CN115140747B - Granular NU-88 molecular sieve and preparation method thereof - Google Patents
Granular NU-88 molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 95
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims abstract description 36
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims abstract description 35
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000012265 solid product Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 alkylene bromide Chemical compound 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
Abstract
The present disclosure relates to a process for preparing a particulate NU-88 molecular sieve, the process comprising the steps of: s1, mixing hexamethylene dichloride and N-methylpyrrolidine with a solvent, and carrying out contact reaction to obtain a contact reaction product; s2, mixing a contact reaction product, an inorganic alkali source, an aluminum source and a silicon source with water to obtain a mixture, carrying out hydrothermal crystallization treatment on the mixture, and recovering a solid product; in step S1, the conditions of the contact reaction are: the reaction temperature is 25-85 ℃ and the reaction time is 10-100 h; the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.85-2.75): (2-22). The method has the advantages that the granular NU-88 molecular sieve with larger particle size is synthesized at low cost, complicated processes of high-cost separation, purification and the like which are needed by the conventional synthesis of the NU-88 molecular sieve template agent are omitted, and a great deal of time consumption, energy consumption and material consumption are avoided.
Description
Technical Field
The present disclosure relates to the field of molecular sieve preparation, and in particular, to a granular NU-88 molecular sieve and a preparation method thereof.
Background
The patent USP60277707 discloses a novel molecular sieve, namely NU-88 molecular sieve for the first time. The synthesis method used in the patent is to select bis (N-methylpyrrolidine) alkylene bromide with the carbon number of 4-6 of alkylene as a template agent, then dynamically crystallize for 9-22 days at 160 ℃, and finally synthesize the NU-88 molecular sieve. Although the specific structure of NU-88 molecular sieves has not been fully resolved so far, it is presumed that they may belong to the BET family and have a three-dimensional twelve-membered ring pore structure based on the existing characterization and reaction evaluation results.
Lee S B in Journal of analysis, 2003,215:151-170, a method of synthesizing NU-88 molecular sieves. 1, 6-bis (N-methylpyrrolidine) hexane bromide is used as a template agent, and is added in N (SiO) 2 )/n(Al 2 O 3 ) 60, n (NaOH)/n (SiO) 2 ) Is 0.73, n (H) 2 O)/n(SiO 2 ) 40, n (R)/n (SiO) 2 ) The NU-88 molecular sieve synthesized by the method has a fixed form under the conditions of 0.15 (R is template agent 1, 6-bis (N-methylpyrrolidine) hexane bromide) and 160 ℃ rotary crystallization.
USP6117307 uses NU-88 molecular sieves in the reaction of hydrocracking, which is found to have higher catalytic activity and selectivity. Meanwhile, the NU-88 molecular sieve also has excellent physicochemical properties, so that the NU-88 molecular sieve has wider application in the petrochemical industry field.
To date, N-methylpyrrolidine and 1, 6-dibromohexane are added into a solvent according to a certain proportion for reaction, and after the reaction, a template agent 1, 6-bis (N-methylpyrrolidine) hexane bromide with better purity is obtained through crystallization and repeated recrystallization. However, this method requires many troublesome operations such as freezing, filtering, washing with organic reagents, dissolving, precipitating, drying, etc. during crystallization and many times of recrystallization, which results in a great deal of time, energy and material consumption.
Disclosure of Invention
The purpose of the present disclosure is to provide a granular NU-88 molecular sieve and a preparation method thereof.
To achieve the above object, a first aspect of the present disclosure provides a method for preparing a granular NU-88 molecular sieve, the method comprising the steps of:
s1, mixing hexamethylene dichloride and N-methylpyrrolidine with a solvent, and carrying out contact reaction to obtain a contact reaction product;
s2, mixing the contact reaction product, an inorganic alkali source, an aluminum source and a silicon source with water to obtain a mixture, carrying out hydrothermal crystallization treatment on the mixture, and recovering a solid product;
in step S1, the conditions of the contact reaction are: the reaction temperature is 25-85 ℃ and the reaction time is 10-100 h;
the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.85-2.75): (2-22).
