CN106466629A - ZSM-23/SAPO-34 composite molecular screen and its synthetic method - Google Patents
ZSM-23/SAPO-34 composite molecular screen and its synthetic method Download PDFInfo
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- CN106466629A CN106466629A CN201510514319.0A CN201510514319A CN106466629A CN 106466629 A CN106466629 A CN 106466629A CN 201510514319 A CN201510514319 A CN 201510514319A CN 106466629 A CN106466629 A CN 106466629A
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Abstract
The present invention relates to a kind of ZSM-23/SAPO-34 composite molecular screen and its synthetic method, the aperture of porous material in order to solve the problems, such as prior art synthesis is single, acid weaker, reactivity is low.The present invention passes through to mix silicon source, silicon source, phosphorus source and organic formwork agent according to a certain percentage first, it is subsequently adding a certain amount of ZSM-23 molecular screen, carry out hydrothermal crystallizing after mix homogeneously, by controlling nucleation and crystal growth condition, synthesize ZSM-23/SAPO-34 composite molecular screen, wherein the silica alumina ratio of composite molecular screen and two-phase proportion are adjustable, preferably solve the problems referred to above.This composite molecular screen can be used in the commercial production that methanol/dimethyl ether reacts aromatic hydrocarbons processed.
Description
Technical field
The present invention relates to a kind of composite molecular screen and its synthetic method.
Background technology
Molecular sieve is that a class has uniform micropore, and the pore size material suitable with general molecular size.Due to its rule
Whole structure, the pore size of adjustable surface acidity and molecular size is so that molecular screen material is as catalyst, gas
Body adsorbent and separating medium, ion-exchanger and efficient drying agent are widely used in oil and gas processing, become more meticulous
The fields such as work, environmental protection.Wherein ZSM-23 molecular screen is a kind of high-silica zeolite of micropore, earliest by C.J.Plank et al. in
20 century 70s successfully synthesize.ZSM-23 molecular screen has the topology framework of MTT structure, wraps in framing structure simultaneously
Containing five-membered ring, hexatomic ring and ten-ring, but be not similar to the intersection duct of MFI structure, its by ten-ring form one-dimensional
Duct is not mutually crosslinked, and duct is shaped as teardrop shape, and aperture size is 0.45 × 0.56nm.Because ZSM-23 molecular screen is unique
Pore passage structure and stronger surface acid characteristic, many catalytic reactions show very high catalysis activity and selectivity.Main
Olefin oligomerization to be used for, olefin/paraffin cracking, alkylating aromatic hydrocarbon and isomerization, straight chain hydrocarbon skeletal isomerizations, desulfurization and absorption point
From waiting in reaction, particularly in terms of olefin oligomerization and preparing low-carbon olefin by catalytically cracking, there is good catalytic performance.
A kind of SAPO-34 molecular sieve SAPO (SAPO) molecular sieve, is developed earliest by U.S. combinating carbide company (UCC)
Success, its topological structure is CHA, and duct has octatomic ring structure, and orifice diameter is 0.4nm, in methanol alkene
It is commonly used in hydrocarbon reaction.By adjusting synthesis condition, can get the SAPO-34 molecular sieve of different acidity.Generally feelings
Under condition, SAPO-34 molecular sieve has the acidity more higher than ZSM-23 and more preferable hydrothermal stability.Due to two kinds of molecular sieves
The more uniform single, Acidity of respective aperture ratio is different, therefore for some complicated reaction systems, relies on single one
Plant molecular sieve can not be processed well.If both being combined and obtaining a kind of composite molecular screen, can be played it many
Level pore passage structure and acid adjustable advantage, thus improve the reactivity of complex reaction system.
For the reaction of methanol aromatic hydrocarbons, its course of reaction is more complicated, and generally accepted reaction mechanism thinks that this process divides two
Step：It is that methanol dehydration under acidic site effect generates dimethyl ether first, dimethyl ether generates low-carbon (LC) in the presence of acidic site again
Alkene, second step low-carbon alkene generates aromatic hydrocarbons through complex processes such as oligomerisation, cyclisation, dehydrogenation, alkylation and de- alkyl.Right
In first step it can be understood as reaction for preparing light olefins from methanol, this reaction needs stronger acidity, former along with reacting
Material and target product are all small molecule hydro carbons, and SAPO-34 has proven to be best suitable for the molecular sieve of this reaction.For second
Individual step is it can be understood as the aromatization process of low-carbon alkene, because the molecular diameter ratio of aromatic hydrocarbons is larger, less in aperture
SAPO-34 molecular sieve internal diffusion is restricted, and therefore SAPO-34 molecular sieve there is no aromatization activity, and ZSM-23
The duct size of molecular sieve then just have matched the molecular size of benzene, toluene and dimethylbenzene, is especially suitable for aromatization of hydrocarbons preparation
The reaction of aromatic hydrocarbons.Therefore, such a complicated reaction system for methanol aromatic hydrocarbons, if can be by SAPO-34 molecule
Sieve and ZSM-23 molecular screen are combined, and jointly play its synergism, then can obtain preferable reaction result.
