CN110407231A - Synthesize the method and cupric CHA structure molecular sieve of cupric CHA structure molecular sieve - Google Patents
Synthesize the method and cupric CHA structure molecular sieve of cupric CHA structure molecular sieve Download PDFInfo
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Abstract
This disclosure relates to it is a kind of synthesize cupric CHA structure molecular sieve method and cupric CHA structure molecular sieve, method includes the following steps: a, by organic formwork agent, silicon source, silicon source and optional water mix, obtain to crystallization mixture；B, Crystallizing treatment is carried out to crystallization mixture by described obtained in step a, collects crystallization product；C, the crystallization product obtained in step b is dried and is roasted, obtain CHA structure molecular sieve；D, CHA structure molecular sieve obtained in step c is subjected in the dipping solution of copper-containing compound impregnation, recycles solid product；Wherein, the organic formwork agent is for 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide and/or to ethenylphenyl-N, N, N- trimethylammonium hydroxide.The disclosure synthesizes CHA structure molecular sieve using new type formwork agent, eliminates alkali metal ion exchange process in the prior art, synthesis step is simple, and production cost is low, no COD discharge of wastewater, no pollution to the environment.
Description
Technical field
This disclosure relates to a kind of method and cupric CHA structure molecular sieve for synthesizing cupric CHA structure molecular sieve.
Background technique
CHA structure Si-Al molecular sieve is a kind of zeolitic material with octatomic ring window and three dimensional intersection cellular structure,
Cellular structure with specific dimensions, shape has good absorption property and selects type, while it is with biggish specific surface
Long-pending and adjustable Acidity is widely used in gas separation and catalysis reaction.
United States Patent (USP) US4,544,538 disclose a kind of method for synthesizing CHA structure Si-Al molecular sieve, and this method is with price
Expensive and toxic adamantane quaternary ammonium ion is template, and template, silicon source, silicon source, alkali metal salt and water are uniformly mixed simultaneously
Hydrothermal crystallizing is more than 3 days at 100~235 DEG C, obtains CHA structure Si-Al molecular sieve.Products therefrom is exchanged with containing ammonium salt solution, so
The CHA structure Si-Al molecular sieve of Hydrogen can be obtained by roasting afterwards, but exchange process generates a large amount of nitrogenous effluents, environmental protection of enterprise pressure
Power is huge.
Summary of the invention
Purpose of this disclosure is to provide it is a kind of synthesize cupric CHA structure molecular sieve method and cupric CHA structure molecular sieve,
This method is avoided using expensive and toxic organic formwork agent.
To achieve the goals above, disclosure first aspect: providing a kind of method for synthesizing cupric CHA structure molecular sieve,
It is characterized in that, method includes the following steps:
A, organic formwork agent, silicon source, silicon source and optional water are mixed, is obtained to crystallization mixture, in terms of oxide simultaneously
In mol, described to R:SiO in crystallization mixture2: Al2O3=(1-100): (10-500): 1, H2O:SiO2=(5-100):
1, wherein R represents the molal quantity to organic formwork agent in crystallization mixture；
B, Crystallizing treatment is carried out to crystallization mixture by described obtained in step a, collects crystallization product；
C, the crystallization product obtained in step b is dried and is roasted, obtain CHA structure molecular sieve；
D, CHA structure molecular sieve obtained in step c is carried out at dipping in the dipping solution of copper-containing compound
Reason recycles solid product；
Wherein, the organic formwork agent is for 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide and/or to vinyl
Phenyl-N, N, N- trimethylammonium hydroxide.
Optionally, this method further include: in step a, first mix the organic formwork agent with silicon source, and in 45-190
DEG C, handle 0.5-50 hour under confined conditions, obtain body containing aluminium glue, then again will described in body containing aluminium glue and silicon source, optional water
Mixing, obtains to crystallization mixture.
Optionally, in step a, source of aluminium is selected from aluminium, boehmite, boehmite, gibbsite, hydroxide
At least one of aluminium, aluminium oxide and aluminum alcoholate.
Optionally, in step a, the silicon source is selected from silicate, silica, silicic acid, silica gel, clay and silester
At least one of.
Optionally, described to alkali in crystallization mixture on the basis of the total weight to crystallization mixture in step a
The content of metal is not higher than 1000ppm.
