CN109592695A - ZSM-5 molecular sieve and its synthetic method - Google Patents
ZSM-5 molecular sieve and its synthetic method Download PDFInfo
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
The invention discloses a kind of ZSM-5 molecular sieve and its synthetic methods.Silicon source and silicon source are synthesized nucleation accelerating agent the following steps are included: S1 by the synthetic method；Waterglass, nucleation accelerating agent and water are mixed to form solution A by S2, and aluminum sulfate, sulfuric acid, organic formwork agent is soluble in water, form solution B；And S3, solution B is added in solution A and forms ZSM-5 molecular sieve synthetic system, is stirred evenly, crystallization obtains ZSM-5 molecular sieve.It applies the technical scheme of the present invention, SiO can be synthesized2/Al2O3High silica ZSM-5 molecular sieve greater than 90, and template dosage is few, generated time is short, low in raw material price, and product acidity and pore structure are suitable for.
Description
Technical field
The present invention relates to Zeolite synthesis technical fields, in particular to a kind of ZSM-5 molecular sieve and its synthesis side
Method.
Background technique
ZSM-5 molecular sieve is a kind of aluminosilicate zeolite molecular sieve developed by the Mobil Oil Corporation in the U.S., is belonged to
Hole series zeolite, because there is unique multidimensional ten-ring duct and hydrothermal stability to become preferred catalysis in shape-selective catalyst for it
Material is one of currently the most important ones molecular sieve catalytic material, is widely used in PETROLEUM PROCESSING, coal chemical industry and fine chemistry industry etc. and urges
Change field.
The synthetic method of ZSM-5 zeolite molecular sieve has very much, and raw material and proportion are also not quite similar.Commonplace synthesis side
Method is using hydrothermal synthesis method.Raw material uses the compound containing silicon and aluminium, matches can close from low silica-alumina ratio to total silicon
At out.In industrialized production, raw material generallys use the silicon source and silicon source of waterglass and aluminum sulfate as production, and process uses
Crystal seed method either template is oriented to method.There are many kinds of the classification for synthesizing ZSM-5 method, can generally be divided into: by crystallization ring
Border is divided into the synthesis of the modes such as hydrothermal system and non-hydrothermal system；It is divided into the conjunction of organic amine Yu inorganic amine system by Template Types
At etc..Although silicon source, silicon source, template used in these synthetic method processes etc. is not quite similar, synthesis is all benefit
The structural rearrangement of sial forms the generation of ZSM-5 crystal.The ZSM-5 molecular sieve of low silica-alumina ratio can not use organic mould
It is synthesized under conditions of plate agent, but high silica ZSM-5 zeolite synthesis then needs a large amount of organic materials as template.JP08272128
ZSM-5 zeolite molecular sieve is just successfully synthesized with dry gel method.CN201210531577.6 is introduced with solid phase transformation mechanism
The research of foundation, the extremely dense system of progress and non-hydrothermal system demonstrates the feasibility of non-hydrothermal system method.It finds under study for action
Gu phase transition method has solid yields height, the high many advantages of crystal structure degree.EP85308747A describes organic-free template
Synthesize ZSM-5 method, and find silica alumina ratio and sodium aluminium ratio be the key that synthesis.It is only 20 in silica alumina ratio, sodium aluminium ratio is
When 2.25, available ZSM-5 pure phase.When sial is relatively low (< 10), product is the mixed of ZSM-5 and a small amount of modenite (MOR)
Close phase；When silica alumina ratio increases, it may appear that the mixed phase of ZSM-5 and alpha-quartz；When silica alumina ratio is especially high (> 80), it can not obtain
ZSM-5, what is obtained is the mixed phase of modenite and alpha-quartz；If silicon source is not added when feeding intake, product if is partially-crystallized
Alpha-quartz.Chen Bingyi etc. has successfully synthesized ZSM-5 molecule using waterglass as silicon source, by the primary raw material of silicon source of aluminum sulfate
Sieve.Result of study shows within the scope of certain temperature, is that can synthesize ZSM-5 using inorganic amine such as ammonium hydroxide as template
Zeolite molecular sieve.It also can successfully synthesize ZSM-5 molecular sieve with other inorganic amines, and the spectrogram of its XRD is essentially identical, tie
Brilliant degree is higher, substantially similar in terms of catalytic performance.CN200510028781.6 is described adds self-control in hydrothermal synthesis system
Seeding director is successfully prepared nano-sized ZSM-5 zeolite, has investigated seeding director, crystallization temperature and synthetic system sial substance
Amount compare synthesis nano-sized ZSM-5 zeolite influence.The seeding director of preparation is the Silicalite-1 zeolite nanometer of total silicon
The SiO of particle, zeolite primary or secondary structure unit2And the mixed colloidal solution of template TPAOH, the results showed that,
Seeding director is added in ZSM-5 zeolite preparation system can effectively reduce the usage amount of organic formwork agent, shorten crystallization time, and
The ZSM-5 zeolite of nano-scale can be obtained, crystallization temperature is reduced and synthetic system silica alumina ratio is conducive to reduce nano-sized ZSM-5 zeolite
Crystalline size.Bai Weidong of Liaoming Petrochemical Univ et al. is prepared for the ZSM-5 catalysis of Template-free method using hydrothermal synthesis method
Agent, the best conditions of preparation pr ocess are as follows: in 45 DEG C of aging 48h, and in 190 DEG C of crystallization 73h.The ZSM-5 phase prepared with this condition
It is 96.82% to crystallinity.After 600 DEG C of roastings, the skeleton of Template-free method ZSM-5 does not collapse, but ZSM-5 feature peak intensity drops
It is low, and there is the skeleton structure of template ZSM-5 to be changed.Institutes Of Technology Of Nanjing reports organic-free template system at high mountain etc.
