CN104556100B - The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve - Google Patents
The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve Download PDFInfo
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Abstract
The removal methods of organic amine template in a kind of borosilicate beta-molecular sieve, after borosilicate beta-molecular sieve is dried, in 150~420 DEG C of baking inphases in air or nitrogen, then reacted in the aqueous solution of oxidant, obtained solid is washed after reaction, is dry, the mass ratio of one or more of the oxidant in perchloric acid, hypochlorous acid, perchlorate and hypochlorite, oxidant and borosilicate beta-molecular sieve is 0.5~2.0.This method is easy to operate, can effectively remove the template in borosilicate beta-molecular sieve.
Description
Technical field
The present invention is a kind of removal methods of organic amine template in molecular sieve, specifically, is had in a kind of beta-molecular sieve
The removal methods of machine amine template.
Background technology
Borosilicate zeolite is a kind of class sial hetero-atom molecular-sieve, i.e., the aluminium on Si-Al molecular sieve skeleton is completely by boron atom
A kind of molecular sieve substituted.Borosilicate beta-molecular sieve Hydrothermal Synthesiss usually in the system containing organic formwork agent, common template
Agent has tetraethyl ammonium hydroxide, tetraethylammonium bromide or their mixture, and other organic amine compounds.By organic formwork
Agent is separated with molecular sieve inorganic skeleton, be molecular sieve as adsorbent or catalyst before, obtain that duct is unobstructed and table is compared in raising
One essential step of area.Method for the common removed template method of sial beta-molecular sieve is high-temperature roasting method, that is, is existed
500~550 DEG C of 2~6h of roasting, make organic formwork agent be decomposed into micro-molecular gas effusion molecular sieve pore passage.But due to beta molecule
Sieve structure stability is poor, and in the process, structure destroys serious, average crystallinity decline 30~40%, even more.Therefore,
People's exploratory development removes the distinct methods of organic amine template.
CN1199858C can be obtained using the organic amine template in the method removing beta-molecular sieve of segmentation constant temperature calcining
Higher crystallization reservation degree.
CN1041617C and CN1041618C is respectively by adding strong oxidizer or reducing agent, then roasts in atmosphere
Removing organic amine is burnt, the crystallinity of beta-molecular sieve after beta-molecular sieve organic amine removal efficiency and de- amine can be effectively improved.
Need to add more organic formwork agent in borosilicate beta-molecular sieve building-up process, just can guarantee that generation high-crystallinity
Pure beta-molecular sieve crystalline phase.Therefore, compared with sial beta-molecular sieve, more templates, and boron are contained in borosilicate beta-molecular sieve original powder
The structural stability of silicon beta-molecular sieve is worse.Effectively or template in borosilicate beta-molecular sieve cannot be taken off using the above method
Remove, otherwise crystallinity loss is big.
The content of the invention
The object of the present invention is to provide a kind of removal methods of organic amine template in borosilicate beta-molecular sieve, this method operation
Simply, the template in borosilicate beta-molecular sieve can effectively be removed.
The removal methods of organic amine template in the borosilicate beta-molecular sieve that the method for the present invention provides, including by borosilicate beta-molecular sieve
After drying, in 150~420 DEG C of baking inphases in air or nitrogen, then reacted, reacted in the aqueous solution of oxidant
Obtained solid is washed afterwards, is dry, the oxidant in perchloric acid, hypochlorous acid, perchlorate and hypochlorite one
Kind is several, and the mass ratio of oxidant and borosilicate beta-molecular sieve is 0.5~2.0.
The method of the present invention is roasted by low temperature multistage and with oxidizer treatment, can effectively remove the organic of borosilicate beta-molecular sieve
Amine template, improves molecular sieve specific surface area, and retains the crystallinity of borosilicate beta-molecular sieve after de- amine to greatest extent.
Embodiment
The organic amine mould for the method removing borosilicate beta-molecular sieve that the method for the present invention is combined using baking inphases and oxidation processes
Plate agent, first baking inphases molecular sieve at a lower temperature, makes organic amine that Hofmann degradation reactions fully occur, then with oxidation
Agent solution processing, makes remaining organic amine further be removed by oxidation.After the method for the present invention takes off amine, molecular sieve specific surface area carries
Height, crystallization reservation degree is high, and carbon residue is low, illustrates that the organic amine in borosilicate beta-molecular sieve has obtained more thoroughly removing.
First borosilicate beta-molecular sieve is dried before baking inphases for the method for the present invention, dry temperature preferably 80~130
DEG C, more preferably 100~120 DEG C, drying time preferably 2~20h, more preferably 8~12h.
