CN108726531A - A kind of Zn ion modifications zeolite molecular sieve and its preparation method and application - Google Patents
A kind of Zn ion modifications zeolite molecular sieve and its preparation method and application Download PDFInfo
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- CN108726531A CN108726531A CN201810707598.6A CN201810707598A CN108726531A CN 108726531 A CN108726531 A CN 108726531A CN 201810707598 A CN201810707598 A CN 201810707598A CN 108726531 A CN108726531 A CN 108726531A
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- 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
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-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
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Abstract
The present invention discloses a kind of Zn ion modifications zeolite molecular sieve and its preparation method and application, including zeolite main body and is replaced in the Zn in zeolite main body2+Ion, it is characterized in that：Zn2+Metal cation Na on ion pair zeolite molecular sieve+Ion carries out aliquot replacement, Zn2+It is 70-90mol% that ion, which accounts for the metal cation molar content in zeolite main body, and distribution is the Na in the original crystal structure of random replacement+Ion, for balancing negative electrical charge caused by aluminum-oxygen tetrahedron；It can be used for dry food-grade and purification, disinfection class product, the technical field for touching skin class articles for use, as drier and inhibit bacterial growth agent.Circulation method of the present invention is easy to operate, and control variable is less, and reaction condition is mildly easily-controllable, low for equipment requirements, is easy to industrialize；This molecular sieve use can improve its fungistatic effect in terms of wet tissue, and detection bacteriostasis rate can be more than 70%.
Description
Technical field
The present invention relates to being modified to crystalline silicate material, more particularly to prepare a kind of Zn ion modifications zeolite molecular sieve and
Preparation method and application.
Background technology
Traditional molecular sieve is a kind of crystal aluminosilicate material containing Na with spacial framework, includes mainly A types
Or X-type, there are the performances such as excellent selective adsorption capacity and ionophore.Molecular sieve is steady by its uniform quality, performance
Calmly, the features such as granularity is controllable, crystallinity is high, thermal stability is good can be very good to be used in molecule selective absorption field（Water,
NH3、H2S、SO2、CO2、C2H5OH、C2H6、C2H4Deng）.Meanwhile excellent thermal stability, dispersibility, it is pollution-free, it is nontoxic to human body
The features such as harmful, non-stimulated, makes it widely apply in chemical field, Material Field, daily life.
Constantly deepening with the research of molecular sieve, people are modified common molecular sieve using the means of ion exchange,
Obtain molecular sieve.Most common is exactly to pass through Ca2+And K+4A common moleculars sieve is modified to 5A and 3A molecular sieves by ion exchange.
The molecular sieve as obtained from the modification to molecular sieve realizes the improvement and promotion of performance, more so as to be widened
Application field in.
But in existing report, it is Ca to be modified often commonly used to molecular sieve by ion exchange2+、K+、Li+、Ag+、Sr2+Equal metal cations, by using transition metal Zn2+To common molecular sieve carry out ion-exchanged research from
It did not reported.
Invention content
The purpose of the invention is to provide a kind of Zn ion modifications zeolite molecular sieve, with and its preparation method and application.
This method is to realize the modification to common zeolite molecular sieve by ion exchange means under simple reaction condition, is realized
A kind of controlledly synthesis of molecular sieve.Meanwhile reaction condition is simple, is easy to industrialized production.Zn2+It is carried by excellent ion
The performances such as body, antibacterial are widely used in numerous areas.Important performance based on zeolite molecular sieve-ion exchange property leads to
It crosses and utilizes aqueous solution ion-exchange, successfully by Zn2+The balancing charge cation in zeolite molecular sieve frame structure is replaced, from
And by Zn2+Possessed superior chemical performance is introduced into molecular sieve, completes performance Optimal improvements.It is this to pass through Zn ion modifications
Zeolite molecular sieve the performances such as certain ionophore, antibacterial are unexpectedly added on the basis of original adsorptivity.It is this only
Special biocidal property binding molecule sieve can be very good to apply in food-grade drying and field of purification, breathing class protector, disinfection class production
Product touch the fields such as skin class articles for use, Medical Devices save set.These purposes are not available for most molecular sieves, thus Zn
Ion modification zeolite molecular sieve has greatly widened the application field of zeolite molecular sieve.
