CN108033460A - A kind of new 3A molecular sieves and preparation method thereof - Google Patents

A kind of new 3A molecular sieves and preparation method thereof Download PDF

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Publication number
CN108033460A
CN108033460A CN201711429647.6A CN201711429647A CN108033460A CN 108033460 A CN108033460 A CN 108033460A CN 201711429647 A CN201711429647 A CN 201711429647A CN 108033460 A CN108033460 A CN 108033460A
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China
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molecular sieves
new
oxide
rare earth
molecular
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CN201711429647.6A
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Chinese (zh)
Inventor
孙玉坤
金雷
张秋双
王治洪
梁劲
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DALIAN HAIXIN CHEMICAL INDUSTRY Co Ltd
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DALIAN HAIXIN CHEMICAL INDUSTRY Co Ltd
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Priority to CN201711429647.6A priority Critical patent/CN108033460A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline 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
    • C01B39/14Type A
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06Joining glass to glass by processes other than fusing
    • C03C27/10Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Abstract

The invention belongs to molecular sieve art, a kind of new 3A molecular sieves, it is to mix 4A molecular sieves, metal oxide or metal hydroxides, rare earth oxide and binding agent for raw material, by turning, pot sprays drying after saline solution containing K is molded, activation is prepared.Preparation process of the present invention is simple, low cost and environmental protection.The usage amount of 4A original powders is reduced in raw material dispensing, the cheaper metal oxide of selection production cost or metal hydroxides do drier active ingredient, and a certain amount of rare-earth oxide is added to improve the heat endurance of sample, after adding Binder Composition mixing, recycling contains K+Spray solution is molded, and new 3A molecular sieves are made after dry activate.

