CN107486146B - 一种混合阳离子LiCa-LSX分子筛制法及应用 - Google Patents

一种混合阳离子LiCa-LSX分子筛制法及应用 Download PDF

Info

Publication number
CN107486146B
CN107486146B CN201710793404.4A CN201710793404A CN107486146B CN 107486146 B CN107486146 B CN 107486146B CN 201710793404 A CN201710793404 A CN 201710793404A CN 107486146 B CN107486146 B CN 107486146B
Authority
CN
China
Prior art keywords
molecular sieve
lica
lsx
exchange
solution
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.)
Active
Application number
CN201710793404.4A
Other languages
English (en)
Other versions
CN107486146A (zh
Inventor
李建波
刘应书
杨雄
郭艳霞
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.)
Luoyang Jianlong Micro Nano New Materials Co ltd
Original Assignee
Luoyang Jianlong Micro Nano New Materials Co 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
Application filed by Luoyang Jianlong Micro Nano New Materials Co ltd filed Critical Luoyang Jianlong Micro Nano New Materials Co ltd
Priority to CN201710793404.4A priority Critical patent/CN107486146B/zh
Publication of CN107486146A publication Critical patent/CN107486146A/zh
Priority to ES18154326T priority patent/ES2832810T3/es
Priority to JP2018015352A priority patent/JP6642932B2/ja
Priority to EP18154326.5A priority patent/EP3453677B1/en
Priority to US15/887,973 priority patent/US10583418B2/en
Application granted granted Critical
Publication of CN107486146B publication Critical patent/CN107486146B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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
    • 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
    • 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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0259—Physical processing only by adsorption on solids
    • C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
    • C01B13/027—Zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C01B33/28—Base exchange silicates, e.g. zeolites
    • C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
    • C01B33/2838—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of faujasite type, or type X or Y (UNION CARBIDE trade names; correspond to GRACE's types Z-14 and Z-14HS, respectively)
    • C01B33/2846—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of faujasite type, or type X or Y (UNION CARBIDE trade names; correspond to GRACE's types Z-14 and Z-14HS, respectively) of type X
    • 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
    • C01B39/026—After-treatment
    • 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
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/22—Type X
    • 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
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
    • C01B2210/0018—Zeolites

Abstract

本发明介绍了一种混合阳离子LiCa‑LSX分子筛制法及应用，步骤一：CaLSX分子筛的制备；采用含有Ca2+的溶液经过多次交换将NaLSX分子筛中的Na+全交换为Ca2+；步骤二：将CaLSX分子筛通过Li+交换成LiCa‑LSX分子筛；采用含有Li+的溶液进行交换，交换之后的样品不清洗，直接进行真空抽滤，常温干燥，样品活化预处理，得到混合阳离子LiCa‑LSX分子筛。将LiCa‑LSX分子筛可以用于PSA/VPSA制氧工艺中做为N2和O2的选择性吸附剂。本发明过滤时不用水洗从而避免水解导致H+取代Li+造成Li+的损失；交换过程中Li+交换度低、用量少，成本易于控制；采用适合LiLSX分子筛充分脱水的最低活化温度，处理时间短，防止Li+迁移到较低位置（SI、SII），可以充分保证Li+存在于SII位。