The ZSM-5 molecular sieve of standby 15nm out, and be crystal seed dip-coating in porous α-A1 using it2O3Ceramic tube outer surface, then it is dense rear dilute with elder generation
The crystallization liquid hydrothermal synthesis of organic-free template goes out the new method of ZSM-5 molecular sieve film.The amount group of the substance of crystal seed and crystallization liquid
As 12Na2O:100SiO2: 2A12O3: (2500~5000) H2O.CN201210535629.7 is described using RUB-50 zeolite
As crystal seed, aperture LEV zeolite has successfully been synthesized under a small amount of alcoholic environment.Pass through XRD, N2The analysis means pairings such as absorption
It is characterized at the product gone out, the results showed that the molecular sieve has good crystallinity, high-specific surface area, regular crystal knot
Structure, Al3+Tetrahedral structure and acid site abundant.Promote molecular sieve crystal growth with nucleation accelerating agent, a small amount of template is added
There is not been reported for the synthetic method of the crystallization of promotion zeolite.
It can be seen that developing, a kind of synthesis process is simple, high silica ZSM-5 molecule environmentally friendly and with lower cost
Sieve material synthesis method is to expand the key point of its application.
Summary of the invention
The present invention is intended to provide a kind of ZSM-5 molecular sieve and its synthetic method, simple to provide a kind of process, to environment friend
Synthetic method good and with lower cost.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of synthesis side of ZSM-5 molecular sieve
Method.Silicon source and silicon source are synthesized nucleation accelerating agent the following steps are included: S1 by the synthetic method；S2 promotes waterglass, nucleation
Agent and water are mixed to form solution A, and aluminum sulfate, sulfuric acid, organic formwork agent is soluble in water, form solution B；And S3, by solution B
It is added in solution A and forms ZSM-5 molecular sieve synthetic system, stir evenly, crystallization obtains ZSM-5 molecular sieve.
Further, S1 is specifically included: after mixing by silicon source, silicon source and organic formwork agent, lye, 130~200
DEG C plastic 10~50 hours, it is dried to obtain nucleation accelerating agent later.
Further, silicon source be one of aluminium isopropoxide, aluminium oxide, sodium chlorate, aluminum sulfate, aluminum nitrate or Aluminum sol or
Several mixtures；Silicon source is the mixture of one or more of Silica hydrogel, silica solution, white carbon black, waterglass.
Further, lye is sodium fluoride or sodium chloride solution.
Further, SiO in nucleation accelerating agent2/Al2O3Control is between 80~120.
Further, SiO in the nucleation accelerating agent synthetic system that silicon source, silicon source and organic formwork agent, lye are formed2、
Al2O3, template, alkali salt, water molar ratio be 1:0.005-0.02:0.05-0.30:0.1-0.5:20-50, preferably 1:
0.005-0.01:0.05-0.15:0.1-0.3:30-50.
Further, S2 is specifically included: it is molten that formation in 0.1~0.5 hour is mixed in waterglass, nucleation accelerating agent and water
Liquid A, by aluminum sulfate, sulfuric acid, organic formwork agent 0.1~0.5 hour formation solution B of stirring soluble in water.
Further, the additional amount of nucleation accelerating agent be ZSM-5 molecular sieve synthetic system dioxide-containing silica 0.5~
5%.
Further, in S3, the temperature of crystallization is 130~200 DEG C；The time of crystallization is 25~40 hours.
