 250 to 750 ° C, preferably at 300 to 550 ° C, for z. B. 1 to 10 hours.
  • the product thus obtained can be used as a catalyst or
  • Catalyst supports are used.
  • the present invention teaches the use of at least one grinding apparatus for treating a Synthetic gels comprising a source of silicon, an aluminum source, and optionally at least one template, in one step prior to the production of crystalline zeolite under hydrothermal conditions.
  • This use can for
  • the present invention provides a zeolite which is suitable for the invention
  • the zeolite may be an MFI zeolite, in particular having a molar Si: Al ratio in the range from 12 to 800, preferably from 24 to 500, particularly preferably from 75 to 250 or a zeolite beta.
  • Catalytically active forms of the zeolites may additionally contain metals of the groups IA, IIA, IIIA to VI IIA, IB, IIB or HIB of the Periodic Table and B, Al, Ga, Si, Ge or P, preferably Li, Na, K, Mg, Ca, Ba, La, Ce, Ti, Zr, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn , B, Al, Ga, Si, Ge or P. More preferably, the catalytically active zeolites contain one or more of Pt, Pd, Cu, Fe, Rh, Ru, P, and Ni. For example, the exchange by means of ion exchange, impregnation or
  • zeolites obtained according to the invention are mixed or further processed with further components.
  • Preferred further processing of the zeolite relate to aqueous ion exchange, solid-state ion exchange (as described, for example, in EP 0 955 080 A),
  • Dealumination for example, by treatment with dilute mineral acid or a dilute organic acid, and by hydrothermal treatment (see eg R. Szostak, Studies in Surface Science Catalysis, 137 (2001) 261-297), producing moldings of any size and shape by conventional methods such as extrusion, tabletting or spray drying, optionally with the aid of binder, or coating Moldings, in particular honeycombs, with a suspension of zeolite and binder as so-called
  • the synthetic zeolites of the invention are particularly useful as catalysts, for example, the zeolites in the H form (with or without occupancy of base metals and / or precious metals) as catalysts for acid-catalyzed reactions, oxidations, reductions and adsorptions
  • reaction include i.a. catalytic cracking (FCC additive) and hydrogenating cracking of hydrocarbons (mild hydrocracking, dewaxing, hydrocracking); Alkylations e.g. of aromatics with olefins, alcohols or halogenated paraffins; Alkylation of aromatics; Alkylation of
  • Isoparaffins with olefins Transalkylation (of aromatics); Disproportionation (e.g., toluene disproportionation, etc.); Isomerization and hydroisomerization (e.g., of paraffins, olefins, aromatics, xylene isomerization, isodewaxing, etc.); Dimerization and oligomerization; polymerizations;
  • the mean diameter dso is defined so that 50% of the total particle volume consists of particles with a smaller particle size
  • Diameter exist.
  • a suitable method for determining the particle size distribution is, for example, the laser diffraction according to ISO 13320-1. c) loss on ignition
  • Porcelain crucibles are annealed at 600 ° C and then stored in a desiccator until use.
  • the homogenized sample is weighed into a porcelain crucible and the crucible is then calcined for 3 h at 1000 ° C. in a laboratory muffle furnace.
  • the crucible is then placed in a desiccator for cooling. By comparing the weight and weight, the loss on ignition can be calculated. The loss on ignition is always determined by a double determination.
  • n5j_ / n7 ⁇ ] _ indicates the ratio of the molar amount of Si in mol to the molar amount of Al in mol, wherein the respective zeolite was previously subjected to heating at 1000 ° C to constant weight.
  • sodium aluminate was used, whereby an aqueous aluminum source was dissolved by dissolving
  • Sodium aluminate (and in the case of Ex. Or Comp. -Bsp. 4 additional NaOH beads) was prepared in water. To completely dissolve the sodium aluminate, the mixture was heated to 60-100 ° C. After the solid had dissolved, the yellowish, slightly turbid fluid was cooled to room temperature and the loss of mass by adding
  • the template tetraethylammonium hydroxide (TEAOH, SACHEM) was first mixed with water at room temperature in the case of the beta zeolite (BEA) or, in the case of the MFI zeolite, the template
  • Tetrapropylammonium bromide (TPABr, SACHEM) dissolved in water.
  • the templated tetraethylammonium hydroxide used was used as a 35 wt.% TEAOH solution.
  • Tetrapropylammonium bromide was used as solid with> 99 wt.% TPABr. Subsequently, precipitated silica (FK320, Degussa) was slurried. c) mixing the source of aluminum and silicon and preparing the synthesis gel
  • the aluminum source was steadily added to the silicon source in a reaction vessel at room temperature (20 ° C) with mixing.
  • the resulting suspension was mixed for a further 140 minutes (in the preparation of beta zeolite) and 30 minutes (in the preparation of MFI zeolite) at room temperature (20 ° C).
  • Hose pump into the grinding chamber of the ball mill (type Fryma M32) promoted. After the grinding chamber was filled, the rotor of the mill was started and the complete synthesis gel through the Grinding chamber pumped while the rotor is running. The ground product was collected in one container and a second
  • the pumping rate was 3 liters / minute (BEA and MFI).
  • Crystallization times were depending on the approach between 1 h and 160 h.
  • Table I gives an overview of the different template contents of the ground or unmilled synthetic gels and the products obtained.
  • the molar template content is given based on the molar Si content.
  • Ratio of the amount of template in moles to the amount of Si in moles 0.18: 1 0.18 d. H. 18 mol%.
  • Beta-zeolite with low impurities of MFI zeolite determined by measurement of an X-ray diffractogram.
  • phase-pure zeolites The zeolites from the unground synthesis gels contained impurities in one case.
  • Fig. 1 shows a significant reduction in
  • Crystallization was determined by measuring the peak intensity of a synthesis gel or reaction mixture sample by measuring the X-ray diffractogram.
  • the product of Example 4 (MFI zeolite) further shows a marked reduction in crystallite size
  • the course of the crystallization was determined by recording the peak number of a synthesis gel sample by measuring the X-ray diffractogram.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
EP11788450.2A 2010-12-01 2011-11-28 Mechanochemische herstellung von zeolithen Withdrawn EP2646367A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010053054A DE102010053054A1 (de) 2010-12-01 2010-12-01 Mechanochemische Herstellung von Zeolithen
PCT/EP2011/071099 WO2012072527A2 (de) 2010-12-01 2011-11-28 Mechanochemische herstellung von zeolithen

Publications (1)

Publication Number Publication Date
EP2646367A2 true EP2646367A2 (de) 2013-10-09

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Application Number Title Priority Date Filing Date
EP11788450.2A Withdrawn EP2646367A2 (de) 2010-12-01 2011-11-28 Mechanochemische herstellung von zeolithen

Country Status (7)

Country Link
US (1) US20130266507A1 (enrdf_load_stackoverflow)
EP (1) EP2646367A2 (enrdf_load_stackoverflow)
JP (1) JP2014501683A (enrdf_load_stackoverflow)
CN (1) CN103269978A (enrdf_load_stackoverflow)
DE (1) DE102010053054A1 (enrdf_load_stackoverflow)
WO (1) WO2012072527A2 (enrdf_load_stackoverflow)
ZA (1) ZA201303567B (enrdf_load_stackoverflow)

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CN104860332A (zh) * 2014-02-21 2015-08-26 中国石油化工股份有限公司 一种制备NaY分子筛的方法
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JP2022550674A (ja) * 2019-09-30 2022-12-05 ダウ グローバル テクノロジーズ エルエルシー エーテル化の方法
CN110893491B (zh) * 2019-12-13 2021-07-27 湖南中镆科技有限公司 一种铝模板铣槽固定装置
CN111001265B (zh) * 2019-12-26 2021-11-12 维珂瑞（北京）环境科技有限公司 高质量沸石转轮生产工艺及其生产设备
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ZA201303567B (en) 2014-07-30
DE102010053054A1 (de) 2012-06-06
US20130266507A1 (en) 2013-10-10
WO2012072527A2 (de) 2012-06-07
WO2012072527A3 (de) 2012-10-11
JP2014501683A (ja) 2014-01-23
CN103269978A (zh) 2013-08-28

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