CN106517232B - The synthetic method of H-MCM-22 molecular sieve and its molecular sieve of synthesis - Google Patents
The synthetic method of H-MCM-22 molecular sieve and its molecular sieve of synthesis Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic method of H-MCM-22 molecular sieve and its molecular sieves of synthesis, mainly solve the prior art there are alkali metal element, alkali earth metal is contained in MCM-22 molecular sieve, need to could be used to be catalyzed after ion exchange；And the H-MCM-22 crystallization time directly synthesized is long, expensive starting materials, the problem of may not apply to industrialized production.The present invention does not add the metallic element in addition to aluminium element in MCM-22 sieve synthesis procedure, has directly synthesized the MCM-22 molecular sieve without alkalies and alkaline earth, can be directly used for catalysis reaction.
Description
Technical field
The present invention relates to a kind of synthetic methods of H-MCM-22 molecular sieve.
Background technique
MCM-22 molecular sieve is a kind of System of Silica/Aluminum Microparticle molecular sieve that the researcher of Mobil company of the U.S. synthesizes in nineteen ninety
Material.The molecular sieve has two sets of independent 10 not connected membered ring channel systems: a set of two dimension sinusoidal pattern intersects duct, hole
Road section is ellipse, 0.41 nanometer × 0.51 nanometer of aperture；0.40 nanometer × 5.5 nanometers of another set of ten-ring duct aperture,
And duct includes the 12 member ring supercage of cylinder having a size of 0.71 nanometer × 0.71 nanometer × 1.82 nanometers；In addition, MCM-22 points
Son sieve is also located at the outer surface of molecular sieve crystal with bowl-shape bowl-shape half supercage of 12 member rings.MCM-22 molecular sieve has good
Thermal stability, hydrothermal stability and unique Acidity, so that MCM-22 molecular sieve has important application in Industrial Catalysis, with
MCM-22 molecular sieve is that catalyst made from active component has been successfully applied to benzene and preparing ethylbenzene by liquid phase alkylation of ethylene technique
With benzene and propylene liquid-phase alkylation preparing isopropylbenzene (cumene) technique.
The synthesis of MCM-22 molecular sieve mainly uses hydrothermal crystallization method, by silicon source, silicon source, alkali source, organic formwork agent and water
It is uniformly mixed, is roasted after crystallization and MCM-22 molecular sieve is made.The MCM-22 molecular sieve synthesized in this way contain a large amount of alkali metal or
Alkaline-earth metal, generally metallic sodium, i.e. Na-MCM-22, and MCM-22 need to use ammonium nitrate solution pair as solid acid catalyst
MCM-22 molecular sieve carries out ion exchange, by Na+It is exchanged for NH4 +, then roast and be converted into H+After, i.e. H-MCM-22 molecular sieve,
It could be used to be catalyzed reaction.
Document CN102092740 describes a kind of method for directly preparing H-MCM-22 molecular sieve, which uses ammonia type
Silica solution, aluminium isopropoxide provide compound, organic formwork agent and the water of ammonium ion as raw material, and MCM-22 points of alkali source synthesis is not added
Son sieve, has been made H-MCM-22 molecular sieve.However, the crystallization time of this method is especially long, need can just obtain MCM-22 within 24-26 days
Molecular sieve.Meanwhile the aluminium isopropoxide that the invention uses is organic silicon source, expensive and reactive difference；Ammonia type raw materials of silica sol
Stability is poor, and expensive.In summary the method for factor, the invention cannot be used for industrialized production.
