CN1565971A - Preparation method of molecular sieve with TON structure - Google Patents

Preparation method of molecular sieve with TON structure Download PDF

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CN1565971A
CN1565971A CN 03133817 CN03133817A CN1565971A CN 1565971 A CN1565971 A CN 1565971A CN 03133817 CN03133817 CN 03133817 CN 03133817 A CN03133817 A CN 03133817A CN 1565971 A CN1565971 A CN 1565971A
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crystallization
sio
mol ratio
accordance
gel
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CN1242920C (en
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谢亮亮
童广明
谢庆华
廖士纲
刘全杰
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WENZHOU SHUANGHUA PETROCHEMICAL THREE-AGENT MANUFACTORY
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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WENZHOU SHUANGHUA PETROCHEMICAL THREE-AGENT MANUFACTORY
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a synthetic method for TON type molecular sieve comprising the steps of, (1) charging auxiliary mould agent into the gel, (2) charging auxiliary agent into the gel, (3) conducting crystallization procedure in several steps.

Description

A kind of preparation method of TON structure molecular screen
Technical field
The present invention relates to the Preparation Method that a kind of TON structure molecular screen reaches.
Background technology
Molecular sieve is the crystalline material with homogeneous aperture, regular pore canal shape and trend, and it comprises natural and two big classes synthetic, and having been found that has so far had hundreds of with synthetic molecular sieve kind.Wherein many sorbent material, catalyzer etc. of being used as.On catalytic material, demonstrate advantages of high activity and selectivity, particularly particularly outstanding in hydrocarbon conversion reactions.Being used as sorbent material and catalyst molecule sieve aperture degree of lip-rounding shape size and duct trend all has considerable influence to its character, then particularly evident to selecting the type reaction.Molecular sieve can be divided into the mesoporous molecular sieve of the small pore molecular sieve less than 8 Yuans rings, 10 Yuans rings and the large pore molecular sieve of 12 Yuans rings by the aperture size.The aperture is big again then belongs to mesoporous molecular sieve analog.
At present molecular sieve has developed and multiple series, and as SAPO, ZSM, SSZ, M41S etc., what wherein belong to the TON structure has ZSM-22, Theta-1, ISI-1, KZ-2 and a NU-10 etc.The TON structure molecular screen has 10 Yuans non-intersection one-dimensional channels of ring, what belong to this structure molecular screen has: USP4481177 discloses a kind of employing N-ethyl bromination pyrroles and has been template, is the method for synthesizing ZSM-22 under the condition of 400r/min at 160 ℃ with stirring velocity, in this preparation process, the subtle change of crystallization parameter all can cause the variation of product crystalline phase, if obtain purified ZSM-22, must carry out accurate control to raw material composition and crystallization condition, the repeated difficulty of product is bigger; USP4900528 discloses a kind of synthetic method of called after NU-10 molecular sieve, employing be to have L 1-(CH 2) n-L 2The organic formwork agent of structure, the L here 1, L 2Or/and amido, crystallization condition is to be 300r/min 180 ℃ and stirring velocity for hydroxyl; USP4483835 discloses the molecular sieve of a kind of called after ISI-1, is that to adopt a kind of salt of derivative of nitrogen-containing heterocycle compound be template, under 150 ℃, the condition of 30r/min, and crystallization 6 days and obtaining; USP5342596 discloses the molecular sieve preparation method of a kind of called after THETA-1, and it is template that this process is to use a kind of halo derivatives of nitrogen-containing heterocycle compound, in the rotation voltage-resistant reactor, and crystallization 144h under 170 ℃ of conditions and obtaining.
The XRD of the molecular sieve of the disclosed TON of having structure the results are shown in Table 1,2,3,4 in the prior art document.
The XRD result of table 1 ZSM-22 molecular sieve
d hkl(nm)?????????????I/I 0
1.090±0.02???????????M-VS
0.870±0.016??????????W
0.694±0.010??????????W-M
0.458±0.007??????????W
0.436±0.007??????????VS
0.368±0.005??????????VS
0.362±0.005??????????S-VS
0.347±0.004??????????M-S
0.330±0.004??????????W
0.274±0.002??????????W
0.252±0.002??????????W
The represented relative intensity of symbol is worth as follows in the form: VS, 60%-100%; S, 40%-60%; M, 20%-40%; W,＜20%; Down together.