Description

一种混合阳离子LiCa-LSX分子筛制法及应用
技术领域
本发明涉及一种分子筛的制备方法，特别涉及一种混合阳离子LiCa-LSX分子筛制法及应用。
背景技术
随着工业和社会经济的发展，高纯氧气和氮气的应用领域越来越广泛，包括炼油、医疗、金属生产、食品加工和化学品等。其中低温蒸馏分离空气和变压吸附(PSA)是制备高纯氧气和氮气的两种主要技术。LiLSX分子筛作为变压吸附空分制氧吸附剂，具有氮气吸附容量大、氮氧分离系数高的优点。制备LiLSX分子筛吸附剂的技术关键是用Li+交换NaLSX分子筛。研究表明，当Li+的交换度低于70%时，分子筛对N2的吸附容量几乎没有变化，只有当Li+的交换度从70%增加到100%时，分子筛对N2的吸附容量才呈线性增加。所以，制备LiLSX分子筛对Li+需求量大，且随着锂离子电池的迅速发展以及锂的储量一直在减少，从2016年以来，锂的价格一直在上涨，造成LiLSX分子筛的生产成本相当高。
分子筛作为吸附剂对空气的分离性能是基于分子筛阳离子的电场梯度与N2的四极矩之间的相互作用，而这种相互作用与分子筛的阳离子位点有很大关系。八面沸石的阳离子位点如图1所示。对于LiX分子筛，只有III (SIII) 位可以与N2（O2）结合，这是因为骨架周围的氧和小尺寸的Li+的电子屏蔽效应使得在SII位置的Li+不能被有效利用。
分子筛在使用之前一般需要经过预先加热脱水处理，通常，400℃条件下至少需要处理4小时。在这种情况下，阳离子会迁移或者扩散到它的平衡位点。对于具有混合阳离子的分子筛，研究发现质量较轻的阳离子倾向于迁移到较低的位点(SI、SI’、SII、SII)。例如，在混合阳离子CeNaCa-X分子筛中，Na和Ca在较低位点，而Ce(III)阳离子在外部的一些位点上。在混合阳离子NaSr-X沸石上，Na+离子在SI位，而Sr2+在 SII位。这种阳离子分布特点也存在于LiNa-LSX分子筛骨架中。
PSA/VPSA空分制氧领域，Li-LSX分子筛备受青睐，在此应用领域，也用到一些其他分子筛，尤其是具有碱金属阳离子的LSX分子筛。Chao et al.研究了含锂(30% - 90%)和碱土金属(10% - 70%)的A型和X型混合阳离子沸石，例如Ca2+和Sr2+，均具有较高的N2吸附容量。这些混合阳离子沸石一般至少需要70 mol% 的Li+（碱金属离子的摩尔量< 30 mol%），且往往需要先交换Li+，然后再交换碱金属离子。本发明旨在合成一种廉价或储量丰富的碱金属阳离子占主导、含少量Li+且可用于气体分离的分子筛吸附剂。
发明内容
本发明所要解决的技术问题是一种混合阳离子LiCa-LSX分子筛制法及应用，容易工业化生产，制备成本低，N2吸附容量高，PSA/VPSA产氧量高。
本发明所进一步解决的技术问题是提供一种骨架中Li含量低且起关键吸附作用的LiCa-LSX分子筛的制备方法。
本发明所更进一步解决的技术问题是采用温和的交换工艺，尽可能的降低分子筛骨架中的Li+含量，使交换上去的Li+全部发挥作用。
本发明所更进一步解决的技术问题是合成一种可用于PSA/VPSA空分制氧领域且具有较高的产氧量的分子筛吸附剂。
为了实现解决上述技术问题的目的，本发明采用了如下技术方案：
一种混合阳离子LiCa-LSX分子筛制法，包括如下过程：
步骤一：CaLSX分子筛的制备；