The baking inphases of molecular sieve are carried out after drying, baking inphases can be two sections or three sections or more, roasting
It can in atmosphere carry out, can also be carried out in inert gas.The preferred nitrogen of the inert gas.
In the method for the present invention, when dried molecular sieve divides two-stage roasting in air or nitrogen, first segment calcination temperature
For 240~280 DEG C, second segment calcination temperature is 380~420 DEG C.
During two-stage roasting, heating rate preferably 0.5~7 DEG C/min of first segment calcination temperature is warming up to from drying temperature,
Heating rate preferably 0.5~7 DEG C/min of second segment calcination temperature is warming up to from first segment calcination temperature.
In the method for the present invention, when dried molecular sieve divides three sections of roastings in air or nitrogen, first segment calcination temperature
For 150~180 DEG C, second segment calcination temperature is 240~280 DEG C, and the 3rd section of calcination temperature is 380~420 DEG C.
During three sections of roastings, heating rate preferably 0.5~7 DEG C/min of first segment calcination temperature is warming up to from drying temperature,
Heating rate preferably 0.5~7 DEG C/min of second segment calcination temperature is warming up to from first segment calcination temperature, temperature is roasted from second segment
Degree is warming up to heating rate preferably 9~12 DEG C/min of the 3rd section of calcination temperature.
In the above method, during baking inphases, every section roasting time preferably 1~8 it is small when, more preferably 1~6 it is small when.
Molecular sieve after baking inphases carries out oxidation processes, i.e., is reacted in the aqueous solution of oxidant, reaction temperature
It is preferred that 100~170 DEG C, more preferably 120~150 DEG C, when the time preferably 2~50 is small, more preferably 10~48 it is small when.Oxidant used
Aqueous solution and the liquid/solid ratio of molecular sieve be 2~20ml/g, preferably 2~15ml/g.The preferred perchloric acid of oxidant used, secondary chlorine
Acid, perchlorate or hypochlorite, the perchlorate or hypochlorite are preferably its ammonium salt, sodium salt or sylvite.
When carrying out oxidation processes to molecular sieve, the concentration of aqueous solution of oxidant used is not limited, as long as making oxidant
Mass ratio with molecular sieve is 0.5~2.0, preferably 0.5~1.5.
After oxidation processes, the small molecule such as remaining organic matter conversion formic acid, acetic acid or carbon dioxide, holds very much in molecular sieve
Easily removed by washing and drying and volatilizing, be finally reached the purpose of removing organic formwork agent completely.The washing can be washing,
Preferably 90~120 DEG C of drying temperature after washing, when the time preferably 2~30 is small.
In the method for the present invention, organic amine template is tetraethyl ammonium hydroxide and/or tetrem in the borosilicate beta-molecular sieve
Base ammonium bromide.
Removing of the method for the present invention especially suitable for borosilicate beta-molecular sieve organic amine template, has higher crystalline with production
The borosilicate beta-molecular sieve of degree, sodium form or Hydrogen beta-molecular sieve of the borosilicate beta-molecular sieve preferably without high-temperature roasting.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
Example 1
Prepare borosilicate beta-molecular sieve.
The tetraethyl oxyammonia solution that 1.0g boraxs, 1.1g sodium hydroxides and 104.7g concentration are 25 mass % is mixed
Uniformly, 20g superfine SiO 2s are added（Cabot companies produce, trade mark CAB-O-SILM-5）, reaction is moved into after stirring evenly
Kettle, 140 DEG C of crystallization 15 days, is rapidly cooled to 40 DEG C, after product is centrifuged washing, obtained solid is in 90 DEG C after crystallization
When drying 10 is small, borosilicate beta-molecular sieve original powder S is obtained0, its anhydrous chemical composition（In terms of oxide mol ratio）For：0.5Na2O·
B2O3·22SiO2.Using this original powder as standard specimen, its relative crystallinity is set to 100%, its characterize data is shown in Table 1.
Example 2
（1）Three sections of roastings
By S made from 10g examples 10Molecular sieve is in 120 DEG C of dry 12h, air atmosphere, with the heating rate of 5 DEG C/min
180 DEG C are warming up to, roasts 2h, then 260 DEG C of roasting 2h are warming up to the heating rate of 5 DEG C/min, then with the liter of 10 DEG C/min
Warm speed is warming up to 420 DEG C of roasting 4h.
（2）Oxidation processes
Take 5g（1）Powder, 5g perchloric acid, 20ml deionized waters after one-step baking are added in hydrothermal reaction kettle, 140 DEG C of standings
12h is reacted, is cooled to 25 DEG C, product is centrifuged, and obtained solid is washed with deionized 3~5 times, 120 DEG C of dry 12h,
Obtain the borosilicate zeolite S of removing organic amine template1, its characterize data is shown in Table 1.
Example 3
By the method removing borosilicate beta-molecular sieve S of example 20In organic amine template, unlike（1）Molecular sieve S in step0
Through 120 DEG C of dry 12h, three sections of roastings are carried out in nitrogen atmosphere, are then pressed again（2）Step carries out oxidation processes, obtained removing
The borosilicate zeolite S of organic amine template2Characterize data be shown in Table 1.
Example 4
By the method removing borosilicate beta-molecular sieve S of example 20In organic amine template, unlike（1）Molecular sieve S in step0
Through 120 DEG C of dry 12h, three sections of roastings are carried out in nitrogen atmosphere,（2）By 5g in step（1）One-step baking powder, 10g ammonium perchlorate,
40ml deionized waters are added in hydrothermal reaction kettle together carries out oxidation processes, the borosilicate point of obtained removing organic amine template
Son sieve S3Characterize data be shown in Table 1.
Example 5
（1）Two-stage roasting
By S made from 10g examples 10Molecular sieve is in 120 DEG C of dry 12h, nitrogen atmosphere, with the heating rate of 5 DEG C/min
240 DEG C of roasting 6h are warming up to, then 420 DEG C of roasting 4h are warming up to the heating rate of 5 DEG C/min.
（2）Oxidation processes
Take 5g（1）Powder, 5g perchloric acid after one-step baking, 30ml deionized waters are added in hydrothermal reaction kettle together, 120 DEG C
Reaction 24h is stood, is cooled to 25 DEG C, product is centrifuged, and obtained solid is washed with deionized 3~5 times, 120 DEG C of dryings
12h, obtains the borosilicate zeolite S of removing organic amine template4, its characterize data is shown in Table 1.
Comparative example 1~2
Using the two-stage roasting method that can effectively remove sial beta-molecular sieve organic amine template, molecule made from example 1 is taken
Sieve S02h is roasted in 290 DEG C, then 550 DEG C are warming up to the heating rate of 5 DEG C/min, roasts 20min and 4h respectively, removing is made
The borosilicate beta-molecular sieve DB of organic amine1And DB2, its characterize data is shown in Table 1.
Comparative example 3
Using the method for CN1199858C embodiments 4, molecular sieve S made from example 1 is taken0Respectively at 170 DEG C roast 2h,
260 DEG C of roasting 2h, 420 DEG C of roasting 4h, 550 DEG C of roasting 6h, are made the borosilicate beta-molecular sieve DB of removing organic amine3, its product characterization
Data are shown in Table 1.
Comparative example 4
Using the method for CN1041618C examples 6, molecular sieve S made from example 1 is taken0Divide 2 times and mixed with ammonium perchlorate soln
Close, roasting, the total amount of ammonium perchlorate used is molecular sieve S0The 10% of quality, is made the borosilicate zeolite DB of removing organic amine4, its
Characterize data is shown in Table 1.
Comparative example 5
Take molecular sieve S made from 10g examples 10, 10g perchloric acid, 40ml deionized waters add hydrothermal reaction kettle in, 140 DEG C
Reaction 24h is stood, is cooled to 25 DEG C, product is centrifuged, and solid is washed with deionized 3~5 times, 120 DEG C of dry 12h,
Obtain the borosilicate zeolite DB of removing organic amine template5, its characterize data is shown in Table 1.
As known from Table 1, using method provided by the invention, remove the borosilicate beta-molecular sieve after organic amine have high-crystallinity,
High-specific surface area and low carbon left.Using the high-temperature roasting method of comparative example 1 and 2, the borosilicate beta-molecular sieve after organic amine is removed
Crystallinity loss is big；Using the baking inphases of comparative example 3, the molecular sieve crystallinity reservation degree for removing organic amine slightly improves, but
It is still undesirable；After comparative example 4 aoxidizes de- amine by several times, gained molecular sieve has higher crystallinity, but carbon residue is higher, pattern of descriptive parts
Agent removing is incomplete, and step is complex；Comparative example 5 directly carries out hydro-thermal reaction using the aqueous solution of oxidant and takes off amine,
Obtained de- amine molecule sieve carbon residue is higher, and template removal is incomplete.