Further, machine template is tetraethylammonium bromide or 4-propyl bromide, dosage Br/SiO2=0.005~
0.20。
Further, SiO in ZSM-5 molecular sieve synthetic system2、Al2O3, template, acid, water, nucleation accelerating agent mole
Than for 1:0.002-0.01:0.05-0.30:0.01-0.05:10-50:0.01-0.05, preferably 1:0.003-0.005:0.1-
0.2:0.01-0.03:10-30:0.02-0.04, more preferably 1:0.0045:0.15:0.02:16.5:0.03.
Further, the mol ratio of each component is SiO in ZSM-5 molecular sieve synthetic system2/Al2O3=200-500,
Na2O/SiO2=0.05-0.30, H2O/SiO2=10-30,
According to another aspect of the present invention, a kind of ZSM-5 molecular sieve is provided.The ZSM-5 molecular sieve is by the above-mentioned side of synthesis
Method is prepared.
It applies the technical scheme of the present invention, SiO can be synthesized2/Al2O3High silica ZSM-5 molecular sieve greater than 90, and template
Agent dosage is few, and generated time is short, low in raw material price, and product acidity and pore structure are suitable for.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the SEM figure of 1 product of comparative example；
Fig. 2 shows the SEM of 2 product of comparative example figures；
Fig. 3 shows the SEM figure of 1 product of embodiment；
Fig. 4 shows the SEM figure of 2 product of embodiment；
Fig. 5 shows the SEM figure of 3 product of embodiment；
Fig. 6 shows the SEM figure of 4 product of embodiment.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
A kind of typical embodiment according to the present invention, provides a kind of synthetic method of ZSM-5 molecular sieve.The synthetic method
The following steps are included: S1, synthesizes nucleation accelerating agent for silicon source and silicon source；Waterglass, nucleation accelerating agent and water are mixed to form by S2
Solution A, aluminum sulfate, sulfuric acid, organic formwork agent is soluble in water, form solution B；And S3, shape in solution A is added in solution B
It at ZSM-5 molecular sieve synthetic system, stirs evenly, crystallization obtains ZSM-5 molecular sieve.
It applies the technical scheme of the present invention, SiO can be synthesized2/Al2O3High silica ZSM-5 molecular sieve greater than 90, and because
Nucleation accelerating agent of the invention has efficient guiding role, can promote the quick formation of sial oxygen key bridge, and be oriented to and to be formed
Crystalline structure, template dosage is few, and generated time is short, low in raw material price, and product acidity and pore structure are suitable for.
A kind of typical embodiment, S1 are specifically included according to the present invention: by silicon source, silicon source and organic formwork agent, lye
After mixing, 130~200 DEG C plastic 10~50 hours, be dried to obtain nucleation accelerating agent later.
Preferably, silicon source is one of aluminium isopropoxide, aluminium oxide, sodium chlorate, aluminum sulfate, aluminum nitrate or Aluminum sol or several
The mixture of kind；Silicon source is the mixture of one or more of Silica hydrogel, silica solution, white carbon black, waterglass.
Preferably, lye is sodium fluoride or sodium chloride solution.
Preferably, SiO in nucleation accelerating agent2/Al2O3Control is between 80~120.
Preferably, SiO in the nucleation accelerating agent synthetic system that silicon source, silicon source and organic formwork agent, lye are formed2、Al2O3、
Template, alkali salt, water molar ratio be 1:0.005-0.02:0.05-0.30:0.1-0.5:20-50, preferably 1:0.005-
0.01:0.05-0.15:0.1-0.3:30-50.
A kind of typical embodiment, S2 are specifically included according to the present invention: waterglass, nucleation accelerating agent and water being mixed and stirred
0.1~0.5 hour formation solution A is mixed, aluminum sulfate, sulfuric acid, organic formwork agent stirring soluble in water are formed for 0.1~0.5 hour
Solution B.
Preferably, the additional amount of nucleation accelerating agent is the 0.5~5% of system dioxide-containing silica.
Preferably, in S3, the temperature of crystallization is 130~200 DEG C；The time of crystallization is 25~40 hours.
Preferably, machine template is tetraethylammonium bromide or 4-propyl bromide, dosage Br-/SiO2=0.005~
0.20。
A kind of typical embodiment according to the present invention, SiO in ZSM-5 molecular sieve synthetic system2、Al2O3, template,
Acid, water, nucleation accelerating agent molar ratio be 1:0.002-0.01:0.05-0.30:0.01-0.05:10-50:0.01-0.05, it is excellent
It is selected as 1:0.003-0.005:0.1-0.2:0.01-0.03:10-30:0.02-0.04, more preferably 1:0.0045:0.15:
0.02:16.5:0.03.