A kind of Zn ion modifications zeolite molecular sieve provided by the invention, including zeolite main body and be replaced in zeolite main body
On Zn2+Ion, wherein Zn2+Metal cation Na on ion pair zeolite molecular sieve+Ion carries out aliquot replacement, Zn2+From
It is 70-90mol% that son, which accounts for the metal cation molar content in zeolite main body, and distribution is the original crystal structure of random replacement
In Na+Ion, for balancing negative electrical charge caused by aluminum-oxygen tetrahedron.
Further specifically, other of the zeolite main body are characterized as：Metal cation in zeolite main body is Zn2+From
Son and Na+, K+, Ca2+One or several kinds of mixtures of three kinds of ions.
A method of Zn ion modification zeolite molecular sieves being prepared, technical solution is as follows：
Step 1：Using Zn2+Ion-exchange, according to the mass ratio 1 of zeolite molecular sieve and water:5-1:40, carry out material stirring
It is mixed to form slurry 1；
Step 2：The mass concentration ratio of liquid is exchanged according to zinc, and slurry 2 is formed in the water in solving zinc source to certain volume；Zinc source
Molar concentration controls between 0.05 mol/L-0.8mol/L；
Step 3：Mixed slurry 1 and 2 forms slurry 3, is stirred at room temperature uniformly；Zn2+The control of ion input amount is zeolite quality
Between 15%-30%；10-30min can specifically be stirred at room temperature；
Step 4：By slurry 3 from room temperature to 50-90 DEG C, constant temperature stirs 1h-6h；So that molecular sieve exchange degree reaches >=70%；
Step 5：It is washed after reaction with water and is dried to obtain molecular sieve；
Specifically, the zeolite molecular sieve is A types and X-type zeolite molecular sieve.
More specifically, the zinc source is any or its mixture of zinc chloride, zinc sulfate, zinc nitrate.More preferably
Zinc source be zinc chloride.
More specifically, it is 70-80 DEG C by velocity interval of the slurry 3 from room temperature to reaction temperature.
More specifically, after slurry is warming up to reaction temperature, the reaction time range of constant temperature stirring is 3-5h.
More specifically, it is washed after reaction with water, the termination condition of washing is Cl-Mass content≤0.2%.
More specifically, it is 70-90 DEG C that the condition of dry molecular sieves, which is drying temperature, and drying time is 2-8h.
A kind of application of Zn ion modifications zeolite molecular sieve, Zn ion modification zeolite molecular sieves are dry and net for food-grade
Change, disinfection class product, the technical field for touching skin class articles for use, as drier and inhibits bacterial growth agent.
The present invention passes through Zn2+Ion exchange completes a kind of preparation of zeolite molecular sieve, and this synthetic method is easy to operate, control
Variable processed is less, and reaction condition is mildly easily-controllable, relatively low to consersion unit requirement, to be easily industrialized production.While this
Kind of zeolite molecular sieve imparts the antibacterial performance of molecular sieve due to the introducing of Zn ions, can be with by using in terms of wet tissue
Its fungistatic effect is improved, detection bacteriostasis rate can be more than 70%.
Specific implementation mode
The present embodiment carries out the preparation of molecular sieve with common A type molecular sieve raw material.The crystal form of embodiment products obtained therefrom uses
X-ray diffraction crystal phase analysis and obtain, according to PDF card numbers 43-0142 compare；Exchange degree passes through n (ZnO)/n (Al2O3) calculate
And it obtains；The absorption of molecular sieve Static Water under the conditions of saturation NaCl solution by 25 DEG C, for 24 hours, measuring.
