CN116692898A - Synthesis method of MWW molecular sieve - Google Patents
Synthesis method of MWW molecular sieve Download PDFInfo
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- CN116692898A CN116692898A CN202210177244.1A CN202210177244A CN116692898A CN 116692898 A CN116692898 A CN 116692898A CN 202210177244 A CN202210177244 A CN 202210177244A CN 116692898 A CN116692898 A CN 116692898A
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- 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 80
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 79
- 238000001308 synthesis method Methods 0.000 title claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004327 boric acid Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 33
- 230000032683 aging Effects 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 230000009977 dual effect Effects 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 238000001514 detection method Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 MCM-36 Chemical compound 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 101001011637 Dendroaspis polylepis polylepis Toxin MIT1 Proteins 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 2
- 229960003805 amantadine Drugs 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000804764 Homo sapiens Lymphotactin Proteins 0.000 description 1
- 102100035304 Lymphotactin Human genes 0.000 description 1
- 101100503363 Schistosoma mansoni SCM-2 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a method for synthesizing an MWW molecular sieve by using a double template agent, which belongs to the technical field of molecular sieve synthesis and specifically comprises the following steps: triethylene diamine and piperazine are used as double templates, a silicon source, an aluminum source, boric acid, sodium hydroxide and deionized water are used as raw materials, reactant gel is prepared after mixing, and then the crystallization molecular sieve is obtained through hydrothermal crystallization. The method breaks through the template agent related to the original synthesis system, can adjust the silicon-aluminum ratio by adjusting the proportion of the template agent and the content of the structure auxiliary agent, has lower toxicity in the synthesis process, lower synthesis cost and high product purity.
Description
Technical Field
The invention belongs to the technical field of MWW molecular sieve synthesis methods, and particularly relates to a low-cost low-toxicity method for synthesizing an MWW molecular sieve by using a double template agent.
Background
In 1990, the company Mobil used hexamethyl imine (HMI) as template agent synthesized a new high silicon molecular sieve MCM-22 for the first time (US 4954325); in 1994, leonowicz proposed a structural model of MCM-22 molecular sieves; the International molecular sieves Association (IZA) in 1997 has named the molecular sieve structure code MWW. The MWW molecular sieve has a layered structure, and layers are connected by oxygen bridges and are perpendicular to the c-axis of the unit cell. The MWW molecular sieve is provided with two independent pore systems which are not communicated with each other, one set is an intra-layer two-dimensional sinusoidal pore, and the effective aperture is a ten-membered ring (0.40 nm multiplied by 0.59 nm); the other set consists of a super cage (0.71 nm×1.82 nm) containing a ten-membered ring, and the opening of the super cage is also a ten-membered ring. The unique pore structure of the MWW molecular sieve enables the MWW molecular sieve to show the characteristics of 10MR and 12MR in certain catalytic reactions, and the MWW molecular sieve can be used independently or cooperatively in the reactions, so that different reaction sites can be provided for different catalytic reaction requirements. The MWW molecular sieve has good catalytic performance in the fields of catalytic cracking, olefin isomerization, hydrocarbon alkylation and the like, has realized industrialization of alkylation reaction of olefin and benzene (US 4992606, US 5334795), and has higher catalytic activity in reactions such as low-temperature toluene disproportionation reaction, 1-butene skeletal isomerization, isobutane/butene alkylation and the like. Following the MCM-22 molecular sieves, structural molecular sieves such as MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-2, SSZ-25, SSZ-70, PSH-3, ERB-1, IEZ-MWW, UZM-8, SCM-1, SCM-2, SCM-6, SRZ-21, EMM-10, EMM-12, EMM-13, ECNU-7, and MIT-1 were successively discovered and synthesized. The main difference between them is the difference in the degree of interlayer bonding. Different molecular sieves have different characteristics and therefore exhibit different catalytic properties in catalytic reactions.
