CN110240175A - A kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve - Google Patents
A kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve Download PDFInfo
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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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
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Abstract
A method of pure silicon CHA molecular sieve being synthesized by template of TMAdaOH, belongs to technical field of zeolite molecular sieve preparation.It is the addition pure silicon CHA molecular sieve seed in Primogel, and pure silicon CHA molecular sieve is synthesized in floride-free system.This method is with cheap silicon source, and alkali source and homemade pure silicon CHA molecular sieve seed are raw material, and first silicon source, template, alkali source and crystal seed are dissolved in distilled water, and stirring forms uniform gel, then carries out hydrothermal crystallizing.Product after hydrothermal crystallizing is arrived into pure silicon CHA molecular sieve of the present invention by washing drying.Compared with prior art, the present invention has the characteristics that simple synthetic method, synthesis process without using fluorine ion, has good prospects for commercial application.
Description
Technical field
The invention belongs to technical field of zeolite molecular sieve preparation, and in particular to specially treated is passed through in addition in Primogel
Obtained pure silicon CHA molecular sieve seed, using N, N, N- trimethyl -1- adamantane ammonium hydroxide is as template, not to anti-
It answers in system and introduces under conditions of fluorine ion, pure silicon CHA molecular sieve is prepared by conventional hydrothermal synthetic method.
Background technique
The synthesis of molecular sieve is usually under the conditions of alkaline system, and Guth et al. replaces OH using fluorine ion-, can be in closely
Synthesis zeolite under property or acid condition.However, fluorine is as a kind of nonmetalloid, the injury to human body be do not allow it is small
It looks.Fluorine poisoning, less serious case form den tal fluorosis, and fluorosis of bone occurs in severe one.Moreover, fluoride can also generate skin, mucous membrane
Strong impulse effect, to cause the skin ulcer for being difficult to heal.If sucking excessive fluoride, it can also cause gastric ulcer
Even gastrorrhagia and directly result in death.In the industrial production, hydrofluoric acid can consumingly corrode metal, siliceous nonmetallic set
It is standby, therefore the requirement to storage container and consersion unit is high, cost and safety problem have both.
Patent CN104925825A discloses the preparation method of total silicon CHA molecular sieve, and this method uses fluorine in synthesis
Ion is unfavorable for industrial production as mineralizer.
Document Broadening the scope for fluoride-free synthesis of siliceous
Zeolites (Angewandte Chemie International Edition, 57 (2018) 3607-3611) reports one kind
Floride-free xerogel, the method for steam auxiliary synthesis pure silicon CHA molecular sieve, the method that this method uses steam auxiliary crystallization, synthesis
Step is complicated, limits its industrial application.
Although pure silicon CHA molecular sieve is widely used, but synthesizing need to be using harmful fluorine ion, or uses more complicated
Synthesis step, this is unfavorable for the industrialized production of pure silicon CHA molecular sieve very much.
Summary of the invention
It is an object of the invention in existing technical foundation, provide one kind with N, N, N- trimethyl -1- adamantane hydrogen
Amine-oxides are template, crystal seed auxiliary, the method that hydro-thermal free-floride synthesizes pure silicon CHA molecular sieve, overcome existing synthesis need using
Fluorine ion is as mineralizer, or the shortcomings that using steam auxiliary crystallization.Compared with prior art, the present invention has operation letter
List is not needed using fluorine ion, can be crystallized to obtain the high pure silicon CHA molecular sieve of crystallinity under the conditions of conventional hydrothermal, have
Good prospects for commercial application.
Crystal seed used in the present invention is laboratory self-control, needs to calcine crystal seed after synthesizing crystal seed, ball-milling treatment, simultaneously
In order to provide enough nucleus, alkali process, further activation seeds are carried out to the crystal seed after ball milling.
The preparation step of crystal seed of the present invention is as follows:
(1) by template N, N, N- trimethyl -1- adamantane ammonium hydroxide (TMAdaOH) and distilled water are added separately to instead
Answer in container, it is closed, under room temperature stirring to both be uniformly mixed；
(2) ethyl orthosilicate or silica solution is added dropwise under stirring into step (1) solution, stirring is equal to solution mixing
It is even；
(3) continue whipping step (2) solution to moisture evaporation, sample is pulverized；
(4) a certain amount of hydrofluoric acid is added into step (3) product, hand operated mixing to the two is uniformly mixed；By positive silicic acid
Ethyl ester or silica solution conversion are SiO2It is calculated, effective component composition and molar ratio are SiO2: TMAdaOH:HF:H2O=(80
~120): (30~80): (30~60): (50~250)；
(5) by mixture obtained by step (4) hydrothermal crystallizing 5~7 days under the conditions of 140~180 DEG C；
(6) after step (5) product is cooled to room temperature, obtained solid is washed with distilled water to neutrality, 60~100 DEG C
Dry 6~10 hours, then to carry out ball-milling treatment 5~10 after dried product is calcined 5~8 hours at 550~650 DEG C small
When；
(7) solid after step (6) ball milling is stirred 0.1~1 in the sodium hydrate aqueous solution of 0.01~0.2mol/L
Hour, be centrifuged, distill water washing, 60~100 DEG C drying 6~10 hours, obtain pure silicon CHA molecular sieve seed.
