CN1093512C - Synthesizing method for high-silicon mordenite - Google Patents

Synthesizing method for high-silicon mordenite Download PDF

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CN1093512C
CN1093512C CN98114197A CN98114197A CN1093512C CN 1093512 C CN1093512 C CN 1093512C CN 98114197 A CN98114197 A CN 98114197A CN 98114197 A CN98114197 A CN 98114197A CN 1093512 C CN1093512 C CN 1093512C
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mordenite
molecular ratio
high silicon
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CN1243100A (en
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许磊
魏迎旭
王公慰
张书力
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a synthesis method of a high silicon mordenite. The method comprises the following steps: an aluminum source substance and water are proportionally mixed, stirred and added with a silicon source substance; then the pH value of the mixture is adjusted to being from 8 to 14 by using of an acid liquid or an alkaline liquid, and the mixture continues to be stirred until the mixture is uniformly mixed; the high silicon mordenite is prepared from the raw materials of the following prportion (according to the molecular ratio of oxides): the molecular ratio of SiO2 to Al2O3 of 17 to 25, the molecular ratio of Na2O to Al2O3 of2 to 15, and the molecular ratio of H2O to Al2O3 of 50 to 150; the initial gelatin mixture is crystallized at a temperature of 100 to 180 DEG C for 24 to 240 hours and is roasted at a temperature of 500 to 600 DEG C for 2 to 8 hours to obtain the high silicon mordenite. The present invention has the advantages of wide raw material source, low price, convenient technological operation and no environmental pollution in the production process.

