CN106608637B - A method of synthesis STT structure molecular screen - Google Patents
A method of synthesis STT structure molecular screen Download PDFInfo
- Publication number
- CN106608637B CN106608637B CN201510708494.3A CN201510708494A CN106608637B CN 106608637 B CN106608637 B CN 106608637B CN 201510708494 A CN201510708494 A CN 201510708494A CN 106608637 B CN106608637 B CN 106608637B
- Authority
- CN
- China
- Prior art keywords
- crystallization
- gained
- silicon source
- aluminium
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses it is a kind of synthesize STT structure molecular screen method, this method comprises: a, organic formwork agent is mixed with silicon source after carry out hydro-thermal process, obtain body containing aluminium glue；Wherein, the mol ratio of the template and the silicon source in terms of aluminium oxide is (1-100): 1；B, gained body containing aluminium glue in step a is mixed with silicon source, water, is obtained to crystallization mixture；Wherein, in terms of oxide and in mol, it is described to silica alumina ratio in crystallization mixture be (10-1000): 1, water silicon ratio be (5-300): 1, on the basis of the gross mass to crystallization mixture, the content to alkali metal in crystallization mixture is less than 1000ppm；C, gained in step b is subjected to Crystallizing treatment to crystallization mixture, obtains crystallization product；D, gained crystallization product in step c is filtered, obtains filtrate and filter cake；E, gained filter cake in step d is dried and is roasted, obtain STT structure molecular screen.Method flow of the invention is simple and discharges without nitrogenous, fluoride waste.
Description
Technical field
The present invention relates to a kind of methods for synthesizing STT structure molecular screen.
Background technique
STT structure molecular screen is a kind of zeolitic material containing heptatomic ring and nine-atomic ring simultaneously, with specific dimensions, shape
The cellular structure of shape, good absorption property and selects type, while it is with biggish specific surface area and adjustable Acidity,
It is widely used in gas separation and catalysis reaction.
US4,859,442 disclose a kind of method for synthesizing STT structure molecular screen, using adamantane quaternary ammonium ion as template
Template, silicon source, silicon source, alkali metal salt and water are uniformly mixed at 140~200 DEG C hydrothermal crystallizing 3~7 days, are had by agent
The molecular sieve of STT structure.Product and NH4NO3Then exchange obtains the STT structure molecular screen of Hydrogen, exchange process by roasting
A large amount of nitrogenous effluents are generated, environmental protection of enterprise pressure is huge.
US8512674 is with N, N, N- trimethyl -1- adamantyl ammonium hydroxide and 1,4- diazabicylo [2.2.2] octane
Dication is as template, and fluorine ion is as mineralizer, by template, fluorine ion, silicon source, silicon source and water when synthesis of molecular sieve
It is uniformly mixed the hydrothermal crystallizing at 125~200 DEG C, a large amount of fluoride waste, enterprise can be generated during entire system with molecular sieve for preparing is standby
Environmental protection pressure is huge.
Summary of the invention
The object of the present invention is to provide a kind of method for synthesizing STT structure molecular screen, this method process it is simple and without it is nitrogenous,
Fluoride waste discharge.
To achieve the goals above, the present invention provides a kind of method for synthesizing STT structure molecular screen, this method comprises: a,
Hydro-thermal process is carried out after organic formwork agent is mixed with silicon source, obtains body containing aluminium glue；Wherein, the template in terms of aluminium oxide
Silicon source mol ratio be (1-100): 1；B, gained body containing aluminium glue in step a is mixed with silicon source, water, is obtained mixed to crystallization
Close object；Wherein, in terms of oxide and in mol, described to silica alumina ratio in crystallization mixture is (10-1000): 1, water silicon ratio is
(5-300): 1, on the basis of the gross mass to crystallization mixture, the content to alkali metal in crystallization mixture is less than
1000ppm；C, gained in step b is subjected to Crystallizing treatment to crystallization mixture, obtains crystallization product；D, by gained in step c
Crystallization product is filtered, and obtains filtrate and filter cake；E, gained filter cake in step d is dried and is roasted, obtain STT structure
Molecular sieve.
Preferably, on the basis of the gross mass to crystallization mixture, to alkali gold in crystallization mixture described in step b
The content of category is less than 500ppm.
Preferably, this method further include: gained filtrate in step d is used for described in preparation steps b to crystallization mixture.