Description

A kind of new 3A molecular sieves and preparation method thereof
Technical field
The invention belongs to molecular sieve art, more particularly to A type molecular sieve and its preparation process.
Background technology
With the high speed development of Chinese national economy and the progress of science and technology, the requirement to building energy conservation is more and more tighter Lattice.The building energy consumption in China accounts for the 1/4 of national energy consumption total amount.Building energy conservation is related to all too many levels.Reality both domestic and external Proof is trampled, improves the heat-insulating property of buildings exterior-protected structure, the heat-insulating property for particularly improving window is to prevent building heat Lost most economical, most efficient method.Application of the hollow glass in building plays the effect of key.The life of hollow glass Production technology originates from the U.S. earliest, since it has prominent unique function-energy saving, in North America, European Countries, Japan, South Korea Promoted rapidly, produced, applied with countries such as China.Its international market is increasingly good, and the U.S. is hollow in the international market Glass production big country, and one of consumption big country.From the point of view of domestic market, hollow glass production and usage amount present uptrend state: 70.3 ten thousand m of nineteen ninety-five2, 95.98 ten thousand m in 19972, usage amount exceedes 5,000,000 m within 20002.It can be seen that hollow glass is in state There is vast potential for future development in inside and outside market.
Hollow glass is made of glazing compound, interval box and drier.Molecular sieve wherein for hollow glass is done Drying prescription has two classes:A classes and X classes, its main function is the moisture adsorbed in air layer, so will consider point when selecting molecular sieve The water absorbing capacity of son sieve.It it is 21 DEG C in temperature, when condensation point is -40 DEG C, the water absorbing capacity highest of 13X, every 100 grams of drier can 16 grams of water is adsorbed, 4A takes second place, and 3A is minimum, every gram of 13.5 grams of water of absorption, it can be seen that it should be that soaking effect is best to select 13X , but 13X water suctions also adsorb air at the same time, can thus change the gas flow in hollow glass, so as to cause the flexure of glass. And 3A only adsorbs water since its aperture is smaller, air is not adsorbed, that is, selecting can be in the same of effectively absorption hollow glass moisture When, and glass is not impacted, therefore research 3A molecular sieves have extremely important meaning.
At the same time, the dry system of some needs for such as alkene, although 4A, 5A, 13X molecular sieve have high water absorption It is widely used in various drying processes, but these molecular sieves can also adsorb other molecules while water suction, i.e., some alkene The drying system of hydrocarbon can only use 3A molecular sieves because 3A molecular sieves can only adsorbed water molecule without adsorbing other materials, therefore efficiently 3A molecular sieves have vast potential for future development.
And existing type body 3A molecular sieves mainly have two kinds of production technologies:First, conventional preparation techniques, former with synthesis 4A zeolites Powder carries out ion exchange with KCl solution, obtains 3A zeolites, then is incorporated clay, using the moulding process such as rolling and extruding, is manufactured into Bar shaped or spherical product, by drying and calcination for activation, obtain zeolite product;Greatest problem existing for the technique is its KCl Consumption it is huge, 1 ton of 3A zeolites of production will generally consume 500 ~ 1000Kg potassium chloride, while be handed over using 4A original powders Change, it is necessary to being beaten, filtering, washing and corresponding equipment is completed to operate, process is cumbersome;Second, it is directed to above-mentioned technical study person The production new technique developed, first 4A zeolites and clay mineral are mixed as introduced in CN103721673A, Ran Houzao Ball, extruded moulding, then K is carried out again after drying roasts+Ion exchange, roasts to obtain type body 3A molecules by secondary drying Sieve, although the technique reduces the usage amount of KCl to a certain extent, still has and exchanges washing process and waste liquid generation.
CN105800638A proposes a kind of solid liposome nanoparticle technique on the basis of above-mentioned technique:I.e. by 4A molecules It is raw material that original powder, which is sieved, with the electrolyte containing potassium element and clay, and after adding water mixed-forming, roasting direct forms.The process program Provide a kind of 3A molecular sieve preparation methods of low energy consumption and zero-emission.But still had using the 3A molecular sieve desiccants of pure phase Production cost is high, and still there are contaminated wastewater environmental problem for the synthesis of 4A original powders.
The content of the invention
The problem to be solved in the present invention is:Overcome traditional 3A molecular sieve productions consumption sylvite amount big, the consumption energy is more, The problems such as seriously polluted, use for reference solid liposome nanoparticle technique, adjustment material proportion, process, there is provided a kind of new 3A molecules Sieve, product stability is excellent, in addition provides its preparation process, and production cost is low, environmental-friendly.
The present invention is that technical solution is used by solving the above problems:A kind of new 3A molecular sieves, it is by 4A molecules Sieve original powder, metal oxide or metal hydroxides, rare earth oxide are mixed with binding agent, contain K by sprinkling+Solution is molded Afterwards, then activate and be made by high-temperature roasting.A kind of new 3A molecular sieves, the parts by weight of its constitutive material are:4A molecules Sieve original powder 40-80, metal oxide or metal hydroxides 5-20, rare earth oxide 0.2-2, binding agent 15-40.
A kind of new 3A molecular sieves, the parts by weight of its constitutive material are:4A molecular screen primary powders 40-80, metal oxide Or metal hydroxides 10-15, rare earth oxide 0.2-1, binding agent 20-30.
It is described to contain K+Solution is potassium chloride, potassium carbonate, saleratus, one kind in potassium sulfate and more than one mixing are molten Liquid, the part by weight that its contained potassium element accounts for new 3A molecular sieves are less than 9 .6%, it is preferable that the weight ratio containing potassium element is 3%-5%.
