CN104591203A - MCM-22 molecular sieve solvothermal synthesis method and product thereof, and uses of MCM-22 molecular sieve - Google Patents
MCM-22 molecular sieve solvothermal synthesis method and product thereof, and uses of MCM-22 molecular sieve Download PDFInfo
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Abstract
The present invention discloses a MCM-22 molecular sieve solvothermal synthesis method, which is characterized in that the solvothermal synthesis of the MCM-22 molecular sieve is performed with an organic amine as a solvent and a template agent of a synthesis system. With the method of the present invention, the MCM-22 molecular sieve with characteristics of high yield and small grain can be obtained, and the synthesized MCM-22 molecular sieve of the present invention can be used as the catalyst or catalyst precursor of the acid-catalyzed reaction.
Description
Invention field
The present invention relates to a kind of synthetic method of MCM-22 molecular sieve, belong to solvent-thermal process technical field.
Background technology
Nineteen ninety, Mobil company reports the synthesis (US4954325) of MCM-22 molecular sieve.This molecular sieve has laminate structure, is connected, and has the independent pore canal system of two covers between aspect with oxo bridge: a set of is two-dimentional sinusoidal duct in layer, and effective pore radius is 0.41nm × 0.51nm, and a set of is supercage [5
126
1410
6], be of a size of 0.71nm × 0.71nm × 1.82nm, supercage is 12 rings along horizontal section, and with the 10 ring openings of 0.40nm × 0.55nm with extraneous to logical (Ref.Science1994,264,1910-1913).1997, International Molecular sieve federation was by this molecular sieve structure called after MWW.There is the hole of some 12 rings in MCM-22 molecular sieve crystal surface, be the half of supercage, the degree of depth is about 0.9nm, and internal diameter is 0.7nm.Therefore, in some catalyzed reaction, MCM-22 had both shown the feature of 10 rings, showed again the feature of 12 rings.Current MCM-22 molecular sieve achieves industrial application (petroleum journal: refining of petroleum in the reaction of benzene alkylation with propylene preparing isopropylbenzene, 2003,19 (5): 47-52), also in the reactions such as catalytic cracking, aromizing, etherificate, heavy aromatic hydrocarbon light and toluene disproportionation, demonstrate wide application prospect (Ref.Appl.Catal.A.1994 simultaneously, 115,121-134; Advanced chemical journal, 2000,21 (6), 949-951; Petrochemical complex, 2012,41 (1), 19-21).MCM-22 is lamellar zeolite, thickness generally tens nanometers, but the diameter of its thin slice generally several to tens microns between.Because the duct of MCM-22 is longer, reactant and product diffusional resistance is on a catalyst comparatively large, very easily causes deep reaction and produces carbon distribution, shortens the reaction life-span.How the synthesizing small-grain MCM-22 molecular sieve of low cost and high yield is still the problem having challenge.
Synthetic method about MCM-22 molecular sieve has had a lot of report, and usual method is made into the reaction mixture mixed, SiO by following proportioning
2/ Al
2o
3for 35-40, H
2o/SiO
2for 35-45, R/SiO
2for 0.5-1, OH/SiO
2for 0.18-0.30.Then at 140-160 DEG C of crystallization 6-7 days, obtaining crystal particle diameter is micron-sized MCM-22 molecular sieve (US4954325).The open CN1179881C of patent provides one and uses comparatively low wash water and basicity, and the synthetic method keeping solution alkali concn simultaneously to keep solution hypersaturated state, prepares little grain MCM-22 molecular sieve.H used
2o/SiO
2molar ratio is minimum reaches 10, obtains the single crystal of hexagonal flake, and its diameter is at 50-900nm, and thickness is at 20-200nm.But because product grains is little, solid-liquid separation process has difficulties, and yield is low.The open CN1699170A of patent provides a kind of method by being added with organic additive synthesizing small-grain MCM-22 molecular sieve, obtains by adding sodium dodecylbenzenesulfonate, polyglycol surfactants or their mixture the layered crystal that granularity is less than 600nm, thickness is less than 100nm.But the method synthesis cost is high, the waste liquid amount obtained is large, be difficult to process.