A kind of method of the present invention for synthesizing pure silicon CHA molecular sieve for hydro-thermal free-floride, its step are as follows:
1) by template N, N, N- trimethyl -1- adamantane ammonium hydroxide (TMAdaOH) and distilled water are proportionally added into
In reaction vessel, it is closed, under room temperature stirring to both be uniformly mixed；
2) silicon source is added into step 1) solution under stirring, continues stirring to solution and is uniformly mixed；
3) sodium hydroxide is added into step 2) solution, it is closed, under room temperature stirring form uniform mixed liquor；
4) pure silicon CHA molecular sieve seed is added in the uniform mixed liquor formed to step 3), continues at room temperature
It stirs to the Primogel of required water silicon ratio；
Silicon source is converted as SiO2It is calculated, the composition of effective component and molar ratio are SiO in Primogel2:
TMAdaOH:NaOH:H2O=(80~130): (10~80): (0~30): (500~3000), the input amount of crystal seed are by silicon source
Conversion is SiO2The 5~10% of quality；
5) by mixture obtained by step 4) hydrothermal crystallizing 5~20 days under the conditions of 100~200 DEG C；
6) after step 5) product is cooled to room temperature, obtained solid is washed with distilled water, this is obtained after dry
Invent the pure silicon CHA molecular sieve.
The method of the present invention is by using N, and N, N- trimethyl -1- adamantane ammonium hydroxide is template, while pure silicon is added
CHA molecular sieve seed, by gained mixture carry out hydrothermal crystallizing, can under the conditions of free-floride hydrothermal synthesis pure silicon CHA molecular sieve,
Such as Examples 1 to 55.
Advantages of the present invention is that pure silicon CHA molecular sieve can be obtained by hydrothermal synthesis under the conditions of free-floride.
Wherein, silicon source can be ethyl orthosilicate, silica solution and white carbon black, preferably ethyl orthosilicate.
In step 4), preferred Primogel group becomes SiO2: TMAdaOH:NaOH:H2O=(90~120): (20~
50): (0~1): (1000~2000).
In step 5), crystallization temperature is preferably 120~180 DEG C, and crystallization time is preferably 5~15 days.
In step 6), the solid-liquid separation method can be used suction filtration or centrifugation, and the drying can be in 75~100 DEG C of temperature
Degree is lower to carry out, and the time of the drying can be selected according to dry temperature, generally can be 6~12 hours.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the X-ray powder diffraction figure of product prepared by embodiment 1, can determine that product is CHA molecular sieve by Fig. 1.
Fig. 2 is the electron scanning micrograph of product prepared by embodiment 1, can determine that embodiment 1 is made by Fig. 2
The specific pattern of standby product.As can be seen from the figure sheet pattern is presented in the product being prepared.
Fig. 3 is the X-ray powder diffraction figure of product prepared by embodiment 2, can determine that product is CHA molecular sieve by Fig. 3.
Fig. 4 is the electron scanning micrograph of product prepared by embodiment 2, can determine that embodiment 2 is made by Fig. 4
The specific pattern of standby product.As can be seen from the figure sheet pattern is presented in the product being prepared.