Summary of the invention
The technical problem to be solved by the present invention is to the prior art, there are contain alkali metal element, alkali in MCM-22 molecular sieve
Earth metal element need to could be used to be catalyzed after ion exchange；And the H-MCM-22 crystallization time directly synthesized is long, raw material is high
Expensive, the problem of may not apply to industrialized production, provides a kind of synthetic method of new H-MCM-22 molecular sieve.This method has
Short, the at low cost feature of crystallization time.The present invention also provides a kind of H-MCM-22 molecular sieves synthesized with this method.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows: a kind of H-MCM-22 molecular sieve
Synthetic method, by silicon source, silicon source, organic formwork agent R, boron source, the compound M for providing ammonium ion and water by SiO2: Al2O3: R:
B2O3: H2O:M=1:(0.0005~0.05): (0.05~2.0): (0.0001~3): (5~100): the molar ratio of (0~2.0)
Mixing, mixture 135~200 DEG C hydrothermal crystallizing 1~10 day, crystallization product is filtered, washed, dried, roast and obtains described in
H-MCM-22 molecular sieve.
In above-mentioned technical proposal, it is preferable that the silicon source in silicic acid, silica gel, silica solution, silicic acid tetraalkyl ester extremely
Few one kind.It is highly preferred that the silicon source is selected from least one of silica solution, silicic acid tetraalkyl ester.
In above-mentioned technical proposal, it is preferable that source of aluminium in aluminum nitrate, aluminum sulfate, aluminium oxide, aluminium hydroxide extremely
Few one kind.It is highly preferred that source of aluminium is selected from least one of aluminium oxide, aluminium hydroxide.
In above-mentioned technical proposal, it is preferable that the organic formwork agent R is selected from hexamethylene imine, piperidines, homopiperazine, N,
N, N- trimethyl-(1- adamantyl) ammonium hydroxide, N, N, N, N', N', N'- vegolysen, 5- pentane di-ammonium salts, N, N, N',
At least one of N'- tetra isopropyl -1,5- pentane hydrogen di-ammonium salts.It is highly preferred that the organic formwork agent R is selected from hexa-methylene
Imines, piperidines, homopiperazine, N, N, at least one of N- trimethyl-(1- adamantyl) ammonium hydroxide.
In above-mentioned technical proposal, it is preferable that the boron source is selected from least one of boric acid, boron oxide.It is highly preferred that institute
It states boron source and is selected from boric acid.
In above-mentioned technical proposal, it is preferable that it is described provide ammonium ion compound M be selected from ammonium hydroxide, ammonium sulfate, ammonium nitrate,
At least one of ammonium chloride, ammonium fluoride, ammonium oxalate, ammonium acetate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium carbonate.
It is highly preferred that the compound M for providing ammonium ion is selected from least one of ammonium hydroxide, ammonium nitrate, ammonium chloride, ammonium fluoride.
In above-mentioned technical proposal, it is preferable that the molar ratio of the mixture is SiO2: Al2O3: R:B2O3: H2O:M=1:
(0.01~0.04): (0.2~1.5): (0.02~2): (12~40): (0~1.0).It is highly preferred that mole of the mixture
Than for SiO2: Al2O3: R:B2O3: H2O:M=1:(0.02~0.04): (0.4~1.4): (0.05~1.4): (15~30):
(0.01~0.8).
In above-mentioned technical proposal, it is preferable that crystallization temperature is 145~170 DEG C, and crystallization time is 1~5 day.It is highly preferred that
Crystallization temperature is 145~160 DEG C, and crystallization time is 1~3 day.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows: it is a kind of by the above method preparation
H-MCM-22 molecular sieve.
In above-mentioned technical proposal, it is preferable that alkalies and alkaline earth content is 0~0.06 weight in the molecular sieve
Measure %.It is highly preferred that alkalies and alkaline earth content is 0.001~0.03 weight % in the molecular sieve.
The present invention is added to boron source in sieve synthesis procedure, does not add the metallic element in addition to aluminium element, with valence
Lattice cheap be selected from least one of aluminum nitrate, aluminum sulfate, aluminium oxide, aluminium hydroxide are silicon source, have directly synthesized alkali metal
And alkaline earth metal content is the H-MCM-22 molecular sieve of 0.001~0.03 weight %, can be directly used for catalysis reaction, and crystallization
Time is short, at low cost, achieves preferable technical effect.