From the current report about synthesizing MCM-22, mostly products obtained therefrom is sodium form molecular sieve, needs it repeatedly to exchange for several times, complicated operation when use further.The open CN102092740A of patent provides a kind of direct method preparing H type MCM-22.Aluminum isopropylate and the ammonium ion compound provided are prepared into the aqueous solution, then drip template and ammonia type silicon sol successively, obtain target product at 140-170 DEG C of Water Under thermal crystallisation after 24-26 days.The method crystallization time is long, and synthesis cost is high.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of low cost, efficiently MCM-22 molecular sieve.Due to the change of reaction medium in system, the particle diameter of gained MCM-22 molecular sieve obviously reduces.And not containing alkali metal cation in this synthetic system, gained sample directly can obtain H type MCM-22 molecular sieve through roasting, greatly facilitates the use of molecular sieve.For this reason, on the one hand, the invention provides a kind of solvent process for thermosynthesizing of MCM-22 molecular sieve, it is characterized in that, key step is as follows:
A) silicon source, aluminium source, alkali source B, organic amine template R and water are mixed according to a certain percentage, form the initial gel mixture with following mol ratio:
SiO
2：Al
2O
3：B：R：H
2O=1：0.0125～0.067：0.05～0.5：0.5～15：3～10；
B) by step a) gained mixture to load in synthesis reactor and seal, crystallization 12 ~ 120 hours at 140 ~ 180 DEG C;
C) after crystallization is complete, namely solid product obtains described MCM-22 molecular sieve through being separated with mother liquor.
In a preferred embodiment, in the initial gel mixture that described step a) obtains, the molar ratio of each raw material is:
SiO
2：Al
2O
3：MOH：R：H
2O＝1：0.0167～0.04：0.05～0.3：0.55～10：3～8。
In a preferred embodiment, described step a) in the volume of organic amine template R be greater than the volume of water.
In a preferred embodiment, described step a) described in alkali source B be alkali metal-free alkali source.
In a preferred embodiment, described step a) in, described silicon source is be selected from one or more in tetraethoxy, silicon sol and white carbon black; Described aluminium source is be selected from one or more in aluminum isopropylate, pseudo-boehmite and aluminium hydroxide; Described organic formwork agent R is the mixture of hexamethylene imine or hexamethylene imine and hexahydroaniline; Described alkali source B is one or more in ammoniacal liquor, methylamine, dimethylamine and Tetramethylammonium hydroxide.
In a preferred embodiment, described step c) in crystallization temperature be 150 ~ 170 DEG C, and crystallization time is 24 ~ 96 hours.
In a preferred embodiment, described steps d) in be separated the mother liquor obtained after described solid product and be recycled.
On the other hand, the invention provides a kind of MCM-22 molecular sieve catalyst, it is characterized in that, described catalyzer becomes Hydrogen MCM-22 molecular sieve by MCM-22 molecular sieve roasting in 400 ~ 700 DEG C of air of being synthesized by aforesaid method and obtains.
On the other hand, the invention provides the purposes of above-mentioned catalyzer for acid catalyzed reaction.
The application adopts solvent process for thermosynthesizing, using organic amine simultaneously as template and the solvent of synthetic system, achieves the synthesis of little grain MCM-22 molecular sieve under alkali metal-free alkali source condition.
Embodiment
The present inventor finds in research process, in initial gel mixture, the crystallization rate of molar ratio to MCM-22 in water and silicon source has a significant impact, when water/silicon mol ratio value reduces, the nucleation rate of MCM-22 is fast, a large amount of nucleus can be formed at the crystallization initial stage, therefore make zeolite product crystal grain diminish.And the preparation of this system without the need to using basic metal alkali source just can realize MCM-22.In one embodiment, the concrete preparation process of the inventive method is as follows:
A) silicon source, aluminium source, alkali source B, organic amine template R and water are mixed according to a certain percentage, form the initial gel mixture with following mol ratio:
SiO
2: Al
2o
3: B:R:H
2o=1:0.0125 ~ 0.067:0.05 ~ 0.5:0.5 ~ 15:3 ~ 10; Preferable range is SiO
2: Al
2o
3: B:R:H
2o=1:0.0167 ~ 0.04:0.05 ~ 0.3:0.55 ~ 10:3 ~ 8; Preferably, the volume of the organic amine used always is greater than the volume of water, to make described organic amine template R also serve as primary solvent in the reaction, the crystallization for molecular sieve provides a brand-new environment, makes it can complete crystallization under alkali source B is the condition of alkali metal-free alkali source.
B) mixture of step a) gained to be loaded in synthesis reactor and airtight, 140 ~ 180 DEG C of crystallization 12 ~ 120 hours;
C) after crystallization is complete, namely solid product obtains described MCM-22 molecular sieve through being separated with mother liquor.