Preferably, the organic formwork agent is selected from N, N, N- trimethyl -1- adamantane-based compound, quinuclidine-3-alcohol
Compound and N, N, at least one of N- trimethyl benzyl compound.
Preferably, the organic formwork agent is N, N, N- trimethyl -1- adamantammonium compound and/or N, N, N- front three
Base benzyl ammonium compounds.
Preferably, source of aluminium is selected from metallic aluminium, boehmite, boehmite, gibbsite, aluminium hydroxide, oxygen
Change at least one of aluminium and aluminum alcoholate.
Preferably, the condition of hydro-thermal process described in step a are as follows: temperature is 45-190 DEG C, and the time is 0.5-50 hours, water
The state of heat treatment is air-tight state.
Preferably, silicon source described in step b is selected from silicate, silica, silicic acid, silica gel, clay and silester
At least one of.
Preferably, silicon source described in step b is selected from silica gel, fume colloidal silica, precipitated silica and silester
At least one of.
Preferably, the condition of Crystallizing treatment described in step c are as follows: temperature is 120-190 DEG C, and the time is 1-10 days, crystallization
The state of processing is air-tight state.
Preferably, condition dry described in step e are as follows: temperature is 50-120 DEG C, and the time is 6-24 hours；In step e
The condition of the roasting are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
Compared with prior art, the method that the present invention synthesizes Hydrogen STT molecular sieve eliminates alkali metal ion exchange process,
Synthesis process is short, and production cost is low, discharges without nitrogenous, fluoride waste, free from environmental pollution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD spectra of STT structure molecular screen S-1 prepared by the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method for synthesizing STT structure molecular screen, this method comprises: a, by organic formwork agent and silicon source
Hydro-thermal process is carried out after mixing, obtains body containing aluminium glue；Wherein, the template and the mol ratio of the silicon source in terms of aluminium oxide are
(1-100): 1, preferably (2-60): 1；B, gained body containing aluminium glue in step a is mixed with silicon source, water, obtains mixing to crystallization
Object；Wherein, in terms of oxide and in mol, described to silica alumina ratio in crystallization mixture is (10-1000): 1, preferably (15-
600): 1, water silicon ratio is (5-300): 1, preferably (6-100): 1, on the basis of the gross mass to crystallization mixture, institute
It states and is less than 1000ppm, preferably smaller than 500ppm to the content of alkali metal in crystallization mixture；C, by gained in step b to crystallization
Mixture carries out Crystallizing treatment, obtains crystallization product；D, gained crystallization product in step c is filtered, obtains filtrate and filter
Cake；E, gained filter cake in step d is dried and is roasted, obtain STT structure molecular screen.
According to the present invention, in order to make full use of the organic formwork agent and water in the filtrate, this method can also include: by
Gained filtrate is used for described in preparation steps b to crystallization mixture in step d.It should be noted that being mixed in step b to crystallization
Water contained by object can come from organic formwork agent, silicon source or silicon source, when can also be in the case where moisture deficit, in step
It is additionally carried out water supplement in b, need to only water silicon ratio be made to meet condition.
According to the present invention, the organic formwork agent, silicon source and silicon source can use commonly used in the art, but in order to make
Described to be lower than 1000ppm to sodium content in crystallization mixture, organic formwork agent of the invention, silicon source and silicon source preferably do not contain alkali
Metal, for example, the organic formwork agent can be for selected from N, N, N- trimethyl -1- adamantane-based compound, quinuclidine-3-alcohol
Close at least one of object and N, N, N- trimethyl benzyl compound, preferably N, N, N- trimethyl -1- adamantyl ammonium chemical combination
Object and/or N, N, N- trimethyl benzyl ammonium compounds；Source of aluminium can for selected from metallic aluminium, boehmite, boehmite,
At least one of gibbsite, aluminium hydroxide, aluminium oxide and aluminum alcoholate；Silicon source described in step b can be for selected from silicic acid
At least one of salt, silica, silicic acid, silica gel, clay and silester, be preferably selected from silica gel, fume colloidal silica,
At least one of precipitated silica and silester.
Unlike the prior art, organic formwork agent and silicon source are first carried out hydro-thermal process by method of the invention, thus
Achieve the purpose that be completely dissolved silicon source, the condition of hydro-thermal process described in step a of the present invention is preferred are as follows: temperature 45-190
DEG C, the time is 0.5-50 hours, and preferably 2-45 hours, the state of hydro-thermal process was air-tight state.