MWW molecular sieve is synthesized mainly through dynamic or static hydrothermal crystallization, and the synthesis condition is relatively harsh. When the hydrothermal temperature is high, ZSM-5, ZSM-35 and the like can compete with the hydrothermal temperature for crystallization, and the crystal transformation can be promoted by prolonging the reaction time. In the comprehensive view, the dynamic crystallization condition is more controllable, and the product quality is more stable. The MCM-22 molecular sieve is synthesized by adopting a nitrogenous organic amine template agent. HMI is the highest frequency of use as the template agent originally reported. However, HMI is a highly toxic chemical and is a serious hazard to human body and environment. As research proceeds, the scope of templates involved in MWW systems is continually widened, as shown in table 1.
The MWW molecular sieves such as PSH-3, MCM-22, MCM-49, MCM-56, ITQ-1 and the like can be synthesized by taking HMI as a template agent. Trimethyl amantadine (TMAdaOH), piperidine (PI) and long chain quaternary ammonium salts are also common templates for the synthesis of Al-MWW molecular sieves. In addition, mobil reports that UZM-8 molecular sieve with MWW topological structure is synthesized by taking dimethyl diethyl ammonium hydroxide (DEDMAOH) as a template agent for the first time; and EMM-10 molecular sieves were first prepared from long chain bis-quaternary ammonium salts of bis (N, N-trimethyl) -1, 5-pentanediium bromide. The Chevron company uses N, N' -diisopropylimidazolium cations as a template agent to obtain the novel SSZ-70 molecular sieve. The Roman-Leshkov et al combines amantadine with long-chain quaternary ammonium salt by reasonably designing a template agent to obtain the MIT-1 molecular sieve with a single-layer structure. ITQ-30, which is typically present as a germanosilicate, can be synthesized from a relatively bulky and rigid templating agent as shown in Table 1.
Table 1 templates commonly used in MWW systems
Thus, the synthesis of the MWW molecular sieve still lacks a nontoxic or low-toxic template agent which is cheap and easily available. From the basic research and the practical application point of view, the new template agent is searched, and the expansion of the synthesis system of the MWW molecular sieve is very significant.
Disclosure of Invention
The invention aims to provide a method for synthesizing an MWW molecular sieve by using a boric acid-assisted double-template agent; the MWW molecular sieve is successfully synthesized by taking the mixture of triethylene diamine and piperazine as the template agent, the synthesis system of the MWW molecular sieve is expanded, and the synthesis cost and the environmental pollution are effectively reduced.
The synthesis method of the MWW molecular sieve provided by the invention comprises the following preparation steps:
(1) Uniformly mixing a silicon source, an aluminum source, boric acid, sodium hydroxide, deionized water and a dual-template agent to obtain gel A, wherein the molar ratio of various materials is xNa 2 O:SiO 2 :yAl 2 O 3 :zB 2 O 3 :wR 1 :vR 2 :sH 2 O；
Wherein R is 1 Is triethylene diamine, R 2 Piperazine, x=0.025-0.1, preferably 0.035-0.075; y=0.02-0.06, z=0.02-0.6, w=0.1-1.2, v=0.1-1.2, s=12.5-50.
(2) Aging gel A at 25-80deg.C for 0.5-24 hr, and then heating to 135-180deg.C for hydrothermal crystallization for 3-20 days;
(3) And (3) centrifuging the crystallized product in the step (2), washing to be neutral, drying, and calcining at 550 ℃ in an air atmosphere for 10 hours to remove the template agent, thereby obtaining the MWW molecular sieve. The silicon source is silica sol, and the aluminum source is sodium metaaluminate.
The aging process described in step 2 of the present invention: the aging temperature is 25-80 ℃, the optimized temperature is 30-70 ℃, and the more optimized temperature is 40-60 ℃; the aging time is 0.5-24 hours, the optimized time is 1-12 hours, and the more optimized time is 2-8 hours.
The hydrothermal crystallization process in the step 2 of the invention comprises the following steps: the crystallization temperature is 135-180deg.C, the optimized temperature is 140-165 deg.C, and the more optimized temperature is 150-160 deg.C; the crystallization time is 3-20 days, the optimization time is 5-15 days, and the more optimization time is 8-13 days.
The hydrothermal crystallization mode in the step 2 is dynamic crystallization, and the rotation speed is kept at 20-30 r/min.
The method breaks through the template agent related to the original synthesis system, can adjust the silicon-aluminum ratio by adjusting the proportion of the template agent and the content of the structure auxiliary agent, has lower toxicity in the synthesis process, lower synthesis cost and high product purity.
Drawings
FIG. 1 is an XRD spectrum of an MWW molecular sieve prepared in accordance with the present invention (example 4);
FIG. 2 is a scanning electron microscope image of the MWW molecular sieve prepared in accordance with the present invention (example 4);
description of the embodiments
The present invention is further illustrated by the following examples, but the application of the present invention is not limited by these examples.
The dynamic crystallization mode is implemented by adopting a commercially available homogeneous phase reactor capable of rotating along a central axis, and the specific structure of the dynamic crystallization mode can be described as follows: a horizontal rotating shaft is arranged in a reaction oven penetrating through the wall surface of the oven, a support (15 cm in arm length of the support) is fixed to the horizontal rotating shaft, a cylindrical hydrothermal reaction kettle with an inner diameter of 8cm is fixed to the support (one end of the support is fixed to the horizontal rotating shaft, the other end of the support is fixedly connected with the outer side wall surface of the middle part of the hydrothermal reaction kettle), the horizontal rotating shaft is driven by a motor to rotate, the reaction kettle in the oven is linked to perform circular motion (the axis of the reaction kettle rotates around the horizontal rotating shaft), and disturbance on reactants in the kettle can be achieved under the action of centrifugal force and gravity.
Example 1
Weighing 0.524g of sodium metaaluminate, 0.4g of sodium hydroxide and 36g of deionized water, and uniformly stirring until the mixture is clear; 10g of TEDA (R1) and 10g of PIP (R2) are added and stirred until dissolved; 0.4g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.02:0.035:0.024:0.667:0.872:20; aging at 25 ℃ for 24 hours; then heating to 145 ℃ in a homophase reactor, and dynamically crystallizing for 20 days at a rotating speed of 30 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 6 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 2 0.699g sodium metaaluminate, 0.45g sodium hydroxide, 18g deionized water were weighed and stirred evenly until clear; 12g of TEDA (R1) and 6g of PIP (R2) are added and stirred until dissolved; 0.45g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.027:0.041:0.027:0.750:0.523:12.5; aging at 40 ℃ for 10 hours; then heating to 150 ℃ in a homogeneous phase reactor, and dynamically crystallizing for 15 days at a rotating speed of 50 revolutions per minute; and centrifuging the product after crystallization, washing to be neutral, drying at 120 ℃ for 8 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 3
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; 15g of TEDA (R1) and 10g of PIP (R2) are added and stirred until dissolvedSolving; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.040:1:0.872:20; aging at 60 ℃ for 4 hours; then heating to 150 ℃ in a homogeneous phase reactor, and dynamically crystallizing for 12 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 4 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 4
1.180g of sodium metaaluminate, 0.55g of sodium hydroxide and 60g of deionized water are weighed and stirred uniformly until the mixture is clear; 10g of TEDA and 8.3g of PIP are added and stirred until dissolved; 2.0g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.046:0.062:0.122:0.668:0.724:30; aging at 50deg.C for 5 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 6 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 5
1.285g of sodium metaaluminate, 0.6g of sodium hydroxide and 78g of deionized water are weighed and stirred uniformly until the mixture is clear; 15g TEDA (R1), 10g PIP (R2), stirring to dissolve; 2.4g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.05:0.07:0.146:1:0.872:37.5; aging at 70 ℃ for 3 hours; then heating to 160 ℃ in a homophase reactor, dynamically crystallizing for 10 days, and rotating at 80 revolutions per minute; and centrifuging the product after crystallization, washing to be neutral, drying at 120 ℃ for 10 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 6