Described step a) in, silicon source is the mixture of one or more in tetraethoxy, silicon sol and white carbon black; Aluminium source is the mixture of one or more in aluminum isopropylate, pseudo-boehmite and Alumina gel; Alkali source B is one or more in ammoniacal liquor, methylamine, dimethylamine and Tetramethylammonium hydroxide; Organic formwork agent R is the mixture of hexamethylene imine or hexamethylene imine and hexahydroaniline.
Step b) in crystallization temperature be preferably 150 ~ 170 DEG C, crystallization time is preferably 24 ~ 96 hours.
Step c) in be separated the mother liquor that obtains can recycle.
The present invention also provides a kind of catalyzer for acid catalyzed reaction or catalyst Precursors, the MCM-22 molecular sieve synthesized according to the method described above, and in 400-700 DEG C of air, roasting 2-10 hour obtains Hydrogen MCM-22 molecular sieve.
Beneficial effect of the present invention includes but not limited to following aspect:
(1) synthetic operation is easy, and mother liquor can reclaim direct utilization, with low cost and environmental protection, is applicable to the scale operation of MCM-22.
(2) MCM-22 zeolite product granularity is little.
(3) directly Hydrogen MCM-22 molecular sieve can be obtained, as acid catalyst and catalyst Precursors by simple roasting.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
The mensuration of sample granularity adopts laser particle size method (the Nano90-nanometer laser granularity & Zeta potential titration instrument of Malvern company).
Sample crystallinity uses PANalytical X'Pert PRO Powder X-ray Diffractometer to measure (Cu target λ=1.54059
, actuating current, voltage is 40mA, 40kV)
Sample specific surface area analysis adopts micromeritics ASAP2020 adsorption instrument to record.
Embodiment 1-7
In 2L synthesis reactor, add a certain amount of alkali source and aluminium source, heated and stirred adds a certain amount of silicon source and organic formwork agent after dissolving successively, and stirring at room temperature is even, rotates crystallization certain hour at a certain temperature after sealing.Solid product, respectively through leaving standstill and centrifugation, collects mother liquor for subsequent use simultaneously.With deionized water wash gained solid product to neutral, after 120 DEG C of air dryings, characterize crystalline phase with XRD.Products obtained therefrom, through 550 DEG C of air atmosphere roasting template agent removings, obtains Hydrogen MCM-22 sieve sample.The mol ratio of concrete raw material used, synthesized gel rubber and the mean particle size of products obtained therefrom are in table 1, and XRD the results are shown in Table 2 and table 3 before the roasting of embodiment 5 gained representative sample and after roasting, and the results are shown in Table 4 as the XRD of the Si-Al molecular sieve MCM-22 of reference.
The reaction conditions of table 1: embodiment 1-7 and median size
Comparative example 1
In 2L synthesis reactor, add 65g hexamethylene imine, 350g silicon sol (content is 30 % by weight), 15g sodium aluminate, 9g sodium hydroxide and 1000g water stir evenly, and are warming up to 145 DEG C, crystallization 120h under stirring.Solid product respectively through leaving standstill and centrifugation, and with deionized water wash sample to neutral, after 120 DEG C of air dryings, obtains MCM-22 sieve sample.Laser particle size method is adopted to record mean particle size at 2um.
In product median size from table 1 and comparative example, median size contrasts known, and solvent thermal system is conducive to the generation of little crystal grain MCM-22.
Table 2: the XRD result of (former powder) before the roasting of embodiment 5 sample
Table 3: the XRD result after the roasting of embodiment 5 sample
Table 4: the XRD (pdf code name: 00-048-0075) of Si-Al molecular sieve MCM-22
Contrast known with table 4, the digital proof gained sample in table 2 and table 3 is pure phase MCM-22 (P) and MCM-22.
Embodiment 8: the preparation of catalyzer and catalyzed reaction
1), after MCM-22 molecular sieve compression molding embodiment 5 prepared, within 6 hours, H-MCM-22 molecular sieve is obtained through 600 DEG C of roastings.
2) MCM-22 molecular sieve concentration comparative example 1 prepared is that the ammonium nitrate solution of 1M carries out ion-exchange 2 times, and exchange temperature is 80 DEG C.Be washed with distilled water to without NO
3 -ion, compression molding after 110 DEG C of dryings, then within 6 hours, obtain H-MCM-22 molecular sieve 550 DEG C of roastings.
3) by step 1) and 2) the H-MCM-22 molecular sieve of gained presses molecular sieve butt respectively: SiO
2the ratio mixing of=9:1, extrusion molding after grinding evenly, is crushed to 20-50 order.Tackiness agent silicon-dioxide accounts for 10% of composite catalyst weight.Obtained catalyst A and B sample.
The catalyst A prepared by 1.5g and B are placed in the continuous flow reactor of fixed bed that internal diameter is 7mm respectively, and raw material 1-butylene is in 620 DEG C, 1atm, 3.5hr
-1contact catalyst under weight space velocity.By online 7890A gas chromatographic analysis effluent, 100m PONA post is analyzed, and FID detects.In following table, all data are weight percentage, feed stock conversion X is defined as the percentage ratio that the raw materials quality transformed accounts for starting raw material weight, yield Y is the summation of propylene and ethene in product, the product quality that the raw material that selectivity of product S is defined as unit mass conversion generates.The reaction result of butylene on catalyzer MCM-22 molecular sieve lists in table 5, and in table, C5+ does not comprise the content of the BTEX (benzene, toluene, ethylbenzene and dimethylbenzene) in product, the summation of C4=butene-1, butene-2 and iso-butylene.
Table 5: reaction conditions and reactivity worth
a
areaction conditions: raw material 1-butylene is in 550 DEG C, butylene pressure 0.1Mpa, 3.5hr
-1contact catalyst under weight space velocity.
As can be seen from Table 5, the catalyst performance obtained by embodiment 5 is obviously better than the performance of the catalyzer that comparative example 1 is synthesized.
It should be pointed out that the professional and technical personnel for making the art, under the premise without departing from the principles of the invention, the multiple amendment to these embodiments can be realized, and these amendments also should be considered as in protection scope of the present invention.
Claims (9)
1. a solvent process for thermosynthesizing for MCM-22 molecular sieve, is characterized in that, said method comprising the steps of:
A) silicon source, aluminium source, alkali source B, organic amine template R and water are mixed according to a certain percentage, form the initial gel mixture with following mol ratio:
SiO
2：Al
2O
3：B：R：H
2O=1：0.0125～0.067：0.05～0.5：0.5～15：3～10；
B) mixture of step a) gained to be loaded in synthesis reactor and to seal, crystallization 12 ~ 120 hours at 140 ~ 180 DEG C;
C) after crystallization is complete, from mother liquor separate solid product, described MCM-22 molecular sieve is namely obtained.
2. in accordance with the method for claim 1, it is characterized in that, in the initial gel mixture that described step a) obtains, the molar ratio of each raw material is:
SiO
2：Al
2O
3：B：R：H
2O=1：0.0167～0.04：0.05～0.3：0.55～10：3～8。
3. in accordance with the method for claim 1, it is characterized in that, described step a) in the volume of organic amine template R be greater than the volume of water.
4. in accordance with the method for claim 1, it is characterized in that, described step a) described in alkali source B be alkali metal-free alkali source.
5. in accordance with the method for claim 1, it is characterized in that, described step a) in, described silicon source is be selected from one or more in tetraethoxy, silicon sol and white carbon black; Described aluminium source is be selected from one or more in aluminum isopropylate, pseudo-boehmite and aluminium hydroxide; Described organic formwork agent R is the mixture of hexamethylene imine or hexamethylene imine and hexahydroaniline; Described alkali source B is one or more in ammoniacal liquor, methylamine, dimethylamine and Tetramethylammonium hydroxide.
6. in accordance with the method for claim 1, it is characterized in that, described step b) in crystallization temperature be 150 ~ 170 DEG C, and crystallization time is 24 ~ 96 hours.
7. in accordance with the method for claim 1, it is characterized in that, described step c) in be separated the mother liquor obtained after described solid product and be recycled.
8. a MCM-22 molecular sieve catalyst, is characterized in that, described catalyzer by by described in any one of claim 1-5 method synthesis MCM-22 molecular sieve directly in 400 ~ 700 DEG C of air roasting obtain.
9. the purposes of acid catalyzed reaction is used for according to catalyzer according to claim 8.
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| CN111099621B (en) * | 2018-10-25 | 2021-10-01 | 中国石油化工股份有限公司 | Synthesis method of MWW structure ultrathin nanosheet molecular sieve |
| CN114433037A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
| CN114433037B (en) * | 2020-10-20 | 2024-01-26 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
| 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 |
| CN117142486B (en) * | 2023-08-31 | 2024-05-10 | 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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