Detailed description of the invention
Fig. 1 is the XRD spectra of the H-MCM-22 molecular sieve of [embodiment 1] synthesis.
Fig. 2 is the Na-MCM-22 molecular sieve XRD spectra of [comparative example 1] synthesis.
In the XRD spectra of [embodiment 1] and two samples in [comparative example 1] 2 θ=7.2 °, 8.0 °, 10.0 °,
13.0 °, 14.4 °, 16.0 °, 20.2 °, 22.0 °, 22.7 °, 23.8 °, 25.1 °, 26.1 °, 27.0 ° nearby there is diffraction
Peak, these diffraction maximums match with the characteristic diffraction peak of MCM-22 molecular sieve.Show both for MCM-22 molecular sieve.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
By 1.495 grams of aluminium hydroxide (Al2O365 weight %), 55.5 grams of deionized waters, 49.5 grams of six methylenes of organic formwork agent
Base imines aqueous solution (80.0 weight % of hexamethylene imine), 13.8 grams of boric acid and 50.0 grams of alkaline silica sol (SiO240.0 weights
Measure %) mixing, the material proportion (molar ratio) of reactant are as follows:
SiO2/Al2O3=35.0
Hexamethylene imine/SiO2=1.2
H2O/SiO2=16
SiO2/B2O3=3.0
After mixing, be fitted into stainless steel cauldron, under agitation in 150 DEG C crystallization 5 days.Mistake after crystallization
Filter, washing, drying, then product is roasted 5 hours to obtain in 550 DEG C of air
H-MCM-22 molecular sieve.The XRD spectra of product is as shown in Figure 1.Through inductive coupling plasma emission spectrum (ICP) point
Analyse Na content in molecular sieve is 0.02 weight %.
[embodiment 2]
By 26.0 grams of aluminum nitrates, 363.0 grams of deionizations, 166.0 grams of organic formwork agent hexamethylene imine aqueous solutions, (six is sub-
80.0 weight % of methylene imine), 16.57 grams of boric acid and 200.0 grams of alkaline silica sol (SiO240.0 weight %) mixing, reactant
Material proportion (molar ratio) are as follows:
SiO2/Al2O3=38.9
Hexamethylene imine/SiO2=1.0
SiO2/B2O3=10
H2O/SiO2=21.5
After mixing, be fitted into stainless steel cauldron, under agitation in 145 DEG C crystallization 6 days.Mistake after crystallization
Filter, washing, drying, then product is roasted 5 hours to obtain in 550 DEG C of air
H-MCM-22 molecular sieve.The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) point
Analyse Na content in molecular sieve is 0.03 weight %.
[embodiment 3]
By 65.2 grams of aluminum sulfate, 642.0 grams of deionized waters, 510.0 grams of organic formwork agent hexamethylene imine aqueous solutions (six
80.0 weight % of methylene imine), 20.0 grams of ammonium hydroxide (NH325 weight %), 243.0 grams of boric acid and 440.0 grams of alkaline silica sols
(SiO240.0 weight %) mixing, the material proportion (molar ratio) of reactant are as follows:
SiO2/Al2O3=30.3
Hexamethylene imine/SiO2=1.4
NH4OH/SiO2=0.1
SiO2/B2O3=1.5
H2O/SiO2=19.4
After mixing, be fitted into stainless steel cauldron, under agitation in 155 DEG C crystallization 4 days.Mistake after crystallization
Filter, washing, drying, then product is roasted 5 hours to obtain in 550 DEG C of air
H-MCM-22 molecular sieve.The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) point
Analyse Na content in molecular sieve is 0.02 weight %.