Description

A kind of synthetic method of high silicon mordenite
The present invention relates to chemical synthesising technology, a kind of high silicon mordenite synthetic method particularly is provided.
Mordenite is that a class is formed by connecting through oxo bridge by five-ring, has the molecular sieve kind of two-dimensional space system pore passage structure.Because it has higher silica alumina ratio, heat and hydrothermal stability, present unique catalytic performance, so be widely used in such as in the reactions such as alkylation, isomerization, disproportionation, catalytic cracking, transalkylation, dewaxing pour point depression and methyl alcohol amination, simultaneously also be used as the sepn process that sorbent material is applied to gas or liquid mixture widely, thereby be a kind of very important functional inorganic materials.
First since the synthesizing flokite, numerous investigators once carried out a large amount of study on the synthesis work from Barrer in 1948.It is mutually unusual with the aluminium source to remove used silicon source, and the selection of additive reagent (or structure directing agent) when its main research is that hydro-thermal is synthetic is as USP 5,219,546; USP 5,219, and 547 adopt 2-methyl cyclohexylamine, 4-methyl cyclohexylamine and 1, and 8-two amido menthanes are as additive reagent; USP 5,137, and 282 adopt 1, the 2-cyclohexanediamine; EP80,615 adopt bromination diethyl piperidines; USP 4,585, and 640 adopt nitrogenous organic dye; USP 5,173, and 282 employing 1-chloromethyl hexalin etc. are as the additive reagent synthesizing flokite.Yet above-mentioned additive reagent mostly is an organic amine, and not only its raw material is rare, cost an arm and a leg, and the building-up process complex process, seriously polluted.
The object of the present invention is to provide a kind of synthetic method of high silicon mordenite, its raw material sources are extensive, and are cheap, and technological operation is convenient, the production process non-environmental-pollution.
The invention provides a kind of synthetic method of high silicon mordenite, it is characterized in that preparation process is as follows:
(1) in proportion aluminium source material is mixed with water, under agitation silicon source material is added again, adjust pH value to 8～14 with acid solution or alkali lye then, continue to stir, get initial gel mixture until mixing;
Used aluminium source material is aluminate or aluminium salt; Silicon source material is water glass or silicon sol; Acid is sulfuric acid, hydrochloric acid or nitric acid, and alkali is sodium hydroxide or potassium hydroxide;
Proportioning between each raw material (by the oxide molecule ratio) is
SiO 2/Al 2O 3＝17～25，
Na 2O/Al 2O 3＝2～15，
H 2O/Al 2O 3＝50～150；
(2) with initial gel mixture at 100～180 ℃, crystallization 24～240 hours;
(3) solid crystallized product is separated the dry former powder of synthesis type that gets of deionized water washing with mother liquor;
(4) synthetic former powder fuses in 500～600 ℃ of following air and got high silicon mordenite in 2～8 hours.
In addition, can also be mixed with additive reagent among the present invention in raw water, additive reagent is low-carbon alcohol (C 1～C 4) or commercially available washing powder, with Al 2O 3Molecular ratio be 1～50.
Aluminium salt is Tai-Ace S 150, aluminum nitrate or aluminum chloride among the present invention, and aluminate is sodium metaaluminate or potassium metaaluminate.
The present invention uses wide material sources, cheap, technological operation is convenient, the saturated low-carbon alcohol of non-environmental-pollution, washing powder or water replace the valency height, deleterious organic amine is as the direct synthesizing flokite of additive reagent, and saturated low-carbon alcohol of the additive reagent that is added or washing powder, the effect of playing " template " or " structure directing agent " in the zeolite synthesis process is not only in its effect, and also can regulate surface tension in the synthetic liquid, thereby can under lower crystallization temperature, promote the formation of mordenite crystalline structure and suppress the stray crystal growth, obtain high-quality high silicon mordenite product.
By embodiment in detail the present invention is described in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 is embodiment 1 a products therefrom XRD analysis spectrogram.
Accompanying drawing 2 is embodiment 1 a products therefrom stereoscan photograph.
Accompanying drawing 3 is embodiment 2 products therefrom XRD analysis spectrograms.
Accompanying drawing 4 is embodiment 3 products therefrom XRD analysis spectrograms.
Accompanying drawing 5 is embodiment 4 products therefrom XRD analysis spectrograms.
Accompanying drawing 6 is embodiment 5 products therefrom XRD analysis spectrograms.
Accompanying drawing 7 is embodiment 6 products therefrom XRD analysis spectrograms.
Accompanying drawing 8 is embodiment 7 products therefrom XRD analysis spectrograms.
Accompanying drawing 9 is embodiment 7 products therefrom stereoscan photographs.
Accompanying drawing 10 is embodiment 8 products therefrom XRD analysis spectrograms.
Accompanying drawing 11 is embodiment 9 products therefrom XRD analysis spectrograms.
Accompanying drawing 12 is embodiment 10 products therefrom XRD analysis spectrograms.
Accompanying drawing 13 is embodiment 11 products therefrom XRD analysis spectrograms.
Accompanying drawing 14 is embodiment 12 products therefrom XRD analysis spectrograms.
Accompanying drawing 15 is embodiment 13 products therefrom XRD analysis spectrograms.
Accompanying drawing 16 is embodiment 14 products therefrom XRD analysis spectrograms.
Accompanying drawing 17 is embodiment 15 products therefrom XRD analysis spectrograms.
Accompanying drawing 18 is embodiment 15 products therefrom stereoscan photographs.
Accompanying drawing 19 is embodiment 16 products therefrom XRD analysis spectrograms.
Example 1
The 5ml dissolve with methanol in the 50ml deionized water, (is contained Al with the 6ml sodium aluminate solution then 2O 31.0mol/l, Na 2O 2.0mol/l, down together) in the 250ml beaker, mix, under agitation condition, slowly add 50ml water glass liquid and (contain SiO 23.15mol/l, Na 2O 0.99mol/l, down together), after stirring, add the 5ml sulphuric acid soln again and (contain H 2SO 44mol/l, down together), continue to stir 30 minutes until mixing, afterwards will the said mixture material move in the synthesis reactor and seal, 120 ℃ of following crystallization 72 hours, after being cooled to room temperature, solid is separated from mother liquor, and solid is extremely neutral for several times with the deionized water washing, at 120 ℃ of following air dryings, roasting is 5 hours in 550 ℃ of following air, shows that through XRD analysis product is mordenite (Fig. 1).Stereoscan photograph as shown in Figure 2, its crystal morphology is spherical.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 21 CH 3OH