A kind of preparation method of new 3A molecular sieves of the present invention, step include:
1) mix:4A molecular screen primary powders, metal oxide or metal hydroxides, rare earth oxide and binding agent are mixed in proportion Close;
2) it is molded:Containing K+Spray solution is turning in pot on mixed material, rolls shaping and 0.5-2.0mm diameter particles are made;
3) it is dry:Particulate matter is placed in baking oven, 100 ± 10 DEG C, dry 1-2h;
4) activate:Dried particulate matter is placed in Muffle furnace, 550 ± 25 DEG C, activates 1-2h, and new 3A molecular sieves are made.
The beneficial effects of the invention are as follows:Composition of raw materials is rationally simple, and performance, which is stablized, to be improved, obtained 3A molecular sieves,
(1) under 25 DEG C and a standard atmosphere condition, selection absorption of the 3A molecular sieves to water and the selection to nitrogen Adsorptivity weight ratio is more than 100;
(2) under 25 DEG C and a standard atmosphere condition, the 3A molecular sieves static water absorption rate is more than 19%;
(3) under 25 DEG C and a standard atmosphere condition, the 3A molecular sieves are more than in relative humidity 11%, static water absorption rate 16%;
(4) the 3A molecular sieves described in are suitable with 3A molecular sieve absorption properties obtained by hydrothermal solvent method.
The new 3A molecular sieves of the present invention, mainly apply hollow glass interlayer adsorbent.
Preparation process of the present invention is simple, low cost and environmental protection.The usage amount of 4A original powders, selection are reduced in raw material dispensing The cheaper metal oxide of production cost or metal hydroxides do drier active ingredient, and add a certain amount of rare earth Metal oxide improves the heat endurance of sample, and after adding Binder Composition mixing, recycling contains K+Spray solution is molded, warp New 3A molecular sieves are made after dry activation.
Brief description of the drawings:
3A molecular sieves before and after Fig. 1 addition rare earth oxides(Embodiment 3 and 4)X-ray powder diffraction(XRD)Contrast collection of illustrative plates.
Embodiment:
The present invention is described in further detail with reference to specific embodiment, but the present invention is not limited only to specific embodiment.
Embodiment 1:
By 4A original powders, lanthana, rod soil by weight 74:1:25 mixing, spray K by turning pot2CO3Solution is molded spherical products, Then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, the new of the present invention is made Spherical 3A molecular sieves.
Embodiment 2:
By 4A original powders, magnesium hydroxide, lanthana, rod soil by weight 55:19:1:25 mixing, spray K by turning pot2CO3Solution into Type spherical products, then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, be made The novel ball 3A molecular sieves of the present invention.
1 4A original powders of table and the quotation contrast table of metal oxide or metal hydroxides
Raw material Price(Member/T)
4A powder(Auxiliary agent) 3500
(Hydrogen)Magnesia 1500
(Hydrogen)Aluminium oxide 3000
Table 2 is added before and after metal oxide or metal hydroxides(Examples 1 and 2)The 24h static water absorptions of 3A molecular sieves
Sample 24h static water absorptions(wt%)
1 sample of embodiment 19.8
2 sample of embodiment 19.7
The raw material quotation of 1 and 2 sample of comparative example and 24h static water absorptions result are understood, by part 4A molecular screen primary powders After replacing with metal oxide or metal hydroxides or metal hydroxides, while cost is reduced, its absorption property is simultaneously It is not affected by influence.
Embodiment 3:
By 4A original powders, aluminium oxide, bentonite by weight 60:15:25 mixing, spray KCl solution shaping spherical products by turning pot, Then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, the new of the present invention is made Spherical 3A molecular sieves.
Embodiment 4:
By 4A original powders, aluminium oxide, lanthana, bentonite by weight 60:15:0.2:25 mixing, spray KCl by turning pot:Solution Spherical products are molded, then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, system Into the novel ball 3A molecular sieves of the present invention.
The XRD spectra of 3 and 4 sample of comparative example is understood, after adding a small amount of rare-earth oxide, its XRD diffraction is special There is reinforced partly at sign peak, it illustrates that its crystallinity increases, i.e., improves the hydrothermal stability of product to a certain extent.
Embodiment 5:
By 4A original powders, aluminium oxide, lanthana, bentonite by weight 60:15:0.2:25 mixing, by turn pot spray KCl and K2SO4(mole metering ratio 2:1) mixed solution shaping spherical products, then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, and the novel ball 3A molecular sieves of the present invention are made.
Embodiment 6:
By 4A original powders, aluminium oxide, europium oxide, bentonite by weight 58:17:0.2:25 mixing, spray KHCO by turning pot3Salt is molten Liquid is molded spherical products, and then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into 550 ± 25 DEG C of Muffle furnace, activates 1-2h, The novel ball 3A molecular sieves of the present invention are made.
Embodiment 7:
By 4A original powders, magnesium hydroxide, aluminium oxide, actinium oxide, kaolin, montmorillonite by weight 55:10:10:0.5:13:12 is mixed Close, spray KCl solution shaping spherical products by turning pot, then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into Muffle furnace 550 ± 25 DEG C, 1-2h is activated, the novel ball 3A molecular sieves of the present invention are made.
Embodiment 8:
By 4A original powders, magnesium hydroxide, lanthana, europium oxide, rod soil, kaolin are by weight 58:17:0.2:0.2:13:12 is mixed Close, spray K by turning pot2CO3Solution is molded spherical products, and then in 100 ± 10 DEG C of drying box, dry 1-2h, is put into Muffle furnace 550 ± 25 DEG C, 1-2h is activated, the novel ball 3A molecular sieves of the present invention are made.
The 3A molecular sieves of above-mentioned gained, after testing function admirable:
(1) under 25 DEG C and a standard atmosphere condition, the selection absorption to water and the Selective adsorption weight ratio to nitrogen More than 100;
(2) under 25 DEG C and a standard atmosphere condition, static water absorption rate is more than 19%;
(3) under 25 DEG C and a standard atmosphere condition, in relative humidity 11%, static water absorption rate is more than 16%;
It is suitable with hydrothermal solvent method gained 3A molecular sieve absorption properties.