Document CN102372291A reports the preparation method of SAPO-18/SAPO-34 coexisting molecular sieve, solves existing
The aperture of porous material of technology synthesis is single, active not high problem, in the reaction of preparing light olefins from methanol, using this altogether
The standby catalyst of raw system with molecular sieve for preparing have catalyst deactivation rate slow advantage.
Document CN102372290A, also by synthesis condition, phosphorus source, silicon source, silicon source and template is mixed, and hydro-thermal is brilliant
It has been combined to out SAPO-5/SAPO-34 coexisting molecular sieve.
Document CN1772611A reports a kind of preparation method of the composite molecular screen of ten-ring structure, including
ZSM-23 and SAPO-11 composite molecular screen, its table during the isomerization dewaxing process of lubricating oil and the isomerization-visbreaking of diesel oil
Reveal excellent catalytic performance.
Document CN200510086493.6 reports a kind of ZSM-22/ZSM-23 composite molecular screen and preparation method thereof.
However, yet there are no synthesis and its application in aromatization of methanol of ZSM-23/SAPO-34 composite molecular screen
Report.
Content of the invention
One of the technical problem to be solved is that the aperture of porous material of prior art synthesis is single, acid weaker, anti-
Should the low problem of activity, provide a kind of composite molecular screen, this molecular sieve has that multistage pore canal, acid distribution be relatively wide, reaction is lived
The higher advantage of property.
The two of the technical problem to be solved are a kind of conjunctions of the above-mentioned composite molecular screen providing prior art to be not directed to
The problem of one-tenth method, provides a kind of synthetic method of composite molecular screen.
The three of the technical problem to be solved are a kind of use of the above-mentioned composite molecular screen providing prior art to be not directed to
On the way.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of composite molecular screen, this molecule
It is sieved to and contain ZSM-23 molecular screen and two kinds of thing phases of SAPO-34 molecular sieve less, and the silica alumina ratio of composite molecular screen and two kinds
The ratio of thing phase is adjustable.
In technique scheme, the silica alumina ratio of ZSM-23 molecular screen is adjustable, the ratio of two kinds of thing phases of ZSM-23 and SAPO-34
Example is also adjustable.
In technique scheme, preferred technical scheme is, in terms of composite molecular screen percentage by weight, to comprise 1～99%
SAPO-34 and 1～99% ZSM-23 molecular screen；Described ZSM-23 molecular screen silicoaluminophosphate molecular is than for 50～200.
In technique scheme, preferred technical scheme is, in terms of composite molecular screen percentage by weight, to comprise 10～90%
SAPO-34 and 10～90% ZSM-23 molecular screen；Described ZSM-23 molecular screen silicoaluminophosphate molecular is than for 60～100.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of synthesis side of composite molecular screen
Method, comprises the following steps：
(1) silicon source, silicon source, phosphorus source, organic formwork agent R and water are mixed to form mixed liquor I according to a certain percentage, with
Al2O3The amount of material on the basis of, the mol ratio of each component is：Al2O3：P2O5：SiO2：R：H2O=1：0.5～1.5：
0.2～2.0：0.2～3.0：30～80；
(2) take a certain amount of ZSM-23 molecular screen to add in the mixed liquor prepared by step (1), and stir, shape
Become mixed liquor II, on the basis of all wgt dry basis by total in final mixed liquor II, the addition of ZSM-23 is 1～99%；
(3) mixed liquor II obtaining step (2) is put in airtight high pressure crystallizing kettle, in 120～220 DEG C of crystallization 24～96h；
(4) product is taken out, through washing, being dried, roasting obtains composite molecular screen.
In technique scheme, preferred technical scheme is that described silicon source is selected from Ludox, waterglass, reactive silica
At least one in silicon, organosilicon；Silicon source be selected from boehmite, aluminum isopropylate., activated alumina, in aluminium salt at least
A kind of；At least one in orthophosphoric acid, phosphorous acid, phosphate for the phosphorus source；Organic formwork agent be selected from tetraethyl ammonium hydroxide,
At least one in triethylamine, morpholine.In step (1), the mol ratio of each component is preferred：Al2O3：P2O5：SiO2：
R：H2O=1：0.8～1.2：0.5～2.0：0.5～3.0：30～60.The ZSM-23 molecular screen adding in step (2) is permissible
It is the ZSM-23 after H type ZSM-23, Na type ZSM-23 or hetero atom are modified, wherein, hetero atom is selected from
At least one element in I B to VIII B, preferably in La, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag, Zn
At least one.