Specific embodiment
The preparation of crystal seed:
(1) 3.995 grams of N, N, N- trimethyl -1- adamantane ammonium hydroxide and 5 milliliters of distilled water are added to reaction vessel
In, it is stirred at room temperature to the two and is uniformly mixed；
(2) 2.25 grams of ethyl orthosilicates are added into above-mentioned solution under stirring, continue stirring to ethyl orthosilicate
Hydrolysis is complete；
(3) continue stirring to moisture evaporation, be in xerogel shape, by sample grind into powder；
(4) 205 microlitres of hydrofluoric acid are pipetted, are added in the powder of step (3), hand operated mixing to the two is uniformly mixed；It will
Silicon source conversion is SiO2It is calculated, gel effective component and molar ratio are SiO2:TMAdaOH:HF:H2O=100:45:45:
100；
(5) by mixture obtained by step (4) hydrothermal crystallizing 7 days under the conditions of 150 DEG C；
(6) after being cooled to room temperature, obtained solid is washed with distilled water, it is dry；
(7) dried product is calcined 6 hours for 600 DEG C in Muffle furnace, by product ball-milling treatment 6 hours after calcining；
(8) solid after ball milling stirs 1 hour in the sodium hydrate aqueous solution that concentration is 0.10mol/L, is centrifuged, and steams
Distilled water washing, 60 DEG C drying 10 hours, obtain CHA type zeolite molecular sieve crystal seed used in the present invention, i.e. pure silicon CHA molecular sieve crystalline substance
Kind, 0.5 gram.
The pure silicon CHA molecular sieve that following embodiment obtains in this approach is as crystal seed.
Embodiment 1:
(1) 2.114 grams of N, N, N- trimethyl -1- adamantane Ammonia and 3 milliliters of distilled water are added to reaction
In container, it is stirred at room temperature to the two and is uniformly mixed；
(2) 1.929 grams of ethyl orthosilicate (wherein SiO are added dropwise into above-mentioned solution under stirring2Quality is 0.54
Gram), it is complete to teos hydrolysis to continue stirring；
(3) 0.02 gram of sodium hydroxide is added in Xiang Shangshu solution, in closed, the uniform mixing of stirring formation under room temperature
Liquid；
(4) 0.027 gram of CHA molecular sieve seed is added in the uniform mixed liquor formed to step (3).It stirs at room temperature
It mixes to the gel of required water silicon ratio, silicon source is converted as SiO2It is calculated, gel effective component and molar ratio are SiO2:
TMAdaOH:NaOH:H2O=90:25:5:1500, the input amount of crystal seed are to convert silicon source used in step (2) for SiO2Matter
The 5% of amount.
(5) by mixture obtained by step (4) hydrothermal crystallizing 12 days under the conditions of 140 DEG C；
(6) after being cooled to room temperature, washed after crystallization product is centrifugated with distilled water, 75 DEG C drying 10 hours
After obtain pure silicon CHA molecular sieve of the present invention.
The X-ray powder diffraction figure of obtained product is shown in attached drawing 1, the product that embodiment 1 is prepared as can be seen from Figure 1
It is CHA molecular sieve.The electron scanning micrograph of product is shown in attached drawing 2, and piece is presented in the product being prepared as can be seen from Figure 2
Stratiform pattern.
Embodiment 2:
(1) 1.691 grams of N, N, N- trimethyl -1- adamantane Ammonia and 3 milliliters of distilled water are added to reaction
In container, it is stirred at room temperature to the two and is uniformly mixed；
(2) 2.143 grams of ethyl orthosilicate (wherein SiO are added dropwise into above-mentioned solution under stirring2Quality is 0.6
Gram), it is complete to teos hydrolysis to continue stirring；
(3) 0.06 gram of sodium hydroxide is added in Xiang Shangshu solution, in closed, the uniform mixing of stirring formation under room temperature
Liquid；
(4) 0.03 gram of CHA molecular sieve seed is added in the uniform mixed liquor formed to step (3).It stirs at room temperature
It mixes to the gel of required water silicon ratio, silicon source is converted as SiO2It is calculated, gel effective component and molar ratio are SiO2:
TMAdaOH:NaOH:H2O=100:20:15:1800, the input amount of crystal seed are to convert silicon source used in step (2) for SiO2
The 5% of quality.
(5) by mixture obtained by step (4) hydrothermal crystallizing 14 days under the conditions of 140 DEG C；
(6) after being cooled to room temperature, washed after crystallization product is centrifugated with distilled water, 100 DEG C drying 7 hours
After obtain pure silicon CHA molecular sieve of the present invention.
The X-ray powder diffraction figure of obtained product is shown in attached drawing 3, the product that embodiment 2 is prepared as can be seen from Figure 3
It is CHA molecular sieve.The electron scanning micrograph of product is shown in attached drawing 4, and piece is presented in the product being prepared as can be seen from Figure 4
Stratiform pattern, and be stacked.
Embodiment 3:
(1) 3.129 grams of N, N, N- trimethyl -1- adamantane Ammonia and 3 milliliters of distilled water are added to reaction
In container, it is stirred at room temperature to the two and is uniformly mixed；
(2) 2.358 grams of ethyl orthosilicate (wherein SiO are added dropwise into above-mentioned solution under stirring2Quality is 0.66
Gram), it is complete to teos hydrolysis to continue stirring；
(3) 0.036 gram of sodium hydroxide is added in Xiang Shangshu solution, it is closed, under room temperature stirring formed it is uniform mixed
Close liquid；
(4) 0.033 gram of CHA molecular sieve seed is added in the uniform mixed liquor formed to step (3).It stirs at room temperature
It mixes to the gel of required water silicon ratio, silicon source is converted as SiO2It is calculated, gel effective component and molar ratio are SiO2:
TMAdaOH:NaOH:H2O=110:37:9:1200, the input amount of crystal seed are to convert silicon source used in step (2) for SiO2
The 5% of quality.
(5) by mixture obtained by step (4) hydrothermal crystallizing 6 days under the conditions of 180 DEG C；
(6) after being cooled to room temperature, washed after crystallization product is centrifugated with distilled water, 90 DEG C drying 8 hours
After obtain pure silicon CHA molecular sieve of the present invention.
Embodiment 4:
(1) 4.228 grams of N, N, N- trimethyl -1- adamantane Ammonia and 3 milliliters of distilled water are added to reaction
In container, it is stirred at room temperature to the two and is uniformly mixed；
(2) 2.572 grams of ethyl orthosilicate (wherein SiO are added dropwise into above-mentioned solution under stirring2Quality is 0.72
Gram), it is complete to teos hydrolysis to continue stirring；
(3) 0.028 gram of sodium hydroxide is added in Xiang Shangshu solution, it is closed, under room temperature stirring formed it is uniform mixed
Close liquid；
(4) 0.054 gram of CHA molecular sieve seed is added in the uniform mixed liquor formed to step (3).It stirs at room temperature
It mixes to the gel of required water silicon ratio, silicon source is converted as SiO2It is calculated, gel effective component and molar ratio are SiO2:
TMAdaOH:NaOH:H2O=120:50:7:1000, the input amount of crystal seed are to convert silicon source used in step (2) for SiO2
The 7.5% of quality.
(5) by mixture obtained by step (4) hydrothermal crystallizing 15 days under the conditions of 140 DEG C；
(6) after being cooled to room temperature, washed after crystallization product is centrifugated with distilled water, 80 DEG C drying 10 hours
After obtain pure silicon CHA molecular sieve of the present invention.
Embodiment 5:
(1) 2.79 grams of N, N, N- trimethyl -1- adamantane Ammonia and 3 milliliters of distilled water are added to reaction and held
In device, it is stirred at room temperature to the two and is uniformly mixed；
(2) 2.143 grams of ethyl orthosilicate (wherein SiO are added dropwise into above-mentioned solution under stirring2Quality is 0.6
Gram), it is complete to teos hydrolysis to continue stirring；
(3) 0.048 gram of sodium hydroxide is added in Xiang Shangshu solution, it is closed, under room temperature stirring formed it is uniform mixed
Close liquid；
(4) 0.06 gram of CHA molecular sieve seed is added in the uniform mixed liquor formed to step (3).It stirs at room temperature
It mixes to the gel of required water silicon ratio, silicon source is converted as SiO2It is calculated, gel effective component and molar ratio are SiO2:
TMAdaOH:NaOH:H2O=110:33:12:2000, the input amount of crystal seed are to convert silicon source used in step (2) for SiO2
The 10% of quality.
(5) by mixture obtained by step (4) hydrothermal crystallizing 10 days under the conditions of 150 DEG C；
(6) after being cooled to room temperature, washed after crystallization product is centrifugated with distilled water, 85 DEG C drying 9 hours
After obtain pure silicon CHA molecular sieve of the present invention.