According to the present invention, the condition of Crystallizing treatment described in step c can use this field normal condition, for example, step c
Described in the condition of Crystallizing treatment can be with are as follows: temperature is 120-190 DEG C, and preferably 60-170 DEG C, the time is 1-10 days, preferably
2-8 days, more preferably 2.5-4 days, the state of Crystallizing treatment are air-tight state.
According to the present invention, dry and roasting described in step e is the conventional use of molecular sieve processing of those skilled in the art
Method, dry condition described in step e can be with are as follows: temperature is 50-120 DEG C, and the time is 6-24 hours；It is roasted described in step e
The condition of burning can be with are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
Adopt the molecular sieve with STT structure being obtained by the present invention, SiO2/Al2O3Molar ratio can be 7-
600, it can have 1000ppm or hereinafter, it is preferred that 500ppm or alkali metal content below, especially sodium content, opposite to tie
Brilliant degree at least should be 90%.
Below by embodiment, the present invention will be further described, but content not thereby limiting the invention.
In embodiment, the chemical composition of molecular sieve is measured by x-ray fluorescence method, and specific method is referring to " with EU1 molecular sieve
ZSM-11 molecular sieve and its characterization are synthesized for crystal seed ", Geng Chenchen etc., " petroleum refining and chemical industry ", 2011,7.
The national standard method side GB/T15337-2008 is used to alkali metal in crystallization mixture (measurement sodium and potassium) content
Method is measured.
Relative crystallinity as described in the examples is prepared with the inventive method product and STT structure molecular screen mark
2 θ of X-ray diffraction (XRD) spectrogram of sample are in 8.18 °, 9.52 °, the sum of 10.57 ° of the peak area of three characteristic diffraction peaks
Ratio is indicated with percentage.XRD is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 millis
Peace, scanning speed are 2 °/minute.Using US4, the STT structure molecular screen of the method synthesis of embodiment 5 is standard specimen in 859,442,
Its crystallinity is set to 100%.
The BET surface area of sample is measured using GB/T 5816-1995 standard method.
Embodiment 1-11 illustrates Zeolite synthesis method provided by the invention.
Embodiment 1
Weigh 1.53g boehmite (Chang Ling catalyst plant, Al2O3Content 75%), by itself and 261g N, N, N- front three
Base -1- adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, mixing
Object molar ratio TMAA/Al2O3=33.It places it in the crystallizing kettle containing polytetrafluoro lining, it is cold after 100 DEG C are reacted 41 hours
But to room temperature, by itself and 6.86g silica gel (Qingdao Marine Chemical Co., Ltd., SiO2Content 98.4%) it mixes and is mixed with 3.11g water
It closes, mixture molar ratio SiO2/Al2O3=10, TMAA/SiO2=3.3, H2O/SiO2=92, alkali metal content 416ppm.It is mixed
Object is closed in a high pressure reaction kettle in 150 DEG C of progress hydrothermal crystallizing 160h.Molecular sieve dries after being filtered, washed in 120 DEG C after crystallization
4 hours dry, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-1.
The XRD spectra of molecular sieve S-1 is as shown in Figure 1, its relative crystallinity 92%, BET surface area 442m2/ g, sial
Than 8.
Embodiment 2
Weighing 2.87g aluminium hydroxide, (Beijing Chemical Plant analyzes pure, Al2O3Content 35%), by itself and 2.56g quinuclidine-
3- alcohol (Quinuclidinol, Wuxi Helen Biotechnology Co., Ltd, purity 98%) mixing, mixture molar ratio
Quinuclidinol/Al2O3=2.It places it in the crystallizing kettle containing polytetrafluoro lining, it is cold after 128 DEG C are reacted 30 hours
But to room temperature, later by itself and 24g silica gel (Qingdao Marine Chemical Co., Ltd., SiO2Content 98.4%) and 40.45g water it is mixed
It closes, mixture molar ratio SiO2/Al2O3=40, TMAA/SiO2=0.05, H2O/SiO2=6, alkali metal content 368ppm.It is mixed
Object is closed in a high pressure reaction kettle in 135 DEG C of progress hydrothermal crystallizing 188h.Molecular sieve dries after being filtered, washed in 120 DEG C after crystallization
5 hours dry, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-2.