Embodiment 1：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 250 mL water and slurry 1 is made, a concentration of 0.15mol/L sulphur of configuration quality
The solution of sour zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 77%, Static Water absorption 27.3%.
Embodiment 2：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 500 mL water and slurry 1 is made, a concentration of 0.15mol/L sulphur of configuration quality
The solution of sour zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 75.8%, Static Water absorption 27.22%.
Embodiment 3：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 1000 mL water and slurry 1 is made, a concentration of 0.15mol/L sulphur of configuration quality
The solution of sour zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 73%, Static Water absorption 27.01%.
Embodiment 4：
A kind of application of Zn ion modifications zeolite molecular sieve, is used for the antibacterial field of wet tissue, and concrete application method is：By embodiment 1
In prepared modified zeolite molecular sieve apply in wet tissue, using the test method of bacteriostasis rate in GB15979-2002, detection
It is 73% to go out bacteriostasis rate.
Comparative example 1：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 250 mL water and slurry 1 is made, a concentration of 0.15mol/L chlorine of configuration quality
The solution for changing zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 76%, Static Water absorption 26.95%.
Comparative example 2：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 500 mL water and slurry 1 is made, a concentration of 0.15mol/L chlorine of configuration quality
The solution for changing zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 77.1%, Static Water absorption 27.45%.
Comparative example 3：
It weighs 50 g 4A molecular screen primary powders and is dissolved into 1000 mL water and slurry 1 is made, a concentration of 0.15mol/L chlorine of configuration quality
The solution for changing zinc is slurry 2, and 1L slurries 2 are slowly added into slurry 1 and obtain slurry 3, after 15 min are stirred at room temperature to slurry 3
It starts to warm up, washing and drying obtains Zn-A molecular sieves after constant temperature stirs 2 h after being warming up to 80 DEG C.It is A type structures by test, hands over
Degree of changing 78.3%, Static Water absorption 27.19%.
Comparative example 4：
A kind of application of Zn ion modifications zeolite molecular sieve, is used for the antibacterial field of wet tissue, and concrete application method is：To normal towel
In, using the test method of bacteriostasis rate in GB15979-2002, detect that bacteriostasis rate is 54%.
The basic principles and main features and advantage of the present invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention
Reason, without departing from the spirit and scope of the present invention, to the present invention make any equivalent variation, modification, replacement, combination,
Simplify, all these equivalent forms are included within the scope of the present invention.The claimed scope of the invention, by appended
Claims define.
Claims (8)
1. a kind of Zn ion modifications zeolite molecular sieve, including zeolite main body and it is replaced in the Zn in zeolite main body2+Ion,
It is characterized in：Zn2+Metal cation Na on ion pair zeolite molecular sieve+Ion carries out aliquot replacement, Zn2+Ion accounts for zeolite main body
On metal cation molar content be 70-90mol%, distribution be the original crystal structure of random replacement in Na+Ion,
For balancing negative electrical charge caused by aluminum-oxygen tetrahedron.
2. other of according to claim 1, the zeolite main body are characterized as：Metal cation in zeolite main body is Zn2 +Ion and Na+, K+, Ca2+One or several kinds of mixtures of three kinds of ions.
3. a kind of method preparing Zn ion modification zeolite molecular sieves, it is characterized in that including following technique：
Step 1：Using Zn2+Ion-exchange, according to the mass ratio 1 of zeolite molecular sieve and water:5-1:40, it is mixed to carry out material stirring
Conjunction forms slurry 1；
Step 2：The mass concentration ratio of liquid is exchanged according to zinc, and slurry 2 is formed in the water in solving zinc source to certain volume；Zinc source
Molar concentration controls between 0.05 mol/L-0.8mol/L；
Step 3：Mixed slurry 1 and 2 forms slurry 3, is stirred at room temperature uniformly；Zn2+The control of ion input amount is zeolite quality
Between 15%-30%；10-30min can specifically be stirred at room temperature；
Step 4：By slurry 3 from room temperature to 50-90 DEG C, constant temperature stirs 1h-6h；So that molecular sieve exchange degree reaches >=70%；
Step 5：It is washed after reaction with water and is dried to obtain molecular sieve.