Preferably, the mol ratio of each component is SiO in the ZSM-5 molecular sieve synthetic system2/Al2O3=200-500,
Na2O/SiO2=0.05-0.30, H2O/SiO2=10-30.
A kind of typical embodiment according to the present invention, provides a kind of ZSM-5 molecular sieve.The ZSM-5 molecular sieve is by above-mentioned
Synthetic method is prepared.The molecular sieve synthesized by means of the present invention is applied to catalytic cracking catalyst and xylene isomerization
Change and shows preferable activity and selectivity in catalyst.
In the present invention, SiO2And Al2O3Refer to the SiO in hydrothermal synthesis system in silicon source and silicon source used2And Al2O3Contain
Amount.Silicon source and silicon source can be commercial product, can also make by oneself.Washing, separation, drying are conventional method；Or, including following step
It is rapid: it filters or is centrifugated, it is 1~5 hour dry at 110 DEG C.
The present invention synthesizes SiO2/Al2O3High silica ZSM-5 molecular sieve greater than 90, raw material is cheap, and consumption of template agent is few,
The pattern and particle size of product can be adjusted by changing organic formwork agent and nucleation accelerating agent dosage.
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
In following embodiment and each comparative example, the measurement of the relative crystallinity of molecular sieve uses X-ray powder diffraction
Method measurement, reference sample are comparison counter sample；The pattern of sample partial size is measured by scanning electron microscope；Plasma atomic-emission
The silica alumina ratio of spectrographic determination sample.
Comparative example 1
By 0.5 gram of aluminum sulfate octadecahydrate and 10 milliliters of 4.0molL-1Sulfuric acid dissolution is slow by the solution in 54 grams of water
It is added dropwise to 58.8 grams of waterglass (SiO2, 28.5%；Sodium oxide molybdena, 9.0%) in, 2.2 grams of (SiO of tetraethylammonium bromide are added2/
Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=33, TEA-/SiO2=0.06, wherein TEA- be tetraethyl ammonium from
Son), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 40 hours, crystallinity is set as 100%, and pattern and partial size are big
It is small as shown in Figure 1, inductively coupled plasma atomic emission spectrometry measures its SiO2/Al2O3Than being 90.
The preparation of 2 nucleation accelerating agent A of comparative example: it by 1.77 grams of aluminum sulfate octadecahydrates and is dissolved in 59 grams of water, by 16.13
Gram silica white is dissolved in 100 grams of water, and 0.67 gram of 3.39 grams of tetraethylammonium bromide, sodium fluoride (SiO is added2/Al2O3=100,
Na2O/SiO2=0.12, H2O/SiO2=33, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 150 DEG C of crystallization
30 hours, obtain nucleation accelerating agent A.Relative crystallinity 102%, pattern and particle size are as shown in Fig. 2, inductively coupled plasma is former
Its SiO of sub- emission spectrometry2/Al2O3Than being 82.
It is by 0.7 gram of aluminum sulfate octadecahydrate and 13 milliliters of 4.0molL-1 sulfuric acid dissolutions in 20 grams of water, the solution is slow
It is added dropwise to 70 grams of waterglass (SiO2, 28.5%；Sodium oxide molybdena, 9.0%) in, 1.4 grams of tetraethylammonium bromide is added and nucleation promotes
0.29 gram of (SiO of agent2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein
TEA- is tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, relative crystallinity 104%,
Pattern and particle size are as shown in Fig. 2, inductively coupled plasma atomic emission spectrometry measures its SiO2/Al2O3Than being 92.
Embodiment 1
The nucleation accelerating agent used is with comparative example 2: by 0.73 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 17 grams of water, which is slowly added dropwise to 48 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%) in, it is added
0.15 gram of (SiO of 1.54 grams of tetraethylammonium bromide and nucleation accelerating agent A2/Al2O3=220, Na2O/SiO2=0.085, H2O/
SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175
DEG C crystallization 30 hours, relative crystallinity 102%, pattern and particle size were as shown in figure 3, inductively coupled plasma atomic emissions light
Spectrum measures its SiO2/Al2O3Than being 90.
Embodiment 2
The nucleation accelerating agent used is with comparative example 2: by 0.73 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 17 grams of water, which is slowly added dropwise to 48 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%) in, it is added
0.30 gram of (SiO of 1.54 grams of tetraethylammonium bromide and nucleation accelerating agent A2/Al2O3=220, Na2O/SiO2=0.085, H2O/
SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175
DEG C crystallization 30 hours, relative crystallinity 104%, pattern and particle size were as shown in figure 4, inductively coupled plasma atomic emissions light
Spectrum measures its SiO2/Al2O3Than being 92.