The XRD spectra of the present embodiment S-2 molecular sieve is similar with Fig. 1.The crystallinity 90% of molecular sieve S-2, BET surface area are
413m2/ g, silica alumina ratio 30.
Embodiment 3
Weigh 3.13g aluminium oxide (Chang Ling catalyst plant, Al2O3Content 98%), by itself and 1058gN, N, N- trimethyl -1-
Adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, mixture mole
Compare TMAA/Al2O3=50.It places it in the crystallizing kettle containing polytetrafluoro lining, after 150 DEG C are reacted 10 hours, is cooled to room
Temperature, later by itself and 359g silica gel (Qingdao Marine Chemical Co., Ltd., SiO2Content 98.4%) and the mixing of 563g water, mixture
Molar ratio SiO2/Al2O3=196, TMAA/SiO2=0.26, H2O/SiO2=12, alkali metal content 238ppm.Mixture exists
In 165 DEG C of progress hydrothermal crystallizing 96h in autoclave.Molecular sieve is small in 120 DEG C of drying 24 after being filtered, washed after crystallization
When, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-3.
The XRD spectra of the present embodiment S-3 molecular sieve is similar with Fig. 1.The crystallinity 95% of molecular sieve S-3, BET surface area are
481m2/ g, silica alumina ratio 161.
Embodiment 4
Weigh 0.53g boehmite (Chang Ling catalyst plant, Al2O3Content 75%), by itself and 153.49gN, N, N- tri-
Methyl-1-adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, is mixed
Close object molar ratio TMAA/Al2O3=56.It places it in the crystallizing kettle containing polytetrafluoro lining, is reacted 0.5 hour in 185 DEG C
Afterwards, it is cooled to room temperature, later by itself and 188.95g fume colloidal silica (Shenyang Chemical Co., Ltd., SiO2Content
99%) it is mixed with 1950g water, mixture molar ratio SiO2/Al2O3=800, TMAA/SiO2=0.07, H2O/SiO2=37, alkali
Tenor is 411ppm.Mixture is in a high pressure reaction kettle in 140 DEG C of progress hydrothermal crystallizing 170h.Molecular sieve passes through after crystallization
Filter, filtrate return to crystallization process, dry 20 hours, 550 DEG C of roasting 6h after Washing of Filter Cake in 120 DEG C, obtain product Hydrogen STT knot
Structure molecular sieve S-4.
The XRD spectra of the present embodiment S-4 molecular sieve is similar with Fig. 1.The crystallinity 98% of molecular sieve S-4, BET surface area are
530m2/ g, silica alumina ratio 720.
Embodiment 5
Weigh 0.13g boehmite (Chang Ling catalyst plant, Al2O3Content 75%), by the filter of itself and 800g embodiment 4
Liquid and mixing, mixture molar ratio TMAA/Al2O3=87.It places it in the crystallizing kettle containing polytetrafluoro lining, it is anti-in 120 DEG C
It after answering 22 hours, is cooled to room temperature, later by itself and 25.98g fume colloidal silica (Shenyang Chemical Co., Ltd., SiO2
Content 99%) mixing, mixture molar ratio SiO2/Al2O3=110, TMAA/SiO2=0.79, H2O/SiO2=102, alkali metal
Content is 352ppm.Mixture is in a high pressure reaction kettle in 155 DEG C of progress hydrothermal crystallizing 150h.After crystallization molecular sieve through filtering,
It is dried 20 hours after washing in 120 DEG C, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-5.
The XRD spectra of the present embodiment S-5 molecular sieve is similar with Fig. 1.The crystallinity 91% of molecular sieve S-5, BET surface area are
390m2/ g, silica alumina ratio 92.
Embodiment 6
Weighing 0.27g aluminium hydroxide, (Beijing Chemical Plant analyzes pure, Al2O3Content 35%), by itself and 13.68gN, N, N-
Trimethyl -1- adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing,
Mixture molar ratio TMAA/Al2O3=21.It places it in the crystallizing kettle containing polytetrafluoro lining, is reacted 43 hours in 80 DEG C
Afterwards, it is cooled to room temperature, later by itself and 53.80g precipitated silica (Zhejiang Jian Fa Chemical Co., Ltd., SiO2Content 93%)
It is mixed with 3588.93g water, mixture molar ratio SiO2/Al2O3=900, TMAA/SiO2=0.02, H2O/SiO2=240, alkali gold
Category content is 233ppm.Mixture is in a high pressure reaction kettle in 180 DEG C of progress hydrothermal crystallizing 60h.After crystallization molecular sieve through filtering,
It is dried 12 hours after washing in 120 DEG C, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-6.