Optionally, in step S1, the solvent is one or more selected from water, monohydric alcohol with 1-6 carbon atoms, ether with 4-6 carbon atoms, ketone with 3-6 carbon atoms, polyhydric alcohol with 2-4 carbon atoms and ester with 3-6 carbon atoms.
Optionally, in step S1, the conditions of the contact reaction are: the reaction temperature is 35-75 ℃ and the reaction time is 15-80 h;
the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.95-2.5): (2-17).
Optionally, in step S1, N-methylpyrrolidine is mixed with the solvent, and then hexamethylene dichloride is added dropwise to the resulting mixture.
Optionally, in step S2, the mixture is prepared with SiO 2 The silicon source is calculated as Al 2 O 3 The molar ratio of the aluminum source, the inorganic alkali source, the contact reaction product and water, calculated as hexamethylenedichloride, is 100: (0.66-10): (5-45): (5-50): (500-7000).
Optionally, in step S2, the inorganic alkali source contains an alkali metal element; the inorganic alkali source is selected from NaOH, KOH, na 2 O、K 2 O、Na 2 CO 3 And K 2 CO 3 One or more of the following;
the aluminum source is selected from NaAlO 2 、Al(NO 3 ) 3 、Al 2 (SO 4 ) 3 、(CH 3 COO) 3 Al and Al [ (CH) 3 ) 2 CHO] 3 One or more of the following;
the silicon source is one or more selected from silica gel, silica sol, white carbon black and tetraethoxysilane.
Optionally, in step S2, the hydrothermal crystallization treatment includes the following steps:
a. carrying out the first stage hydrothermal crystallization for 24-72 h at 135-145 ℃;
b. and performing the second stage hydrothermal crystallization at 175-185 ℃ for 48-120 h.
Optionally, the method further comprises: and (3) washing, filtering and drying the solid product after recovering the solid product.
A second aspect of the present disclosure provides a particulate NU-88 molecular sieve, the particulate NU-88 molecular sieve produced by the method of the first aspect of the present disclosure.
Optionally, the particulate NU-88 molecular sieve comprises a spherical NU-88 molecular sieve; the particle size of the spherical NU-88 molecular sieve is 0.85-1.00 mm;
in the granular NU-88 molecular sieve, the weight percentage of the spherical NU-88 molecular sieve with the grain diameter of 0.85-1.00 mm is more than 95 percent.
Through the technical scheme, the granular NU-88 molecular sieve with larger particle size can be prepared by adopting the hexamethylene dichloride as the raw material, and the method has low cost and simple operation. When the crystallization reaction is finished and the solid-liquid separation is carried out on the molecular sieve, the large-particle solid is beneficial to the separation, the separation efficiency can be greatly improved, and the discharge of wastewater such as ammonia nitrogen, acid and the like caused by using a flocculating agent in the traditional method is avoided. In addition, the method can directly mix the contact reaction product obtained by the contact reaction of the hexamethylene dichloride, the N-methylpyrrolidine and the solvent with other raw materials for synthesizing the molecular sieve in a certain proportion without complicated processes such as high-cost separation, purification and the like, and synthesize the NU-88 molecular sieve through hydrothermal crystallization, thereby avoiding a great amount of time consumption, energy consumption and material consumption.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is an X-ray diffraction pattern of the NU-88 molecular sieve synthesized in example 1.
FIG. 2 is a photograph of NU-88 molecular sieve pellets synthesized in example 1.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a process for preparing a particulate NU-88 molecular sieve, the process comprising the steps of:
s1, mixing hexamethylene dichloride and N-methylpyrrolidine with a solvent, and carrying out contact reaction to obtain a contact reaction product;
s2, mixing the contact reaction product, an inorganic alkali source, an aluminum source and a silicon source with water to obtain a mixture, carrying out hydrothermal crystallization treatment on the mixture, and recovering a solid product;
in step S1, the conditions of the contact reaction are: the reaction temperature is 25-85 ℃ and the reaction time is 10-100 h;
the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.85-2.75): (2-22).