The XRD result of table 2 NU-10 molecular sieve
d hkl(nm)?????????????I/I 0
1.095±0.025??????????M-S
0.88±0.014???????????W-M
0.699±0.014??????????W-M
0.541±0.010??????????W
0.457±0.008??????????W
0.438±0.007??????????VS
0.369±0.007??????????VS
0.363±0.007??????????VS
0.348±0.006??????????M-S
0.336±0.006??????????W
0.331±0.005??????????W
0.278±0.005??????????W
0.253±0.004??????????M
0.244±0.003??????????W
0.237±0.003??????????W
0.188±0.002??????????W
The XRD result of table 3 Theta-1 molecular sieve
d hkl(nm)??????????????I/I 0
1.150-1.02?????????????VS
0.829-0.914????????????W
0.720-0.666????????????W
0.558-0.525????????????W
0.468-0.445????????????W
0.447-0.426????????????VS
0.375-0.362????????????VS
0.368-0.354????????????W
0.352-0.339????????????M
0.255-0.248????????????M
The XRD result of table 4 KZ-2 molecular sieve
d hkl(nm)??????????????I/I 0
1.089+0.002????????????VS
0.877+0.002????????????W
0.693+0.002????????????W
0.540+0.002????????????W
0.458+0.002????????????W
0.438+0.002????????????VS
0.369+0.002????????????VS
0.362+0.002????????????VS
0.346+0.002????????????S
0.339+0.002????????????W
0.334+0.002????????????W
0.331+0.002????????????W
0.322+0.002????????????W
0.298+0.002????????????W
0.294+0.002????????????W
0.292+0.002????????????W
Existing technical literature preparation has the method for TON structure molecular screen, all is that the single organism of employing is a template, does not add any auxiliary agent and directly is warmed up to the preset temperature crystallization, and general crystallization time is length, product purity and the low problem of yield.
Summary of the invention
At the deficiency of existing patent, this patent provides a kind of novel method of synthetic TON type molecular sieve, and the inventive method crystallization temperature is low, crystallization time is short, product yield is high.
The main preparation process of TON type molecular sieve provided by the invention comprises:
(a) preparation is a kind of is selected from III in the periodic table of elements by at least a A, IV AElement compound, mineral alkali, organic even gel of touching edition agent and water composition preferably also contain auxiliary agent in the gel.Wherein template is preferably double template, and the master module agent is a diamine compounds, and the auxiliary template agent is generally nitrogen-containing heterocycle compound, and auxiliary agent is one or more alkane.
(b) gel of heating steps (a) preparation under the condition of crystallization, makes the gel crystallization complete, through aftertreatment, obtains molecular sieve of the present invention, and crystallization preferably adopts the segmentation crystallization method.
Use auxiliary template agent, auxiliary agent, three features of segmentation crystallization can adopt wherein 1～3 in the such scheme.
The TON type molecular sieve silica alumina ratio (SiO that method provided by the present invention is produced 2/ Al 2O 3, mol) 30～300, be generally 40～100, be needle crystal, the XRD result of molecular sieve provided by the invention has
Table 5 feature belongs to TON type molecular sieve.
The XRD result of table 5 TON molecular sieve of the present invention
d hkl(nm)?????????????I/I 0
1.090±0.02???????????M-S
0.875±0.016??????????W
0.696±0.010??????????W
0.543±0.008??????????W
0.459±0.007??????????W
0.437±0.007??????????VS
0.369±0.005??????????VS
0.361±0.005??????????VS
0.348±0.004??????????M
0.335±0.004??????????W
0.322±0.004??????????W
0.292±0.002??????????W
0.273±0.002??????????W
Compare with the correlation technique document, the method that the present invention prepares molecular sieve has crystallization temperature low (generally low 10 ℃), crystallization time short (generally reducing 12h), product purity and degree of crystallinity height and product yield advantages of higher.
Embodiment
The present invention prepares the method for TON structure molecular screen, and its principal feature is double template for the template used, and preferably adds auxiliary agent and adopt the segmentation crystallization method, the selection of other condition and various raw materials and
Prior art is similar.