The XRD spectra of the present embodiment S-6 molecular sieve is similar with Fig. 1.The crystallinity 99% of molecular sieve S-6, BET surface area are
521m2/ g, silica alumina ratio 810.
Embodiment 7
Weigh 1g aluminium oxide (Chang Ling catalyst plant, Al2O3Content 98%), by itself and 594.66gN, N, N- trimethyl -1-
Adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, mixture mole
Compare TMAA/Al2O3=88.It places it in the crystallizing kettle containing polytetrafluoro lining, after 145 DEG C are reacted 24 hours, is cooled to room
Temperature, later by itself and 247.94g precipitated silica (Zhejiang Jian Fa Chemical Co., Ltd., SiO2Content 93%) and 949.87g
Water mixing, mixture molar ratio SiO2/Al2O3=400, TMAA/SiO2=0.22, H2O/SiO2=20, alkali metal content is
117ppm.Mixture is in a high pressure reaction kettle in 190 DEG C of progress hydrothermal crystallizing 26h.After crystallization molecular sieve after being filtered, washed in
120 DEG C dry 24 hours, and 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-7.
The XRD spectra of the present embodiment S-7 molecular sieve is similar with Fig. 1.The crystallinity 92% of molecular sieve S-7, BET surface area are
423m2/ g, silica alumina ratio 361.
Embodiment 8
Weigh 0.31g boehmite (Chang Ling catalyst plant, Al2O3Content 75%), by itself and 99.40gN, N, N- front three
Base -1- adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, mixing
Object molar ratio TMAA/Al2O3=62.It places it in the crystallizing kettle containing polytetrafluoro lining, it is cold after 160 DEG C are reacted 9 hours
But to room temperature, later by itself and 38.23g precipitated silica (Zhejiang Jian Fa Chemical Co., Ltd., SiO2Content 93%) and
The mixing of 567.64g water, mixture molar ratio SiO2/Al2O3=260, TMAA/SiO2=0.24, H2O/SiO2=60, alkali metal contains
Amount is 192ppm.Mixture is in a high pressure reaction kettle in 125 DEG C of progress hydrothermal crystallizing 230h.Molecular sieve is filtered, is washed after crystallization
It is dried 24 hours after washing in 120 DEG C, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-8.
The XRD spectra of the present embodiment S-8 molecular sieve is similar with Fig. 1.The crystallinity 95% of molecular sieve S-8, BET surface area are
481m2/ g, silica alumina ratio 253.
Embodiment 9
Weigh 1.05g aluminium oxide (Chang Ling catalyst plant, Al2O3Content 98%), by itself and 96.41gN, N, N- trimethyl benzyl
Base ammonium hydroxide (Shanghai Mai Ruier chemical technology Co., Ltd, purity 98%) mixing, mixture molar ratio TMBA/Al2O3=
56.It places it in the crystallizing kettle containing polytetrafluoro lining, after 180 DEG C are reacted 0.6 hour, is cooled to room temperature, later by it
It is mixed with 103.76g silester (Zhangjiagang new Asia Chemical Co., Ltd., content >=98%) and 2955.83g water, mixture rubs
You compare SiO2/Al2O3=72, TMAA/SiO2=0.77, H2O/SiO2=99, alkali metal content 371ppm.Mixture is in high pressure
In 185 DEG C of progress hydrothermal crystallizing 50h in reaction kettle.After crystallization molecular sieve after being filtered, washed in 120 DEG C dry 24 hours, 550
DEG C roasting 6h, obtain product Hydrogen STT structure molecular screen S-9.
The XRD spectra of the present embodiment S-9 molecular sieve is similar with Fig. 1.The crystallinity 92% of molecular sieve S-9, BET surface area are
430m2/ g, silica alumina ratio 66.