Product S iO 2/ Al 2O 3Molecular ratio is: 18.8
Example 2
In example 1, only methyl alcohol is replaced with 5 ml ethanol, all the other components are constant, and product is mordenite (Fig. 3) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 15 C 2H 5OH
Product S iO 2/ Al 2O 3Molecular ratio is: 19.2
Example 3
In example 1, only methyl alcohol is replaced with the 5ml propyl alcohol, all the other components are constant, and product is than geolyte (Fig. 4) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 11 C 3H 7OH
Product S iO 2/ Al 2O 3Molecular ratio is: 18.5
Example 4
In example 3, only propyl alcohol is replaced with the 5ml Virahol, all the other components are constant, and product is mordenite (Fig. 5) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 11 C 3H 7OH
Product S iO 2/ Al 2O 3Molecular ratio is: 19.8
Example 5
In example 1, only methyl alcohol is replaced with the 5ml butanols, all the other components are constant, and product is mordenite (Fig. 6) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 9 C 4H 9OH
Product S iO 2/ Al 2O 3Molecular ratio is: 19.5
Example 6
In example 5, only butanols is replaced with the 5ml isopropylcarbinol, all the other components are constant, and product is mordenite (Fig. 7) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1074 H 2O: 9 C 4H 9OH
Product S iO 2/ Al 2O 3Molecular ratio is: 19.8
Example 7
In example 1, only methyl alcohol is replaced with 5g " white cat " washing powder (M), all the other components are constant, and product is mordenite (Fig. 8) through XRD analysis.Stereoscan photograph as shown in Figure 9, as can be seen, its pattern is a styloid.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1028 H 2O: M
Product S iO 2/ Al 2O 3Molecular ratio is: 20.4
Example 8
In example 1, only methyl alcohol is replaced with 5g " green wave " washing powder (N), all the other components are constant, and product is mordenite (Figure 10) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1028 H 2O: N
Product S iO 2/ Al 2O 3Molecular ratio is: 20.0
Example 9
In example 1, only methyl alcohol is replaced with 5g " Tide " washing powder (P), all the other components are constant, and product is mordenite (Figure 11) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1028 H 2O: P
Product S iO 2/ Al 2O 3Molecular ratio is: 19.0
Example 10
In example 1, only methyl alcohol is replaced with 5g " profoundness " washing powder (Q), all the other components are constant, and product is mordenite (Figure 12) through XRD analysis.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 6.9 Na 2O: 1028 H 2O: Q
Product S iO 2/ Al 2O 3Molecular ratio is: 17.3
Example 11
In example 1, only change methyl alcohol into 10ml, water glass liquid changes 60ml into, and all the other components are constant, and product is mordenite (Figure 13) through XRD analysis.
The reaction mixture molecular ratio is: 31.5 SiO 2: Al 2O 3: 8.6 Na 2O: 1213 H 2O: 42 CH 3OH
Product S iO 2/ Al 2O 3Molecular ratio is: 19.2
Example 12
4g Tai-Ace S 150 is dissolved in the 50ml water, in the 250ml beaker, mixes, under agitation condition, slowly add 60ml water glass liquid, after stirring, add the 6ml sodium hydroxide solution again and (contain Na with 10ml methyl alcohol 2O3mol/l, down together), continue to stir 30 minutes, make mixture until mixing, afterwards the said mixture material is moved in the synthesis reactor and seal, 150 ℃ of following crystallization 72 hours, be cooled to room temperature after, solid is separated from mother liquor, solid is extremely neutral for several times with the deionized water washing, at 120 ℃ of following air dryings, roasting is 5 hours in 550 ℃ of following air, shows that through XRD analysis product is mordenite (Figure 14).
The reaction mixture molecular ratio is: 31.5 SiO 2: Al 2O 3: 14.9 Na 2O: 1139 H 2O: 42 CH 3OH
Product S iO 2/ Al 2O 3Molecular ratio is: 24.5
Example 13
In example 12, methyl alcohol is replaced with 10ml ethanol, Tai-Ace S 150 replaces with 3g aluminum chloride, and all the other components are constant, and product is mordenite (Figure 15) through XRD analysis.
The reaction mixture molecular ratio is: 31.5 SiO 2: Al 2O 3: 14.9 Na 2O: 1213 H 2O: 30 C 2H 5OH
Product S iO 2/ Al 2O 3Molecular ratio is: 20.0
Example 14
In example 12, methyl alcohol is replaced with 10g " white cat " washing powder, all the other components are constant, and product is mordenite (Figure 16) through XRD analysis.
The reaction mixture molecular ratio is: 31.5 SiO 2: Al 2O 3: 14.9 Na 2O: 1O28 H 2O: 2M
Product S iO 2/ Al 2O 3Molecular ratio is: 21.3
Example 15
50ml deionized water and 6ml sodium aluminate solution are mixed in the 250ml beaker, after slowly adding 50ml water glass liquid stirs under agitation condition, add the 2ml sodium hydroxide solution again and continue to stir 30 minutes until mixing, afterwards the said mixture material is moved in the synthesis reactor and seal, 120 ℃ of following crystallization 192 hours, after being cooled to room temperature, solid is separated from mother liquor, for several times to neutral, at 120 ℃ of following air dryings, roasting is 5 hours in 550 ℃ of following air with the deionized water washing for solid, show that through XRD analysis product is mordenite (Figure 17), stereoscan photograph such as Figure 18 (a, b) shown in, its pattern is regular fusiform crystal.
The reaction mixture molecular ratio is: 26 SiO 2: Al 2O 3: 11.3 Na 2O: 1000 H 2O
Product S iO 2/ Al 2O 3Molecular ratio is: 23.0
Example 16
4g Tai-Ace S 150 is dissolved in the 50ml water, under agitation condition, slowly add 60ml water glass liquid, after stirring, add the 6ml sodium hydroxide solution again, continue to stir 30 minutes until mixing, make mixture, afterwards the said mixture material is moved in the synthesis reactor and seal, 120 ℃ of following crystallization 240 hours, be cooled to room temperature after, solid is separated from mother liquor, solid is extremely neutral for several times with the deionized water washing, at 120 ℃ of following air dryings, roasting is 5 hours in 550 ℃ of following air, shows that through XRD analysis product is mordenite (Figure 19).
The reaction mixture molecular ratio is: 31.5 SiO 2: Al 2O 3: 14.9 Na 2O: 1074 H 2O
Product S iO 2/ Al 2O 3Molecular ratio is: 21.5

