WO2019068135A1 - Synthèse de zéolites - Google Patents

Synthèse de zéolites Download PDF

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Publication number
WO2019068135A1
WO2019068135A1 PCT/AU2018/050940 AU2018050940W WO2019068135A1 WO 2019068135 A1 WO2019068135 A1 WO 2019068135A1 AU 2018050940 W AU2018050940 W AU 2018050940W WO 2019068135 A1 WO2019068135 A1 WO 2019068135A1
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WO
WIPO (PCT)
Prior art keywords
leach
hours
residue
zeolite
conducted
Prior art date
Application number
PCT/AU2018/050940
Other languages
English (en)
Inventor
Yatendra Sharma
Goutam Kumar DAS
Original Assignee
Neomaterials Pty Ltd
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
Priority claimed from AU2017904004A external-priority patent/AU2017904004A0/en
Application filed by Neomaterials Pty Ltd filed Critical Neomaterials Pty Ltd
Publication of WO2019068135A1 publication Critical patent/WO2019068135A1/fr

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Classifications

    • 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
    • C01B39/14—Type A
    • C01B39/18—Type A from a reaction mixture containing at least one aluminium silicate or aluminosilicate of a clay type, e.g. kaolin or metakaolin or its exotherm modification or allophane
    • 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
    • B01J29/7003—A-type
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures

Definitions

  • the present invention relates to a method for the synthesis of zeolites. More particularly, the zeolite of the present invention is synthesised in the form of Linde Type A zeolite.
  • the present invention further relates to the synthesis of zeolites from the residue of a leach of a spodumene ore or concentrate.
  • the zeolite synthesised in accordance with the method of the present invention is intended for use, in one form, as either a molecular sieve or an adsorbent.
  • Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents, molecular sieves and catalysts. Their structure is based on a three dimensional network of an aluminium and silicon tetrahedral linked by shared oxygen atoms.
  • Linde Type A (or LTA) zeolite was the first synthetic zeolite commercialised as an adsorbent in 1953 when Union Carbide used it to remove an oxygen impurity from argon. Due to specific pore sizes and large surface areas, LTA Zeolites are used in the various applications noted above, as each of adsorbents, molecular sieves, and catalysts.
  • Zeolites have the chemical formula M2 nOAl2O3.xSiO2.yH2O, where the charge-balancing non-framework cation M has valence n, x is 2.0 or more, and y is the moles of water in the voids.
  • the Al and Si tetrahedral atoms (T-atoms) form a three dimensional framework comprising AIO4 and S1O4 tetrahedra linked by shared oxygen ions.
  • the chemistry of zeolite synthesis is subject to the presence of impurities in the source materials. Such contaminants may remain insoluble during the
  • the process of the present invention has as one object thereof to
  • a method for the synthesis of zeolites comprising the addition of a predominantly alumina-silicate starting material to a stoichiometric excess of sodium hydroxide, with additional water, and calcining at a temperature of greater than about 400°C.
  • the alumina-silicate starting material is the residue from a leach of a spodumene ore or concentrate to extract lithium therefrom.
  • the spodumene ore or concentrate is in the form of beta spodumene prior to the leach.
  • the leach is a sulphuric acid leach.
  • the calcine temperature is at least about 600°C for a residence time of at least about 4 hours
  • the additional water is provided in the amount of between about 1 to 4 times the weight of the alumina-silicate starting material.
  • the pressure is in the range of atmospheric to about 15 psig.
  • the leach residue comprises hydrogen Catena-Aluminodisilicate, Hydrogen Tecto-Aluminodisilicate and silica as the predominant components thereof.
  • the leach residue has a Pso of about 75 ⁇ .
  • the molar ratio of silicon to aluminium in the leach residue is adjusted to about 1 .0:1 .1 prior to calcining. Still preferably, the molar ratio of silicon to aluminium in the leach residue is adjusted through the addition of AI(OH)3 to the leach residue.
  • An amount of an NaOH solution is preferably added to the leach residue prior to calcining.
  • the NaOH solution is a 50% w/w solution.
  • the NaOH solution is added with a stoichiometric sodium requirement of between 3 and 4 times. Most preferably, a 50% w/w solution of NaOH is added with a stoichiometric sodium requirement of 4 times.
  • the method of the present invention further comprises a cooling step.
  • the method of the present invention still further comprises a subsequent grinding step.
  • the resulting material is preferably added to a volume of water in a water leach and thereby provides a zeolite yield.
  • the water leach is preferably conducted over a period of between about 1 to 2 hours.
  • the synthesised zeolite is in the form of an LTA zeolite.
  • the LTA zeolite comprises
  • an aging step is provided immediately after the water leach.
  • the aging step is preferably conducted in two periods. Collectively the two periods preferably provide a residence time of between about 36 to 48 hours. At least a part of the aging step is still preferably conducted at elevated temperature. Still further preferably, one of the periods of the aging step is conducted at about room temperature.
  • the elevated temperature of the aging step is preferably 50°C or higher. Still preferably, the elevated temperature of the aging step is in the range of 50°C to 70°C.
  • the aging step comprises a first period conducted at about room temperature for a period of between 22 to 24 hours, and a second period conducted at a temperature in the range of 50°C to 70°C for a period of between 15 to 24 hours.
  • Figure 1 is a scanning electron micrograph (SEM) of an LTA zeolite formed in accordance with a first embodiment of the method of the present invention, showing the crystal structure thereof;
  • Figure 2 is a diagrammatic representation of a method for the synthesis of zeolites in accordance with the second embodiment of the method of the present invention
  • Figure 3 is an X-Ray Diffraction (XRD) trace of an LTA zeolite formed in accordance with the second embodiment of the present invention, including aging of the leach slurry at 50°C for 1 5 to 16 hours;
  • XRD X-Ray Diffraction
  • Figure 4 is an X-Ray Diffraction (XRD) trace of an LTA zeolite formed in accordance with the second embodiment of the present invention, including aging of the leach slurry at 70°C for 1 5 to 16 hours;
  • XRD X-Ray Diffraction
  • Figure 5 is an X-Ray Diffraction (XRD) trace of a pure reference LTA zeolite, utilised for comparison purposes in the traces of Figures 3 and 4;
  • Figure 6 is a Scanning Electron Microscope (SEM) image of the LTA zeolite of Figure 3;
  • Figure 7 is a Scanning Electron Microscope (SEM) image of the LTA zeolite of Figure 4.
  • the present invention provides a method for the synthesis of zeolites, the method comprising the addition of a predominantly alumina-silicate starting material to a stoichiometric excess of sodium hydroxide, with additional water, at a
  • the alumina-silicate starting material is, in one particularly preferred form, the residue from a leach of a spodumene ore or concentrate to extract lithium therefrom.
  • the spodumene ore or concentrate is in the form of beta spodumene prior to the leach.
  • the leach is an acid leach, for example a sulphuric acid leach, or as a further example, a hydrochloric acid leach.
  • a leach of a beta spodumene ore or concentrate is described, by way of example, in each of International Patent
  • the leach residue has, for example, a Pso of about 75 ⁇ .
  • the temperature of the addition of the starting material to the sodium hydroxide, or the fusion is, for example, at least about 600°C.
  • the additional water is provided in the amount of between about 1 to 4 times the weight of the alumina- silicate starting material.
  • the pressure is in the range of atmospheric to about 15 psig.
  • the leach residue comprises hydrogen Catena-Aluminodisilicate, Hydrogen Tecto-Aluminodisilicate and silica as the predominant components thereof.
  • the method of the present invention further comprises subjecting the fused material to a cooling step and a subsequent grinding step.
  • the resulting material is then added to a volume of water and thereby provides a zeolite yield.
  • the synthesised zeolite is in the form of an LTA zeolite, for example
  • An aging step is provided immediately after the water leach.
  • the aging step is conducted in two periods. Collectively the two periods provide a residence time of between about 36 to 48 hours. At least a part of the aging step is conducted at elevated temperature. One of the periods of the aging step is conducted at about room temperature. The elevated temperature of the aging step is 50°C or higher, for example in the range of 50°C to 70°C.
  • the aging step comprises a first period conducted at about room temperature for a period of between 22 to 24 hours, and a second period conducted at a temperature in the range of 50°C to 70°C for a period of between 15 to 24 hours.
  • the present invention further provides a method for the synthesis of zeolites as described hereinabove in combination with a leach of a spodumene ore or concentrate, wherein a residue from the leach is utilised as the predominantly alumina-silicate starting material.
  • the present invention still further provides an LTA zeolite formed by the method described hereinabove.
  • the method of the present invention may be further understood with reference to the following non-limiting examples.
  • a spodumene leach residue having the chemical composition set out Table 1 below, is utilised as a starting material.
  • Table 4 illustrates the particle size distribution of the leach residue. Predominantly, it is in the range of Pso 75 ⁇ .
  • Example 1 The procedure adopted was substantially similar to Example 1 , here including the calcination of a spodumene leach residue mixed with an amount of AI(OH)3 solid and a volume of 50% w/w NaOH soln, water leaching of the calcined ground sample at room temperature (RT), an aging step comprising the aging of water leach slurry at RT (Aging-1 ) for a first period of 22 hours, and further aging of the Aging-1 slurry at room temperature (RT), 50°C or 70°C, separately (Aging-2), for a second period of 15 to 16 hours.
  • the leach slurry was passed to an aging step 32, in which a first period 32a is conducted at RT for a period of about 22 to 24 hours (Aging-1 ), for example 22 hours, and subsequently a second period 32b, conducted at any of RT, 50°C and 70°C for between about 15 to 24 hours (Aging-2), for example 15-16 hours.
  • a final slurry 34 containing zeolite and excess NaOH is collected and then centrifuged 36, producing a filtrate 35 and a zeolite product, the wet zeolite product in turn being washed 38 with water by
  • repulping/centrifuging 40 is recycled to the water leach 28.
  • the filtrate 35 from the centrifuge 36 is passed to a concentration step 42 and in turn to a NaOH store 44. From here NaOH solution may be recycled for the preparation of the uniform slurry/paste 18 of leach residue, AI(OH)3 and NaOH.
  • Evaporated liquids from the evaporator 19 may be added to this recycle stream.
  • Solids from repulping/centrifuging 40 are passed to a store for washed, wet zeolite 46 before being passed to a drying step 48, in turn providing a Linde Type A Zeolite 50 as the final product.
  • the pore volume data indicates the capacity of gas that can be adsorbed within pores of the molecules in the prepared zeolite samples. This confirms that 4 times caustic addition during calcination will produce higher pore volume capacity compared to lower caustic addition during calcination.
  • the method of the present invention provides an alkali fusion method for the synthesis of an LTA zeolite from spodumene leach residue.
  • the Applicant has determined that during fusion, the majority of the phases in the leach residue material were converted into soluble sodium silicate and then converted to amorphous material through agitation.
  • the LTA type Zeolite phase was detected in the product.
  • alumina silicate from the spodumene leach residue is understood to react with the sodium hydroxide giving rise to alumina-sodium silicate.
  • the aged material, or fused product was
  • LTA zeolite synthesised using the method of the present invention may be used as a molecular sieve or an adsorbent.
  • the method of the present invention has found that when special conditions are observed, the yield of LTA Zeolite can be greatly improved (the yield obtained when using a fly ash starting material is known to be less than 50%, whereas when using the spodumene leach residue in accordance with the present invention the yield has been found to be greater than about 85%) and the properties of the LTA Zeolite are modified (wherein a prior art fly ash starting material ultimately produces an X Type zeolite, the spodumene leach residue in accordance with the present invention produces an LTA zeolite), thus providing a number of advantages.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne une méthode (10) pour la synthèse de zéolites (50), la méthode (10) comprenant l'ajout d'un matériau de départ principalement à base d'alumine-silicate (12) à un excès stoechiométrique d'hydroxyde de sodium (16), avec de l'eau supplémentaire (30), et la calcination (20) à une température supérieure à environ 400°C pendant une période d'au moins environ 4 heures, le matériau de départ à base d'alumine-silicate (12) étant le résidu d'une lixiviation d'un minerai ou concentré de spodumène pour en extraire le lithium. L'invention concerne également une zéolite LTA formée par la méthode (10).
PCT/AU2018/050940 2017-10-04 2018-08-31 Synthèse de zéolites WO2019068135A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2017904004 2017-10-04
AU2017904004A AU2017904004A0 (en) 2017-10-04 Synthesis of Zeolites

