CN1124980C - Si-Zn molecular sieve and its synthesizing process - Google Patents

Si-Zn molecular sieve and its synthesizing process Download PDF

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CN1124980C
CN1124980C CN 00118289 CN00118289A CN1124980C CN 1124980 C CN1124980 C CN 1124980C CN 00118289 CN00118289 CN 00118289 CN 00118289 A CN00118289 A CN 00118289A CN 1124980 C CN1124980 C CN 1124980C
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molecular sieve
zinc
solution
silicon
template
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CN1304874A (en
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王建国
董梅
孙予罕
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The present invention discloses a silicon-zinc molecular sieve and a synthesizing method thereof. The molecular sieve of the present invention is mordenite containing silicon and zinc, and the molar ratio of SiO2 to ZnO is 5 to 45. Initial powder of the molecular sieve has X-ray diffraction lines in the table 1. Complexing agents of citric acid are added during the synthesizing process of a zinc containing molecular sieve, and the complexing action of the complexing agents and zinc ions is utilized to maintain the stability of zinc in alkaline solution and colloid and inhibit the generation of zinc oxide or hydroxide, so that the zinc content of the frame of the molecular sieve and the crystallization degree of the molecular sieve are enhanced, and the silicon-zinc molecular sieve with MOR structure is synthesized. The method has the advantages of simplicity, easy implementation and favorable repetitiveness.

Description

A kind of Si-Zn molecular sieve and synthetic method thereof
The invention belongs to molecular sieve and synthetic method thereof, relate in particular to a kind of molecular sieve and synthetic method thereof of siliceous zinc.
Heteroatoms is introduced skeleton can carry out effective modulation to the acidity and the pore passage structure of molecular sieve, and the catalysis characteristics of heteroatoms (especially transition metal) self also helps molecular sieve to realize difunctional or multi-functional catalysis simultaneously.Verified: P 5+, Al 3+, Ge 4+, Ti 4+, Fe 3+, Zr 4+All can be introduced into framework of molecular sieve Deng heteroatoms, synthesize the novel molecular sieve material that comprises aluminium phosphate molecular sieve, heteroatoms phosphate molecule sieve, metal silicate molecular sieve etc.But because the restriction of heteroatoms self chemical property, the hetero-atom molecular-sieve building-up process often needs strict condition control and to the selection of reagent.Be to improve the combined coefficient of hetero-atom molecular-sieve, people adopt the method for adding different mineralizers such as F, ammonia/organic amine, purpose all be to improve metal ion in the aqueous solution or colloid solubility and the activity of hydrolysis-condensation reaction takes place.
Because the excellent properties that is shown in a series of catalyzed reactions such as aromatization, dehydrating alkanes reaction, skeleton contains the synthetic of Zn molecular sieve and comes into one's own.The synthetic of Zn molecular sieve that contain with MFI, Beta and LOV topological framework appears in the newspapers.Inui etc. are " Surface Science and catalyticing research " 1988,37 volumes, and report has synthesized the zinciferous ZSM-5 molecular sieve of skeleton in " research of alkane aromatization reaction on the Ga-of Pt exchange and the Zn-silicates molecular sieve " literary composition of 487 pages.Annen etc. have reported a kind of silicon zinc poromerics with triatomic ring of synthetic in 245 pages of " the physico-chemical property research of VPI-7 " literary compositions of " investigation of materials academic meeting paper collection " 1991 233 volumes, this material has the LOV topological framework.The synthetic of Zn-Beta zeolite described in " the synthetic and sign of Zn-Beta zeolite " literary composition of 88 pages in 1994 at " the 7th national catalysis academic meeting paper summary collection " by poplar main forces etc.In addition, the synthetic of zinciferous phosphorus aluminium molecule of the skeleton sieve also appears in the newspapers, and reported for 708 pages at " zeolite " magazine nineteen ninety-fives 15 volume as Tusar etc. to contain the synthetic of zinc CHA type phosphate aluminium molecular sieve.The skeleton component is that the mordenite molecular sieve (MOR) of silicon zinc does not appear in the newspapers as yet.
Mordenite molecular sieve and synthetic method thereof that to the purpose of this invention is to provide a kind of skeleton component be silicon and zinc.
The object of the present invention is achieved like this: adopt citric acid complex method promptly to add citric acid complexing agent in containing the building-up process of Zn molecular sieve, utilize the complexing action of complexing agent and zine ion to keep the stability of zinc in basic solution and colloid, suppress the oxide compound of zinc or the generation of oxyhydroxide, improve framework of molecular sieve zinc content and molecular sieve crystallinity, synthesize Si-Zn molecular sieve with MOR structure.
Molecular sieve of the present invention is the mordenite that contains silicon zinc, and its constitutive molar ratio is: SiO 2/ ZnO=5-45.
Described molecular screen primary powder has the x-ray diffraction line of table 1.
The x-ray diffraction line data of table 1 Si-Zn molecular sieve
2 θ d (A) relative intensities
6.5 13.591 M
9.76 9.066 S
13.46 6.576 S
14.58 6.077 W
15.3 5.792 M
19.64 4.52 S
22.28 3.989 VS
23.21 3.832 M
25.67 3.47 VS
26.3 3.389 VS
27.74 3.216 VS
30.97 2.887 M
The X-ray diffractogram that table 1 provides is based on the relative intensity scope, wherein is that the strongest line is decided to be numerical value 100:W (weak) less than 20 in the X-ray diffractogram; M (in) be 20-40; S (by force) is 40-60; VS (very strong) is greater than 60.Because the difference of instrumental error and sample room, diffraction angle (2 θ) measuring error are estimated as ± 0.10 degree.The X-ray diffractogram of table 1 is the representative diagram of synthetic silicon zinc mordenite.The little deviation of diffractogram can be caused than changing by the silicon zinc of specific sample by the variation of lattice constant.In addition, enough little crystal can influence the shape and the intensity at peak, and the peak is obviously widened.X-ray powder diffraction figure measured by standard techniques, copper target K alpha-ray.
The step of the synthetic above-mentioned molecular sieve of the present invention is as follows:
1. complexing agent, zinc source, silicon source and template are mixed with the aqueous solution that concentration is 1Wt.%-80Wt.% respectively;
2. enveloping agent solution is slowly added in the solution of zinc source, stir 10-60min and make it to mix, obtain solution A; A, template solution are dropped in the solution of silicon source gradually, carry out brute force simultaneously and stir, obtain mixture B, with the scope of acid or alkali adjusting pH to 10.5-13;
3. with B ageing 0.5-5h under brute force stirs, the colloid C that the obtains crystallizing kettle of packing into, static or stirred following 160-200 ℃ of crystallization 4-20 days;
4. the solid after the crystallization takes out, and is dry under 90-140 ℃ through the deionized water filtering and washing, obtains molecular screen primary powder; Contain the zinc mordenite through what ion-exchange can obtain hydrogen shape and other cation type;
Above-mentioned synthetic middle each component mol ratio is: SiO 2/ ZnO=5-45
Template/SiO 2=0.02-1.5
ZnO/ complexing agent=0.2-5.
Described complexing agent is citric acid or Citrate trianion.
Described silicon source is water glass, water glass, tetraethoxy (TEOS), hydrated SiO 2, silicon oxide particle, the silicon oxide water-sol or silica gel.
Described zinc source is: zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
Described template is: tetraethyl-amine bromide, tetraethyl ammonium hydroxide or tetra-alkyl ammonium hydroxide.
Described alkali is sodium hydroxide, potassium hydroxide, ammonia or organic amine.
Described acid is sulfuric acid, nitric acid, hydrochloric acid or acetic acid.
The present invention compared with prior art has following advantage:
Compare with general synthetic method, the citric acid complex method that contains Zn molecular sieve that the present invention proposes is simple and easy to do, good reproducibility.With the citric acid is complexing agent, has increased substantially the activity of surely the writing property of zinc in solution or colloid and its generation hydrolysis-copolycondensation, makes synthetic silicon zinc mordenite molecular sieve have quite perfectly crystalline form and high degree of crystallinity.
The embodiment of the invention is as follows:
Embodiment 1
Adopting water glass is the silicon source, and zinc nitrate is the zinc source, and the tetraethyl-amine bromide is a template.With the 2g citric acid, the 3.0g zinc nitrate is dissolved in the 10ml water altogether, and note is made solution A; 28.4g water glass is dissolved in the 50ml water, note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtains relaxing uniform white colloid.Add 5g template tetraethyl-amine bromide, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100ml crystallizing kettle, 180 ℃ of crystallization 10 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves.Wherein zinc content is 8.6wt.%.XRD shows the diffraction data with table 1, and the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 2
Adopting silicon sol is the silicon source, and zinc acetate is the zinc source, and the tetraethyl-oxyammonia is a template.With the 3g citric acid, the 2.2g zinc acetate is dissolved in the 5ml water altogether, and note is made solution A; Get in silicon sol 30ml (20wt.%) water, note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtains relaxing uniform white colloid.Add 5g template tetraethyl-oxyammonia, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100ml crystallizing kettle, stirred following 160 ℃ of crystallization 10 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves.Wherein zinc content is 8.5wt.%.XRD characterizes and shows the diffraction data with table 1, shows that the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 3
Adopting tetraethoxy is the silicon source, and zinc sulfate is the zinc source, and the tetraethyl-amine bromide is a template.With the 1g citric acid, 2.7g zinc sulfate is dissolved in the 10mL water altogether, and note is made solution A.The powerful stirring down slowly drops to solution A in the 21.0g tetraethoxy settled solution that obtains mixing.Add 5g template tetraethyl-amine bromide and ammonia soln (5%), be adjusted to pH12.Stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100mL crystallizing kettle, 170 ℃ of crystallization 12 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves, and zinc content is 8.2wt.%.XRD characterizes and shows the diffraction data with table 1, shows that the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 4
Present embodiment has compared the influence (seeing Table 2) to the molecular sieve that obtains of citric acid complexing agent in the building-up process.The building-up process of adding citric acid is with embodiment 1, and note is made ZM-1.The building-up process (comprising order of addition(of ingredients), material rate, potential of hydrogen) of not adding citric acid is the same, and note is made ZM-2.Although the building-up process of these two kinds of samples is identical, do not add the sample that citric acid complexing agent obtains and obviously do not have molecular sieve structure, be amorphous substance.
Whether depositing of table 2 citric acid to containing the effect of Zn molecular sieve synthetic
Synthetic method crystallization situation degree of crystallinity unit cell volume
ZM-1 citric acid complex method crystalline form good 94% 2.808
ZM-2 do not have citric acid exist amorphous //
Embodiment 5
Adopting water glass is the silicon source, and zinc nitrate is the zinc source, and the tetraethyl-amine bromide is a template.With the 5g citric acid, the 5.9g zinc nitrate is dissolved in the 10mL water altogether, and note is made solution A; 28.4g water glass is dissolved in the 50mL water.Note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtains relaxing uniform white colloid.Add 5g template tetraethyl-amine bromide, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100mL crystallizing kettle, 180 ℃ of crystallization 15 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves.Wherein zinc content is 11.5wt.%.XRD shows the diffraction data with table 1, and the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 6
Adopting water glass is the silicon source, and zinc nitrate is the zinc source, and the tetraethyl-amine bromide is a template.With the 2g citric acid, the 1.5g zinc nitrate is dissolved in the 10mL water altogether, and note is made solution A; 28.4g water glass is dissolved in the 50mL water, note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtains relaxing uniform white colloid.Add 5g template tetraethyl-amine bromide, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100mL crystallizing kettle, 180 ℃ of crystallization 8 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves.Wherein zinc content is 4.7wt.%.XRD shows the diffraction data with table 1, and the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 7
Adopting water glass is the silicon source, and zinc nitrate is the zinc source, and the tetraethyl-amine bromide is a template.With the 1g citric acid, the 1g zinc nitrate is dissolved in the 10mL water altogether, and note is made solution A; 28.4g water glass is dissolved in the 50mL water, note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtains relaxing uniform white colloid.Add 5g template tetraethyl-amine bromide, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100mL crystallizing kettle, 180 ℃ of crystallization 6 days.The washing of crystallization product, drying obtain the former powder of zinc si molecular sieves.Wherein zinc content is 3.3wt.%.XRD shows the diffraction data with table 1, and the synthetic Si-Zn molecular sieve has mordenite structure.
Embodiment 8
Adopting water glass is the silicon source, and zinc nitrate is the zinc source, and the tetraethyl-amine bromide is a template.With the 1g citric acid, the 0.75g zinc nitrate is dissolved in the 10mL water altogether, and note is made solution A; 28.4g water glass is dissolved in the 50mL water, note is made solution B.The powerful stirring down slowly drops to solution A in the solution B, obtain delaying white uniformly colloid.Add 5g template tetraethyl-amine bromide, stir ageing 3 hours under the room temperature.The colloid that obtains is changed in the teflon-lined 100mL crystallizing kettle, and 180 ℃ of crystallization 5 days, the washing of crystallization product, drying obtained the former powder of zinc si molecular sieves.Wherein zinc content is 2.4wt.%.XRD shows the diffraction data with table 1, and the synthetic Si-Zn molecular sieve has mordenite structure.