Claims (3)

1. the synthetic method of a high silicon mordenite is characterized in that preparation process is as follows:
(1) in proportion aluminium source material is mixed with water, under agitation silicon source material is added again, adjust pH value to 8～14 with acid solution or alkali lye then, continue to stir, get initial gel mixture until mixing;
Used aluminium source material is aluminate or aluminium salt; Silicon source material is water glass or silicon sol; Acid is sulfuric acid, hydrochloric acid or nitric acid, and alkali is sodium hydroxide or potassium hydroxide;
Proportioning between each raw material by the oxide molecule ratio is:
SiO 2/Al 2O 3＝17～25，
Na 2O/Al 2O 3＝2～15，
H 2O/Al 2O 3＝50～150；
(2) with initial gel mixture at 100～180 ℃, crystallization 24～240 hours;
(3) solid crystallized product is separated the dry former powder of synthesis type that gets of deionized water washing with mother liquor;
(4) roasting in 500～600 ℃ of following air of synthetic former powder got high silicon mordenite in 2～8 hours.
2. by the synthetic method of the described high silicon mordenite of claim 1, it is characterized in that: be mixed with additive reagent in the raw water, additive reagent is low-carbon alcohol (C 1～C 4) or commercially available washing powder, with Al 2O 3Molecular ratio be 1～50.
3. by the synthetic method of the described high silicon mordenite of claim 1, it is characterized in that: aluminium salt is Tai-Ace S 150, aluminum nitrate or aluminum chloride, and aluminate is sodium metaaluminate or potassium metaaluminate.
CN98114197A 1998-07-29 1998-07-29 Synthesizing method for high-silicon mordenite Expired - Fee Related CN1093512C (en)

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CN100344537C (en) * 2005-02-03 2007-10-24 复旦大学 Prepn process of high-silicon mordenite
CN101804995A (en) * 2010-04-13 2010-08-18 中国地质大学（武汉） Method for preparing high-silicon mordenite by using raw mineral material
JP5351216B2 (en) * 2010-07-01 2013-11-27 日本化学工業株式会社 Method for producing zeolite
CN102838339B (en) * 2012-08-28 2016-02-10 李云飞 A kind of Gel-type chemical stemming and preparation method thereof
CN104016371B (en) * 2013-03-01 2016-03-16 上海碧科清洁能源技术有限公司 The in-situ synthetic method of cupric mordenite
CN104276586B (en) 2013-07-03 2016-10-05 中国石油大学(北京) A kind of preparation method of modenite
CN103601213A (en) * 2013-12-06 2014-02-26 天津大学 Preparation method for low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve
CN105366688B (en) * 2014-08-27 2018-04-06 中国石油化工股份有限公司 The preparation method of adhesive-free mordenite
CN107758685B (en) * 2016-08-23 2020-09-04 中国石油化工股份有限公司 Nano aggregated sheet mordenite
AU2016431572B2 (en) * 2016-12-09 2020-05-21 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for synthesizing mordenite MOR molecular sieve, and product and use thereof
CN112661167B (en) * 2019-10-16 2022-11-08 中国科学院大连化学物理研究所 Synthesis method of nano mordenite molecular sieve and molecular sieve
CN114644344B (en) * 2020-12-18 2024-03-12 中国石油化工股份有限公司 Mordenite and preparation method thereof

Citations (3)

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CN1050611A (en) * 1989-09-25 1991-04-10 日本钢管株式会社 Magnetic defect detector for steel strip
US5137282A (en) * 1991-01-07 1992-08-11 Folsom Sports, Inc. Plastic molded arrowhead and method
US5219546A (en) * 1991-10-04 1993-06-15 Mobil Oil Corp. Synthesis of crystalline mordenite-type material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050611A (en) * 1989-09-25 1991-04-10 日本钢管株式会社 Magnetic defect detector for steel strip
US5137282A (en) * 1991-01-07 1992-08-11 Folsom Sports, Inc. Plastic molded arrowhead and method
US5219546A (en) * 1991-10-04 1993-06-15 Mobil Oil Corp. Synthesis of crystalline mordenite-type material

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