In the process of preparation TON structure molecular screen provided by the invention, other raw material and operational condition can be determined by prior art, as the raw material and the operational condition of various TON structure molecular screens (ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10) preparation process employing in the prior art.Usually the said template of step (a) is a double template, promptly is made up of two kinds of template, and wherein the master module agent is a diamine compounds, can be C 2-C 10Diamines, be preferably C 5-C 8Diamines, hexanediamine more preferably; The auxiliary template agent is generally nitrogen-containing heterocycle compound, is preferably pyrrole derivative, more preferably tetramethyleneimine.Said auxiliary agent can be C 5-C 10Alkane, be preferably C 5-C 8Normal paraffin or naphthenic hydrocarbon, C more preferably 5-C 7Naphthenic hydrocarbon.IV in the said periodic table of elements AElement compound, can be selected from the compound of silicon or germanium one or more, be preferably the compound of silicon, can be all silicon-containing compounds that can be used in other molecular sieve of preparation, for example, silica-gel powder, active silica, silicate, vaporific silicon, white carbon black, silicon sol and siliceous organism etc. are preferably silicate, silicon sol and silica-gel powder, more preferably silica-gel powder.Said III AElement can be boron, aluminium, gallium, indium etc., is preferably aluminium.The aluminium source can be to be selected from activated alumina and precursor, aluminum soluble salt and the organic aluminum contained compound one or more, for example clay, hydrated aluminum oxide, aluminium colloidal sol, aluminate, aluminium salt and aluminiferous organism, be preferably aluminate and aluminium salt, more preferably aluminium salt, for example AlCl 3, Al 2(SO 4) 3, Al (NO 3) 3Deng.Said mineral alkali can be all alkaline matters, and the oxyhydroxide of for example alkali-metal oxyhydroxide, carbonate, alkaline-earth metal and ammoniacal liquor etc. are preferably alkali-metal oxyhydroxide, more preferably potassium hydroxide.A) preparation method of said gel carries out thorough mixing with required material, obtains the homogeneous phase colloidal mixture.The composition of gained gel has the listed feature of table 6.
The mole of hydrogel is formed before table 6 crystallization of the present invention
Mol ratio is general more preferably preferred
SiO 2/Al 2O 3??30～∝?????????50～500???????80～300
M +/SiO 2??????0.01～1.0??????0.05～0.8?????0.1～0.5
OH-/SiO 2??????????0.01～1.0????0.05～0.8?????0.1～0.5
H 2O/SiO 2?????????10～200??????20～150???????30～100
Master module agent RN/SiO 20.01～1.0 0.05～0.8 0.3～0.7
Auxilliary template PY/SiO 20～0.5 0.02～0.3 0.03～0.1
Auxiliary agent CH/SiO 20～0.5 0.05～0.3 0.08～0.15
M wherein +Be the monovalence metallic cation, RN is the master module agent, and PY is auxilliary template, and CH is an auxiliary agent
Said crystallization is to carry out in the high-pressure reactor of autogenous pressure in the step (b), and crystallization can be that the single hop crystallization also can be the segmentation crystallization.During the single hop crystallization, general crystallization temperature is 120 ℃～180 ℃, is preferably 130 ℃～170 ℃, and crystallization time is 8～96h, and being preferably is 24～60h.During for the segmentation crystallization, for two sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and preferred 85 ℃～95 ℃, crystallization time is 4h～48h, is preferably 8h～36h.Second section crystallization temperature is 120 ℃～180 ℃, and preferred 130 ℃～170 ℃, crystallization time is 8h～48h, is preferably 12～24h.For three sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and preferred 85 ℃～95 ℃, crystallization time is 4h～36h, is preferably 8h～24h.Second section crystallization temperature is 100 ℃～140 ℃, and preferred 110 ℃～130 ℃, crystallization time is 4h～24h, is preferably 12～24h.The 3rd section crystallization temperature is 140 ℃～180 ℃, and preferred 150 ℃～170 ℃, crystallization time is 12h～96h, is preferably 24h～48h.Said aftertreatment refers to through processing such as collection, washing and dryings, can adopt method commonly used at present to carry out, and for example collects and uses method of pumping filtration, uses deionized water wash, makes the sample thorough drying at 100 ℃～250 ℃ then.
Give further instruction below by embodiment to technology of the present invention.
Embodiment 1～6
Get quantitative water and place beaker, add silicon source, aluminium source and alkali successively, thorough mixing, add master module agent, auxilliary template and auxiliary agent more successively, together add after also three kinds of organism can being mixed, behind the thorough mixing, move into autoclave and carry out crystallization, the gel of each embodiment is formed and crystallization condition sees Table 7, and the XRD of product shows that product is a TON type structure molecular screen, the results are shown in Table 8,9.
