CN103058221B - Method for synthesizing mordenite - Google Patents
Method for synthesizing mordenite Download PDFInfo
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- CN103058221B CN103058221B CN201110324663.5A CN201110324663A CN103058221B CN 103058221 B CN103058221 B CN 103058221B CN 201110324663 A CN201110324663 A CN 201110324663A CN 103058221 B CN103058221 B CN 103058221B
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- directing agent
- structure directing
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Abstract
The invention discloses a method for synthesizing mordenite. The method comprises the steps of firstly treating mordenite with an alkaline solution to prepare a structure-directing agent, stirring inorganic alkalis, aluminium sources, silicon sources and water to synthesize silicon-aluminium gel, then adding the structure-directing agent and obtaining the mordenite after hydrothermal crystallization. The method has the advantages that the mordenite synthesized by the method has a high degree of crystallinity and effectively avoids mixed crystals; and the method is simple and easy to operate, is cheap and available in raw materials, and avoids using toxic and harmful organic template agents.
Description
Technical field
The present invention relates to a kind of synthetic method of mordenite, specifically a kind of method of green low cost synthesizing flokite, belong to molecular sieve catalytic material synthesis field.
Background technology
Mordenite (MOR) is one of human knowledge's zeolite the earliest.Mordenite crystal has two class pore canal system, one class is that the tetra-atomic ring that connected by 5-3 structural unit and five-ring (five-ring is preponderated) form oval 12 ring main channels, be of a size of 0.695 × 0.581 nm, between main channel, have octatomic ring passage to link up.Another kind of is octatomic ring passage, irregular arrangement, and aperture 0.28 nm, general molecule not easily passes in and out.Mordenite has excellent heat-resisting, acidproof and water vapor performance, so be industrially widely used as sorbent material and petrochemical complex and fine chemistry industry catalyzer that gas or liquid mixture be separated.Especially at oil catalytic field, such as, in the reaction process such as esterification, etherificate, amination of the disproportionation of the disproportionation of aromatic hydrocarbons, isomerization, alkylation, transalkylation, alkane, isomerization, alcohols, catalytic performance is excellent, so quite pay attention to by people.
The synthesis great majority of mordenite will rely on template, as CN101519217A discloses a kind of preparation method of microcrystal mordenites.Aluminium source, sodium source, template and water are made into mixing solutions by the method, are soaked by Silica Surface with this mixing solutions, then synthetic system is carried out two sections of crystallization at different temperature, finally synthesize microcrystal mordenites.But owing to using organic ammonium as template, cause synthesis high cost.
CN1050011 A discloses a kind of synthesis of high silicon mordenite.The method is with industrial raw material synthesizing flokites such as water glass cheap and easy to get, mineral acid, mineral alkali, aluminium salt or aluminates, its principal character uses inorganic ammonia to replace organic amine and adds mordenite crystal seed to reduce production cost, but the use of inorganic ammonia still can bring environmental pollution and work the mischief to human body.
CN1257831A discloses a kind of method that synthesis has the zeolite of mordenite structure.Should with direct with water glass cheap and easy to get, aluminium salt or aluminate, fluorochemical for raw material, under certain temperature, obtain crystallization mordenite by crystallization.Although the method does not use organic ammonium as template, but use poisonous fluorochemical, some all can be caused to endanger to human body and environment.
CN1843915A discloses a kind of method without amine synthesizing high silicon content mordenite.The method for raw material, take polyvalent alcohol as additive with silicon source, aluminium source and deionized water, hydrothermal crystallizing in the stainless steel cauldron of teflon lined, and crystallization temperature is 120 ~ 200 DEG C, and crystallization time is synthesize mordenite in 12 ~ 240 hours.CN1243100A also discloses a kind of synthetic method of high silicon mordenite.The principal character of the method is the use of low-carbon (LC) alcohols or washing powder is that additive is to prepare mordenite.These two kinds of methods all avoid and use expensive organic ammonium template and use the surrogates such as alcohols.But the surrogates such as alcohols still can increase synthesis cost, be unfavorable for large-scale commercial production.
CN101033071A discloses a kind of method of synthetic zeolite.The method, by synthesis materials such as solid silicon source, aluminium sources, stirs under highly alkaline conditions, after fully mixing, carries out crystallization in steam, synthesizing flokite.The method can not use template for the synthesis of during mordenite, and this patented method needs to transform synthesis device, is applicable to the study on the synthesis in laboratory, is not suitable for large-scale industrial production.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of green syt mordenite.The method synthesizes the mordenite of high-crystallinity when not using organic formwork agent.Synthesis material is general inorganic material, and not containing hazardous and noxious substances, whole preparation process environmental protection, operation steps is simple.