Preferably technical scheme is that the composite molecular screen obtaining in step (4) is ZSM-23/SAPO-34 composite molecular screen.
Described ZSM-23 molecular screen silicoaluminophosphate molecular is than for 50-200.
Preferably technical scheme is, the composite molecular screen obtaining, and by weight percentage, comprises 1～99% SAPO-34
With 1～99% ZSM-23 molecular screen.
In order to solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：Described composite molecular screen is used for first
In the reaction of alcohol aromatic hydrocarbons.
The present invention, using the reactant liquor of first configuration synthesis SAPO-34 molecular sieve, then adds ZSM-23 molecular screen, leads to
Cross the silica alumina ratio changing the ZSM-23 molecular screen adding, the acidity of adjustable ZSM-23, by adjusting ZSM-23 molecule
Sieve addition, biphase ratio in adjustable composite molecular screen, simultaneously pass through adjust various crystallization synthetic reaction things ratio,
The conditions such as crystallization temperature, crystallization time, can synthesize that grain size is adjustable, acid distribution is adjustable, thing Phase Proportion is adjustable
ZSM-23/SAPO-34 composite molecular screen.This composite molecular screen has that multi-stage artery structure, acid distribution be relatively wide, reaction is lived
Property higher feature, be particularly suitable for the reaction of methanol aromatic hydrocarbons, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
(1) 15g boehmite, 8g Ludox (40%), 19g orthophosphoric acid (85%), 15g triethylamine, 10g are weighed
Tetraethyl ammonium hydroxide and 80g water, mix homogeneously under stirring condition；
(2) weigh 15g H type ZSM-23 molecular screen, add in the mixed liquor that step (1) obtains, stir；
(3) mixed liquor obtaining step (2) is transferred in airtight high pressure crystallizing kettle, in 180 DEG C of crystallization 48h；
(4) product is taken out, through washing, dry, roasting, obtain ZSM-23/SAPO-34 composite molecular screen, lead to
Cross XRD diffraction quantitative, in product, the weight content of SAPO-34 molecular sieve is 62%, and the weight of ZSM-23 molecular screen contains
Measure as 38%.
【Embodiment 2】
(1) 16g boehmite, 12g Ludox (40%), 23g orthophosphoric acid (85%), 28g tetraethyl hydrogen are weighed
Amine-oxides and 100g water, mix homogeneously under stirring condition；
(2) weigh 8g Na type ZSM-23 molecular screen, add in the mixed liquor that step (1) obtains, stir；
(3) mixed liquor obtaining step (2) is transferred in airtight high pressure crystallizing kettle, in 165 DEG C of crystallization 62h；
(4) product is taken out, through washing, dry, roasting, obtain ZSM-23/SAPO-34 composite molecular screen, lead to
Cross XRD diffraction quantitative, in product, the weight content of SAPO-34 molecular sieve is 75%, and the weight of ZSM-23 molecular screen contains
Measure as 25%.
【Embodiment 3】
(1) 40g aluminum isopropylate., 22g Ludox (40%), 28g orthophosphoric acid (85%), 40g morpholine, 10g are weighed
Tetraethyl ammonium hydroxide mixes with 120g water stirring condition；
(2) weigh the ZSM-23 molecular screen of 60g Zn ion exchange, add in the mixed liquor that step (1) obtains, stirring
Uniformly；
(3) mixed liquor obtaining step (2) is transferred in airtight high pressure crystallizing kettle, in 200 DEG C of crystallization 64h；
(4) product is taken out, through washing, dry, roasting, obtain ZSM-23/SAPO-34 composite molecular screen, lead to
Cross XRD diffraction quantitative, in product, the weight content of SAPO-34 molecular sieve is 25%, and the weight of ZSM-23 molecular screen contains
Measure as 75%.
By this composite molecular screen tabletting, crush, take the sample 9g of 10～20 mesh to be placed in fixed bed reactors, at 450 DEG C
Under the conditions of make it with methanol haptoreaction, the mass space velocity of methanol charging is 1h-1, product entrance gas chromatogram after insulation
On-line analyses, result is listed in table 1.
【Embodiment 4～7】
Weigh a certain amount of H type ZSM-23 molecular screen, mix with a certain amount of nitrate solution equal-volume, through drying,
Roasting respectively obtains the La that load capacity is 1.0%, 1.0% Cr, the ZSM-23 of 1.0% Co, 1.0%La and 1.0%Zn
Molecular sieve.According to the method for embodiment 3, the ZSM-23 molecular screen of 40g Zn ion exchange therein is substituted for above-mentioned etc.
The hetero atom that volume impregnation method obtains modifies ZSM-23 molecular screen, obtains a series of compound molecules through the method for embodiment 3
Sieve.And the reactivity worth of its methanol conversion for preparing arene has been investigated using the method for embodiment 3, result is listed in table 1.