Embodiment 3
The nucleation accelerating agent used is with comparative example 2: by 0.73 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 17 grams of water, which is slowly added dropwise to 48 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%) in, it is added
0.45 gram of (SiO of 1.54 grams of tetraethylammonium bromide and nucleation accelerating agent A2/Al2O3=220, Na2O/SiO2=0.085, H2O/
SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175
DEG C crystallization 30 hours, relative crystallinity 105%, pattern and particle size were as shown in figure 5, inductively coupled plasma atomic emissions light
Spectrum measures its SiO2/Al2O3Than being 92.
Embodiment 4
The nucleation accelerating agent used is with comparative example 2: by 0.84 gram of aluminum sulfate octadecahydrate and 14 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 96 grams of water, which is slowly added dropwise to 50 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%) in, it is added
0.36 gram of (SiO of 2.65 grams of tetraethylammonium bromide and nucleation accelerating agent A2/Al2O3=200, Na2O/SiO2=0.15, H2O/SiO2
=28, TEA-/SiO2=0.05, wherein TEA- be tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175 DEG C of crystallization
30 hours, relative crystallinity 96%, pattern and grain size were as shown in fig. 6, inductively coupled plasma atomic emission spectrometry measures
Its SiO2/Al2O3Than being 88.
Embodiment 5
The nucleation accelerating agent used is with comparative example 2: by 0.30 gram of aluminum sulfate octadecahydrate and 16 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 71 grams of water, which is slowly added dropwise to 50 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%) in, it is added
0.42 gram of (SiO of 1.62 grams of tetraethyl bromination and nucleation accelerating agent A2/Al2O3=500, Na2O/SiO2=0.10, H2O/SiO2=
22, TEA-/SiO2=0.03, wherein TEA- be tetraethyl ammonium ion), stir 1 hour, after mixing uniformly after in 175 DEG C of crystallization 30
Hour, relative crystallinity 88%, inductively coupled plasma atomic emission spectrometry measures its SiO2/Al2O3Than being 152.
Embodiment 6
The preparation of nucleation accelerating agent B: by 0.95 gram of aluminum sulfate octadecahydrate and being dissolved in 34 grams of water, and 54 grams of silica solution are molten
0.86 gram of 3.62 grams of tetraethylammonium bromide, sodium chloride (SiO is added in 100 grams of water in solution2/Al2O3=200, Na2O/SiO2=
0.1, H2O/SiO2=33, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 150 DEG C crystallization 30 hours, obtain into
Core accelerant B.Relative crystallinity 98%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 101.
By 0.73 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1 sulfuric acid dissolutions in 10 grams of water, by 48 grams of water glass
Glass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%), 1.54 grams of tetraethylammonium bromide and 0.15 gram of nucleation accelerating agent B are dissolved in 7 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 20 hours,
Relative crystallinity 100%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 94.
Embodiment 7
The nucleation accelerating agent used is with embodiment 4: by 0.73 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 10 grams of water, by 48 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%), 1.54 grams of tetraethylammonium bromide and at
0.30 gram of core accelerant B is dissolved in (SiO in 7 grams of water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5,
TEA-/SiO2=0.03, wherein TEA- is tetraethyl ammonium ion), two solution are mixed after mixing evenly, are stirred 1 hour, mixing
Afterwards uniformly after in 175 DEG C crystallization 30 hours, relative crystallinity 102%, inductively coupled plasma atomic emission spectrometry measures it
SiO2/Al2O3Than being 93.
Embodiment 8
The nucleation accelerating agent used is with embodiment 4: by 6.6 grams of aluminum sulfate octadecahydrates and 17 milliliters of 4.0molL-1Sulfuric acid is molten
Solution is in 50 grams of water, by 48 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%), 1.54 grams of tetraethylammonium bromide and nucleation
0.37 gram of accelerant B is dissolved in (SiO in 23 grams of water2/Al2O3=100, Na2O/SiO2=0.09, H2O/SiO2=23, TEA-/
SiO2=0.03, wherein TEA-For tetraethyl ammonium ion), two solution are mixed after mixing evenly, are stirred 1 hour, after mixing uniformly
Afterwards in 175 DEG C crystallization 30 hours, relative crystallinity 98%, inductively coupled plasma atomic emission spectrometry measures its SiO2/Al2O3
Than being 90.