Optionally, this method further include: collect the crystallization mother liquor that the Crystallizing treatment obtains, and the crystallization mother liquor is returned
It is described to crystallization mixture to be back to preparation.
Optionally, in step b, the condition of the Crystallizing treatment are as follows: temperature is 120-190 DEG C, and the time is 1-10 days.
Optionally, in step c, the condition of the drying are as follows: temperature is 50-120 DEG C, and the time is 4-24 hours；
The condition of the roasting are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
Optionally, in step d, the copper-containing compound is selected from copper nitrate, copper chloride, copper sulphate, sulfurous acid copper, sulfurous
Sour at least one of cuprous, copper acetate and copper bromide.
Optionally, in step d, the condition of the impregnation include: the copper-containing compound in terms of CuO with butt
The weight ratio of the CHA structure molecular sieve of poidometer be (0.11-0.32): 1, the dipping solution with dry basis
The weight ratio of the CHA structure molecular sieve is (6-25): 1；The temperature of the dipping is 30-90 DEG C, and the time is 0.5-3 hours.
Optionally, this method further include: the step of being washed, dried and roasted after collection solid product.
Disclosure second aspect: a kind of CHA structure molecular sieve that the method described in disclosure first aspect synthesizes is provided.
Through the above technical solutions, the disclosure synthesizes CHA structure molecular sieve using new type formwork agent, avoid high using price
Expensive and toxic N, N, N- trimethyl-adamantyl ammonium hydroxide eliminate alkali metal ion exchange process in the prior art,
Synthesis step is simple, and production cost is low, no COD discharge of wastewater, no pollution to the environment.Using prepared by disclosed method
CHA structure molecular sieve can achieve higher silica alumina ratio, and relative crystallinity with higher.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of CHA structure molecular sieve prepared by embodiment 1.
Fig. 2 is the stereoscan photograph of CHA structure molecular sieve prepared by embodiment 1.
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect: a kind of method for synthesizing cupric CHA structure molecular sieve is provided, this method includes following step
It is rapid:
A, organic formwork agent, silicon source, silicon source and optional water are mixed, is obtained to crystallization mixture, in terms of oxide simultaneously
In mol, described to R:SiO in crystallization mixture2: Al2O3=(1-100): (10-500): 1, H2O:SiO2=(5-100):
1, wherein R represents the molal quantity to organic formwork agent in crystallization mixture；
B, Crystallizing treatment is carried out to crystallization mixture by described obtained in step a, collects crystallization product；
C, the crystallization product obtained in step b is dried and is roasted, obtain CHA structure molecular sieve；
D, CHA structure molecular sieve obtained in step c is carried out at dipping in the dipping solution of copper-containing compound
Reason recycles solid product；
Wherein, the organic formwork agent is for 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide and/or to vinyl
Phenyl-N, N, N- trimethylammonium hydroxide.
The disclosure synthesizes CHA structure molecular sieve using new type formwork agent, avoids using expensive and toxic N, N, N-
Trimethyl-adamantyl ammonium hydroxide eliminates alkali metal ion exchange process in the prior art, and synthesis step is simple, raw
Produce at low cost, no COD discharge of wastewater, no pollution to the environment.
According to the disclosure, described 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide chemical formula is C13H20NOH,
Structural formula are as follows:
It is described to ethenylphenyl-N, N, the chemical formula of N- trimethylammonium hydroxide is C11H16NOH, structural formula are as follows:
According to the disclosure, the organic formwork agent is preferably 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide.Institute
It states 5,6,7,8- naphthane -2- base-trimethylammonium hydroxide and/or to ethenylphenyl-N, N, N- trimethylammonium hydroxide can
It can be the form of aqueous solution to be prepared using method in the prior art, the disclosure does not have the concentration of aqueous solution
Special limitation.
According to the disclosure, this method can also include: first the organic formwork agent is mixed with silicon source in step a, and
45-190 DEG C, handle 0.5-50 hour under confined conditions, obtain body containing aluminium glue, then again will described in body containing aluminium glue and silicon source, can
The water of choosing mixes, and obtains to crystallization mixture.Under preferable case, the time of the processing is 2-45 hours.In this way, first will be organic
Template and silicon source are handled, and aluminium can be made all to dissolve, be conducive to the progress of Crystallizing treatment.The organic formwork agent and aluminium
The dosage in source is to meet both may be used within the scope of said ratio to the composition of crystallization mixture, that is, the organic formwork agent with
Al2O3The molar ratio of the silicon source of meter is (1-100): 1, preferably (2-60): 1.