[embodiment 4]
By 36.0 grams of aluminum sulfate, 883.0 grams of deionized waters, 138.0 grams of organic formwork agent piperidines, 31.45 grams of boric acid and
300.0 grams of alkaline silica sol (SiO240.0 weight %) mixing, the material proportion (molar ratio) of reactant are as follows:
SiO2/Al2O3=37.4
Piperidines/SiO2=0.8
SiO2/B2O3=7.9
H2O/SiO2=29.6
After mixing, be fitted into stainless steel cauldron, under agitation in 155 DEG C crystallization 4 days.Mistake after crystallization
Filter, washing, drying, then product is roasted 5 hours to obtain in 550 DEG C of air
H-MCM-22 molecular sieve.The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) point
Analyse Na content in molecular sieve is 0.02 weight %.
[embodiment 5]
With [embodiment 1], only use homopiperazine for template, the material proportion (molar ratio) of reactant are as follows:
SiO2/Al2O3=26
Homopiperazine/SiO2=0.4
SiO2/B2O3=6.0
H2O/SiO2=18
After mixing, be fitted into stainless steel cauldron, under agitation in 155 DEG C crystallization 6 days.Mistake after crystallization
Filter, washing, drying, then product is roasted 5 hours to obtain in 550 DEG C of air
H-MCM-22 molecular sieve.The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) point
Analyse Na content in molecular sieve is 0.02 weight %.
[embodiment 6]
With [embodiment 3], NH is only used4Cl provides ammonium ion, and ammonium hydroxide, the material proportion (molar ratio) of reactant is not added
Are as follows: SiO2/Al2O3=45, NH4Cl/SiO2=0.2, hexamethylene imine/SiO2=0.8, SiO2/B2O3=30, H2O/SiO2=
17,150 DEG C crystallization 128 hours.
The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) analyze in molecular sieve
Na content is 0.01 weight %.
[embodiment 7]
With [embodiment 4], NH is only used4NO3Ammonium ion, the material proportion (molar ratio) of reactant are as follows: SiO are provided2/
Al2O3=28, NH4NO3/SiO2=0.1, piperidines/SiO2=0.5, SiO2/B2O3=10, H2O/SiO2=26,150 DEG C of crystallization 136
Hour.
The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) analyze in molecular sieve
Na content is 0.04 weight %.
[embodiment 8]
With [embodiment 5], NH is only used4Cl provides ammonium ion, the material proportion (molar ratio) of reactant are as follows: SiO2/
Al2O3=33, NH4Cl/SiO2=0.2, homopiperazine/SiO2=0.5, SiO2/B2O3=10, H2O/SiO2=26,150 DEG C of crystallization
136 hours.
The XRD spectra of product is similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) analyze in molecular sieve
Na content is 0.02 weight %.
[embodiment 9]
With [embodiment 1], N, N, N- trimethyl-(1- adamantyl) ammonium hydroxide and hexamethylene imine two are only used
Kind organic formwork agent, the material proportion (molar ratio) of reactant are as follows:
SiO2/Al2O3=27.0
Hexamethylene imine/SiO2=0.2
N, N, N- trimethyl-(1- adamantyl) ammonium hydroxide/SiO2=0.2
H2O/SiO2=20
SiO2/B2O3=100.0
After mixing, be fitted into stainless steel cauldron, under agitation in 150 DEG C crystallization 5 days.The XRD of product is composed
Scheme similar to Fig. 1.Through inductive coupling plasma emission spectrum (ICP) analyze Na content in molecular sieve is 0.01 weight %.
[comparative example 1]
According to document US4954325, feed intake SiO2/Al2O3=30, NaOH/SiO2=0.12, hexamethylene imine/SiO2
=0.5, H2O/SiO2=26,150 DEG C crystallization 5 days, synthesize Na-MCM-22 molecular sieve.The XRD spectra of sample is as shown in Figure 2.Through
Inductive coupling plasma emission spectrum (ICP) analyze Na content in molecular sieve is 0.58 weight %.
