CN104591221B - A kind of SAPO-34 and EU-1 composite molecular screen and synthetic method thereof - Google Patents
A kind of SAPO-34 and EU-1 composite molecular screen and synthetic method thereof Download PDFInfo
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Abstract
The invention provides a kind of SAPO-34/EU-1 composite molecular screen, there are two kinds of crystal formations of EU-1 molecular sieve and SAPO-34 molecular sieve simultaneously. The synthetic method of SAPO-34/EU-1 composite molecular screen provided by the invention is that EU-1 molecular sieve is joined and in glucose solution, carries out ultrasonic processing, after filtration, obtain processing rear EU-1 molecular sieve after dry and roasting; Then water, alkali source, template, aluminium source, silicon source and EU-1 molecular sieve after treatment are mixed, at 150～240 DEG C of crystallization 15～100h, obtain SAPO-34/EU-1 composite molecular screen. The present invention introduces glucose in the micropore canals of EU-1 molecular sieve, change carbon into through roasting, occupy the duct of EU-1 molecular sieve, avoid alkali to enter EU-1 molecular sieve crystal inside, EU-1 molecular sieve is not destroyed in crystallization process, keep the integrality of crystal structure, be conducive to promote physical and chemical performance and the catalytic activity of SAPO-34/EU-1 composite molecular screen.
Description
Technical field
The invention belongs to molecular sieve catalytic material synthetic field, specifically a kind of SAPO-34/EU-1 composite molecular screen and synthetic method thereof.
Background technology
Composite molecular screen is a kind of complex type molecular sieve that has special construction, is the cocrystallization being formed by two or more molecular sieves, or has the composite crystal of two or more molecular sieve structure features. Due to the particularity of compound molecule sieve structure, so that this molecular sieve has had the acidity of reasonable layout and good hydrothermal stability more, overcome the limitation of its component self, better meet the demand of commercial Application, have broad application prospects.
At present more about the technology of composite molecular screen, as CN101279288A discloses a kind of synthetic method and application of core-shell structure compound molecular sieve. The method is first phosphorus, aluminium to be loaded on ZSM-5 zeolite, then ZSM-5 zeolite after treatment is mixed with phosphorus source, aluminium source, silicon source, obtains the hud typed composite molecular screen that contains SAPO-34 and ZSM-5 zeolite component by hydrothermal crystallizing.
CN1583562A discloses a kind of double-micropore zeolites molecular sieve and preparation method. The method is divided into two large steps, is first to synthesize Y zeolite; Then be that Y zeolite is mixed according to a certain percentage with tetraethylammonium bromide, ammoniacal liquor, Ludox, finally synthesize the composite molecular screen of the two microcellular structures of Y/ β.
CN1944254A is the modified patent of CN1583562A, the main body step of two patented methods is basically identical, difference is to mix according to a certain percentage with tetraethylammonium bromide, ammoniacal liquor, Ludox with ready-made high-Si Y-type molecular sieve, finally synthesizes the composite molecular screen of the two microcellular structures of Y/ β.
CN101514009A discloses a kind of mordenite/beta zeolite/Y zeolite coexisting material and synthetic method thereof. The method is that silicon source, aluminium source, alkali source, template, water, y-type zeolite crystal seed are mixed with batching order according to a certain percentage, and hydrothermal crystallizing goes out to contain the composite zeolite of modenite, β, tri-kinds of components of Y.
CN101279747A discloses a kind of ZSM-5/ modenite/Y zeolite coexisting molecular sieve and synthetic method thereof, the method is that silicon source, aluminium source, alkali source, template, water, y-type zeolite presoma crystal seed are mixed with batching order according to a certain percentage, and hydrothermal crystallizing goes out to contain the composite zeolite of modenite, ZSM-5, tri-kinds of components of Y.
CN101514008A discloses a kind of modenite/Y zeolite coexisting molecular sieve and synthetic method thereof. The method is that silicon source, aluminium source, alkali source, template and water are mixed with in modenite building-up process, adds the crystal seed containing Y zeolite precursor body, controls nucleation and the growth course of molecular sieve well, has prepared a kind of modenite/Y zeolite coexisting molecular sieve.
CN200410012333.2 discloses a kind of pair of micro porous molecular sieve and preparation method thereof, to adopt orderly synthetic method, first utilizing sodium metasilicate, Ludox, sodium metaaluminate, distilled water, NaOH, the concentrated sulfuric acid is raw material, tentatively synthesizes Y zeolite by certain material proportion; After it is mixed with the tetraethyl amine bromide solution that is dissolved with ammoniacal liquor, finally add again a certain amount of Ludox fully to stir and make it even, crystallization 4～7 days at 130～140 DEG C, template is removed in washing and drying roasting, finally obtains having the composite molecular screen of the two microcellular structures of Y/ β.
CN200810012195.6 discloses a kind of synthetic method of β/Y compound molecular sieve, adopts two-step method: the first step, preparation Y structure directing agent; Second step, stirs NaOH, water, aluminium source, beta-molecular sieve slurries and Y structure directing agent according to a certain ratio, carries out crystallization, makes β/Y compound molecular sieve.
CN200410012336.6 discloses a kind of twelve-ring double-micropore composite molecular sieve and preparation method thereof, is specifically the preparation method about a kind of β/Y compound molecular sieve, it is characterized in that adopting two-step method, and the first step is prepared Na type beta-molecular sieve; On the basis of the Na type beta-molecular sieve that second step makes in the first step, add appropriate sodium aluminate solution, regulate the basicity of material system, synthetic β/Y compound molecular sieve.
" the synthetic and sign of MOR/EU-1 composite molecular screen " " contemporary chemical industry " (the 40th the 3rd phase of volume in 2011) discloses the synthetic method of MOR/EU-1 composite molecular screen. The method is that silicon source, aluminium source, alkali source, template, water, EU-1 molecular sieve are mixed with batching order according to a certain percentage, and hydrothermal crystallizing goes out to contain the composite zeolite of EU-1 and MOR bi-component.
But the synthetic technology of composite molecular screen also has many defects and deficiency at present, thereby causes the physico-chemical property of composite molecular screen to have some deficiency. Such as the composite construction of composite molecular screen is wayward, Acidity is more difficult adjusting also. And the synthetic method of many composite molecular screens is to adopt two step method synthetic, the destruction of easily causing the first component in compound process is consequently reduced the physical and chemical performance of composite molecular screen, thereby affects absorption and catalytic performance. The improvement of these defects all need to improve from synthetic method kind.
Summary of the invention
The deficiency existing for prior art, the invention provides a kind of SAPO-34/EU-1 composite molecular screen and synthetic method thereof. The inventive method is for the defect of prior art; in recombination process, the EU-1 type molecular sieve in composite molecular screen is protected; make it not to be destroyed in building-up process, can obtain the SAPO-34/EU-1 composite molecular screen that crystal structure is complete, make it to there is good absorption and catalytic performance.
SAPO-34/EU-1 composite molecular screen provided by the invention, has following feature: synthetic product characterizes through x-ray diffractometer, has two kinds of crystal formations simultaneously, and one is EU-1 molecular sieve, and another kind is SAPO-34 molecular sieve; Measure through physical absorption, specific area is 500～900m2/ g, it is 500～800m that micropore surface amasss2/ g, mesoporous surface area is 100～300m2/g。
The synthetic method of SAPO-34/EU-1 composite molecular screen of the present invention, comprises the following steps:
(1) EU-1 molecular sieve is joined in glucose solution, carries out ultrasonic processing, gained mixture after filtration, dry and roasting, obtain processing rear EU-1 molecular sieve;
(2) by phosphorus source, silicon source, aluminium source, water and template according to a mole proportioning 0.3～1.5P:0.2～1.5SiO2：A12O3：20～100H2O:0.5～1.5 masterplate agent mixes, and then adds EU-1 molecular sieve after the processing that step (1) obtains, crystallization 15～100h at 150～240 DEG C, then through separating, washing, dry and roasting, obtain SAPO-34/EU-1 composite molecular screen.
According to synthetic method of the present invention, wherein in step (1), glucose solution concentration is 20～50wt%, preferably 30～40wt%, and the mass ratio of glucose solution and EU-1 molecular sieve is 8:1～25:1, preferably 10:1～20:1.
The ultrasonic processing time of step (1) is 1～3h, described being dried as dry 5～15h under 100～140 DEG C of conditions.
Roasting described in step (1) is in nitrogen or inert gas atmosphere, roasting 1～3h under 300～600 DEG C of conditions.
The described phosphorus source of step (2) is phosphoric acid; Aluminium source can be one or more in aluminium isopropoxide, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate; Silicon source can be ethyl orthosilicate, White Carbon black, silica gel, in one or more; Template is any in ethylenediamine, triethylamine, morpholine.
With A1 in aluminium source in step (2)2O3Weight is benchmark, A1 in EU-1 molecular sieve and aluminium source after pretreatment2O3Mass ratio be 0.3～1.5, preferably 0.5～1.2.
Roasting described in step (2) is roasting 1～3h at 300～600 DEG C; Described being dried as dry 5～15h under 100～140 DEG C of conditions.
SAPO-34/EU-1 composite molecular screen provided by the invention can be used as catalyst carrier or acidic catalyst component, has the good performance such as hydrocarbon molecules cracking, isomerization, and good MTO catalytic activity, can be widely used in PETROLEUM PROCESSING field.
Compared with prior art, SAPO-34/EU-1 composite molecular screen provided by the invention and synthetic method thereof have the following advantages:
(1) in SAPO-34/EU-1 composite molecular screen synthetic method of the present invention, by EU-1 molecular sieve is carried out to pretreatment, glucose is introduced in the micropore canals of EU-1 molecular sieve, then change carbon into through roasting, occupy the duct of EU-1 molecular sieve, reach the object of blocking duct, avoid alkali or other material to enter EU-1 molecular sieve crystal inside, only make the outer surface of crystal be exposed in reaction system, and the ratio of the shared whole crystal of outer surface is minimum, even negligible, even if outer surface is destroyed in recombination process, also can not be corrupted to the inner bulk phase of crystal. therefore can make EU-1 molecular sieve exempt from destruction in recombination reaction process, keep the integrality of crystal structure, avoid degree of crystallinity to decline, be conducive to promote physical and chemical performance and the catalytic activity of end-product SAPO-34/EU-1 composite molecular screen.
(2) in the inventive method, adopted ultrasonic processing EU-1 molecular sieve and glucose solution, because the duct of EU-1 molecular sieve is narrow micropore, when glucose enters micropore, existed larger sterically hindered. Adopt ultrasonic method can make glucose at utmost enter in the micropore canals of EU-1 molecular sieve, allow to greatest extent glucose fill up duct, be conducive to so finally to the protection of inside mutually of the crystal body of EU-1 molecular sieve.
(3) adopt the synthetic SAPO-34/EU-1 composite molecular screen of the inventive method; because EU-1 molecular sieve is protected in recombination reaction process; so EU-1 molecular sieve crystal keep complete, there is very high degree of crystallinity, complete maintenance the characteristic of EU-1 molecular sieve. After recombination reaction, synthesize SAPO-34/EU-1 composite molecular screen, formed the composite construction of SAPO-34 and two kinds of molecular sieves of EU-1. Aspect pore passage structure, form the compound pore canal system of micropore-mesopore, optimized diffusion in crystal, be conducive to the mass transfer in catalytic process; Also produce more strong acid and middle strong acid, reduced weak acid content, optimized Acidity, promoted the raising of catalytic activity.
Brief description of the drawings
The XRD spectra of the synthetic SAPO-34/EU-1 composite molecular screen of Fig. 1 embodiment 1.
Detailed description of the invention
Below by specific embodiment, SAPO-34/EU-1 composite molecular screen synthetic method of the present invention is given to detailed description, but be not limited to embodiment. Sial raw material, acid, alkali and the solvent using in the embodiment of the present invention is analyzes pure chemistry reagent.
Embodiment 1
(1) 40g glucose is dissolved in 100mL distilled water, under stirring condition, 8gEU-1 molecular sieve is added in glucose solution, stir after 30min, mixture is placed in to ultrasonic cleaner and processes 2h, then mixture is filtered, products therefrom is at 120 DEG C of dry 12h, and then in nitrogen atmosphere roasting 2h at 500 DEG C, obtain pretreated EU-1 molecular sieve.
(2) get 11g aluminium isopropoxide and be dissolved in 45mL distilled water, stir 30min. Then add 4.6mL phosphoric acid, stir 30min. Add again 5mL ethyl orthosilicate, stir 30min. Then add 4mL ethylenediamine, stir 30min. Then add EU-1 prepared by 8g step (1), stir 30min; Then pack in closed reactor 200 DEG C of crystallization 50h in baking oven into. Then by obtained product with distilled water washing 4 times to neutral, then dry 12h under 120 DEG C of conditions, finally in air atmosphere at 500 DEG C roasting 2h, gained sample is SAPO-34/EU-1 composite molecular screen, is numbered CL1.
Embodiment 2
(1) 40g glucose is dissolved in 100mL distilled water, under stirring condition, 8gEU-1 molecular sieve is added in glucose solution, stir after 30min, mixture is placed in to ultrasonic cleaner and processes 2h, then mixture is filtered, products therefrom is at 120 DEG C of dry 12h, and then in nitrogen atmosphere roasting 2h at 500 DEG C, obtain pretreated EU-1 molecular sieve.
(2) get 10g aluminium isopropoxide and be dissolved in 45mL distilled water, stir 30min. Then add 5mL phosphoric acid, stir 30min. Add again 8mL ethyl orthosilicate, stir 30min. Then add 10mL ethylenediamine, stir 30min. Then add EU-1 prepared by 8g step (1), stir 30min; Then pack in closed reactor 210 DEG C of crystallization 45h in baking oven into. Then by obtained product with distilled water washing 4 times to neutral, then dry 12h under 120 DEG C of conditions, finally in air atmosphere at 500 DEG C roasting 2h, gained sample is SAPO-34/EU-1 composite molecular screen, is numbered CL2.
Embodiment 3
(1) 35g glucose is dissolved in 100mL distilled water, under stirring condition, 7gEU-1 molecular sieve is added in glucose solution, stir after 30min, mixture is placed in to ultrasonic cleaner and processes 2h, then mixture is filtered, products therefrom is at 120 DEG C of dry 12h, and then in nitrogen atmosphere roasting 1.5h at 550 DEG C, obtain pretreated EU-1 molecular sieve.
(2) get 8.5g aluminium isopropoxide and be dissolved in 50mL distilled water, stir 30min. Then add 4.6mL phosphoric acid, stir 30min. Add again 7g white carbon, stir 30min. Then add 7mL ethylenediamine, stir 30min. Then add EU-1 prepared by 6g step (1), stir 30min; Then pack in closed reactor 180 DEG C of crystallization 60h in baking oven into. Then by obtained product with distilled water washing 4 times to neutral, then dry 12h under 120 DEG C of conditions, finally in air atmosphere at 500 DEG C roasting 2h, gained sample is SAPO-34/EU-1 composite molecular screen, is numbered CL3.
Embodiment 4
(1) 40g glucose is dissolved in 80mL distilled water, under stirring condition, 8gEU-1 molecular sieve is added in glucose solution, stir after 30min, mixture is placed in to ultrasonic cleaner and processes 1.5h, then mixture is filtered, products therefrom is at 120 DEG C of dry 12h, and then in nitrogen atmosphere roasting 1.5h at 560 DEG C, obtain pretreated EU-1 molecular sieve.
(2) get 5g boehmite and be dissolved in 45mL distilled water, stir 30min. Then add 4.6mL phosphoric acid, stir 30min. Add again 5mL ethyl orthosilicate, stir 30min. Then add 4.5mL ethylenediamine, stir 30min. Then add EU-1 prepared by 7.5g step (1), stir 30min; Then pack in closed reactor 185 DEG C of crystallization 35h in baking oven into. Then by obtained product with distilled water washing 4 times to neutral, then dry 12h under 120 DEG C of conditions, finally in air atmosphere at 500 DEG C roasting 2h, gained sample is SAPO-34/EU-1 composite molecular screen, is numbered CL4.
Comparative example 1
Get 11g aluminium isopropoxide and be dissolved in 45mL distilled water, stir 30min. Then add 4.6mL phosphoric acid, stir 30min. Add again 5mL ethyl orthosilicate, stir 30min. Then add 4mL ethylenediamine, stir 30min. Then add the untreated EU-1 of 8g, stir 30min; Then pack in closed reactor 200 DEG C of crystallization 50h in baking oven into. Then by obtained product with distilled water washing 4 times to neutral, then dry 12h under 120 DEG C of conditions, finally in air atmosphere at 500 DEG C roasting 2h, gained sample number into spectrum is CL5.
Table 1 is embodiment and comparative example gained sample physico-chemical property
By embodiment and known with comparative example, the inventive method can synthesize high-quality SAPO-34/EU-1 composite molecular screen, and the degree of crystallinity of SAPO-34 and EU-1 molecular sieve is good, especially the degree of crystallinity of EU-1 molecular sieve will be far above the degree of crystallinity of EU-1 molecular sieve in comparative example, illustrates that the SAPO-34/EU-1 composite molecular screen that the inventive method provides has good physico-chemical property.
Claims (13)
1. a SAPO-34/EU-1 composite molecular screen, is characterized in that: described SAPO-34/EU-1 composite molecular screen characterizes through x-ray diffractometer, has two kinds of crystal formations simultaneously, and one is EU-1 type molecular sieve, and another kind is SAPO-34 molecular sieve; Measure through physical absorption, specific area is 500～900m2/ g, it is 500～800m that micropore surface amasss2/ g, mesoporous surface area is 100～300m2/ g; Total acid content is 0.3～1mmol/g, and wherein strong acid and middle strong acid account for 50～80% of total acid content.
2. the synthetic method of SAPO-34/EU-1 composite molecular screen described in claim 1, is characterized in that step is as follows:
(1) EU-1 molecular sieve is joined in glucose solution, carries out ultrasonic processing, gained mixture after filtration, dry and roasting, obtain processing rear EU-1 molecular sieve;
(2) by phosphorus source, silicon source, aluminium source, water and template according to a mole proportioning 0.3～1.5P:0.2～1.5SiO2：A12O3：20～100H2O:0.5～1.5 masterplate agent mixes, and then adds EU-1 molecular sieve after the processing that step (1) obtains, crystallization 15～100h at 150～240 DEG C, then through separating, washing, dry and roasting, obtain SAPO-34/EU-1 composite molecular screen.
3. it is characterized in that in accordance with the method for claim 2: in step (1), glucose solution concentration is 20～50wt%.
4. it is characterized in that in accordance with the method for claim 2: in step (1), glucose solution concentration is 30～40wt%.
5. it is characterized in that in accordance with the method for claim 2: in step (1), the mass ratio of glucose solution and EU-1 molecular sieve is 8:1～25:1.
6. it is characterized in that in accordance with the method for claim 2: in step (1), the mass ratio of glucose solution and EU-molecular sieve is 10:1～20:1.
7. in accordance with the method for claim 2, it is characterized in that: the ultrasonic processing time of step (1) is 1～3h described being dried as dry 5～15h under 100～140 DEG C of conditions.
8. in accordance with the method for claim 2, it is characterized in that: roasting described in step (1) is in nitrogen or inert gas atmosphere, roasting 1～3h under 300～600 DEG C of conditions.
9. it is characterized in that in accordance with the method for claim 2: the described phosphorus of step (2) source is phosphoric acid; Aluminium source is one or more in aluminium isopropoxide, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate; Silicon source be ethyl orthosilicate, White Carbon black, silica gel, in one or more, template is any in ethylenediamine, triethylamine, morpholine.
10. it is characterized in that in accordance with the method for claim 2: with A1 in aluminium source in step (2)2O3Weight is benchmark, A1 in EU-1 molecular sieve and aluminium source after pretreatment2O3Mass ratio be 0.3～1.5.
11. in accordance with the method for claim 2, it is characterized in that: with A1 in aluminium source in step (2)2O3Weight is benchmark, A1 in EU-1 molecular sieve and aluminium source after pretreatment2O3Mass ratio be 0.5～1.2.
12. in accordance with the method for claim 2, it is characterized in that: roasting described in step (2) in air atmosphere at 300～600 DEG C roasting 1～3h.
13. in accordance with the method for claim 2, it is characterized in that: described in step (2), be dried as dry 5～15h under 100～140 DEG C of conditions.
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| CN105000571B (en) * | 2015-07-08 | 2017-06-16 | 中国石油大学(北京) | A kind of coexisting molecular sieves of EU 1/ZSM 48 and its preparation and application |
| CN106946266B (en) * | 2016-01-07 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method |
| CN107096563A (en) * | 2017-05-26 | 2017-08-29 | 中国石油天然气股份有限公司 | A kind of composite molecular screens of SAPO 11/ZSM 5 and preparation method thereof |
| CN108689414B (en) * | 2018-08-20 | 2019-11-29 | 中触媒新材料股份有限公司 | A kind of multi-stage porous EU-1 molecular sieve and its synthetic method |
| CN108975353B (en) * | 2018-08-20 | 2020-02-14 | 中触媒新材料股份有限公司 | Hierarchical porous EU-1 molecular sieve and preparation method thereof |
| CN111097367A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbent for adsorbing normal alkane and preparation method and application thereof |
| CN112744841B (en) * | 2019-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | Mesoporous SAPO-34 molecular sieve and synthetic method thereof |
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| CN102861607A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | EU-1/ZSM-5 composite molecular sieve, preparation method of EU-1/ZSM-5 composite molecular sieve and application of EU-1/ZSM-5 composite molecular sieve |
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