It is described to R:SiO in crystallization mixture under preferable case according to the disclosure2: Al2O3=(2-60): (15-450):
1, H2O:SiO2=(6-70): 1, wherein R represents the molal quantity to organic formwork agent in crystallization mixture.It needs to illustrate
It is that the water in crystallization mixture can come from organic formwork agent, silicon source or silicon source, in the case where moisture deficit
When, can also other water supplement, only water silicon ratio need to be made to meet the scope of the present disclosure.
According to the disclosure, in order to keep the alkali metal content of synthesized CHA structure molecular sieve lower, in step a, with described
On the basis of the total weight of crystallization mixture, the content to alkali metal in crystallization mixture can for not higher than 1000ppm,
Preferably not higher than 500ppm.
According to the disclosure, source of aluminium and silicon source can be described mixed to crystallization in order to make using commonly used in the art
The alkali metal content closed in object is lower, and the silicon source and silicon source of the disclosure preferably do not contain alkali metal.For example, in step a, the aluminium
Source can in aluminium, boehmite, boehmite, gibbsite, aluminium hydroxide, aluminium oxide and aluminum alcoholate at least
It is a kind of.The silicon source can for selected from least one of silicate, silica, silicic acid, silica gel, clay and silester,
The silica can be any form of silica, such as fume colloidal silica and/or precipitated silica；The silicon source
It is preferably selected from least one of silica gel, fume colloidal silica, precipitated silica and silester.
According to the disclosure, after the completion of Crystallizing treatment, the obtained mixture of Crystallizing treatment is separated by solid-liquid separation, can be obtained
Crystallization product and crystallization mother liquor, in order to make full use of the crystallization mother liquor, this method can also include: to collect the Crystallizing treatment
Obtained crystallization mother liquor, and crystallization mother liquor return is used to prepare described to crystallization mixture.The crystallization mother liquor can be made
It is described to crystallization mixture for preparing for the return of supplement water, avoid the discharge of the waste water containing COD.
According to the disclosure, the condition of the Crystallizing treatment can synthesize the conventional crystallization of CHA structure molecular sieve for this field
Condition.For example, in step b, the condition of the Crystallizing treatment can be with are as follows: temperature is 120-190 DEG C, preferably 160-170 DEG C；When
Between be 1-10 days, preferably 2-8 days, more preferably 2.5-4 days.The Crystallizing treatment carries out in confined conditions.
According to the disclosure, in step c, the drying and roasting are the conventional steps of this field synthesis of molecular sieve, the disclosure
There is no special limitation to its condition.For example, the condition of the drying can be with are as follows: temperature is 50-120 DEG C, and the time is that 4-24 is small
When.The condition of the roasting can be with are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
According to the disclosure, in step d, the copper-containing compound can be for selected from copper nitrate, copper chloride, copper sulphate, sulfurous
At least one of sour copper, cuprous sulfite, copper acetate and copper bromide.The condition of the impregnation can be conventional for this field
, for example, the condition of the impregnation may include: the copper-containing compound in terms of CuO and the institute with dry basis
The weight ratio for stating CHA structure molecular sieve is (0.11-0.32): 1, the dipping solution is tied with the CHA of dry basis
The weight ratio of structure molecular sieve is (6-25): 1；The temperature of the dipping is 30-90 DEG C, and the time is 0.5-3 hours.
According to the disclosure, this method can also include: the step of washed, dried and roasted after collecting solid product.
The washing, dry and roasting are the conventional steps of synthesis of molecular sieve, and the disclosure does not have special limitation to its condition.For example,
The condition of the drying can be with are as follows: temperature is 50-120 DEG C, and the time is 4-24 hours；The condition of the roasting can be with are as follows: temperature
It is 450-750 DEG C, the time is 0.5-6 hours.
Disclosure second aspect: a kind of CHA structure molecular sieve that the method described in disclosure first aspect synthesizes is provided.