Table 1
| Instance number | Molecular sieve is numbered | Relative crystallinity, % | Specific surface area, m2/g | Carbon residue, quality % |
| 1 | S0 | 100 | 320 | - |
| 2 | S1 | 89.9 | 531 | 0.28 |
| 3 | S2 | 95.2 | 564 | 0.09 |
| 4 | S3 | 93.4 | 545 | 0.23 |
| 5 | S4 | 92.6 | 537 | 0.27 |
| Comparative example 1 | DB1 | 62.6 | 428 | 1.89 |
| Comparative example 2 | DB2 | 51.8 | 360 | 0.42 |
| Comparative example 3 | DB3 | 73.7 | 476 | 0.15 |
| Comparative example 4 | DB4 | 80.2 | 502 | 1.31 |
| Comparative example 5 | DB5 | 85.9 | 404 | 2.35 |
Claims (9)
1. the removal methods of organic amine template in a kind of borosilicate beta-molecular sieve, including after borosilicate beta-molecular sieve is dried, in air
Or dividing two-stage roasting in nitrogen, first segment calcination temperature is 240~280 DEG C, and second segment calcination temperature is 380~420 DEG C；Or
Point three sections of roastings, first segment calcination temperature are 150~180 DEG C in air or nitrogen, and second segment calcination temperature is 240~280 DEG C,
3rd section of calcination temperature is 380~420 DEG C；
Then reacted in the aqueous solution of oxidant, obtained solid is washed after reaction, is dry, the oxidant is selected from
The mass ratio of one or more in perchloric acid and perchlorate, oxidant and borosilicate beta-molecular sieve is 0.5~2.0.
2. in accordance with the method for claim 1, it is characterised in that the drying temperature of borosilicate beta-molecular sieve is 80~130 DEG C.
3. in accordance with the method for claim 1, it is characterised in that for two-stage roasting, first segment roasting is warming up to from drying temperature
The heating rate for burning temperature is 0.5~7 DEG C/min, and the heating rate of second segment calcination temperature is warming up to from first segment calcination temperature
For 0.5~7 DEG C/min.
4. in accordance with the method for claim 1, it is characterised in that for three sections of roastings, first segment roasting is warming up to from drying temperature
The heating rate for burning temperature is 0.5~7 DEG C/min, and the heating rate of second segment calcination temperature is warming up to from first segment calcination temperature
For 0.5~7 DEG C/min, the heating rate that the 3rd section of calcination temperature is warming up to from second segment calcination temperature is 9~12 DEG C/min.
5. in accordance with the method for claim 1, it is characterised in that when the time of every section of roasting is 1~8 small.
6. in accordance with the method for claim 1, it is characterised in that the molecular sieve after baking inphases is in the aqueous solution of oxidant
The temperature reacted is 100~170 DEG C, when the time is 2~50 small.
7. in accordance with the method for claim 1, it is characterised in that the aqueous solution of oxidant and the liquid/solid ratio of molecular sieve for 2~
15ml/g。
8. in accordance with the method for claim 1, it is characterised in that the organic amine template for tetraethyl ammonium hydroxide and/
Or tetraethylammonium bromide.
9. in accordance with the method for claim 1, it is characterised in that the perchlorate or hypochlorite are its ammonium salt, sodium salt
Or sylvite.
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| CN110803706B (en) * | 2019-12-04 | 2023-03-28 | 宝鸡文理学院 | Method for quickly and efficiently removing mesoporous silicon oxide material template agent |
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| US4683214A (en) * | 1984-09-06 | 1987-07-28 | Mobil Oil Corporation | Noble metal-containing catalysts |
| CN1041618C (en) * | 1994-08-22 | 1999-01-13 | 中国石油化工总公司石油化工科学研究院 | Method No.1 for removing organic amine from silica-alumina zeolite or its compound |
| IT1314237B1 (en) * | 1999-11-19 | 2002-12-06 | Venezia Tecnologie S P A | INDIO PHOSPHIDE DIRECT SYNTHESIS PROCEDURE |
| CN1199858C (en) * | 2002-03-13 | 2005-05-04 | 中国石油化工股份有限公司 | Method for removing organic amine from beta-zoolite |
| CN1219701C (en) * | 2003-08-26 | 2005-09-21 | 复旦大学 | Method for removing organic-inorganic composite porous material organic template agent |
| CN102616800B (en) * | 2011-01-27 | 2014-04-30 | 中国石油化工股份有限公司 | Method for removing organic amine template in molecular sieve |
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