Embodiment 9
The nucleation accelerating agent used is with embodiment 4: by 0.84 gram of aluminum sulfate octadecahydrate and 16 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 26 grams of water, by 50 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%), 1.60 grams of tetraethylammonium bromide and at
0.38 gram of core accelerant B is dissolved in (SiO in 10 grams of water2/Al2O3=200, Na2O/SiO2=0.10, H2O/SiO2=16.5,
TEA-/SiO2=0.03, wherein TEA-For tetraethyl ammonium ion), two solution are mixed after mixing evenly, are stirred 1 hour, mixing
Afterwards uniformly after in 175 DEG C crystallization 30 hours, relative crystallinity 87%, inductively coupled plasma atomic emission spectrometry measures it
SiO2/Al2O3Than being 86.
Embodiment 10
The nucleation accelerating agent used is with embodiment 4: by 0.30 gram of aluminum sulfate octadecahydrate and 14 milliliters of 4.0molL-1Sulfuric acid
It is dissolved in 60 grams of water, by 50 grams of waterglass (SiO2, 30.5%；Sodium oxide molybdena, 11.5%), 1.60 grams of tetraethylammonium bromide and at
0.36 gram of core accelerant B is dissolved in (SiO in 21 grams of water2/Al2O3=500, Na2O/SiO2=0.15, H2O/SiO2=24,
TEA-/SiO2=0.03, wherein TEA-For tetraethyl ammonium ion), two solution are mixed after mixing evenly, are stirred 1 hour, mixing
Afterwards uniformly after in 175 DEG C crystallization 30 hours, relative crystallinity 92%, inductively coupled plasma atomic emission spectrometry measures it
SiO2/Al2O3Than being 132.
Embodiment 11
The preparation of nucleation accelerating agent C: by 1.17 grams of aluminum sulfate octadecahydrates and being dissolved in 35 grams of water, and 60 grams of silica solution are molten
1.92 grams of 4.0 grams of tetraethylammonium bromide, sodium chloride (SiO is added in 100 grams of water in solution2/Al2O3=180, Na2O/SiO2=
0.1, H2O/SiO2=33, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 150 DEG C crystallization 30 hours, obtain into
Core accelerant C, relative crystallinity 98%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 116.
By 0.78 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1 sulfuric acid dissolutions in 10 grams of water, by 69 grams of water glass
Glass (SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.32 gram of nucleation accelerating agent C are dissolved in 9 grams
(SiO in water2/Al2O3=200, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 102%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 88.
Embodiment 12
The preparation of nucleation accelerating agent D: it by 1.36 grams of aluminum sulfate octadecahydrates and is dissolved in 42 grams of water, by 18.62 grams of silica gel
Powder is dissolved in 100 grams of water, and 1.86 grams of 3.9 grams of tetraethylammonium bromide, sodium chloride (SiO is added2/Al2O3=150, Na2O/SiO2
=0.2, H2O/SiO2=25, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 150 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent D, relative crystallinity 99%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 96.
By 0.70 gram of aluminum sulfate octadecahydrate and 15 milliliters of 4.0molL-1 sulfuric acid dissolutions in 20 grams of water, by 69 grams of water glass
Glass (SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.26 gram of nucleation accelerating agent D are dissolved in 29
(SiO in gram water2/Al2O3=180, Na2O/SiO2=0.10, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 96%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 105.
Embodiment 13
The preparation of nucleation accelerating agent E: it by 4.08 grams of aluminum sulfate octadecahydrates and is dissolved in 50 grams of water, by 18.62 grams of silica gel
Powder is dissolved in 85 grams of water, and 2.09 grams of 3.9 grams of tetraethylammonium bromide, sodium chloride (SiO is added2/Al2O3=50, Na2O/SiO2=
0.24, H2O/SiO2=22, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 150 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent E, relative crystallinity 96%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 46.
By 0.86 gram of aluminum sulfate octadecahydrate and 19 milliliters of 4.0molL-1Sulfuric acid dissolution is in 13.4 grams of water, by 69 grams of water glass
Glass (SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 20 grams are dissolved in for 1.54 grams and E0.18 grams of nucleation accelerating agent of tetraethylammonium bromide
(SiO in water2/Al2O3=250, Na2O/SiO2=0.08, H2O/SiO2=18, TEA-/SiO2=0.03, wherein TEA- is tetrem
Base ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, relatively
Crystallinity 94%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 91.
Embodiment 14
The preparation of nucleation accelerating agent F: by 0.96 gram of aluminum sulfate octadecahydrate and being dissolved in 80 grams of water, and 60 grams of silica solution are molten
1.21 grams of 3.3 grams of tetraethylammonium bromide, sodium chloride (SiO is added in 160 grams of water in solution2/Al2O3=220, Na2O/SiO2=
0.15, H2O/SiO2=50, TEA-/SiO2=0.05), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent F, relative crystallinity 99%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 104.