The inventors of the present disclosure unexpectedly found that: the method is characterized in that hexamethylene dichloride with lower reactivity is used as a raw material to synthesize a template agent 1, 6-bis (N-methylpyrrolidine) hexane chloride, and the template agent is mixed with other raw materials for synthesizing a molecular sieve to perform hydrothermal crystallization reaction to obtain a granular NU-88 molecular sieve, wherein the granular molecular sieve is obviously different from the powdery NU-88 molecular sieve prepared by the existing method in appearance, and the particle size is greatly improved.
The method omits complicated processes such as high-cost separation, purification and the like which are necessary for the conventional synthesis of the NU-88 molecular sieve template agent, avoids a great deal of time consumption, energy consumption and material consumption, and simultaneously, the price of the adopted hexamethylene dichloride is only about half of that of 1, 6-dibromohexane, so that the cost can be further reduced.
According to the disclosure, the hexa-methylene dichloride has a CAS number of 2163-00-0 and the structure is as follows:
according to the disclosure, the CAS number of the N-methylpyrrolidine is 120-94-5, and the structure is as follows:
in one embodiment of the present disclosure, in step S1, the solvent may be a common organic solvent and/or water as long as it is capable of being miscible with hexamethylene dichloride and/or N-methylpyrrolidine, for example, the solvent may be one or more selected from water, monohydric alcohol having 1 to 6 carbon atoms, ether having 4 to 6 carbon atoms, ketone having 3 to 6 carbon atoms, polyhydric alcohol having 2 to 4 carbon atoms, and ester having 3 to 6 carbon atoms; preferably, the solvent is one or more selected from water, monohydric alcohol with 1-4 carbon atoms, ether with 4-5 carbon atoms, ketone with 3-4 carbon atoms, polyhydric alcohol with 2-3 carbon atoms and ester with 3-4 carbon atoms; specifically, the solvent may be selected from water, methanol, ethanol, diethyl ether, acetone, and the like.
In one embodiment of the present disclosure, in step S1, the molar ratio of hexamethylene dichloride in terms of elemental chlorine, N-methylpyrrolidine in terms of elemental nitrogen, and solvent is 2: (1.85-2.75): (2 to 22), preferably 2: (1.95-2.5): (2 to 17), more preferably 2: (2.08-2.28): (3-13).
In one embodiment of the present disclosure, in step S1, the mixing manner of the hexamethylenedichloride, the N-methylpyrrolidine and the solvent may be conventional in the art, and preferably, the N-methylpyrrolidine may be mixed with the solvent first, and then the hexamethylenedichloride may be added dropwise to the obtained mixed solution, and the dropping speed may be 1 to 60 drops/second. The contact reaction can be carried out in a closed reaction kettle or a reaction kettle with a reflux device. The conditions of the contact reaction may preferably be: the temperature is 35-75 ℃ and the time is 15-80 h. In order to obtain the desired effect, the mixing and the contact reaction may be performed under stirring.
In one embodiment of the present disclosure, in step S2, the mixing manner of the contact reaction product, the inorganic alkali source, the aluminum source, the silicon source and the water may be conventional in the art, and preferably, the contact reaction product, the inorganic alkali source and the aluminum source may be dissolved in water to obtain a mixed solution; and then, under the stirring condition, the mixed solution is contacted with a silicon source to obtain a mixture. In the mixture, siO is used as 2 The silicon source is calculated as Al 2 O 3 The molar ratio of the aluminum source, the inorganic alkali source, the contact reaction product and water, calculated as hexamethylenedichloride, is 100: (0.66-10): (5-45): (5-50): (500 to 7000), preferably 100: (0.5-10): (10-40): (6-30): (600-5000).