Embodiment 10
Weigh 0.16g boehmite (Chang Ling catalyst plant, Al2O3Content 75%), by itself and 81.09gN, N, N- front three
Base -1- adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) mixing, mixing
Object molar ratio TMAA/Al2O3=98.It places it in the crystallizing kettle containing polytetrafluoro lining, it is cold after 65 DEG C are reacted 44 hours
But later that it is mixed with 5.29g silester (Zhangjiagang new Asia Chemical Co., Ltd., content >=98%) and 0.2g water to room temperature
It closes, mixture molar ratio SiO2/Al2O3=30, TMAA/SiO2=3.27, H2O/SiO2=90, alkali metal content 137ppm.
Mixture in a high pressure reaction kettle in 190 DEG C of progress hydrothermal crystallizings for 24 hours.Molecular sieve dries after being filtered, washed in 120 DEG C after crystallization
24 hours dry, 550 DEG C of roasting 6h obtain product Hydrogen STT structure molecular screen S-10.
The XRD spectra of the present embodiment S-10 molecular sieve is similar with Fig. 1.The crystallinity 98% of molecular sieve S-10, BET surface area
For 518m2/ g, silica alumina ratio 27.
Embodiment 11
0.12g aluminium powder (8 57 new material Co., Ltd of Chengdu core, content 99.52%) is weighed, by itself and 28.00gN,
N, N- trimethyl -1- adamantyl ammonium hydroxide (Sichuan Zhong Bang development in science and technology Co., Ltd analyzes pure, TMAA content 30%) are mixed
It closes, mixture molar ratio TMAA/Al2O3=18.It places it in the crystallizing kettle containing polytetrafluoro lining, it is small in 50 DEG C of reactions 49
Shi Hou is cooled to room temperature, later that it is mixed with 7.63g silester (Zhangjiagang new Asia Chemical Co., Ltd., content >=98%)
It closes, mixture molar ratio SiO2/Al2O3=23, TMAA/SiO2=0.78, H2O/SiO2=21, alkali metal content 99ppm.It is mixed
Object is closed in a high pressure reaction kettle in 150 DEG C of progress hydrothermal crystallizing 72h.Molecular sieve is dried after being filtered, washed in 120 DEG C after crystallization
24 hours, 550 DEG C of roasting 6h obtained product Hydrogen STT structure molecular screen S-11.
The XRD spectra of the present embodiment S-11 molecular sieve is similar with Fig. 1.The crystallinity 95% of molecular sieve S-11, BET surface area
For 467m2/ g, silica alumina ratio 18.
Claims (11)
1. a kind of method for synthesizing STT structure molecular screen, this method comprises:
A, hydro-thermal process is carried out after mixing organic formwork agent with silicon source, obtains body containing aluminium glue；Wherein, the template with oxygen
The mol ratio for changing the silicon source of aluminium meter is (1-100): 1；
B, gained body containing aluminium glue in step a is mixed with silicon source, water, is obtained to crystallization mixture；Wherein, in terms of oxide and with
Mole meter, described to silica alumina ratio in crystallization mixture is (10-1000): 1, water silicon ratio is (5-300): and 1, with described mixed to crystallization
On the basis of the gross mass for closing object, the content to alkali metal in crystallization mixture is less than 1000ppm；
C, gained in step b is subjected to Crystallizing treatment to crystallization mixture, obtains crystallization product；
D, gained crystallization product in step c is filtered, obtains filtrate and filter cake；
E, gained filter cake in step d is dried and is roasted, obtain STT structure molecular screen.
2. the method according to claim 1, wherein on the basis of the gross mass to crystallization mixture, described in step b to
The content of alkali metal is less than 500ppm in crystallization mixture.
3. the method according to claim 1, this method further include: by step d gained filtrate be used for described in preparation steps b to
Crystallization mixture.
4. the method according to claim 1, wherein the organic formwork agent is selected from N, N, N- trimethyl -1- adamantyl
Close at least one of object, quinuclidine-3-alcohol compound and N, N, N- trimethyl benzyl compound.
5. the method according to claim 1, wherein the organic formwork agent is N, N, N- trimethyl -1- adamantyl ammonium chemical combination
Object and/or N, N, N- trimethyl benzyl ammonium compounds.
6. the method according to claim 1, wherein source of aluminium is selected from metallic aluminium, boehmite, boehmite, three water
At least one of aluminium stone, aluminium hydroxide, aluminium oxide and aluminum alcoholate.