The gel of each embodiment of table 7 is formed and crystallization condition
The embodiment numbering ??1① ??2② ??3③ ??4④ ??5⑤ ??6⑥ Relatively
??Al 2O 3/SiO 2 ??0.01 ??0.01 ??0.02 ??0.005 ??0.03 ??0.03 ??0.011
??M +/SiO 2 ??0.2 ??0.2 ??0.6 ??0.3 ??0.1 ??0.4 ??0.3
??OH -/SiO 2 ??0.2 ??0.2 ??0.3 ??0.5 ??0.3 ??0.4 ??0.2
??RN/SiO 2 ??0.3 ??0.3 ??0.6 ??0.4 ??0.2 ??0.5 ??0.3
??H 2O/SiO 2 ??80 ??45 ??120 ??90 ??60 ??70 ??40
??PY/SiO 2 ??0.1 ??0.1 ??0.2 ??- ??0.4 ??0.05 ??-
??CH/SiO 2 ??- ??0.05 ??0.1 ??0.2 ??0.5 ??- ??-
Crystallization temperature, ℃ ??180 ??160 ??80+170 ??120+150 ??70+100+ ??150 ??70+100+ ??150 ??190
Crystallization time, h ??48 ??48 ??12+24 ??8+48 ??24+6+12 ??24+6+12 ??72
Product structure ??TON ??TON ??TON ??TON ??TON ??TON ??TON
Degree of crystallinity, % ??100 ??106 ??110 ??122 ??128 ??104 ??100
??SiO 2/Al 2O 3，mol ??92 ??92 ??44 ??188 ??31 ??88 ??78
Yield, w% ??85 ??86 ??90 ??85 ??95 ??84 ??81
Annotate: 1. silicon source: silicon sol, aluminium source: AlCl 3, alkali: KOH, master module agent: hexanediamine, auxilliary template: tetramethyleneimine;
2. silicon source: silicon sol, aluminium source: Al 2(SO 4) 3, alkali: KOH, master module agent: hexanediamine, auxilliary template: tetramethyleneimine, auxiliary agent: hexanaphthene;
3. silicon source: silica-gel powder, aluminium source: Al (OH) 3, alkali: NaOH, master module agent: octamethylenediamine, auxilliary template: N-crassitude, auxiliary agent: Skellysolve A+hexanaphthene (mol ratio 1: 1);
4. silicon source: Na 2SiO 3, aluminium source: NaAlO 2, alkali: KOH, master module agent: hexanediamine, auxiliary agent: pentamethylene;
5. silicon source: tetraethoxy, aluminium source: aluminium colloidal sol, alkali: KOH, master module agent: heptamethylene diamine, auxilliary template: N-ethyl pyrrolidine, auxiliary agent: octane;
6. silicon source: tetraethoxy, aluminium source: aluminium colloidal sol, alkali: NaOH, master module agent: pentamethylene diamine, auxilliary template: N-ethyl pyrrolidine.
The comparative example raw material is with 1. identical.
Continuous table 7
The embodiment numbering ??7 ????8
Raw material With 4 crystallization temperatures is 170 ℃ Just do not add auxiliary lamina membranacea agent and auxiliary agent with 5
??PY/SiO 2 ??- ????-
??CH/SiO 2 ??0.35 ????-
Crystallization temperature, ℃ ??170 ????80+120+160
Crystallization time, h ??50 ????12+6+24
Product structure ??TON ????TON
Degree of crystallinity, % ??105 ????109
??SiO 2/Al 2O 3，mol ??188 ????75
Yield, w% ??88 ????86
From embodiment as can be seen, the method for the TON of preparation structure molecular screen provided by the invention is compared with correlation technique, and crystallization time obviously shortens, and crystallization temperature reduces, and product yield and degree of crystallinity are improved.
The XRD of table 8 embodiment 1 product is the XRD result of table 9 embodiment 2 products as a result
d hkl(nm)?????????I/I 0?????????????d hkl(nm)???????????I/I 0
1.092?????????????38????????????????1.092???????????????36
0.875?????????????12????????????????0.875???????????????10
0.696?????????????8?????????????????0.696???????????????10
0.541?????????????16????????????????0.541???????????????12
0.437?????????????100???????????????0.437???????????????100
0.367?????????????78????????????????0.367???????????????72
0.364?????????????72????????????????0.364???????????????68
0.347?????????????38????????????????0.347???????????????41
0.292?????????????6?????????????????0.292???????????????5
0.279?????????????8?????????????????0.279???????????????7
0.274?????????????4?????????????????0.274???????????????4

Claims (10)

1, a kind of preparation method of TON type molecular sieve may further comprise the steps:
(a) preparation is a kind of by at least aly being selected from IIIA in the periodic table of elements, IVA element compound, mineral alkali, organicly touching the even gel that edition agent and water are formed;
(b) gel of heating steps (a) preparation under the condition of crystallization, makes the gel crystallization complete, through aftertreatment, obtains molecular sieve of the present invention;
Below it is characterized in that in preparation process adopting in three features 1～3: 1. add auxiliary lamina membranacea agent in gel, 2. add auxiliary agent in gel, 3. crystallization process is the segmentation crystallization.
2, in accordance with the method for claim 1, it is characterized in that the described template of step (a) is the master module agent, be selected from diamine compounds; Auxiliary lamina membranacea agent is selected from nitrogen-containing heterocycle compound; Auxiliary agent is one or more alkane.
3, in accordance with the method for claim 2, it is characterized in that described diamine compounds is C 2-C 10Diamines, described nitrogen-containing heterocycle compound is selected from pyrrole derivative, alkane is selected from C 5-C 10Alkane.
4, in accordance with the method for claim 2, it is characterized in that described diamine compounds is C 5-C 8Diamines, described nitrogen-containing heterocycle compound is selected from tetramethyleneimine, alkane is selected from C 5-C 8Normal paraffin or naphthenic hydrocarbon.
5, in accordance with the method for claim 1, it is characterized in that described III AElement is boron, aluminium, gallium or indium; IV AElement is silicon or germanium.
6, in accordance with the method for claim 5, it is characterized in that described III AElement is an aluminium, and the aluminium source is selected from one or more in activated alumina and precursor, aluminum soluble salt and the organic aluminum contained compound; Described IV AElement is a silicon, and the silicon source is selected from silica-gel powder, active silica, silicate, vaporific silicon, white carbon black, silicon sol and siliceous organism; Described mineral alkali is selected from the oxyhydroxide and the ammoniacal liquor of alkali-metal oxyhydroxide, carbonate, alkaline-earth metal.
7, in accordance with the method for claim 1, it is characterized in that described gel consists of: SiO 2/ Al 2O 3Mol ratio 30～∝, M +/ SiO 2Mol ratio 0.01～1.0, OH -/ SiO 2Mol ratio 0.01～1.0, H 2O/SiO 2Mol ratio 10～200, RN/SiO 2Mol ratio 0.01～1.0, PY/SiO 2Mol ratio 0～0.5, CH/SiO 2Mol ratio 0～0.5, wherein M +Be the monovalence metallic cation, RN is the master module agent, and PY is auxilliary template, and CH is an auxiliary agent.
8, in accordance with the method for claim 7, it is characterized in that described SiO 2/ Al 2O 3Mol ratio 50～500, M +/ SiO 2Mol ratio 0.05～0.8, OH -/ SiO 2Mol ratio 0.05～0.8, H 2O/SiO 2Mol ratio 20～150, RN/SiO 2Mol ratio 0.05～0.8, PY/SiO 2Mol ratio 0.02～0.3, CH/SiO 2Mol ratio 0.05～0.3.
9, in accordance with the method for claim 7, it is characterized in that described SiO 2/ Al 2O 3Mol ratio 80～300, M +/ SiO 2Mol ratio 0.1～0.5, OH -/ SiO 2Mol ratio 0.1～0.5, H 2O/SiO 2Mol ratio 30～100, RN/SiO 2Mol ratio 0.3～0.7, PY/SiO 2Mol ratio O.03～0.1, CH/SiO 2Mol ratio 0.08～0.15.
10, in accordance with the method for claim 1, it is characterized in that described crystallization is to carry out in the high-pressure reactor of autogenous pressure, crystallization process adopts single hop crystallization or segmentation crystallization; During the single hop crystallization, crystallization temperature is 120 ℃～180 ℃, and crystallization time is 8～96h; The segmentation crystallization adopts two sections or three sections crystallization, and for two sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and crystallization time is 4h～48h, and second section crystallization temperature is 120 ℃～180 ℃, and crystallization time is 8h～48h; For three sections crystallization, first section crystallization temperature is 80 ℃～100 ℃, and crystallization time is 4h～36h, and second section crystallization temperature is 100 ℃～140 ℃, and crystallization time is 4h～24h, and the 3rd section crystallization temperature is 140 ℃～180 ℃, and crystallization time is 12h～96h.
CN 03133817 2003-06-25 2003-06-25 Preparation method of molecular sieve with TON structure Expired - Lifetime CN1242920C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105585028A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Synthetic method of small-crystal-grain nano zeolite molecular sieve
CN110980759A (en) * 2019-12-19 2020-04-10 万华化学集团股份有限公司 Silico-indate molecular sieve and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105585028A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Synthetic method of small-crystal-grain nano zeolite molecular sieve
CN105585028B (en) * 2014-10-24 2018-01-09 中国石油化工股份有限公司 Little crystal grain molecular sieve of Nano zeolite synthetic method
CN110980759A (en) * 2019-12-19 2020-04-10 万华化学集团股份有限公司 Silico-indate molecular sieve and preparation method and application thereof
CN110980759B (en) * 2019-12-19 2021-06-29 万华化学集团股份有限公司 Silico-indate molecular sieve and preparation method and application thereof

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