The synthetic method of mordenite provided by the invention, comprises the following steps:
(1) preparation of structure directing agent
Mordenite is joined in alkaline solution, wherein the liquid-solid ratio of alkaline solution and mordenite is 10 ~ 50 mL/g, preferably 20 ~ 30 mL/g, after being uniformly mixed, at 80 ~ 180 DEG C under air tight condition, preferably 100 ~ 140 DEG C of process 0.5 ~ 8.0h, preferably 2.0 ~ 4.0h, gained suspension liquid product is structure directing agent;
(2) synthesis of mordenite
According to 3 ~ 10Na
2o:20 ~ 80SiO
2: A1
2o
3: 400 ~ 1800H
2o mol ratio, by mineral alkali, aluminium source, silicon source and water, stirs synthesizing Si-Al gel, then adds structure directing agent prepared by step (1), wherein the add-on of structure directing agent in mordenite with added silicon source with SiO
2the mass ratio of meter is 0.005 ~ 0.060, preferably 0.010 ~ 0.040, and then at 140 ~ 220 DEG C of temperature, crystallization 10 ~ 50h, through being separated, washing and drying obtain mordenite.
According to synthetic method of the present invention, wherein the mordenite described in step (1) is sodium form mordenite, its SiO
2/ A1
2o
3mol ratio is 10 ~ 100.
Alkaline solution described in step (1) can be the mixing solutions of one or more in NaOH, KOH and LiOH aqueous solution.The concentration of alkaline solution is 0.1 ~ 5.0 mol/L, preferably 0.5 ~ 2.0 mol/L.The described churning time be uniformly mixed is generally 10 ~ 60min, preferably 20 ~ 40min.
Mineral alkali described in step (2) can be one or more in NaOH, KOH, LiOH; Aluminium source can be one or more in sodium aluminate, aluminium hydroxide, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminum oxide; Silicon source can be one or more in White Carbon black, silica gel, silicon sol, water glass.
Operation steps described in step (2) is: be first that mineral alkali, aluminium source is soluble in water, to be dissolved completely after add silicon source, vigorous stirring 10 ~ 60min, preferably 20 ~ 40min; Then the structure directing agent prepared according to step (1) is added, vigorous stirring 10 ~ 60min, preferably 20 ~ 40min.Then load in closed reactor and carry out crystallization, temperature of reaction is 140 ~ 220 DEG C, preferably 150 ~ 190 DEG C, and the reaction times is 10 ~ 50h, preferably 17 ~ 30h.Finally obtain product through separation, washing and drying again.Described separation and washing are routine operation well known to those skilled in the art.Can take the method for filtering as being separated, washing generally refers to uses deionized water wash.Generally include separating for several times and washing operation, be generally 1 ~ 6 time.Drying conditions is generally dry 5 ~ 15h under 100 ~ 140 DEG C of conditions.
Following feature is had: synthetic product characterizes through x-ray diffractometer, and its crystal formation is pure mordenite, and degree of crystallinity is high, not containing other Crystal impurity according to the mordenite of the inventive method synthesis.
The sorbent material that mordenite provided by the invention can be used as gas, liquid mixture is separated, also can as the carrier of catalyzer or an acidic catalyst component.During as an acidic catalyst component, can according to different catalyzed reaction demand, play a role in the catalytic reaction process such as esterification, etherificate, amination of the disproportionation of the disproportionation of aromatic hydrocarbons, isomerization, alkylation, transalkylation, alkane, isomerization, alcohols.
Compared with the synthetic technology of existing mordenite, the synthetic method of mordenite provided by the invention has the following advantages:
(1) synthetic method provided by the invention can synthesize mordenite when the additive such as do not use organic formwork agent, inorganic ammonia, fluorochemical etc. expensive or poisonous, and synthetic product not only degree of crystallinity is high, and not containing other Crystal impurity.
(2), in the inventive method, need first to carry out suitable alkaline solution treatment to prepare high reactivity structure directing agent to mordenite.Mordenite is after suitable basic solution process, and its crystalline structure major part can be caved in, and is formed and has highly active secondary structure and other feature cage units in a large number.These secondary structure units directly as the nucleus of mordenite growth, or can have the growth of very strong inducing action to mordenite and play guide effect using other feature cage units.On the one hand, highly active directed agents can promote the synthesis of high-crystallinity, avoids the generation of other impurity crystal; On the other hand, do compared with the technology of crystal seed with directly using mordenite, the present invention, due to the use of structure directing agent, can reduce the consumption of mordenite, thus reduces synthesis cost.
(3) operation is simple for synthetic method of the present invention, and cheaper starting materials is easy to get, nontoxic, avoids raw materials such as using expensive, poisonous organic template agent, not only greatly reduce production cost, and whole preparation process environmental protection.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the mordenite that embodiment 1 obtains.
Fig. 2 is the XRD spectrogram of the sample that comparative example 2 obtains.
Embodiment
Below by specific embodiment, detailed description is given to MOR synthetic method of the present invention, but be not limited to embodiment.
The raw material MOR(SiO used in the embodiment of the present invention
2/ A1
2o
3mol ratio is 12) purchased from Fushun Petrochemical Company catalyst plant.White carbon black, water glass (SiO
28 mol/L), silicon sol (SiO
2content is 30wt%), purchased from Haiyang Chemical Plant, Qingdao, tetraethyl ammonium hydroxide (25 wt %).The acid used, alkali and other reagent are analytical pure chemical reagent.
Embodiment 1
The sodium hydroxide solution 1000mL getting 40g MOR, 1mol/L is placed in beaker, stirs 30min under room temperature condition, proceeds in a closed reactor, 120 DEG C of process 4h in baking oven.Gained suspension liquid is structure directing agent, stand-by.
Get 13.9 g sodium hydroxide, 10.4 g sodium aluminates are placed in 500 mL distilled water, vigorous stirring is until all dissolve.Slowly add 72 g white carbon blacks again, vigorous stirring 30 min.Then the structure directing agent that on 40mL, step is made is added, vigorous stirring 30 min.Then load in closed reactor, 170 DEG C of crystallization 24h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL1, and gained sample as shown in Figure 1, is pure mordenite, not containing other impurity.
Embodiment 2
The sodium hydroxide solution 1000mL getting 30g MOR, 0.8mol/L is placed in beaker, stirs 30min under room temperature condition, proceeds in a closed reactor, 120 DEG C of process 4h in baking oven.Gained suspension liquid is structure directing agent, stand-by.
Get 18.5 g sodium hydroxide, 14 g sodium aluminates are placed in 500 mL distilled water, vigorous stirring is until all dissolve.Slowly add 93 g white carbon blacks again, vigorous stirring 25min.Then the structure directing agent that on 50mL, step is made is added, vigorous stirring 25 min.Then load in closed reactor, 175 DEG C of crystallization 30h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL2, is pure mordenite.
Embodiment 3
The sodium hydroxide solution 1500mL getting 40g MOR, 1.2mol/L is placed in beaker, stirs 30min under room temperature condition, proceeds in a closed reactor, 120 DEG C of process 3h in baking oven.Gained suspension liquid is structure directing agent, stand-by.
Get 10.4 g sodium hydroxide, 9.5 g sodium aluminates are placed in 400 mL distilled water, vigorous stirring is until all dissolve.Slowly add 145mL water glass again, vigorous stirring 20 min.Then the structure directing agent that on 35mL, step is made is added, vigorous stirring 40 min.Then load in closed reactor, 190 DEG C of crystallization 20h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL3, is pure mordenite.
Embodiment 4
The potassium hydroxide solution 1000mL getting 40g MOR, 1mol/L is placed in beaker, stirs 30min under room temperature condition, proceeds in a closed reactor, 120 DEG C of process 4h in baking oven.Gained suspension liquid is structure directing agent, stand-by.
Get 14 g sodium hydroxide, 22g Tai-Ace S 150 is placed in 500 mL distilled water, vigorous stirring is until all dissolve.Slowly add 70 g white carbon blacks again, vigorous stirring 30 min.Then the structure directing agent that on 25mL, step is made is added, vigorous stirring 30 min.Then load in closed reactor, 160 DEG C of crystallization 28h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL4, is pure mordenite.
Comparative example 1
Get 13.9 g sodium hydroxide, 10.4 g sodium aluminates, 280mL tetraethyl ammonium hydroxide be placed in 220 mL distilled water, vigorous stirring is until all dissolve.Slowly add 72 g white carbon blacks again, vigorous stirring 30 min.Then load in closed reactor, 170 DEG C of crystallization 24h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL5, is mordenite.
Comparative example 2
Get 13.9 g sodium hydroxide, 10.4 g sodium aluminates are placed in 500 mL distilled water, vigorous stirring is until all dissolve.Slowly add 72 g white carbon blacks again, vigorous stirring 30 min.Then 1.6g MOR is added, vigorous stirring 30 min.Then load in closed reactor, 170 DEG C of crystallization 24h in baking oven.By obtained product with distilled water wash 4 times to neutral, 120 DEG C of dry 12h, gained sample number into spectrum is CL6, and gained sample is mordenite, as shown in Figure 2.
The crystalline phase character of table 1 embodiment and comparative example gained MOR
Sample ID | Crystalline phase | Relative crystallinity, % |
CL1 | MOR | 100 |
CL2 | MOR | 99 |
CL3 | MOR | 97 |
CL4 | MOR | 98 |
CL5 | MOR | 93 |
CL6 | MOR | 72 |
Note: the relative crystallinity that table 1 is given is for reference with the degree of crystallinity of CL1.