在制备CaLSX分子筛的过程中，采用含有Ca2+的溶液经过多次交换将NaLSX分子筛中的Na+全交换为Ca2+，交换液温度为室温，洗涤除去表面附着的Ca2+和Cl-，洗涤之后的滤饼经过干燥得到CaLSX分子筛；
具体的，该含有Ca2+的溶液为常见的含有Ca2+的盐溶液，优选采用CaCl2溶液；采用多次含有Ca2+的溶液交换方法，优选为六次交换，每次交换时间不低于6小时；优选的，前几次交换的交换液用到下一批次的Ca2+交换成CaLSX过程中；
更具体的，含有Ca2+的溶液的Ca2+的浓度为1.0 M。
步骤二：将CaLSX分子筛通过Li+交换成LiCa-LSX分子筛；控制得到的LiCa-LSX分子筛的Li+离子的摩尔百分含量范围为2-5%；
Li+交换成CaLi-LSX分子筛过程中，采用含有Li+的溶液进行交换，CaLSX分子筛加入到含有Li+的溶液的加入量为：Li+的初始物质的量分别为CaLSX分子筛原粉中含有的Ca2+的0.15-0.3倍，交换温度为室温，交换时间为0.5-2小时，优选为1小时，交换之后的样品不清洗，直接进行真空抽滤，常温干燥；通过控制加入的含有Li+的溶液的加入量，制备的混合阳离子LiCa-LSX分子筛的Li+离子的摩尔百分含量为2-5%之间；
本处所述的Li+离子的摩尔百分含量，是指Li+离子量占ICP检测时加入的混合阳离子分子筛原粉干基的物质的量的百分比。
该含有Li+的溶液为常见的含有Li+的盐溶液，优选LiCl溶液，
更具体的，含有Li+的溶液的Li+的浓度为1.0 M。
步骤三：样品活化预处理：将常温干燥后的产物加热，升温速度为5-15℃/min，最高温度为330-350℃，脱气时间0.5-3小时，优选为1小时，脱气结束后自然冷却至室温，即得到混合阳离子LiCa-LSX分子筛。
所述的混合阳离子LiCa-LSX分子筛制法还可以包括步骤四：等温线测试。
所述的具有混合阳离子LiCa-LSX分子筛的制备方法，所述的NaLSX分子筛为硅铝比SiO2/Al2O3为2.0的分子筛原粉。
一种混合阳离子LiCa-LSX分子筛的应用，其特征是：将LiCa-LSX分子筛用于PSA/VPSA制氧工艺中作为N2和O2的选择性吸附剂。
这些技术方案，包括改进的技术方案以及进一步改进的技术方案也可以互相组合或者结合，从而达到更好的技术效果。
本发明的具有混合阳离子LiCa-LSX分子筛的制备方法，可以将Li+离子的交换度控制在较低的范围内（2.5%和4.2%），即得到两种具有混合阳离子的LiCa-LSX分子筛原粉（Li2.5Ca46.75-LSX 和 Li4.2Ca45.9-LSX）。本专利采用温和的两步交换方法制备出含Li+少于5%的混合阳离子LiCa-LSX分子筛，有效减少了传统制氧分子筛中的Li+的使用量，节约了生产成本。通过对比LiCa-LSX分子筛和其它纯阳离子Li-LSX和Ca-LSX分子筛对N2和O2的吸附量、吸附热数据证明一部分Li+位于暴露的SIII位点，从而参与对N2和O2的吸附。采用PSA和VPSA制氧模拟装置对比了混合阳离子LiCa-LSX分子筛与纯阳离子Li-LSX 和 Ca-LSX分子筛的产氧量。模拟结果表明，只用少量Li+交换Ca-LSX分子筛得到的Li4.2Ca45.9-LSX 分子筛可以有效提高PSA产氧量。
通过采用上述技术方案，本发明具有以下的有益效果：
一、本发明在所述Li交换过程中采用稀的LiCl溶液，过滤时不用水洗从而避免水解导致H+取代Li+造成Li+的损失。
二、本发明是采用Li+交换CaLSX分子筛中的Ca2+，而不是用Ca2+交换LiLSX中的Li+。在X型分子筛的离子交换中，Li+不容易直接将Na+从分子筛骨架中交换下来，所以先交换Li+会存在交换困难、Li+离子利用率低的问题，而先交换Ca2+，再采用Li+交换Ca2+，低Li+交换度的情况下易于控制Li+的用量。
三、本发明在交换过程中Li+交换度低、用量少，成本易于控制。通过控制Li溶液加入量，控制Li+交换度，交换液中Li+含量低自然交换度就低。本发明所合成样品的交换度较低，少量的Li+较可以满足所需交换度的要求，因而在较低的交换度下，所需要的Li+用量就会大大减少。
四、本发明采用适合LiLSX分子筛充分脱水的最低活化温度，处理时间短，防止Li+迁移到较低位置（SI、SII），可以充分保证Li+存在于SII位。
附图说明
图1是八面沸石的晶胞以及位点分布图。
图2是四种样品在25 oC，1 atm测试条件下的N2吸附等温线。
图3是四种样品在50oC/ 1 atm测试条件下的N2吸附等温线。
图4是四种样品在70oC/ 1 atm测试条件下的N2吸附等温线。
图5是四种样品在25 oC，1 atm测试条件下对O2的吸附等温线。
图6是四种样品在50oC，1 atm测试条件下对O2的吸附等温线。
图7是四种样品在70oC，1 atm测试条件下对O2的吸附等温线。
具体实施方式
下面结合附图和实施例对本专利进一步解释说明。但本专利的保护范围不限于具体的实施方式。
实施例1
1、Na-LSX交换为Ca-LSX。
采用玻璃烧杯进行罐式交换，每次交换6小时，交换液温度为25℃，具体操作为：
50g NaLSX原粉（干基）加入88 mL 浓度为1.0 M的CaCl2溶液中，采用磁力搅拌器进行混合搅拌，每次交换时间为6小时，重复交换6次，最后用500 mL去离子水在真空抽滤瓶上抽滤洗涤，滤饼在25℃的炉子内干燥。
2、混合离子交换。
采用玻璃烧杯进行罐式交换，每次交换1小时，交换液温度为25℃，具体操作为：
取两个玻璃烧杯，分别加入1.5 g上述制备的CaLSX原粉，采用0.1M的LiCl溶液分别与之进行交换，控制烧杯内的Li+的初始物质的量分别为CaLSX原粉中含有的Ca2+的0.15---0.3倍，磁力搅拌1小时，交换液的温度为25℃，无需调整溶液pH值。交换之后的固液混合物倒入布氏漏斗内进行真空抽滤，不用清水洗涤，滤饼在25℃条件下干燥24小时。所得交换后的混合阳离子分子筛原粉的化学组成采用电感耦合等离子体发射光谱仪（ICP-OES）进行检测，检测结果表明Li+的交换度分别是2.5%和4.2%（指干基中的摩尔比百分含量），分别命名为Li2.5Ca46.75-LSX 和 Li4.2Ca45.9-LSX。
3、样品预处理
进行等温线测试前的样品需要经过脱水处理，具体操作为：
采用麦克ASAP 3020吸附仪上配套的脱气活化装置进行原位脱气/脱水处理，对于Li2.5Ca46.75-LSX 和 Li4.2Ca45.9-LSX两种混合阳离子分子筛，在350℃条件下脱水处理1小时，对于Li-LSX和Ca-LSX分子筛则分别在375℃和350℃条件下处理8小时，样品处理过程中均设定升温速度为10℃/min，处理之后自然冷却至室温。混合阳离子较短的预处理有利于避免Li+迁移到较低为位点（SI、SII）。
4、吸附等温线测试及结果分析
吸附等温线测试采用麦克ASAP 3020吸附仪，测试温度分别为25℃，50℃，70℃，测试压力为1 atm。测试结果如图2-图7。