By 0.78 gram of aluminum sulfate octadecahydrate and 18 milliliters of 4.0molL-1 sulfuric acid dissolutions in 10 grams of water, by 69 grams of water glass
Glass (SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.26 gram of nucleation accelerating agent C are dissolved in 9 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.095, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 99%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 96.
Embodiment 15
The preparation of nucleation accelerating agent G: by 1.17 grams of aluminum sulfate octadecahydrates and being dissolved in 49 grams of water, and 60 grams of silica solution are molten
2.42 grams of 4.0 grams of tetraethylammonium bromide, sodium chloride (SiO is added in 100 grams of water in solution2/Al2O3=180, Na2O/SiO2=
0.3, H2O/SiO2=33, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, obtain into
Core promotor G, relative crystallinity 92%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 92.
By 0.98 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid dissolution is in 26 grams of water, by 69 grams of waterglass
(SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.35 gram of nucleation accelerating agent C are dissolved in 30 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 96%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 92.
Embodiment 16
The preparation of nucleation accelerating agent H: it by 1.02 grams of aluminum sulfate octadecahydrates and is dissolved in 67 grams of water, by 18.62 grams of silica gel
Powder is dissolved in 100 grams of water, and 3.91 grams of 4.0 grams of tetraethylammonium bromide, sodium chloride (SiO is added2/Al2O3=200, Na2O/SiO2
=0.5, H2O/SiO2=30, TEA-/SiO2=0.06), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent H, relative crystallinity 88%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 95.
By 0.98 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid dissolution is in 26 grams of water, by 69 grams of waterglass
(SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.32 gram of nucleation accelerating agent C are dissolved in 30 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 92%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 95.
Embodiment 17
The preparation of nucleation accelerating agent I: it by 0.93 gram of aluminum sulfate octadecahydrate and is dissolved in 84 grams of water, by 18.62 grams of silica gel
Powder is dissolved in 100 grams of water, and 1.56 grams of 9.76 grams of tetraethylammonium bromide, sodium chloride (SiO is added2/Al2O3=220, Na2O/SiO2
=0.2, H2O/SiO2=33, TEA-/SiO2=0.15), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent I, relative crystallinity 90%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 101.
By 0.98 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid dissolution is in 26 grams of water, by 69 grams of waterglass
(SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.36 gram of nucleation accelerating agent C are dissolved in 30 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 98%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 104.
Embodiment 18
The preparation of nucleation accelerating agent J: it by 0.85 gram of aluminum sulfate octadecahydrate and is dissolved in 95 grams of water, by 18.62 grams of silica gel
Powder is dissolved in 100 grams of water, and 19.53 grams of 4.0 grams of tetraethylammonium bromide, sodium chloride (SiO is added2/Al2O3=240, Na2O/SiO2
=0.15, H2O/SiO2=35, TEA-/SiO2=0.3), stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours, obtain
Nucleation accelerating agent J, relative crystallinity 90%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 108.
By 0.98 gram of aluminum sulfate octadecahydrate and 17 milliliters of 4.0molL-1Sulfuric acid dissolution is in 26 grams of water, by 69 grams of waterglass
(SiO2, 28.5%；Sodium oxide molybdena, 9.01%), 1.54 grams of tetraethylammonium bromide and 0.29 gram of nucleation accelerating agent C are dissolved in 30 grams
(SiO in water2/Al2O3=220, Na2O/SiO2=0.085, H2O/SiO2=16.5, TEA-/SiO2=0.03, wherein TEA- be
Tetraethyl ammonium ion), after mixing evenly by two solution mix, stir 1 hour, after mixing uniformly after in 175 DEG C crystallization 30 hours,
Relative crystallinity 95%, inductively coupled plasma atomic emission spectrometry measure its SiO2/Al2O3Than being 98.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Compared with the prior art, synthetic system provided by the invention has used for reference the technology of Solid phase synthesis molecular sieve, exploitation
The synthetic system of ultrahigh concentration, water consumption is few, energy needed for heating systems is smaller, facilitate it is energy saving, after reaction
Soiling solution discharge amount greatly reduces, and has huge advantage in environmental protection.
Compared with the prior art, synthetic system provided by the invention can achieve rapid synthesis (such as embodiment 6), improve
Production efficiency reduces energy consumption.
Zeolite product prepared by the present invention can be used for catalytic cracking (corresponding SiO2/Al2O3Molar ratio 28-250) and two
Toluene isomerization (corresponding SiO2/Al2O3Molar ratio 150-400), there is preferable activity and selectivity.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of synthetic method of ZSM-5 molecular sieve, which comprises the following steps:
Silicon source and silicon source are synthesized nucleation accelerating agent by S1；
Waterglass, the nucleation accelerating agent and water are mixed to form solution A, aluminum sulfate, sulfuric acid, organic formwork agent are dissolved in by S2
In water, solution B is formed；And
The solution B is added in the solution A and forms ZSM-5 molecular sieve synthetic system, stirs evenly, crystallization, obtain institute by S3
State ZSM-5 molecular sieve.