In one embodiment of the present disclosure, in step S2, the inorganic alkali source, aluminum source, silicon source may be of conventional type used for synthesizing NU-88 molecular sieves. The inorganic alkali source contains alkali metal element, and the inorganic alkali source can be selected from NaOH, KOH, na 2 O、K 2 O、Na 2 CO 3 And K 2 CO 3 One or more of the following; the aluminum source may be selected from NaAlO 2 、Al(NO 3 ) 3 、Al 2 (SO 4 ) 3 、(CH 3 COO) 3 Al and Al [ (CH) 3 ) 2 CHO] 3 One or more of the following; the silicon source can be one or more selected from silica gel, silica sol, white carbon black and tetraethoxysilane.
In one embodiment of the present disclosure, in step S2, the hydrothermal crystallization process includes the steps of:
a. carrying out the first stage hydrothermal crystallization for 24-72 h at 135-145 ℃;
b. and performing the second stage hydrothermal crystallization at 175-185 ℃ for 48-120 h.
In order to promote the progress of the reaction, the hydrothermal crystallization may be performed under stirring.
In one embodiment of the present disclosure, the method further comprises: and (3) washing, filtering and drying the solid product after recovering the solid product. Wherein the washing, filtering and drying are conventional steps for synthesizing molecular sieves, and the conditions thereof are not particularly limited in the present disclosure. For example, the conditions of the drying may be: the temperature is 80-110 ℃ and the time is 10-24 h.
A second aspect of the present disclosure provides a particulate NU-88 molecular sieve, the particulate NU-88 molecular sieve produced by the method of the first aspect of the present disclosure.
In one embodiment of the present disclosure, the particulate NU-88 molecular sieve is formed primarily as spherical particles, i.e., the particulate NU-88 molecular sieve comprises a spherical NU-88 molecular sieve. Wherein the spherical NU-88 molecular sieve is similar to sphere in appearance. In other embodiments, the particulate NU-88 molecular sieve may be ellipsoidal, irregular, or the like.
In a further embodiment, the spherical NU-88 molecular sieve has a particle size of 0.85 to 1.00mm; in the granular NU-88 molecular sieve, the weight percentage of the spherical NU-88 molecular sieve with the grain diameter of 0.85-1.00 mm is more than 95%, for example, 95.1-97.6%. Wherein, the particle size of the spherical NU-88 molecular sieve is determined by a sieving method.
When the crystallization reaction is finished to carry out solid-liquid separation on the molecular sieve, the large-particle solid is beneficial to separation, the separation efficiency can be greatly improved, and the problems that in the traditional method, in order to facilitate filtration and separation, flocculant is added into the molecular sieve slurry after the crystallization reaction to flocculate, then the flocculant is filtered and washed to remove ammonia nitrogen emission or acid emission and a large amount of wastewater emission caused by the flocculant and the like are avoided. The prepared spherical NU-88 molecular sieve can be directly used as adsorbent or used as catalyst after modification.
The present disclosure is further illustrated by the following examples, which are not intended to limit the disclosure.
In examples and comparative examples, XRD analysis was carried out using a Japanese physics type D/MAX-IIIA diffractometer under the following test conditions: cu target, K alpha radiation, ni filter, tube voltage of 35kV, tube current of 35mA and scanning range 2 theta of 4-50 degrees;
the particle size of the spherical NU-88 molecular sieve was tested by screening with a sieve.
In the examples and comparative examples, the specifications and sources of the various reagents used were as follows:
NaOH, absolute ethyl alcohol, methanol and acetone are all analytically pure and produced by Beijing chemical plant;
hexamethylene dichloride, >98.0%, tokyo chemical industry Co., ltd;
1, 6-bis (N-methylpyrrolidine) hexane chloride aqueous solution having a solids content of 50% by weight, produced by the Guangzhou Kogyo having a fine plant;
n-methylpyrrolidine, >98.0 wt%, tokyo chemical industry co;
1, 6-dibromohexane, >98.0%, tokyo chemical industry strain;
NaAlO 2 solution of Al 2 O 3 The content of Na is 13.64 wt.% 2 O content was 20.2% by weight, manufactured by Kagaku Co., ltd;
solid silica gel, water content 7.1 wt%, produced by chinese petrochemical long-term catalyst division.