7. the method according to claim 1, wherein the condition of hydro-thermal process described in step a are as follows: temperature is 45-190 DEG C, when
Between be 0.5-50 hour, the state of hydro-thermal process is air-tight state.
8. the method according to claim 1, wherein silicon source described in step b is selected from silicate, silica, silicic acid, silicon
At least one of glue, clay and silester.
9. the method according to claim 1, wherein silicon source described in step b is selected from silica gel, fume colloidal silica, the precipitation method
At least one of white carbon black and silester.
10. the method according to claim 1, wherein the condition of Crystallizing treatment described in step c are as follows: temperature is 120-190 DEG C,
Time is 1-10 days, and the state of Crystallizing treatment is air-tight state.
11. the method according to claim 1, wherein dry condition described in step e are as follows: temperature is 50-120 DEG C, and the time is
6-24 hours；The condition of roasting described in step e are as follows: temperature is 300-700 DEG C, and the time is 1-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510708494.3A CN106608637B (en) | 2015-10-27 | 2015-10-27 | A method of synthesis STT structure molecular screen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510708494.3A CN106608637B (en) | 2015-10-27 | 2015-10-27 | A method of synthesis STT structure molecular screen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106608637A CN106608637A (en) | 2017-05-03 |
| CN106608637B true CN106608637B (en) | 2019-02-01 |
Family
ID=58614458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510708494.3A Active CN106608637B (en) | 2015-10-27 | 2015-10-27 | A method of synthesis STT structure molecular screen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106608637B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859442A (en) * | 1986-01-29 | 1989-08-22 | Chevron Research Company | Zeolite SSZ-23 |
| CN102821836A (en) * | 2010-02-01 | 2012-12-12 | 约翰逊马西有限公司 | Three way catalyst comprising extruded solid body |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104918884B (en) * | 2012-09-28 | 2018-01-09 | 太平洋工业发展公司 | It is used as the preparation method of the STT type zeolites of catalyst in selective catalytic reduction reaction |
-
2015
- 2015-10-27 CN CN201510708494.3A patent/CN106608637B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859442A (en) * | 1986-01-29 | 1989-08-22 | Chevron Research Company | Zeolite SSZ-23 |
| CN102821836A (en) * | 2010-02-01 | 2012-12-12 | 约翰逊马西有限公司 | Three way catalyst comprising extruded solid body |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106608637A (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110342536A (en) | A kind of preparation method of low silica-alumina ratio ZSM-48 molecular sieve | |
| CN106608635A (en) | Preparation method of ZSM-48 molecular sieve | |
| CN109626394A (en) | A method of SAPO-35 molecular sieve is prepared by template of N- methyl piperidine | |
| EP2739374A1 (en) | Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-23 | |
| CN106608637B (en) | A method of synthesis STT structure molecular screen | |
| EP0107908A1 (en) | Zeolites | |
| CN102897791B (en) | Synthesis method for ZSM-5 molecular sieve | |
| CN103864092A (en) | Synthesis method and application of composite pore zeolite beta | |
| JPH0357050B2 (en) | ||
| CN102897793B (en) | Sodium-free synthesis method for ZSM-5 molecular sieve | |
| CN103964466A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN102897789B (en) | Synthesis method for ZSM-5 molecular sieve | |
| CN110407229A (en) | Synthesize the method and CHA structure molecular sieve of CHA structure molecular sieve | |
| CN102897790B (en) | Synthesis method for ZSM-5 molecular sieve | |
| CN103964467B (en) | A kind of preparation method of ZSM-5 molecular sieve | |
| JP4882202B2 (en) | Method for synthesizing high silica mordenite | |
| CN110407231B (en) | Method for synthesizing copper-containing CHA structure molecular sieve and copper-containing CHA structure molecular sieve | |
| CN110451521B (en) | Preparation method of Beta molecular sieve and preparation method of SCR catalyst | |
| JPH0940417A (en) | Production of crystalline microporous substance | |
| CN110407230B (en) | Method for synthesizing CHA structure molecular sieve and CHA structure molecular sieve | |
| AU2012250221B2 (en) | Germanosilicate SSZ-75 | |
| KR101777831B1 (en) | Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-28 | |
| JP4470003B2 (en) | High silica mordenite and its synthesis method | |
| CN104649290A (en) | Organic-template-free [beta]-molecular sieve synthesizing method | |
| CN102897792B (en) | Synthesis method for ZSM-5 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |