CN102311125A - Method for preparing high-crystallinity EUO type molecular sieves - Google Patents
Method for preparing high-crystallinity EUO type molecular sieves Download PDFInfo
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Abstract
The invention discloses a method for preparing high-crystallinity EUO type molecular sieves, which comprises the steps of: uniformly mixing and crystallizing crystal seeds S, silicon sources, alkali, water and template agents and preparing EUO molecular sieves through filtering, washing, drying and roasting, wherein the template agents are tetraethyl ammonium hydroxide or tetraethyl ammonium bromide, and the consumption of the crystal seeds in reaction mixtures is properly regulated, so the EUO type molecular sieves are synthesized. Compared with the prior art, the EUO type molecular sieves synthesized by the method have the characteristic that the crystallinity is high and is ordinarily 5 percent to 20 percent higher than that of the existing molecular sieves, and simultaneously, the method disclosed by the invention also has the characteristics that the synthesis is fast, and the crystallization time is short.
Description
Technical field
The present invention relates to a kind of molecular sieve and preparation method thereof, a kind of specifically preparation method of EUO type molecular sieve.
Background technology
The EUO structure molecular screen is a kind of mesopore high-silica zeolite; Have the netted micropore canals structure of one dimension, contain the straight-through duct of ten-ring (orifice diameter be 0.58 * 0.41nm) and with it the twelve-ring side pocket of vertical UNICOM (be of a size of 0.68 * 0.58 * 0.81nm) structure.Because the singularity in duct, EUO structure molecular screen show excellent catalytic performance in reactions such as YLENE isomery, straight-chain paraffin isomerizing, Hydrodewaxing, have favorable industrial application prospect.
The EUO structure molecular screen comprises EU-1, TPZ-3 and ZSM-50 molecular sieve at present, and they generally have the chemical formula of following anhydrous form: 1～100XO
2: 0～10T
2O
3: 0～20R, X represent silicon and/or germanium, and T represents at least a element that is selected from aluminium, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese.Usually the preparation method of EUO structure molecular screen comprises, in water-bearing media, the organic compounds containing nitrogen of a kind of element X source, a kind of element T source, a kind of alkali metal source and a kind of rapping plate agent effect is mixed.
European patent EP 0042226 proposes EU-1 molecular sieve and preparation method thereof the earliest.The template that is adopted is polymethylene α-ω-diammonium ion, or the degraded product of said verivate or said verivate precursor.The preparation method of EU-1 molecular sieve is following: silicon source, aluminium source, mineralizer, organic formwork agent and water are mixed, through hydrothermal crystallizing, make the EU-1 molecular sieve.
European patent EP 0051318 has been described the TPZ molecular sieve, has used and the employed template on the same group of synthetic EU-1 molecular sieve.Described 1 especially, 6-N, N, N, N ', N ', N '-hexamethyl hexa-methylene two ammonium compounds are as the preparation method of template.
European patent EP 0159845 has proposed the ZSM-50 molecular sieve with U.S. Pat P4640829, is to use diphenyl-methyl Dimethyl Ammonium verivate as the template synthetic.
U.S. Pat P4537754 discloses a kind of EU-1 molecular sieve and preparation method thereof.The alkyl derivative of employing polymethylene α-ω-diammonium ion or its precursor are as the template of molecular sieve.Described template precursor is parent two ammoniums and alcohol or alkyl halide.
U.S. Pat P6514479 and Chinese patent CN99127713.9 disclose a kind of method of the EUO of preparation molecular sieve; Adopt template precursor synthesis of molecular sieve; Used precursor is monoamine and dihalo alkane or alkane diol; Adopting Trimethylamine 99 and dibromo-hexane among the embodiment is the template precursor, adds crystal seed and inorganic salt when synthetic, shortens crystallization time.U.S. Pat 6723301 and US6616910 disclose a kind of compound method of EUO structure molecular screen; Adopt diphenyl-methyl Dimethyl Ammonium and its verivate as template; Adopting benzyldimethylamine and halogenation benzyl among the embodiment is the template precursor; Through adding crystal seed and inorganic salt, shorten crystallization time.
Adopt different template synthetic EUO type molecular sieves to have different physicochemical property; Existing EU-1 and ZSM-50 molecular sieve adopt C6 and diphenyl-methyl Dimethyl Ammonium to synthesize respectively; Though they have identical matrix topology, their character is significantly different.The active sites of EU-1 molecular sieve mainly in the bottom and ten-ring duct of twelve-ring side pocket, shows the duct characteristic of ten-ring, and the active sites of ZSM-50 molecular sieve mainly is positioned at the collar extension of twelve-ring side pocket, shows the duct characteristic of twelve-ring.(Inmaculada Peral; Camile Y.Jones; Saji P; Et al.structural comparison of tow EUO-type zeolite investigated by neutron diffraction, Micropor.Mesopor.Mater.2004 71:125-133.) must demonstrate different catalytic performances on the catalyzed reaction that do not coexist of physico-chemical property.With the n-decane hydrogenation reaction is example, and reactant is a n-decane, generates single branched chain isomer and two branched chain isomers through hydroisomerizing.Two kinds of different acidic sites of molecular sieve cause the mol ratio of two kinds of single branched chain isomers in the reaction product, and there were significant differences.(Wim?Souverijns，Lieve?Rombouts，John?A.Martens，molecular?shape?selectivity?of?EUO?zeolites，Microporous?Materials，1995，4：123-130.)
Different physicochemical characteristics in the past will inevitably appear in the EUO type molecular sieve that therefore adopts brand-new template to synthesize, thereby demonstrate different catalytic performances.
Summary of the invention
The technical problem that the present invention will solve provides a kind of preparation method of high-crystallinity EUO type molecular sieve.The present invention has adopted a kind of new template cheaply to synthesize EUO type molecular sieve.
The preparation method of EUO type molecular sieve provided by the invention comprises the steps:
(1) crystal seed S, silicon source, alkali, water and template thorough mixing is even, reaction mixture has following composition, representes with oxide form:
S/SiO
2(gram/gram)=0.1～1
R/SiO
2(moles/mole)=0.25～1.57
Na
2O/SiO
2(moles/mole)=0.27～0.8
H
2O/SiO
2(moles/mole)=22～120
R represents template; S represents crystal seed.
Preferably, reaction mixture has following composition, representes with oxide form:
S/SiO
2(gram/gram)=0.25～1
R/SiO
2(moles/mole)=0.25～0.55
Na
2O/SiO
2(moles/mole)=0.27～0.65
H
2O/SiO
2(moles/mole)=30～85
(2) crystallization: the reaction mixture gel of step (1) preparation is warming up to 140 ℃～180 ℃, hydrothermal crystallizing 1～3 day;
(3) after crystallization is accomplished, make EUO type molecular sieve through filtration, washing, drying and roasting.
According to method provided by the invention, the template R described in the step (1) is selected from tetraethyl ammonium hydroxide or tetraethylammonium bromide, is preferably tetraethylammonium bromide.
Normally used any silicon source when the silicon source described in the step (1) can be synthetic zeolite, for example white carbon black, silicon sol, water glass, silicic acid or tetraethoxy, preferred white carbon black.
Kind S described in the step (1) is the EU-1 molecular sieve.The sodium type molecular sieve that described EU-1 molecular sieve can be roasting or the molecular sieve of roasting not are preferably the sodium type EU-1 molecular sieve of roasting.
Hydrothermal crystallizing described in the step (2) is to place pressure vessel under temperature constant state, to carry out the reaction mixture gel of preparing, i.e. thermostatic crystallization.Said hydrothermal crystallizing can be static crystallization or dynamic crystallization.
Filtration, washing, drying and roasting described in the step (3) all adopts this area to prepare the normal condition of EUO type molecular sieve.Like described drying is 100～140 ℃ of dryings 12～48 hours; Described roasting is 450～650 ℃ of following roastings 3～12 hours.
For EUO type molecular sieve, can use the ordinary method of this area to carry out the modification processing according to the inventive method preparation.EUO type molecular sieve and acidic substance (like the aqueous solution of an ammonium nitrate, ammonium chloride etc.) through with preparation carry out IX, can prepare hydrogen type molecular sieve.Plant method of modifying but the present invention is not limited thereto.
The EUO molecular sieve of the inventive method preparation can be used in the different hydrocarbon conversion reactions, and in particular for reaction process such as polymerization, aromizing, isomerizing, for example the EUO molecular sieve of the inventive method preparation is to C
8The aromatics isomerization reaction table reveals very high reactive behavior.
Compare with the preparation method of existing EUO type molecular sieve, the inventive method has following characteristics:
1, the inventive method uses less tetraethyl ammonium hydroxide of toxicity or tetraethylammonium bromide as template, and suitably increases the consumption of crystal seed, thereby synthesizes EUO type molecular sieve.
2, the inventive method synthetic EUO type molecular sieve has the high characteristics of relative crystallinity, and its relative crystallinity is usually above the percent crystallinity about 5%～20% of existing molecular sieve.
3, the inventive method has quick synthetic characteristics, and preparing method's crystallization time provided by the invention only has 24～72 hours, and crystallization time is shorter.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the molecular sieve of comparative example 1 preparation.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 1 preparation.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 2 preparations.
Embodiment
The x-ray diffractometer that the thing of EU-1 molecular sieve of the present invention is measured mutually and the mensuration of percent crystallinity adopts is that the D/max-2500 type that Japanese Co., Ltd. of science produces automatically rotates the target x-ray diffractometer.During experiment, sample is ground to the above compressing tablet of 300 orders, the machine of going up then characterizes.Experiment condition: the Cu target, K α source of radiation, graphite monochromator, WV 40kV, tube current 80mA, sweep limit is 5～40 °, and sweep velocity is 8 °/min, and step-length is 0.01 °.
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Comparative example 1
In beaker, successively add 1.70g sodium hydroxide, 0.80g sodium aluminate, 80mL zero(ppm) water; Stir; Add 24mL Trimethylamine 99,6.48mL 1 again, the 6-dibromo-hexane stirs 10min; Add the not EU-1 molecular sieve crystal seed of roasting of white carbon black of 10.14g and 0.4g at last, stir the synthesis reactor of packing into after 1 hour.180 ℃ of crystallization 192h in baking oven.Resulting product is filtered, be washed with distilled water to neutrality, drying at 550 ℃ of following roasting 5h, promptly obtains EUO type molecular sieve.The percent crystallinity of EUO type molecular sieve is 100.
Comparative example 2
In beaker, successively add 1.70g sodium hydroxide, 0.80g sodium aluminate, 80mL zero(ppm) water; Stir, add the 22g tetraethylammonium bromide again, stir 10min; Add the not EU-1 molecular sieve crystal seed of roasting of white carbon black of 10.14g and 0.4g at last, stir the synthesis reactor of packing into after 1 hour.180 ℃ of crystallization 144h in baking oven.Resulting product is filtered, be washed with distilled water to neutrality, drying, at 550 ℃ of following roasting 5h, products therefrom is unformed.
Embodiment 1
In beaker, successively add 2.2g sodium hydroxide, 6.6g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 3.5g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 5g at last, stir the synthesis reactor of packing into after 1 hour.140 ℃ of heating 24h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 108.
Embodiment 2
In beaker, successively add 2.0g sodium hydroxide, 8.25g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 2.0g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 5g at last, stir the synthesis reactor of packing into after 1 hour.140 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 113.
Embodiment 3
In beaker, successively add 1.8g sodium hydroxide, 5.4g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 3g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 5g at last, stir the synthesis reactor of packing into after 1 hour.140 ℃ of heating 72h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 115.
Embodiment 4
In beaker, successively add 1.35g sodium hydroxide, 3.1g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 1.55g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 2.75g at last, stir the synthesis reactor of packing into after 1 hour.180 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 118.
In beaker, successively add 1.28g sodium hydroxide, 2.6g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 2.3g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 2.75g at last, stir the synthesis reactor of packing into after 1 hour.170 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 116.
Embodiment 6
In beaker, successively add 1.35g sodium hydroxide, 3.1g tetraethylammonium bromide, 50mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 1.3g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 2.75g at last, stir the synthesis reactor of packing into after 1 hour.170 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 105.
Embodiment 7
In beaker, successively add 1.35g sodium hydroxide, 3.1g tetraethylammonium bromide, 40mL zero(ppm) water; Stir, the EU-1 molecular sieve of roasting that adds 1.6g comparative example 1 preparation again stirs 10min as crystal seed; Add the white carbon black of 2.75g at last, stir the synthesis reactor of packing into after 1 hour.170 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying promptly obtains EUO type molecular sieve at 550 ℃ of following roasting 5h.The percent crystallinity of EUO type molecular sieve is 117.
Claims (11)
1. the preparation method of a high-crystallinity EUO type molecular sieve comprises the steps:
(1) crystal seed S, silicon source, alkali, water and template thorough mixing is even, reaction mixture has following composition, representes with oxide form:
S/SiO
2(gram/gram)=0.1～1
R/SiO
2(moles/mole)=0.25～1.57
Na
2O/SiO
2(moles/mole)=0.55～1.55
H
2O/SiO
2(moles/mole)=22～120
R represents template; S represents crystal seed;
(2) crystallization: the reaction mixture of step (1) preparation is warming up to 140 ℃～180 ℃, and hydrothermal crystallizing 1～3 day;
(3) after crystallization is accomplished, make EUO type molecular sieve through filtration, washing, drying and roasting.
2. according to the described preparation method of claim 1, it is characterized in that the reaction mixture composition is expressed as with oxide form:
S/SiO
2(gram/gram)=0.25～1
R/SiO
2(moles/mole)=0.25～0.55
Na
2O/SiO
2(moles/mole)=0.55～1.16
H
2O/SiO
2(moles/mole)=30～85.
3. according to claim 1 or 2 described preparing methods, it is characterized in that the template described in the step (1) is tetraethyl ammonium hydroxide or tetraethylammonium bromide.
4. according to claim 1 or 2 described preparing methods, it is characterized in that described template is a tetraethylammonium bromide.
5. according to the described preparation method of claim 1, it is characterized in that the described silicon of step (1) source is white carbon black, silicon sol, water glass, silicic acid or tetraethoxy.
6. according to the described preparation method of claim 1, it is characterized in that the silicon source described in the step (1) is white carbon black.
7. according to the described preparation method of claim 1, it is characterized in that the crystal seed S described in the step (1) is the EU-1 molecular sieve.
8. according to the described preparation method of claim 1, it is characterized in that the sodium type molecular sieve that described EU-1 molecular sieve is roasting or the molecular sieve of roasting not.
9. according to the described preparation method of claim 1, it is characterized in that described EU-1 molecular sieve is the molecular sieve of roasting.
10. according to the described preparation method of claim 1, it is characterized in that described hydrothermal crystallizing is static crystallization or dynamic crystallization.
11., it is characterized in that the drying described in the step (3) is meant 100～140 ℃ of dryings 12～48 hours according to the described preparation method of claim 1; Described roasting is meant 450～650 ℃ of following roastings 3～12 hours.
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| CN102745709A (en) * | 2012-07-30 | 2012-10-24 | 西北化工研究院 | Method for preparing EUO type molecular sieve by utilizing kaolin |
| CN104591215A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | EU-1 and Y composite molecular sieve and synthesizing method thereof |
| CN105776242A (en) * | 2014-12-19 | 2016-07-20 | 中国石油天然气股份有限公司 | Synthesis method of ZSM-50 molecular sieve |
| CN106698454A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Nanometer EU-1 molecular sieve synthesizing method |
| CN106809846A (en) * | 2017-01-10 | 2017-06-09 | 浙江大学 | The method that crystal seed synthetic method prepares the molecular sieves of EU 1 |
| CN113830781A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | EUO molecular sieve and synthesis method and application thereof |
| CN114436277A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of EU-1 molecular sieve |
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| CN101054183A (en) * | 2007-04-26 | 2007-10-17 | 太原理工大学 | Method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder |
| CN101134171A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method of producing C8 arene isomerization catalyst |
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Patent Citations (2)
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| CN101134171A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Method of producing C8 arene isomerization catalyst |
| CN101054183A (en) * | 2007-04-26 | 2007-10-17 | 太原理工大学 | Method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder |
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| CN102745709A (en) * | 2012-07-30 | 2012-10-24 | 西北化工研究院 | Method for preparing EUO type molecular sieve by utilizing kaolin |
| CN104591215A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | EU-1 and Y composite molecular sieve and synthesizing method thereof |
| CN104591215B (en) * | 2013-11-04 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of EU-1 and Y compound molecular sieve and synthetic method thereof |
| CN105776242A (en) * | 2014-12-19 | 2016-07-20 | 中国石油天然气股份有限公司 | Synthesis method of ZSM-50 molecular sieve |
| CN106698454A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Nanometer EU-1 molecular sieve synthesizing method |
| CN106698454B (en) * | 2015-11-12 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of synthetic method of nanometer of EU-1 molecular sieve |
| CN106809846A (en) * | 2017-01-10 | 2017-06-09 | 浙江大学 | The method that crystal seed synthetic method prepares the molecular sieves of EU 1 |
| CN113830781A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | EUO molecular sieve and synthesis method and application thereof |
| CN114436277A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of EU-1 molecular sieve |
| CN114436277B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of EU-1 molecular sieve |
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