1.542g of sodium metaaluminate, 0.75g of sodium hydroxide and 102g of deionized water are weighed and stirred uniformly until the mixture is clear; 18g of TEDA (R1) and 13.8g of PIP (R2) are added and stirred until dissolved; 4.8g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.06:0.075:0.365:1.2:1.2:50; aging at 50deg.C for 5 hr; then heating to 160 ℃ in a homophase reactor, and dynamically crystallizing for 8 days at a rotating speed of 100 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 4 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 7
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; 10g of TEDA and 8.3g of PIP are added and stirred until dissolved; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.040:0.668:0.724:20; aging at 60 ℃ for 5 hours; then heating to 165 ℃ in a homophase reactor, and dynamically crystallizing for 7 days at a rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 5 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 8
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear;10g of TEDA and 13.8g of PIP are added and stirred until dissolved; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.040:0.668:1.2:20; aging at 30deg.C for 15 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 2 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Example 9
Weighing 0.774g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water, and uniformly stirring until the mixture is clear; 10g of TEDA and 9.6g of PIP are added and stirred until dissolved; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.030:0.047:0.040:0.668:0.840:20; aging at 40 ℃ for 10 hours; then heating to 165 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at a rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 12 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection shows that the MWW molecular sieve is obtained, and the MWW molecular sieve is pure MWW molecular sieve crystal.
Comparative example 1
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; 15g of TEDA and 10g of PIP are added and stirred until dissolved; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0:1:0.872:20; aging at 50deg.C for 3 hr; then heating to 155 ℃ in a homophase reactor, dynamically crystallizing for 10 days, and rotating at 60 turnsA/min; and centrifuging the product after crystallization, washing to be neutral, drying at 120 ℃ for 10 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD gave a crystalline mixture of 40% ZSM-5 and 60% ZSM-35 molecular sieves. It can be seen that the MWW molecular sieve cannot be obtained without boric acid as a crystallization aid.
Comparative example 2
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; 15g of TEDA are added and stirred until dissolved; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0:1:0:20; aging at 50deg.C for 3 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to be neutral, drying at 120 ℃ for 8 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection is carried out to obtain the ZSM-5 molecular sieve. It can be seen that only ZSM-5 molecular sieve can be obtained when boric acid is absent as a crystallization aid and only triethylenediamine is present.
Comparative example 3
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; adding 10g of PIP, and stirring until the PIP is dissolved; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0:0:0.872:20; aging at 50deg.C for 3 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 6 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection is carried out to obtain the ZSM-35 molecular sieve. It can be seen that the lack of boric acid as a crystallization aid, and only piperazine present, only a ZSM-35 molecular sieve was obtained.
Comparative example 4
0.874g of aluminum alloy is weighedSodium acid, 0.5g sodium hydroxide and 36g deionized water, and uniformly stirring until the mixture is clear; 15g of TEDA are added and stirred until dissolved; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.040:1:0:20; aging at 50deg.C for 3 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 12 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD gave a mixture of 30% ZSM-5 molecular sieve and 70% amorphous. Comparison of comparative example 2 shows that boric acid acts as a crystallization aid in the presence of only triethylenediamine, which is detrimental to the crystallization of the ZSM-5 molecular sieve.
Comparative example 5
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; adding 10g of PIP, and stirring until the PIP is dissolved; 0.66g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.040:0:0.872:20; aging at 50deg.C for 3 hr; then heating to 155 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 3 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection is carried out to obtain the ZSM-35 molecular sieve. It can be seen that when triethylenediamine is absent as a common template agent, the crystal is ZSM-35, and the MWW molecular sieve cannot be obtained.