Table 1
| Embodiment | Molecular sieve | Total arenes yield (wt%) | BTX yield (wt%) |
| Embodiment 3 | ZnZSM-23/SAPO-34 | 48.3 | 36.1 |
| Embodiment 4 | LaZSM-23/SAPO-34 | 50.3 | 39.0 |
| Embodiment 5 | CrZSM-23/SAPO-34 | 46.2 | 34.7 |
| Embodiment 6 | CoZSM-23/SAPO-34 | 49.8 | 38.5 |
| Embodiment 7 | LaZnZSM-23/SAPO-34 | 54.5 | 43.3 |
Claims (10)
1. a kind of composite molecular screen, this molecular sieve at least contains ZSM-23 molecular screen and two kinds of thing phases of SAPO-34 molecular sieve,
And the ratio of the silica alumina ratio of composite molecular screen and two kinds of thing phases is adjustable.
2. composite molecular screen according to claim 1 is it is characterised in that in terms of composite molecular screen percentage by weight,
Comprise 1～99% SAPO-34 and 1～99% ZSM-23 molecular screen；Described ZSM-23 molecular screen silicoaluminophosphate molecular ratio
For 50～200.
3. composite molecular screen according to claim 1 is it is characterised in that in terms of composite molecular screen percentage by weight,
Comprise 10～90% SAPO-34 and 10～90% ZSM-23 molecular screen；Described ZSM-23 molecular screen silicoaluminophosphate molecular
Than for 60～100.
4. the synthetic method of the composite molecular screen described in claim 1, comprises the following steps：
(1) silicon source, silicon source, phosphorus source, organic formwork agent R and water are mixed to form mixed liquor I according to a certain percentage, with
Al2O3The amount of material on the basis of, the mol ratio of each component is：Al2O3：P2O5：SiO2：R：H2O=1：0.5～1.5：
0.2～2.0：0.2～3.0：30～80；
(2) take a certain amount of ZSM-23 molecular screen to add in the mixed liquor prepared by step (1), and stir, shape
Become mixed liquor II, on the basis of all wgt dry basis by total in final mixed liquor II, the addition of ZSM-23 is 1～99%；
(3) mixed liquor II obtaining step (2) is put in airtight high pressure crystallizing kettle, in 120～220 DEG C of crystallization 24～96h；
(4) product is taken out, through washing, being dried, roasting obtains composite molecular screen.
5. the synthetic method of composite molecular screen according to claim 4 is it is characterised in that described silicon source is molten selected from silicon
At least one in glue, waterglass, active silica, organosilicon；Silicon source is selected from boehmite, aluminum isopropylate., work
At least one in property aluminium oxide, aluminium salt；At least one in orthophosphoric acid, phosphorous acid, phosphate for the phosphorus source；Organic mould
At least one in tetraethyl ammonium hydroxide, triethylamine, morpholine for the plate agent.
6. the synthetic method of composite molecular screen according to claim 4 is it is characterised in that obtain in step (4) answers
Conjunction molecular sieve is ZSM-23/SAPO-34 composite molecular screen.
7. the synthetic method of composite molecular screen according to claim 4 is it is characterised in that each component in step (1)
Mol ratio is：Al2O3：P2O5：SiO2：R：H2O=1：0.8～1.2：0.5～2.0：0.5～3.0：30～60.
8. the synthetic method of composite molecular screen according to claim 4 is it is characterised in that described ZSM-23 molecule
Sieve at least one in the ZSM-23 after modifying for H type ZSM-23, Na type ZSM-23, hetero atom, wherein, miscellaneous former
At least one element in I B to VIII B for the son；Described ZSM-23 molecular screen silicoaluminophosphate molecular is than for 50-200.
9. the synthetic method of composite molecular screen according to claim 8 is it is characterised in that described hetero atom is selected from
At least one in La, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag, Zn.
10. the composite molecular screen described in claims 1 to 3 is used in the reaction of methanol/dimethyl ether aromatic hydrocarbons.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030045764A1 (en) * | 2001-08-30 | 2003-03-06 | Brown Stephen H. | Process for converting natural gas to higher value products using a methanol refinery remote from the natural gas source |
| CN104556143A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | SAPO-34/ZSM-5 composite molecular sieve and synthesis method of composite molecular sieve |
-
2015
- 2015-08-20 CN CN201510514319.0A patent/CN106466629A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030045764A1 (en) * | 2001-08-30 | 2003-03-06 | Brown Stephen H. | Process for converting natural gas to higher value products using a methanol refinery remote from the natural gas source |
| CN104556143A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | SAPO-34/ZSM-5 composite molecular sieve and synthesis method of composite molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 徐如人等: "《沸石分子筛的结构与合成》", 31 August 1987, 吉林大学出版社 * |
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Application publication date: 20170301 |