Examples 1-3 are presented to illustrate the method of synthesizing NU-88 molecular sieves of the present disclosure.
Example 1
58.8g of N-methylpyrrolidine and 114mL of absolute ethanol are mixed under stirring, 51.5g of hexamethylene dichloride is added dropwise to the mixed solution at a speed of 5 drops/second, and contact reaction is carried out for 60 hours at 65 ℃ to obtain a contact reaction product A1. The molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent ethanol is 2:2.08:5.88.
contact reaction product A1, 28.9g NaAlO 2 Dissolving 67.1g 30wt% NaOH solution in deionized water, mixing, slowly adding 150g solid silica gel under stirring to obtain milky colloid mixture with molar composition of SiO 2 ：Al 2 O 3 ：Na 2 O：A1：H 2 O=100: 1.66:18.5:14:1200, stirring for 1h, transferring to a 1L high-pressure reaction kettle with mechanical stirring. And (3) carrying out the first-stage hydrothermal crystallization for 24 hours at 142 ℃, then raising the temperature to 178 ℃, carrying out the second-stage hydrothermal crystallization for 96 hours, stopping the crystallization reaction, washing and filtering the product, and drying at 80 ℃ for 12 hours to obtain the small spherical molecular sieve B1. The morphology, particle size and synthesis cost are shown in Table 1.
XRD testing was performed after grinding of molecular sieve B1, and the spectra are shown in FIG. 1. B1 can be determined to be NU-88 molecular sieve by comparing the obtained XRD spectrum with the XRD spectrum of NU-88 molecular sieve disclosed in patent USP 6027707. A photograph of the small spherical molecular sieve B1 is shown in FIG. 2.
Example 2
NU-88 molecular sieves were synthesized according to the method of example 1, except that 61.6g of N-methylpyrrolidine and 72mL of acetone were mixed under stirring, and 51.5g of hexamethylenedichloride was added dropwise to the above mixed solution at a rate of 10 drops/sec, followed by contact reaction at 35℃for 80 hours to give contact reaction product A2. The molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent acetone is 2:2.18:3. the contact reaction product A2 is used for replacing A1, and the small spherical molecular sieve B2 is obtained.
After XRD test and spectrogram comparison, the molecular sieve B2 is determined to be NU-88 molecular sieve, and the morphology, particle size and synthesis cost are shown in Table 1.
Example 3
NU-88 molecular sieves were synthesized according to the method of example 1, except that 64.4g of N-methylpyrrolidine was mixed with 76mL of deionized water under stirring, 51.5g of hexamethylenedichloride was added dropwise to the above mixture at a rate of 20 drops/sec, and contact reaction was carried out at 75℃for 15 hours to give contact reaction product A3. The molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent water is 2:2.28:12.7. the contact reaction product A3 is used for replacing A1, and the molecular sieve pellets B3 are obtained.
After XRD test and spectrogram comparison, the molecular sieve B3 is determined to be NU-88 molecular sieve, and the morphology, particle size and synthesis cost are shown in Table 1.
Comparative example 1
This comparative example is for illustration of a process for synthesizing NU-88 molecular sieves using the precursors of the synthetic template 1, 6-bis (N-methylpyrrolidine) hexane bromide, N-methylpyrrolidine and 1, 6-dibromohexane, followed by a contact reaction, the reaction product being mixed with an inorganic source of alkalinity, an aluminum source, a silicon source and water, followed by a hydrothermal crystallization reaction.