Claims (6)
1. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve, its step are as follows:
1) by template N, N, N- trimethyl -1- adamantane ammonium hydroxide and distilled water are proportionally added into reaction vessel,
It is closed, under room temperature stirring to both be uniformly mixed；
2) silicon source is added into step 1) solution under stirring, continues stirring to solution and is uniformly mixed；
3) sodium hydroxide is added into step 2) solution, it is closed, under room temperature stirring form uniform mixed liquor；
4) pure silicon CHA molecular sieve seed is added in the uniform mixed liquor formed to step 3), continues to stir at room temperature
To the Primogel of required water silicon ratio；
Silicon source is converted as SiO2It is calculated, the composition of effective component and molar ratio are SiO in Primogel2: TMAdaOH:
NaOH:H2O=(80~130): (10~80): (0~30): (500~3000), the input amount of crystal seed are to be by silicon source conversion
SiO2The 5~10% of quality；TMAdaOH represents N, N, N- trimethyl -1- adamantane ammonium hydroxide；
5) by mixture obtained by step 4) hydrothermal crystallizing 5~20 days under the conditions of 100~200 DEG C；
6) after step 5) product is cooled to room temperature, obtained solid is washed with distilled water, obtains the present invention after dry
The pure silicon CHA molecular sieve；
Wherein, the preparation step of the molecular sieve seed of pure silicon CHA described in step 4) is as follows,
(1) by template N, N, N- trimethyl -1- adamantane ammonium hydroxide and distilled water are added separately in reaction vessel, close
It closes, stirring to the two is uniformly mixed under room temperature；
(2) ethyl orthosilicate or silica solution is added dropwise under stirring into step (1) solution, stirring to solution is uniformly mixed；
(3) continue whipping step (2) solution to moisture evaporation, sample is pulverized；
(4) a certain amount of hydrofluoric acid is added into step (3) product, hand operated mixing to the two is uniformly mixed, effective component composition
And molar ratio is SiO2: TMAdaOH:HF:H2O=(80~120): (30~80): (30~60): (50~250)；
(5) by mixture obtained by step (4) hydrothermal crystallizing 5~7 days under the conditions of 140~180 DEG C；
(6) after step (5) product is cooled to room temperature, obtained solid is washed with distilled water to neutrality, 60~100 DEG C of dryings
6~10 hours, dried product carried out ball-milling treatment 5~10 hours after calcining 5~8 hours at 550~650 DEG C；
(7) solid after step (6) ball milling is stirred 0.1~1 hour in the sodium hydrate aqueous solution of 0.01~0.2mol/L,
Be centrifuged, distill water washing, 60~100 DEG C drying 6~10 hours, obtain pure silicon CHA molecular sieve seed.
2. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve as described in claim 1, it is characterised in that: step (2)
Middle silicon source is ethyl orthosilicate, silica solution and white carbon black.
3. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve as described in claim 1, it is characterised in that: step (4)
In crystal seed to pass through specially treated.
4. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve as described in claim 1, it is characterised in that: step (4)
In initial gel mixture, effective component composition and molar ratio are SiO2: TMAdaOH:NaOH:H2O=(90~120): (20
~50): (0~15): (1000~2000).
5. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve as described in claim 1, it is characterised in that: step (5)
Middle crystallization is that temperature is 120~180 DEG C, and crystallization time is 5~15 days.
6. a kind of method of hydro-thermal free-floride synthesis pure silicon CHA molecular sieve as described in claim 1, it is characterised in that: step (6)
Drying be 75~100 DEG C at a temperature of carry out, the dry time be 6~12 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547735A (en) * | 2020-04-30 | 2020-08-18 | 上海工程技术大学 | Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN114920265A (en) * | 2022-05-26 | 2022-08-19 | 嘉兴学院 | Method for rapidly preparing all-silicon SSZ-13 zeolite by using guide agent method |
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| US20170022066A1 (en) * | 2015-07-23 | 2017-01-26 | Chevron U.S.A. Inc. | Crystalline molecular sieves and synthesis thereof |
| CN108002396A (en) * | 2017-12-21 | 2018-05-08 | 吉林大学 | A kind of method that Silicalite-1 molecular sieves are synthesized using TPABr as template |
| CN108751221A (en) * | 2018-05-03 | 2018-11-06 | 浙江大学 | The method of the floride-free synthesis Silicon-rich SSZ-13 zeolite molecular sieves of crystal seed auxiliary |
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- 2019-07-16 CN CN201910638841.8A patent/CN110240175A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170022066A1 (en) * | 2015-07-23 | 2017-01-26 | Chevron U.S.A. Inc. | Crystalline molecular sieves and synthesis thereof |
| CN108002396A (en) * | 2017-12-21 | 2018-05-08 | 吉林大学 | A kind of method that Silicalite-1 molecular sieves are synthesized using TPABr as template |
| CN108751221A (en) * | 2018-05-03 | 2018-11-06 | 浙江大学 | The method of the floride-free synthesis Silicon-rich SSZ-13 zeolite molecular sieves of crystal seed auxiliary |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547735A (en) * | 2020-04-30 | 2020-08-18 | 上海工程技术大学 | Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN114920265A (en) * | 2022-05-26 | 2022-08-19 | 嘉兴学院 | Method for rapidly preparing all-silicon SSZ-13 zeolite by using guide agent method |
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