Using the molecular sieve for the CHA structure that the method for disclosure first aspect synthesizes, micropore specific area can be 540-
710m2/ g, SiO2/Al2O3Molar ratio can be 10-500, can have 1000ppm or hereinafter, it is preferred that 500ppm or below
Alkali metal content, especially sodium content, relative crystallinity can be 75% or more, size of microcrystal between 0.1-5 μm, with
CuO meter and on the basis of the dry weight of cupric CHA structure molecular sieve, the CuO content of the cupric CHA structure molecular sieve can be with
For 2-25 weight %.
The disclosure is described further below by embodiment, but does not therefore limit content of this disclosure.
In embodiment, the chemical composition of molecular sieve is measured by x-ray fluorescence method, and specific method is referring to " with EU-1 molecular sieve
ZSM11 molecular sieve and its characterization are synthesized for crystal seed ", Geng Chenchen etc., " petroleum refining and chemical industry ", 2011,7.
The side 15337-2008 national standard method GBT is used to alkali metal in crystallization mixture (measurement sodium and potassium) content
Method is measured.
Relative crystallinity as described in the examples is with product prepared by disclosed method and CHA structure molecular sieve mark
2 θ of X-ray diffraction (XRD) spectrogram of sample are at 9.5 °, 14.0 °, 16.1 °, 17.8 °, the peaks of 20.5 ° of five characteristic diffraction peaks
The ratio of the sum of area is indicated with percentage.XRD is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44
Kilovolt, 40 milliamperes, scanning speed is 2 °/minute.Using the CHA structure point of the method synthesis of embodiment 5 in patent US4859442
Son sieve is standard specimen, its crystallinity is set to 100%.
The specific surface area of molecular sieve uses the AS-3 of Quantachrome instrument company production, and AS-6 static state n2 absorption apparatus is surveyed
It is fixed.Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 300 DEG C-2Pa, heat-insulation pressure keeping 4h, only
Change sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance of nitrogen and de-
Attached amount obtains N2Adsorption-desorption isothermal curve.Then specific surface area is calculated using two parameter BET formula.
In embodiment, 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide or to vinyl benzene-N, N, N- trimethyl
Ammonium hydroxide the preparation method comprises the following steps: being generated using 5,6,7,8- naphthane -2- base-amine (or to ethenylphenyl amine) iodomethylation
Corresponding 5,6,7,8- naphthane -2- bases-trimethyl ammonium iodide (or to ethenylphenyl-N, N, N- trimethyl ammonium iodide),
Again with the corresponding 5,6,7,8- naphthane -2- base-trimethylammonium hydroxide of sodium hydroxide reaction generation (or to ethenylphenyl -
N, N, N- trimethylammonium hydroxide).
The method that embodiment 1-8 is used to illustrate the synthesis cupric CHA structure molecular sieve that the disclosure provides.
Embodiment 1
Weigh 0.50g boehmite (Chang Ling catalyst plant, Al2O375 weight % of content), by itself and 82.19g 5,6,
7,8- naphthane -2- bases-trimethylammonium hydroxide (25 weight % aqueous solution) mixing, is placed in the reaction kettle containing polytetrafluoro lining
In, after 100 DEG C, under confined conditions reaction 41 hours, it is cooled to room temperature, (Qingdao Haiyang chemical industry has with 3.14g silica gel again later
Limit company, SiO298.4 weight % of content) and the mixing of 3.99g water, it obtains to crystallization mixture, mole group becomes R:SiO2:
Al2O3=27:14:1, H2O:SiO2=71:1, alkali metal content 416ppm.It will be to crystallization mixture in a high pressure reaction kettle
It is filtered, washed, is dried 4 hours in 120 DEG C, 550 DEG C of roasting 6h are obtained after 160 DEG C of progress Crystallizing treatment 96h, crystallization
3.13gCHA structure molecular screen.It will stir evenly after being warming up to 50 DEG C, be added above-mentioned in 0.72g copper sulphate addition 19.62g water
CHA structure molecular sieve, the weight ratio of copper sulphate (in terms of CuO) and CHA structure molecular sieve are 0.12:1, boucherizing solution with
The weight ratio of CHA structure molecular sieve is 6.5:1, is filtered, washed mixture after constant temperature stirring 1h at 50 DEG C, dries, 550
1h is roasted at DEG C, obtains cupric CHA structure Si-Al molecular sieve C-1.
The XRD spectra of molecular sieve C-1 as shown in Figure 1, as seen from Figure 1, molecular sieve C-1 have 9.5 °, 14.0 °, 16.1 °,
17.8 °, 20.5 five characteristic diffraction peaks, it was demonstrated that it is CHA structure molecular sieve.Scanning electron microscopic picture is as shown in Figure 2.Its CuO
Content is 9 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 2
Weighing 9.71g aluminium hydroxide, (Beijing chemical industry produces, and analyzes pure, Al2O335 weight % of content), by itself and 71.57g pairs
Vinyl benzene-N, N, N- trimethylammonium hydroxide (25 weight % aqueous solution) mixing, are placed in the reaction kettle containing polytetrafluoro lining
In, in 128 DEG C, under confined conditions react 30 hours after, be cooled to room temperature, later again with 81.26g silica gel (Qingdao Haiyang chemical industry
Co., Ltd, SiO298.4 weight % of content) and the mixing of 82.64g water, it obtains to crystallization mixture, mole group becomes R:SiO2:
Al2O3=3:40:1, H2O:SiO2=6:1, alkali metal content 368ppm.Will to crystallization mixture in a high pressure reaction kettle in
135 DEG C of progress Crystallizing treatment 188h are filtered, washed after crystallization, are dried 14 hours in 120 DEG C, 550 DEG C of roasting 6h obtain 75g
CHA structure molecular sieve.It will be stirred evenly in 27.94g copper chloride addition 1668g water after being warming up to 90 DEG C, above-mentioned CHA structure be added
The weight ratio of molecular sieve, copper chloride (in terms of CuO) and CHA structure molecular sieve is 0.22:1, copper chloride impregnating solution and CHA structure
The weight ratio of molecular sieve is 22.6:1, is filtered, washed mixture after constant temperature stirring 3h at 90 DEG C, dries, roasts at 700 DEG C
5h is burnt, cupric CHA structure Si-Al molecular sieve C-2 is obtained.
The XRD spectra of molecular sieve C-2 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 14 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 3
Weigh 0.10g aluminium oxide (Chang Ling catalyst plant, Al2O398 weight % of content), by itself and 39.78g 5,6,7,8-
Naphthane -2- base-trimethylammonium hydroxide (25 weight % aqueous solution) mixing, is placed in the reaction kettle containing polytetrafluoro lining,
After 150 DEG C, under confined conditions reaction 10 hours, it is cooled to room temperature, (Qingdao Haiyang chemical industry is limited with 11.95g silica gel again later
Company, SiO298.4 weight % of content) and the mixing of 12.30g water, it obtains to crystallization mixture, mole group becomes R:SiO2: Al2O3
=50:204:1, H2O:SiO2=12:1, alkali metal content 238ppm.It will be to crystallization mixture in a high pressure reaction kettle in 165
DEG C Crystallizing treatment 96h is carried out, is filtered, washed after crystallization, is dried 20 hours, 550 DEG C of roasting 6h in 120 DEG C, obtain 10g CHA and tie
Structure molecular sieve.It will be stirred evenly in 7.27g copper nitrate addition 189.71g water after being warming up to 70 DEG C, above-mentioned CHA structure molecule be added
The weight ratio of sieve, copper nitrate (in terms of CuO) and CHA structure molecular sieve is 0.31:1, copper nitrate dipping solution and CHA structure molecule
The weight ratio of sieve is 19.7:1, is filtered, washed mixture after constant temperature stirring 3h at 70 DEG C, dries, roasts at 650 DEG C
3h obtains cupric CHA structure Si-Al molecular sieve C-3.
The XRD spectra of molecular sieve C-3 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 20 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 4
Weigh 0.36g boehmite (Chang Ling catalyst plant, Al2O375 weight % of content), by itself and 138.08g 5,6,
7,8- naphthane -2- bases-trimethylammonium hydroxide (25 weight % aqueous solution) mixing, is placed in the reaction kettle containing polytetrafluoro lining
In, in 185 DEG C, under confined conditions react 0.5 hour after, be cooled to room temperature, later again with 64.97g fume colloidal silica (Shenyang
Chemical inc, SiO299 weight % of content) and the mixing of 185.14g water, it obtains to crystallization mixture, a mole group becomes
R:SiO2: Al2O3=63:405:1, H2O:SiO2=15:1, alkali metal content 411ppm.Seeing will be to crystallization mixture in high pressure
It is filtered after 180 DEG C of progress Crystallizing treatment 170h, crystallization in reaction kettle, filtrate, that is, crystallization mother liquor returns mixed to crystallization for preparing
Object is closed, is dried 20 hours after Washing of Filter Cake in 120 DEG C, 550 DEG C of roasting 6h obtain 51.64g CHA structure molecular sieve.It will
It is stirred evenly in 17.30g copper chloride addition 645.5g water after being warming up to 70 DEG C, above-mentioned CHA structure molecular sieve, copper chloride is added
The weight ratio of (in terms of CuO) and CHA structure molecular sieve is 0.20:1, the weight of copper chloride impregnating solution and CHA structure molecular sieve
Than mixture being filtered, washed after constant temperature stirring 0.5h at 65 DEG C, is dried, 0.5h is roasted at 500 DEG C, obtains for 12.8:1
To cupric CHA structure Si-Al molecular sieve C-4.
The XRD spectra of molecular sieve C-4 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 9 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 5
Weigh 0.15g boehmite (Chang Ling catalyst plant, Al2O375 weight % of content), by itself and 80g embodiment 4
Crystallization mother liquor, 55.71g organic formwork agent 5,6,7,8- naphthane -2- base-trimethylammonium hydroxide (25 weight % aqueous solution) are mixed
It closes, is placed in the reaction kettle containing polytetrafluoro lining, after 120 DEG C, under confined conditions reaction 22 hours, be cooled to room temperature, it
Afterwards again with 7.42g fume colloidal silica (Shenyang Chemical Co., Ltd., SiO299 weight % of content) and the mixing of 34.57g water,
It obtains to crystallization mixture, mole group becomes R:SiO2: Al2O3=61:111:1, H2O:SiO2=71:1, alkali metal content are
352ppm.It will be filtered, washed after 125 DEG C of progress Crystallizing treatment 150h, crystallization in a high pressure reaction kettle to crystallization mixture, in
120 DEG C dry 20 hours, and 550 DEG C of roasting 6h obtain 6.1g CHA structure molecular sieve.1.33g copper chloride is added in 74.4g water
It stirs evenly after being warming up to 70 DEG C, above-mentioned CHA structure molecular sieve, the weight of copper chloride (in terms of CuO) and CHA structure molecular sieve is added
Ratio is measured as 0.13:1, the weight ratio of copper chloride impregnating solution and CHA structure molecular sieve is 12.4:1, the constant temperature stirring at 65 DEG C
Mixture is filtered, washed after 2.5h, is dried, roasts 1h at 500 DEG C, obtains cupric CHA structure Si-Al molecular sieve C-5.
The XRD spectra of molecular sieve C-5 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 6 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 6
Weigh 0.12g aluminium oxide (Chang Ling catalyst plant, Al2O398 weight % of content), by it with 23.11g to vinyl
Benzene-N, N, N- trimethylammonium hydroxide (25 weight % aqueous solution) mixing, are placed in the reaction kettle containing polytetrafluoro lining, in
After 145 DEG C, under confined conditions reaction 24 hours, it is cooled to room temperature, (hairization is built in Zhejiang with 29.31g precipitated silica again later
Work Co., Ltd, SiO293 weight % of content) and the mixing of 144.16g water, it obtains to crystallization mixture, mole group becomes R:SiO2:
Al2O3=28:394:1, H2O:SiO2=20:1, alkali metal content 117ppm.It will be to crystallization mixture in a high pressure reaction kettle
It is filtered, washed, is dried 24 hours in 120 DEG C, 550 DEG C of roasting 6h are obtained after 160 DEG C of progress Crystallizing treatment 60h, crystallization
23.29g CHA structure molecular sieve.It will stir evenly after being warming up to 70 DEG C, be added above-mentioned in 14.34g copper sulphate addition 200g water
CHA structure molecular sieve, the weight ratio of copper sulphate (in terms of CuO) and CHA structure molecular sieve are 0.31:1, boucherizing solution with
The weight ratio of CHA structure molecular sieve is 9.2:1, is filtered, washed mixture after constant temperature stirring 2.5h at 65 DEG C, dries, In
2.5h is roasted at 500 DEG C, obtains cupric CHA structure Si-Al molecular sieve C-6.
The XRD spectra of molecular sieve C-6 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 14 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 7
Weigh 0.19g aluminium oxide (Chang Ling catalyst plant, Al2O398 weight % of content), by itself and 84.64g 5,6,7,8-
Naphthane -2- base-trimethylammonium hydroxide (25 weight % aqueous solution) mixing, is placed in the reaction kettle containing polytetrafluoro lining,
In 180 DEG C, under confined conditions react 0.6 hour after, be cooled to room temperature, later again with 27.94g silester (Zhangjiagang new Asia
Chemical Co., Ltd., content >=98 weight %) and the mixing of 78.30g water, it obtains to crystallization mixture, mole group becomes R:SiO2:
Al2O3=56:72:1, H2O:SiO2=60:1, alkali metal content 371ppm.It will be to crystallization mixture in a high pressure reaction kettle
It is filtered, washed, is dried 24 hours in 120 DEG C, 550 DEG C of roasting 6h are obtained after 170 DEG C of progress Crystallizing treatment 96h, crystallization
6.94g CHA structure molecular sieve.It will stir evenly after being warming up to 70 DEG C, be added above-mentioned in 5.10g copper nitrate addition 168.4g water
CHA structure molecular sieve, the weight ratio of copper sulphate (in terms of CuO) and CHA structure molecular sieve are 0.31:1, boucherizing solution with
The weight ratio of CHA structure molecular sieve is 25:1, is filtered, washed mixture after constant temperature stirring 1h at 75 DEG C, dries, 600
2.5h is roasted at DEG C, obtains cupric CHA structure Si-Al molecular sieve C-7.
The XRD spectra of molecular sieve C-7 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 21 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Embodiment 8
Cupric CHA structure molecular sieve is synthesized according to the method for embodiment 1, difference is, not first by boehmite and 5,
6,7,8- naphthane -2- bases-trimethylammonium hydroxide is handled, but directly by boehmite, 5,6,7,8- naphthanes -
2- base-trimethylammonium hydroxide, silica gel and water mixing carry out Crystallizing treatment.The present embodiment synthesizes to obtain cupric CHA structure molecule
Sieve C-8.
The XRD spectra of molecular sieve C-8 is similar with Fig. 1, and zeolite product is not reunited, and dispersion degree is similar with Fig. 2.Its CuO contains
Amount is 8 weight %, and the parameters such as size of microcrystal, relative crystallinity are listed in table 1.
Table 1
| Embodiment | Size of microcrystal, μm | Relative crystallinity, % | BET surface area, m2/g | SiO2/Al2O3Molar ratio |
| Embodiment 1 | 0.9 | 83 | 610 | 13 |
| Embodiment 2 | 1.7 | 81 | 591 | 35 |
| Embodiment 3 | 0.8 | 92 | 645 | 180 |
| Embodiment 4 | 0.5 | 80 | 579 | 378 |
| Embodiment 5 | 1.2 | 76 | 550 | 92 |
| Embodiment 6 | 0.7 | 95 | 683 | 321 |
| Embodiment 7 | 2.1 | 87 | 628 | 66 |
| Embodiment 8 | 2.2 | 80 | 545 | 11 |
By embodiment 1-8 as it can be seen that can be avoided using the present processes using expensive and toxic organic formwork agent, institute
The cupric CHA structure molecular sieve micropore specific area with higher and relative crystallinity of preparation.By pair between embodiment 1-7
Than as it can be seen that when described to R:SiO in crystallization mixture2: Al2O3=(2-60): (15-450): 1, H2O:SiO2=(6-70): 1
When；Or the temperature of Crystallizing treatment is 160-170 DEG C, when the time is 2.5-4 days, is conducive to further increase cupric CHA structure point
The specific surface area and relative crystallinity of son sieve.By the comparison of embodiment 1 and embodiment 8 as it can be seen that in the ban by the organic formwork agent
Mixed with silicon source, and 45-190 DEG C, under confined conditions handle 0.5-50 hour and then when being mixed again with silicon source, optional water,
Be conducive to further increase the specific surface area and relative crystallinity of cupric CHA structure molecular sieve.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (12)
1. a kind of method for synthesizing cupric CHA structure molecular sieve, which is characterized in that method includes the following steps:
A, organic formwork agent, silicon source, silicon source and optional water are mixed, is obtained to crystallization mixture, in terms of oxide and to rub
You count, described to R:SiO in crystallization mixture2: Al2O3=(1-100): (10-500): 1, H2O:SiO2=(5-100): 1,
Middle R represents the molal quantity to organic formwork agent in crystallization mixture；
B, Crystallizing treatment is carried out to crystallization mixture by described obtained in step a, collects crystallization product；
C, the crystallization product obtained in step b is dried and is roasted, obtain CHA structure molecular sieve；
D, CHA structure molecular sieve obtained in step c is subjected in the dipping solution of copper-containing compound impregnation, returned
Receive solid product；
Wherein, the organic formwork agent is for 5,6,7,8- naphthane -2- bases-trimethylammonium hydroxide and/or to ethenylphenyl -
N, N, N- trimethylammonium hydroxide.