58.8g of N-methylpyrrolidine and 114mL of absolute ethyl alcohol are mixed under stirring, 81g of 1, 6-dibromohexane is added into the mixed solution dropwise at the speed of 5 drops/second, and the contact reaction is carried out for 60 hours at the temperature of 65 ℃ to obtain a contact reaction product D. The mole ratio of 1, 6-dibromohexane calculated as bromine element, N-methylpyrrolidine calculated as nitrogen element and solvent ethanol is 2:2.08:5.88.
contact reaction product D, 28.9g NaAlO 2 Dissolving 67.1g 30wt% NaOH solution in deionized water, mixing, slowly adding 150g solid silica gel under stirring to obtain milky colloid mixture with molar composition of SiO 2 ：Al 2 O 3 ：Na 2 O：D：H 2 O=100: 1.66:18.5:14:1200, stirring was continued for 1h and transferred to a 1L autoclave with mechanical stirring. And (3) carrying out the first-stage hydrothermal crystallization for 24 hours at 142 ℃, then raising the temperature to 178 ℃, carrying out the second-stage hydrothermal crystallization for 96 hours, stopping the crystallization reaction, washing and filtering the product, and drying at 80 ℃ for 12 hours to obtain the molecular sieve raw powder E1. The morphology, particle size and synthesis cost are shown in Table 1.
XRD testing was performed on molecular sieve E1. Comparing the obtained XRD spectrum with the XRD spectrum of NU-88 molecular sieve disclosed in patent USP6027707, it can be determined that E1 is NU-88 molecular sieve.
Comparative example 2
The embodiment is used for explaining a method for synthesizing the NU-88 molecular sieve by taking 1, 6-bis (N-methylpyrrolidine) hexane chloride (represented by R) as a template agent, and the specific steps are as follows:
will be 28.9g NaAlO 2 The solution, 67.1mL30wt% NaOH solution, 211.59g 1, 6-bis (N-methylpyrrolidine) hexane chloride solution are dissolved in a proper amount of deionized water, and evenly mixed, 150g solid silica gel is slowly added under the condition of stirring, and a milky white colloid-like mixture is prepared, wherein the molar composition of the milky white colloid-like mixture is as follows: siO (SiO) 2 ：Al 2 O 3 ：Na 2 O：R：H 2 O=100: 1.66:18.5:14:1200, continuing stirring for 1h, transferring to a 1L high-pressure reaction kettle with mechanical stirring, carrying out hydrothermal crystallization at 142 ℃ for 24h, heating to 178 ℃ for hydrothermal crystallization for 96h, stopping crystallization reaction, washing and filtering a product, and drying at 80 ℃ for 12h to obtain the molecular sieve raw powder E2. After XRD test and spectrogram comparison, E2 can be determined to be NU-88 molecular sieve. The morphology, particle size and synthesis cost are shown in Table 1.
Comparative example 3
NU-88 molecular sieves were synthesized according to the method of example 1, except that 50.8g of N-methylpyrrolidine was mixed with 302mL of methanol under stirring, and 51.5g of hexamethylenedichloride was added dropwise to the above mixture at a rate of 30 drops/sec, followed by contact reaction at 60℃for 30 hours to give contact reaction product A4. The molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent methanol is 2:1.8:22.47. the contact reaction product A4 is used for replacing A1 to obtain molecular sieve raw powder E3, and the molecular sieve raw powder E3 can be determined to be NU-88 molecular sieve after XRD test and spectrogram comparison, and the morphology, the particle size and the synthesis cost are shown in Table 1.
Comparative example 4
NU-88 molecular sieves were synthesized as described in example 1, except that the molar ratio of hexamethylenedichloride as elemental chlorine, N-methylpyrrolidine as elemental nitrogen, and solvent ethanol was 2:2.08:1.8, obtaining molecular sieve raw powder E4, determining that E4 is NU-88 molecular sieve after XRD test and spectrogram comparison, and the morphology, particle size and synthesis cost are listed in Table 1.