Claims (9)

1. a Si-Zn molecular sieve is characterized in that described molecular sieve is the mordenite that contains silicon zinc, and its constitutive molar ratio is: SiO 2/ ZnO=5-45.
2. a kind of Si-Zn molecular sieve as claimed in claim 1 is characterized in that described molecular screen primary powder has the x-ray diffraction line of table 1:
The x-ray diffraction line data of table 1 Si-Zn molecular sieve
2 θ d (A) relative intensities
6.5 13.591 M
9.76 9.066 S
13.46 6.576 S
14.58 6.077 W
15.3 5.792 M
19.64 4.52 S
22.28 3.989 VS
23.21 3.832 M
25.67 3.47 VS
26.3 3.389 VS
27.74 3.216 VS
30.97 2.887 M。
3. the method for synthetic claim 1 or 2 described molecular sieves is characterized in that step is as follows:
(1) complexing agent, zinc source, silicon source and template are mixed with the aqueous solution that concentration is 1Wt.%-80Wt.% respectively;
(2) enveloping agent solution is slowly added in the solution of zinc source, stir and made it to mix in 10-60 minute, obtain solution A; A, template solution are dropped in the solution of silicon source gradually, stir simultaneously, obtain mixture B, with the scope of acid or alkali adjusting pH to 10.5-13;
(3) with B ageing 0.5-5h under brute force stirs, the colloid C that the obtains crystallizing kettle of packing into, static or stirred following 160-200 ℃ of crystallization 4-20 days;
(4) solid after the crystallization takes out, through the deionized water filtering and washing, 90-140 ℃ dry down, obtain molecular screen primary powder, contain the zinc mordenite through what ion-exchange obtained hydrogen shape and other cation type;
Above-mentioned synthetic middle each component mol ratio is:
SiO 2/ZnO＝5-45
Template/SiO 2=0.02-1.5
ZnO/ complexing agent=0.2-5.
4. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described complexing agent is citric acid or Citrate trianion.
5. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described silicon source is water glass, water glass, tetraethoxy, hydrated SiO 2, silicon oxide particle, the silicon oxide water-sol or silica gel.
6. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described zinc source is: zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
7. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described template is: tetraethyl-amine bromide, tetraethyl ammonium hydroxide or tetra-alkyl ammonium hydroxide.
8. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described alkali is sodium hydroxide, potassium hydroxide, ammonia or organic amine.
9. the method for a kind of synthesis of molecular sieve as claimed in claim 3 is characterized in that described acid is sulfuric acid, nitric acid, hydrochloric acid or acetic acid.
CN 00118289 2000-06-13 2000-06-13 Si-Zn molecular sieve and its synthesizing process Expired - Fee Related CN1124980C (en)

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CN103771433B (en) * 2012-10-25 2015-11-25 中国石油化工股份有限公司 A kind of preparation method of hetero atom SAPO-11 molecular sieve
CN107497481B (en) * 2017-08-23 2019-12-13 河北科技大学 Preparation method of transition metal modified silicon magnesium zeolite catalyst
CN110180316A (en) * 2019-06-10 2019-08-30 哈尔滨理工大学 Zinc modified molecular sieve type deodorant preparation method
CN112209397A (en) * 2019-07-12 2021-01-12 中国石油化工股份有限公司 CHA type topological structure zinc-silicon molecular sieve with high zinc-silicon ratio and synthesis method thereof
CN112678840A (en) * 2020-12-29 2021-04-20 东北大学 Preparation method and application of zinc-silicon molecular sieve

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