Claims (6)

  1. A kind of 1. new 3A molecular sieves, it is characterised in that:It is by 4A molecular screen primary powders, metal oxide or metal hydroxide Thing, rare earth oxide are mixed with binding agent, contain K by sprinkling+After solution shaping, then activate and be made by high-temperature roasting.
  2. 2. a kind of new 3A molecular sieves according to claim 1, it is characterised in that the parts by weight of its constitutive material are:4A points Son sieve original powder 40-80, metal oxide or metal hydroxides 5-20, rare earth oxide 0.2-2, binding agent 15-40.
  3. 3. a kind of new 3A molecular sieves according to claim 1, it is characterised in that the parts by weight of its constitutive material are:4A points Son sieve original powder 40-80, metal oxide or metal hydroxides 10-15, rare earth oxide 0.2-1, binding agent 20-30.
  4. A kind of 4. new 3A molecular sieves according to claim 1, it is characterised in that:It is described to contain K+Solution is potassium chloride, carbonic acid One kind and more than one mixed solution in potassium, saleratus, potassium sulfate, the part by weight of its contained potassium element are less than 9 .6%.
  5. A kind of 5. new 3A molecular sieves according to claim 4, it is characterised in that:Weight ratio containing potassium element is 3%- 5%.
  6. 6. according to a kind of preparation method of any new 3A molecular sieves of claim 1-5, step includes:
    Mixing:4A molecular screen primary powders, metal oxide or metal hydroxides, rare earth oxide and binding agent are mixed in proportion Close;
    Shaping:Containing K+Spray solution is turning in pot on mixed material, rolls shaping and 0.5-2.0mm diameter particles are made;
    It is dry:Particulate matter is placed in baking oven, 100 ± 10 DEG C, dry 1-2h;
    Activation:Dried particulate matter is placed in Muffle furnace, 550 ± 25 DEG C, activates 1-2h, and new 3A molecular sieves are made.
CN201711429647.6A 2017-12-26 2017-12-26 A kind of new 3A molecular sieves and preparation method thereof Pending CN108033460A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1663675A (en) * 2004-12-24 2005-09-07 上海化工研究院 Formulation of dry filter core for refrigerating system
CN1981910A (en) * 2005-12-12 2007-06-20 上海化工研究院 Production of drying filter core for refrigerating system
CN101097113A (en) * 2007-07-11 2008-01-02 冯诗庆 Composite type zeolite drier and method for making same
CN103159226A (en) * 2012-04-16 2013-06-19 淄博绿能化工有限公司 Low-potassium type 3A zeolite molecular sieve and preparation method thereof
CN103724150A (en) * 2013-12-13 2014-04-16 山东九恒集团有限公司 Environment-friendly drying method and device for wet acetylene gas
JP2015509832A (en) * 2013-01-19 2015-04-02 デシカント・ローターズ・インターナショナル・プライヴェート・リミテッド Desiccant-supporting honeycomb chemical filter and manufacturing method thereof
CN105289477A (en) * 2015-11-19 2016-02-03 上海绿强新材料有限公司 Adsorbent for removing impurities in olefin flow of coal chemical industry and use thereof
CN106423114A (en) * 2016-09-28 2017-02-22 大连海鑫化工有限公司 Purification adsorbent for hydrocarbon impurities, preparing method and application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1663675A (en) * 2004-12-24 2005-09-07 上海化工研究院 Formulation of dry filter core for refrigerating system
CN1981910A (en) * 2005-12-12 2007-06-20 上海化工研究院 Production of drying filter core for refrigerating system
CN101097113A (en) * 2007-07-11 2008-01-02 冯诗庆 Composite type zeolite drier and method for making same
CN103159226A (en) * 2012-04-16 2013-06-19 淄博绿能化工有限公司 Low-potassium type 3A zeolite molecular sieve and preparation method thereof
JP2015509832A (en) * 2013-01-19 2015-04-02 デシカント・ローターズ・インターナショナル・プライヴェート・リミテッド Desiccant-supporting honeycomb chemical filter and manufacturing method thereof
CN103724150A (en) * 2013-12-13 2014-04-16 山东九恒集团有限公司 Environment-friendly drying method and device for wet acetylene gas
CN105289477A (en) * 2015-11-19 2016-02-03 上海绿强新材料有限公司 Adsorbent for removing impurities in olefin flow of coal chemical industry and use thereof
CN106423114A (en) * 2016-09-28 2017-02-22 大连海鑫化工有限公司 Purification adsorbent for hydrocarbon impurities, preparing method and application

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Application publication date: 20180515