Claims (5)

1.一种混合阳离子LiCa-LSX分子筛制法，其特征是：包括如下过程：
步骤一：CaLSX分子筛的制备；
在制备CaLSX分子筛的过程中，采用含有Ca2+的溶液经过多次交换将NaLSX分子筛中的Na+全交换为Ca2+，交换液温度为室温，洗涤除去表面附着的Ca2+和Cl-，洗涤之后的滤饼经过干燥得到CaLSX分子筛；
步骤二：将CaLSX分子筛通过Li+交换成LiCa-LSX分子筛；控制得到的LiCa-LSX分子筛的Li+离子的摩尔百分含量范围为2-5%；
Li+交换成CaLi-LSX分子筛过程中，采用含有Li+的溶液进行交换，CaLSX分子筛加入到含有Li+的溶液的加入量为：Li+的初始物质的量分别为CaLSX分子筛原粉中含有的Ca2+的0.15-0.3倍，交换温度为室温，交换时间为0.5-2小时，交换之后的样品不清洗，直接进行真空抽滤，常温干燥；
步骤三：样品活化预处理：将常温干燥后的产物加热，升温速度为5-15℃/min，最高温度为330-350℃，脱气时间0.5-3小时，脱气结束后自然冷却至室温，即得到混合阳离子LiCa-LSX分子筛。
2.根据权利要求1所述混合阳离子LiCa-LSX分子筛制法，其特征是：所述的含有Li+的溶液为LiCl溶液。
3.根据权利要求1所述混合阳离子LiCa-LSX分子筛制法，其特征是：所述的混合阳离子LiCa-LSX分子筛制法还包括步骤四：等温线测试。
4.根据权利要求1所述混合阳离子LiCa-LSX分子筛制法，其特征是：所述的NaLSX分子筛为硅铝比SiO2/Al2O3为2.0的分子筛原粉。
5.一种权利要求1所述制法制备的混合阳离子LiCa-LSX分子筛的应用，其特征是：将LiCa-LSX分子筛用于PSA/VPSA制氧工艺中作为N2和O2的选择性吸附剂。
CN201710793404.4A 2017-09-06 2017-09-06 一种混合阳离子LiCa-LSX分子筛制法及应用 Active CN107486146B (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201710793404.4A CN107486146B (zh) 2017-09-06 2017-09-06 一种混合阳离子LiCa-LSX分子筛制法及应用
ES18154326T ES2832810T3 (es) 2017-09-06 2018-01-31 Métodos de preparación de tamices moleculares LiCa-LSX con cationes mixtos y aplicaciones de los mismos
JP2018015352A JP6642932B2 (ja) 2017-09-06 2018-01-31 混合カチオンＬｉＣａ−ＬＳＸ分子篩の製造方法及び応用
EP18154326.5A EP3453677B1 (en) 2017-09-06 2018-01-31 Methods for preparing lica-lsx molecularsieves with mixed cations and applications thereof
US15/887,973 US10583418B2 (en) 2017-09-06 2018-02-02 Methods for preparing LiCa-LSX molecular sieves with mixed cations and applications thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710793404.4A CN107486146B (zh) 2017-09-06 2017-09-06 一种混合阳离子LiCa-LSX分子筛制法及应用

Publications (2)

Publication Number Publication Date
CN107486146A CN107486146A (zh) 2017-12-19
CN107486146B true CN107486146B (zh) 2020-10-23

Family

ID=60652169

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710793404.4A Active CN107486146B (zh) 2017-09-06 2017-09-06 一种混合阳离子LiCa-LSX分子筛制法及应用

Country Status (5)

Country Link
US (1) US10583418B2 (zh)
EP (1) EP3453677B1 (zh)
JP (1) JP6642932B2 (zh)
CN (1) CN107486146B (zh)
ES (1) ES2832810T3 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108862303A (zh) * 2018-07-04 2018-11-23 洛阳建龙微纳新材料股份有限公司 一种碱土阳离子Sr-LSX分子筛及其制备方法和应用
CN108854947B (zh) * 2018-07-04 2021-08-17 洛阳建龙微纳新材料股份有限公司 一种混合阳离子AgCa-LSX分子筛及其制备方法和应用
CN110743492A (zh) * 2019-10-18 2020-02-04 苏州立昂新材料有限公司 混有多价阳离子的锂型低硅八面沸石、其制备方法及用途
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
CN115487776A (zh) * 2021-11-26 2022-12-20 北京科技大学 一种酮类VOCs吸附剂及其制备方法和应用