From table 1 and Fig. 1 ~ 2, the mordenite of the inventive method gained has higher degree of crystallinity, and the inventive method does not adopt template, environmental protection, reduces preparation cost.
Claims (10)
1. a synthetic method for mordenite, process is as follows:
(1) preparation of structure directing agent
Joined by mordenite in alkaline solution, wherein the liquid-solid ratio of alkaline solution and mordenite is 10 ~ 50 mL/g, and after being uniformly mixed, at 80 ~ 180 DEG C of process 0.5 ~ 8.0h under air tight condition, gained suspension liquid product is structure directing agent; Described alkaline solution is the mixing solutions of one or more in NaOH, KOH and LiOH aqueous solution; The concentration of alkaline solution is 0.1 ~ 5.0 mol/L;
(2) synthesis of mordenite
According to 3 ~ 10Na
2o:20 ~ 80SiO
2: A1
2o
3: 400 ~ 1800H
2o mol ratio, by mineral alkali, aluminium source, silicon source and water, stirs synthesizing Si-Al gel, then adds structure directing agent prepared by step (1), wherein the add-on of structure directing agent in mordenite with added silicon source with SiO
2the mass ratio of meter is 0.005 ~ 0.060, and then at 160 ~ 220 DEG C of temperature, crystallization 10 ~ 50h, obtains mordenite through separation, washing and drying.
2. the liquid-solid ratio that in accordance with the method for claim 1, it is characterized in that alkaline solution and mordenite in step (1) is 20 ~ 30 mL/g.
3. in accordance with the method for claim 1, it is characterized in that the treatment condition in step (1) are as follows: at 100 ~ 140 DEG C of process 2.0 ~ 4.0h.
4. in accordance with the method for claim 1, it is characterized in that in step (2), the add-on of structure directing agent in mordenite with added silicon source with SiO
2the mass ratio of meter is 0.010 ~ 0.040.
5. in accordance with the method for claim 1, it is characterized in that the mordenite described in step (1) is sodium form mordenite, its SiO
2/ A1
2o
3mol ratio is 10 ~ 100.
6. in accordance with the method for claim 1, it is characterized in that the churning time be uniformly mixed described in step (1) is 10 ~ 60min.
7. in accordance with the method for claim 1, it is characterized in that the mineral alkali described in step (2) is one or more in NaOH, KOH, LiOH; Aluminium source is one or more in sodium aluminate, aluminium hydroxide, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminum oxide; Silicon source is one or more in White Carbon black, silica gel, silicon sol, water glass.
8. in accordance with the method for claim 1, it is characterized in that in step (2), is first that mineral alkali, aluminium source is soluble in water, to be dissolved completely after add silicon source, vigorous stirring 10 ~ 60min; Then the structure directing agent prepared according to step (1) is added, vigorous stirring 10 ~ 60min.
9. in accordance with the method for claim 1, it is characterized in that the crystallization condition of step (2) is as follows: temperature of reaction is 150 ~ 190 DEG C, the reaction times is 17 ~ 30h.
10. in accordance with the method for claim 1, it is characterized in that the drying conditions described in step (2) is dry 5 ~ 15h under 100 ~ 140 DEG C of conditions.
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CN103787364A (en) * | 2014-01-23 | 2014-05-14 | 大连理工大学 | Method for preparing mordenite by using diatomite |
CN106698453B (en) * | 2015-11-12 | 2018-07-20 | 中国石油化工股份有限公司 | A method of synthesis nanometer MOR molecular sieves |
CN108217680B (en) * | 2016-12-09 | 2021-05-25 | 延长中科(大连)能源科技股份有限公司 | Method for synthesizing mordenite MOR molecular sieve, product and application thereof |
CN108609631B (en) * | 2018-06-15 | 2022-03-25 | 山西大同大学 | Method for synthesizing SAPO-20 molecular sieve |
CN111573690A (en) * | 2020-05-13 | 2020-08-25 | 西安交通大学 | Template-free preparation method of mordenite for gaseous radioactive iodine adsorption |
CN112551546B (en) * | 2020-11-16 | 2022-08-19 | 复榆(张家港)新材料科技有限公司 | Preparation method and application of binder-free macroporous high-silicon Na-type MOR zeolite molecular sieve |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
CN101935053A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | ZSM-5 zeolite and synthesis method thereof |
CN102060308A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
CN101935053A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | ZSM-5 zeolite and synthesis method thereof |
CN102060308A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
Non-Patent Citations (3)
Title |
---|
Direct synthesis of high-silica mordenite using seed crystals;Baowang Lu,et al.;《Microporous and Mesoporous Materials》;20041231;第76卷(第1期);第1页至第7页 * |
JP特开2005-219988A 2005.08.18 * |
无有机模板剂条件下合成沸石催化材料;孟祥举等;《催化学报》;20090930;第30卷(第9期);第969页第2栏 * |
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