Comparative example 5
NU-88 molecular sieves were synthesized as described in example 1, except that the molar ratio of hexamethylenedichloride as elemental chlorine, N-methylpyrrolidine as elemental nitrogen, and solvent ethanol was 2:2.8:6, obtaining molecular sieve raw powder E5, determining that E5 is NU-88 molecular sieve after XRD test and spectrogram comparison, and the morphology, particle size and synthesis cost are listed in Table 1.
TABLE 1
As can be seen from the data in Table 1, using the process of the present disclosure, a granular NU-88 molecular sieve can be produced that includes more than 95 wt.% spherical particles and is less costly to synthesize.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (7)
1. A process for preparing a particulate NU-88 molecular sieve, the process comprising the steps of:
s1, mixing hexamethylene dichloride and N-methylpyrrolidine with a solvent, and carrying out contact reaction to obtain a contact reaction product;
s2, mixing the contact reaction product, an inorganic alkali source, an aluminum source and a silicon source with water to obtain a mixture, carrying out hydrothermal crystallization treatment on the mixture, and recovering a solid product;
in step S1, the conditions of the contact reaction are: the reaction temperature is 25-85 ℃ and the reaction time is 10-100 h;
the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.85-2.75): (2-22);
in step S2, siO is used in the mixture 2 The silicon source is calculated as Al 2 O 3 Calculated as the aluminum source, in alkaliThe molar ratio of the inorganic alkali source calculated as metal oxide, the contact reaction product calculated as hexamethylene dichloride and water is 100: (0.66-10): (5-45): (5-50): (500-7000);
the hydrothermal crystallization treatment comprises the following steps:
a. performing first-stage hydrothermal crystallization for 24-72 h at 135-145 ℃;
b. performing the second-stage hydrothermal crystallization at 175-185 ℃ for 48-120 h;
the granular NU-88 molecular sieve comprises a spherical NU-88 molecular sieve;
the particle size of the spherical NU-88 molecular sieve is 0.85-1.00 mm;
in the granular NU-88 molecular sieve, the weight percentage of the spherical NU-88 molecular sieve with the particle size of 0.85-1.00 mm is more than 95%.
2. The method according to claim 1, wherein in the step S1, the solvent is one or more selected from the group consisting of water, monohydric alcohol having 1 to 6 carbon atoms, ether having 4 to 6 carbon atoms, ketone having 3 to 6 carbon atoms, polyhydric alcohol having 2 to 4 carbon atoms, and ester having 3 to 6 carbon atoms.
3. The method according to claim 1, wherein in step S1, the conditions of the contact reaction are: the reaction temperature is 35-75 ℃ and the reaction time is 15-80 h;
the molar ratio of hexamethylene dichloride calculated as chlorine element, N-methylpyrrolidine calculated as nitrogen element and solvent is 2: (1.95-2.5): (2-17).
4. The method according to claim 1, wherein in step S1, N-methylpyrrolidine is mixed with the solvent, and then hexamethylene dichloride is added dropwise to the resulting mixture.
5. The method according to claim 1, wherein in step S2, the inorganic alkali source contains an alkali metal element; the inorganic alkali source is selected from NaOH, KOH, na 2 O、K 2 O、Na 2 CO 3 And K 2 CO 3 One or more of the following;
the aluminum source is selected from NaAlO 2 、Al(NO 3 ) 3 、Al 2 (SO 4 ) 3 、(CH 3 COO) 3 Al and Al [ (CH) 3 ) 2 CHO] 3 One or more of the following;
the silicon source is one or more selected from silica gel, silica sol, white carbon black and tetraethoxysilane.
6. The method of claim 1, wherein the method further comprises: and (3) washing, filtering and drying the solid product after recovering the solid product.
7. A granular NU-88 molecular sieve, wherein the granular NU-88 molecular sieve is prepared by the method of any one of claims 1-6.
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