2. according to the method described in claim 1, wherein, this method further include: in step a, first by the organic formwork agent with
Silicon source mixing, and 45-190 DEG C, under confined conditions handle 0.5-50 hour, obtain body containing aluminium glue, then again will described in containing aluminium
Colloid is mixed with silicon source, optional water, is obtained to crystallization mixture.
3. according to the method described in claim 1, wherein, in step a, source of aluminium is selected from aluminium, boehmite, intends thin water aluminium
At least one of stone, gibbsite, aluminium hydroxide, aluminium oxide and aluminum alcoholate.
4. according to the method described in claim 1, wherein, in step a, the silicon source is selected from silicate, silica, silicon
At least one of acid, silica gel, clay and silester.
5. according to the method described in claim 1, wherein, in step a, on the basis of the total weight to crystallization mixture,
The content to alkali metal in crystallization mixture is not higher than 1000ppm.
6. according to the method described in claim 1, wherein, this method further include: it is female to collect the crystallization that the Crystallizing treatment obtains
Liquid, and crystallization mother liquor return is used to prepare described to crystallization mixture.
7. according to the method described in claim 1, wherein, in step b, the condition of the Crystallizing treatment are as follows: temperature 120-190
DEG C, the time is 1-10 days.
8. according to the method described in claim 1, wherein, in step c, the condition of the drying are as follows: temperature is 50-120 DEG C, when
Between be 4-24 hours；
The condition of the roasting are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
9. the method according to claim 1, wherein in step d, the copper-containing compound is selected from copper nitrate, copper chloride, sulfuric acid
At least one of copper, sulfurous acid copper, cuprous sulfite, copper acetate and copper bromide.
10. the method according to claim 1, wherein in step d, the condition of the impregnation include: in terms of CuO described in
Copper-containing compound with the weight ratio of the CHA structure molecular sieve of dry basis be (0.11-0.32): 1, it is described dipping it is molten
Liquid with the weight ratio of the CHA structure molecular sieve of dry basis be (6-25): 1；The temperature of the dipping is 30-90
DEG C, the time is 0.5-3 hours.
11. according to the method described in claim 1, wherein, this method further include: collect and washed after solid product, dried
The step of with roasting.
12. a kind of cupric CHA structure molecular sieve that the method described in any one of claim 1-11 synthesizes.
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| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
| CN105236440A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent |
| CN105645426A (en) * | 2014-11-18 | 2016-06-08 | 中触媒有限公司 | A synthetic method of an SSZ-13 molecular sieve |
| CN106927474A (en) * | 2015-12-30 | 2017-07-07 | 中触媒新材料股份有限公司 | A kind of SSZ-13 molecular sieves and preparation method and application |
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| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
| CN105645426A (en) * | 2014-11-18 | 2016-06-08 | 中触媒有限公司 | A synthetic method of an SSZ-13 molecular sieve |
| CN105236440A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA molecular sieve by using tetraethyl ammonium hydroxide as templating agent |
| CN106927474A (en) * | 2015-12-30 | 2017-07-07 | 中触媒新材料股份有限公司 | A kind of SSZ-13 molecular sieves and preparation method and application |
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