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Publication Number Publication Date
WO2019068135A1 true WO2019068135A1 (fr) 2019-04-11

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200133467A (ko) * 2019-05-20 2020-11-30 주식회사 포스코 리튬 부산물을 이용한 제올라이트 제조 방법
CN113264538A (zh) * 2021-05-29 2021-08-17 山西腾茂科技股份有限公司 一种基于LiNaKLSX分子筛吸附剂的制备方法及应用
WO2022082258A1 (fr) * 2020-10-20 2022-04-28 Zeotech Limited Procédé de traitement d'un matériau
KR20220075904A (ko) * 2020-11-30 2022-06-08 재단법인 포항산업과학연구원 리튬 부산물을 이용한 제올라이트 제조방법
CN116786078A (zh) * 2023-05-25 2023-09-22 苏州博睿特环保科技有限公司 硅酸锂铁改性锂辉石矿渣锂离子筛、其前驱体及制备方法
WO2024050600A1 (fr) * 2022-09-08 2024-03-14 Commonwealth Scientific And Industrial Research Organisation Méthode de production de zéolite à partir d'une composition minérale réfractaire aux acides

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CN101591025A (zh) * 2009-06-29 2009-12-02 中南大学 一种利用高岭土制备无粘结剂a型沸石分子筛的方法
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CN102351213A (zh) * 2011-07-21 2012-02-15 中国地质大学（武汉） 一种制备3a型沸石分子筛的方法
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200133467A (ko) * 2019-05-20 2020-11-30 주식회사 포스코 리튬 부산물을 이용한 제올라이트 제조 방법
KR102271298B1 (ko) * 2019-05-20 2021-06-29 주식회사 포스코 리튬 부산물을 이용한 제올라이트 제조 방법
WO2022082258A1 (fr) * 2020-10-20 2022-04-28 Zeotech Limited Procédé de traitement d'un matériau
KR20220075904A (ko) * 2020-11-30 2022-06-08 재단법인 포항산업과학연구원 리튬 부산물을 이용한 제올라이트 제조방법
KR102508854B1 (ko) 2020-11-30 2023-03-09 재단법인 포항산업과학연구원 리튬 부산물을 이용한 제올라이트 제조방법
CN113264538A (zh) * 2021-05-29 2021-08-17 山西腾茂科技股份有限公司 一种基于LiNaKLSX分子筛吸附剂的制备方法及应用
CN113264538B (zh) * 2021-05-29 2022-11-08 山西腾茂科技股份有限公司 一种基于LiNaKLSX分子筛吸附剂的制备方法及应用
WO2024050600A1 (fr) * 2022-09-08 2024-03-14 Commonwealth Scientific And Industrial Research Organisation Méthode de production de zéolite à partir d'une composition minérale réfractaire aux acides
CN116786078A (zh) * 2023-05-25 2023-09-22 苏州博睿特环保科技有限公司 硅酸锂铁改性锂辉石矿渣锂离子筛、其前驱体及制备方法

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