2. synthetic method according to claim 1, which is characterized in that the S1 is specifically included: by silicon source, silicon source with it is organic
Template, lye after mixing, 130~200 DEG C plastic 10~50 hours, be dried to obtain the nucleation accelerating agent later.
3. synthetic method according to claim 1 or 2, which is characterized in that source of aluminium is aluminium isopropoxide, aluminium oxide, chlorine
The mixture of one or more of sour sodium, aluminum sulfate, aluminum nitrate or Aluminum sol；The silicon source is Silica hydrogel, silica solution, hard charcoal
The mixture of one or more of black, waterglass.
4. synthetic method according to claim 2, which is characterized in that the lye is sodium fluoride or sodium chloride solution.
5. synthetic method according to claim 2, which is characterized in that SiO in the nucleation accelerating agent2/Al2O3Control exists
Between 80~120.
6. synthetic method according to claim 2, which is characterized in that the silicon source, silicon source and organic formwork agent, lye shape
At nucleation accelerating agent synthetic system in SiO2、Al2O3, template, alkali salt, water molar ratio be 1:0.005-0.02:0.05-
0.30:0.1-0.5:20-50, preferably 1:0.005-0.01:0.05-0.15:0.1-0.3:30-50.
7. synthetic method according to claim 1, which is characterized in that the S2 is specifically included: by the waterglass, described
Nucleation accelerating agent and water, which are mixed 0.1~0.5 hour, forms the solution A, and aluminum sulfate, sulfuric acid, organic formwork agent are dissolved in
It is stirred 0.1~0.5 hour in water and forms the solution B.
8. synthetic method according to claim 1, which is characterized in that the additional amount of the nucleation accelerating agent is the ZSM-
The 0.5~5% of 5 Zeolite synthesis system dioxide-containing silicas.
9. synthetic method according to claim 1, which is characterized in that in the S3, the temperature of crystallization is 130~200 DEG C；
The time of crystallization is 25~40 hours.
10. synthetic method according to claim 1 or 2, which is characterized in that the machine template be tetraethylammonium bromide or
4-propyl bromide, dosage Br/SiO2=0.005~0.20.
11. synthetic method according to claim 1, which is characterized in that SiO in the ZSM-5 molecular sieve synthetic system2、
Al2O3, template, acid, water, nucleation accelerating agent molar ratio be 1:0.002-0.01:0.05-0.30:0.01-0.05:10-50:
0.01-0.05, preferably 1:0.003-0.005:0.1-0.2:0.01-0.03:10-30:0.02-0.04, more preferably 1:
0.0045:0.15:0.02:16.5:0.03.
12. synthetic method according to claim 1, which is characterized in that each component in the ZSM-5 molecular sieve synthetic system
Mol ratio be SiO2/Al2O3=200-500, Na2O/SiO2=0.05-0.30, H2O/SiO2=10-30.
13. a kind of ZSM-5 molecular sieve, which is characterized in that the synthetic method as described in any one of claims 1 to 12 is prepared into
It arrives.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269340A (en) * | 2008-04-30 | 2008-09-24 | 复旦大学 | High silicon-aluminum ratio ZSM-5 zeolite catalyst, preparation method and application thereof |
| CN101898767A (en) * | 2010-07-20 | 2010-12-01 | 华东师范大学 | Synthetic method of high silica ZSM-5 zeolite |
| CN102730712A (en) * | 2012-07-24 | 2012-10-17 | 黑龙江大学 | Preparation method of nano GaZSM-5 molecular sieve |
| CN106904634A (en) * | 2015-12-22 | 2017-06-30 | 中国石油天然气股份有限公司 | A kind of ZSM-5 molecular sieve and its synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269340A (en) * | 2008-04-30 | 2008-09-24 | 复旦大学 | High silicon-aluminum ratio ZSM-5 zeolite catalyst, preparation method and application thereof |
| CN101898767A (en) * | 2010-07-20 | 2010-12-01 | 华东师范大学 | Synthetic method of high silica ZSM-5 zeolite |
| CN102730712A (en) * | 2012-07-24 | 2012-10-17 | 黑龙江大学 | Preparation method of nano GaZSM-5 molecular sieve |
| CN106904634A (en) * | 2015-12-22 | 2017-06-30 | 中国石油天然气股份有限公司 | A kind of ZSM-5 molecular sieve and its synthetic method |
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