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5152813A (en) * 1991-12-20 1992-10-06 Air Products And Chemicals, Inc. Nitrogen adsorption with a Ca and/or Sr exchanged lithium X-zeolite
US5604169A (en) * 1996-03-04 1997-02-18 Praxair Technology, Inc. Process for producing mixed-cation zeolites
DE69708790T2 (de) * 1996-08-30 2002-08-08 Tosoh Corp Wärmebeständiges Zeolith mit niedrigem Kieselsäuregehalt und Verfahren zu dessen Herstellung und Verwendung
FR2758739B1 (fr) * 1997-01-24 1999-02-26 Ceca Sa Perfectionnement dans les procedes psa de purification de l'hydrogene
FR2771943B1 (fr) * 1997-12-05 2000-01-14 Air Liquide Procede de purification de fluides inertes par adsorption sur zeolite lsx
US6780806B1 (en) * 1998-12-30 2004-08-24 The Regents Of The University Of Michigan Lithium-based zeolites containing silver and copper and use thereof for selective absorption
FR2792220B1 (fr) * 1999-04-19 2001-06-15 Air Liquide Procede psa mettant en oeuvre un adsorbant a resistance intrinseque favorable a la cinetique d'adsorption
FR2811241B1 (fr) * 2000-07-07 2002-12-13 Ceca Sa Procede pour la purification de melanges gazeux a base d'hydrogene utilisant une zeolite x au calcium
US7396387B2 (en) * 2005-11-01 2008-07-08 Praxair Technology, Inc. Pressure swing adsorption process for large capacity oxygen production
CN101708456B (zh) * 2009-11-23 2013-03-06 洛阳市建龙化工有限公司 一种变压吸附空分制氧的分子筛吸附剂及其制备方法
FR2970184B1 (fr) * 2011-01-07 2013-08-02 Air Liquide Composition zeolitique adaptee a l'epuration d'air
CN103539150A (zh) * 2013-10-15 2014-01-29 北京工业大学 一种低硅铝比X型沸石分子筛[(Li, Ca)-LSX]的制备方法

Also Published As

Publication number Publication date
EP3453677A1 (en) 2019-03-13
EP3453677B1 (en) 2020-10-21
US10583418B2 (en) 2020-03-10
US20190070584A1 (en) 2019-03-07
JP2019043832A (ja) 2019-03-22
JP6642932B2 (ja) 2020-02-12
ES2832810T3 (es) 2021-06-11
CN107486146A (zh) 2017-12-19

Similar Documents

Publication Publication Date Title
CN107486146B (zh) 一种混合阳离子LiCa-LSX分子筛制法及应用
US5868818A (en) Adsorbent for air separation, production method thereof, and air-separation method using it
CN1037156C (zh) 从空气中回收氧或氮的真空变压吸附系统
CA2085180C (en) Nitrogen adsorption with a ca and/or sr exchanged lithium x-zeolite
JPH0525527B2 (zh)
CN102784617B (zh) 一种含银分子筛吸附剂及其制备方法和应用
CN111039303B (zh) 改性m-sapo-rho型沸石分子筛作为乙烯选择吸附剂的应用
CN104254493A (zh) 硅酸铝及其制造方法
CA2148893A1 (en) Li-exchanged low silica emt-containing metallosilicates
CN101289196B (zh) 一种LiLSX分子筛的制备方法
CN106276968A (zh) 一种改性heu型沸石的制备方法及作为氮气选择吸附剂的应用
CN111250036A (zh) 一种钠离子吸附剂、其制备方法及其应用
US6878657B2 (en) Process for the preparation of a molecular sieve adsorbent for the size/shape selective separation of air
CN113264538B (zh) 一种基于LiNaKLSX分子筛吸附剂的制备方法及应用
CN108854947B (zh) 一种混合阳离子AgCa-LSX分子筛及其制备方法和应用
CN108862303A (zh) 一种碱土阳离子Sr-LSX分子筛及其制备方法和应用
US5997841A (en) Zincoaluminosilicates of the FAU structure
CN114349019A (zh) 一种粉煤灰基沸石分子筛的制备方法
JPH0685870B2 (ja) 吸着分離剤
US7041155B1 (en) Selective adsorbent for nitrogen and method for separating air using the same
CN106698458A (zh) 锂型低硅八面沸石、其制备方法及用途
CN117509657A (zh) 一种以海砂作为硅源合成方沸石的制备方法
CN116351396A (zh) 一种气体吸附剂的制备方法及应用
CN112777608A (zh) 一种钾交换率高的3a型沸石分子筛制备方法
CN102795634B (zh) 一种降低β型分子筛中氧化钠含量的交换改性方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information

Inventor after: Liu Yingshu

Inventor after: Li Jianbo

Inventor after: Yang Xiong

Inventor after: Guo Yanxia

Inventor before: Li Jianbo

Inventor before: Liu Yingshu

Inventor before: Yang Xiong

Inventor before: Guo Yanxia

CB03 Change of inventor or designer information