Claims (9)
1. a kind of synthetic method of H-MCM-22 molecular sieve by silicon source, silicon source, organic formwork agent R, boron source, provides ammonium ion
Compound M and water press SiO2: Al2O3: R:B2O3: H2O:M=1:(0.0005~0.05): (0.05~2.0): (0.0001~3):
(5~100): (0~2.0) molar ratio mixing, mixture 135~200 DEG C hydrothermal crystallizing 1~10 day, crystallization product pass through
Filter, washing, dry, roasting obtain the H-MCM-22 molecular sieve；The silicon source is selected from alkaline silica sol；Source of aluminium is selected from nitre
At least one of sour aluminium, aluminum sulfate, aluminium oxide, aluminium hydroxide.
2. the synthetic method of H-MCM-22 molecular sieve according to claim 1, it is characterised in that
The organic formwork agent R is selected from hexamethylene imine, piperidines, homopiperazine, N, N, N- trimethyl-(1- adamantyl) hydrogen-oxygen
Change ammonium, N, N, N, N', N', N'- vegolysen, 5- pentane di-ammonium salts, N, N, N', N'- tetra isopropyl -1,5- pentane hydrogen di-ammonium salts
At least one of；
The boron source is selected from least one of boric acid, boron oxide, aluminium borate；
The compound M for providing ammonium ion is selected from ammonium hydroxide, ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium oxalate, acetic acid
At least one of ammonium, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium carbonate.
3. the synthetic method of H-MCM-22 molecular sieve according to claim 2, it is characterised in that the silicon source be selected from silica solution,
At least one of silicic acid tetraalkyl ester；
Source of aluminium is selected from least one of aluminium oxide, aluminium hydroxide；
The organic formwork agent R is selected from hexamethylene imine, piperidines, homopiperazine, N, N, N- trimethyl-(1- adamantyl) hydrogen-oxygen
Change at least one of ammonium；
The boron source is selected from boric acid；
The compound M for providing ammonium ion is selected from least one of ammonium hydroxide, ammonium nitrate, ammonium chloride, ammonium fluoride.
4. the synthetic method of H-MCM-22 molecular sieve according to claim 1, it is characterised in that the molar ratio of the mixture
For SiO2: Al2O3: R:B2O3: H2O:M=1:(0.01~0.04): (0.2~1.5): (0.01~1/30): (12~40): (0~
1.0)。
5. the synthetic method of H-MCM-22 molecular sieve according to claim 1, it is characterised in that crystallization temperature is 140~190
DEG C, crystallization time is 1~7 day.
6. the synthetic method of H-MCM-22 molecular sieve according to claim 5, it is characterised in that crystallization temperature is 145~170
DEG C, crystallization time is 1~5 day.
7. a kind of H-MCM-22 molecular sieve is prepared by claim 1~6 either method.
8. H-MCM-22 molecular sieve according to claim 7, it is characterised in that alkalies and alkaline earth in the molecular sieve
Content is 0~0.06 weight %.
9. H-MCM-22 molecular sieve according to claim 8, it is characterised in that alkalies and alkaline earth in the molecular sieve
Content is 0.001~0.01 weight %.
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| CN117142486A (en) * | 2023-08-31 | 2023-12-01 | 中国石油大学(北京) | MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural |
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| CN101554592A (en) * | 2008-04-08 | 2009-10-14 | 中国科学院大连化学物理研究所 | Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst |
| CN102092740A (en) * | 2010-12-07 | 2011-06-15 | 哈尔滨师范大学 | Method for directly preparing H-MCM-22 molecular sieve |
| EP3050848A1 (en) * | 2013-09-24 | 2016-08-03 | China Petroleum & Chemical Corporation | Molecular sieve, manufacturing method therefor, and uses thereof |
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| CN101554592A (en) * | 2008-04-08 | 2009-10-14 | 中国科学院大连化学物理研究所 | Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst |
| CN102092740A (en) * | 2010-12-07 | 2011-06-15 | 哈尔滨师范大学 | Method for directly preparing H-MCM-22 molecular sieve |
| EP3050848A1 (en) * | 2013-09-24 | 2016-08-03 | China Petroleum & Chemical Corporation | Molecular sieve, manufacturing method therefor, and uses thereof |
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