4. the method for preparing Zn ion modification zeolite molecular sieves according to claim 2, it is characterized in that：The zeolite molecules
Sieve is A types and X-type zeolite molecular sieve.
5. the method for preparing Zn ion modification zeolite molecular sieves according to claim 2, it is characterized in that：The zinc source is chlorine
Change any or its mixture of zinc, zinc sulfate, zinc nitrate.
6. the method for preparing Zn ion modification zeolite molecular sieves according to claim 2, it is characterized in that：By slurry 3 from room temperature
The velocity interval for being warming up to reaction temperature is 70-80 DEG C.
7. the method for preparing Zn ion modification zeolite molecular sieves according to claim 2, it is characterized in that：Water is used after reaction
It is washed, the termination condition of washing is Cl-Mass content≤0.2%.
8. the application of Zn ion modifications zeolite molecular sieve described in a kind of claim 1, it is characterized in that：Zn ion modification zeolite molecules
Sieve as drier and inhibits bacterium to give birth to for the technical field that food-grade is dry and purifies, sterilizes class product, touches skin class articles for use
Long agent.
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| CN1145209A (en) * | 1995-09-12 | 1997-03-19 | 田树霖 | Production method of nylon toothbrush filament with long-acting antibacterial function |
| CN1425704A (en) * | 2002-12-27 | 2003-06-25 | 济南正昊化纤新材料有限公司 | Process for preparing antibiotic polyester |
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| CN101362099A (en) * | 2008-09-19 | 2009-02-11 | 上海化工研究院 | Metal modified molecular screen and preparation method thereof |
| CN103611495A (en) * | 2013-12-16 | 2014-03-05 | 上海绿强新材料有限公司 | Adsorbent for removing organic chlorides in hydrocarbon-containing substance flow and preparation method thereof |
| CN104186545A (en) * | 2014-08-09 | 2014-12-10 | 三河市京纳环保技术有限公司 | Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent |
-
2018
- 2018-07-02 CN CN201810707598.6A patent/CN108726531A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5152972A (en) * | 1990-08-31 | 1992-10-06 | E. I. Du Pont De Nemours And Company | Process for producing molecular sieves and novel molecular sieve compositions |
| CN1113480A (en) * | 1995-06-20 | 1995-12-20 | 北京新奇材料研究所 | Zeolite molecular sieve water purifying material and its manufacture |
| CN1145209A (en) * | 1995-09-12 | 1997-03-19 | 田树霖 | Production method of nylon toothbrush filament with long-acting antibacterial function |
| CN1425704A (en) * | 2002-12-27 | 2003-06-25 | 济南正昊化纤新材料有限公司 | Process for preparing antibiotic polyester |
| CN101167451A (en) * | 2007-09-17 | 2008-04-30 | 苏州科技学院 | Zeolite base composite antibiotic material and its preparation method |
| CN101176468A (en) * | 2007-11-28 | 2008-05-14 | 暨南大学 | Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof |
| CN101362099A (en) * | 2008-09-19 | 2009-02-11 | 上海化工研究院 | Metal modified molecular screen and preparation method thereof |
| CN103611495A (en) * | 2013-12-16 | 2014-03-05 | 上海绿强新材料有限公司 | Adsorbent for removing organic chlorides in hydrocarbon-containing substance flow and preparation method thereof |
| CN104186545A (en) * | 2014-08-09 | 2014-12-10 | 三河市京纳环保技术有限公司 | Novel large-scale simple preparation method of zeolite zinc-loaded inorganic antibacterial agent |
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