Comparative example 6
Weighing 0.699g of sodium metaaluminate, 0.45g of sodium hydroxide and 18g of deionized water, and uniformly stirring until the mixture is clear; 12g of TEDA (R1) and 6g of PIP (R2) are added and stirred until dissolved; 9.2g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, stirringA gel is obtained, wherein the reactant gel composition is: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.027:0.041:0.7:0.750:0.523:12.5; aging at 40 ℃ for 10 hours; then heating to 150 ℃ in a homogeneous phase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 12 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection gave a 90% amorphous material and a 10% MWW molecular sieve crystal mixture. It can be seen that boric acid is added in an amount outside the range of the proportions described herein, which is detrimental to crystallization of the MWW molecular sieve.
Comparative example 7
0.874g of sodium metaaluminate, 0.5g of sodium hydroxide and 36g of deionized water are weighed and stirred uniformly until the mixture is clear; 25g of TEDA (template one) and 16g of PIP (template two) are added and stirred until dissolved; 2.4g boric acid is added and stirred until the solution is clear; 20g of SiO are added 2 Silica sol with 40wt% content, and stirring to obtain gel, wherein the reactant gel comprises the following components: siO (SiO) 2 :Al 2 O 3 :Na 2 O:B 2 O 3 :TEDA:PIP:H 2 O=1:0.034:0.047:0.146:1.667:1.395:20; aging at 70deg.C for 3 hr; then heating to 160 ℃ in a homophase reactor, and dynamically crystallizing for 10 days at the rotating speed of 60 revolutions per minute d; and centrifuging the product after crystallization, washing to neutrality, drying at 120 ℃ for 5 hours, and calcining at 550 ℃ for 10 hours in an air atmosphere to remove the template agent. XRD detection gave a mixture of 80% amorphous material and 20% MWW molecular sieve crystals. It can be seen that the addition of triethylenediamine and piperazine outside the ratio ranges described in this document is detrimental to the crystallization of the MWW molecular sieve.
Claims (5)
1. The synthesis method of the MWW molecular sieve is characterized by comprising the following steps of:
(1) Uniformly mixing a silicon source, an aluminum source, boric acid, sodium hydroxide, deionized water and a dual-template agent to obtain gel A, wherein the molar ratio of various materials is xNa 2 O:SiO 2 :yAl 2 O 3 :zB 2 O 3 :wR 1 :vR 2 :sH 2 O；
Wherein R is 1 Is triethylene diamine, R 2 Piperazine, R 1 And R is 2 Triethylenediamine (TEDA) and piperazine (PIP) in dual template agents, respectively; x=0.025-0.1, preferably 0.035-0.075, y=0.02-0.06, preferably 0.025-0.05, z=0.02-0.6 (preferably 0.05-0.5), w=0.1-1.2 (preferably 0.3-0.8), v=0.1-1.2 (preferably 0.3-0.8), s=12.5-50 (preferably 15-40);
(2) Aging gel A at 25-80deg.C for 0.5-24 hr, and then heating to 135-180deg.C for hydrothermal crystallization for 3-20 days;
(3) And (3) centrifuging the crystallized product in the step (2), washing to be neutral, drying, and calcining for 6-24 hours at 500-650 ℃ in an air atmosphere to remove the template agent, thereby obtaining the MWW molecular sieve.
2. The method of claim 1, wherein the silicon source in step (1) is silica sol and the aluminum source is sodium metaaluminate.
3. The method according to claim 1, wherein the hydrothermal crystallization in the step (2) is dynamic crystallization, and the rotation speed is maintained at 20-100 rpm.
4. The synthetic method of claim 1 wherein the aging process of step (2): the aging temperature is 25-80 ℃, the optimized temperature is 30-70 ℃, and the more optimized temperature is 40-60 ℃; the aging time is 0.5-24 hours, the optimized time is 1-10 hours, and the more optimized time is 2-6 hours.
5. The synthetic method of claim 1 wherein the hydrothermal crystallization process of step (2): the crystallization temperature is 135-180deg.C, the optimized temperature is 140-165 deg.C, and the more optimized temperature is 150-160 deg.C; the crystallization time is 3-20 days, the optimization time is 5-15 days, and the more optimization time is 8-13 days.
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