CN1303816A - Method for quickly synthesizing small crystal grain ZSM-5 molecular sieve by using guide agent method - Google Patents
Method for quickly synthesizing small crystal grain ZSM-5 molecular sieve by using guide agent method Download PDFInfo
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Abstract
A preparation method of small crystal grain ZSM-5 molecular sieve mainly includes two steps of preparation of guide agent and synthesis of molecular sieve. In first step, firstly, according to the ratio of ingredients, making silicone source and deionized water into solution A, adding templete agent, stirring, dripping aluminium source whose pH valve is properly regulated by inorganic acid into the above-mentioned material, uniformly mixing and reacting heating and separating out transparent portion from the solution so as to obtain the invented guide agent. The synthesis process of molecular sieve is identical to that of guide agent, only the organic template agent is substituted for guide agent, its crystallization process has need or 65-75 hr. so as to obtain ZSM-5 molecular sieve whose means grain size is 0.1 micrometer. Said invention is simple in preparation, and short in synthesis period.
Description
The present invention relates to a kind of method of utilizing directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve.
Zeolite catalysis is the main flow in current zeolite scientific and technical research field, and the ZSM-5 series of studies is a class catalyzer the most widely, and it is used for petrochemical industry and fine chemistry industry industry in a large number.1998 17 (1) P64-67 reports of tool " electron microscope journal " are through studies show that in a large number often catalytic reaction activity increases the zeolite catalyst that adopts along with reducing of zeolite grain degree in similar reaction.This is because the average grain diameter of zeolite reduces, and can shorten the residence time of resultant in the duct, reduces the incidence of secondary reaction, reduces the influence of internal diffusion to resultant, delays the decay of activity speed of this kind zeolite, improves the purpose product yield." petrochemical complex " nineteen eighty-three 12 (12): P744 has reported hydrothermal method synthesizing small crystal grain ZSM-5-5 zeolite, crystallization process general requirement low temperature, with salt and at mixing speed under 400-500 rev/min condition, and requiring the crystallization cycle to reach more than 300 hours in the time of 100 ℃ just can finish, though can reduce to 50 hours along with synthesis temperature increases to 130 ℃ of generated times, the average grain diameter of molecular sieve increases to 0.7 μ m by 0.1 μ m.
The purpose of this invention is to provide a kind of method of utilizing directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve, this method generated time is short, and need be with salt, the degree of crystallinity height (more than 98%) of synthesis of molecular sieve.
Directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve step of the present invention is as follows:
A. the preparation method of directed agents:
(1) half of silicon source and total water amount is mixed with A solution;
(2) with second half wiring solution-forming of aluminium source and total water amount, be adjusted to contained Na in the solution with mineral acid or mineral alkali
+Volumetric molar concentration is 0.027-2.223M, then is B solution;
(3) A solution is packed in the synthesis reactor, stir;
(4) drip organic amine in still, continue to stir 10-30 minute, make solution even fully;
(5) at last B solution is splashed into fully, opening for feed can be closed, restir 20-30 minute can begin to heat up;
(6) at first rise to 115-125 ℃ by room temperature, kept constant temperature 15-20 hour with speed less than 20 ℃/hour;
(7) continue again can finish to rise to 150-155 ℃ of constant temperature 1-2 hour by 115-125 ℃ less than 15 ℃/hour speed;
(8) liquid in the still is shifted out in cooling, cooling;
(9) adopt centrifugal settling method or centrifugal separation with solution separating, the upper strata that obtains is directed agents near transparent liquid portion;
Each above-mentioned constitutive molar ratio is:
Al
2O
3SiO
2Na
2O organic amine water
1???????????20-100??????3-10???????25-40??????2500-5000
Described silicon source is: the water glass of modulus 2.8-3.2, silicon sol, white carbon black (SiO
2＞99wt%);
Described aluminium source is: Tai-Ace S 150, aluminum nitrate;
Described organic amine is: n-Butyl Amine 99, quadrol, ethamine, 1.6 hexanediamines;
Described mineral acid is: sulfuric acid, nitric acid, phosphoric acid;
Described mineral alkali is: hydroxide sodium, yellow soda ash;
Described water all adopts deionized water;
B. molecular sieve is synthetic:
(1) half of silicon source and total water amount is mixed with C solution;
(2), be adjusted to Na in the solution with mineral acid or mineral alkali with second half wiring solution-forming of aluminium source and total water amount
+Volumetric molar concentration is 0.045-3.335M, then is D solution;
(3) C solution is packed in the synthesis reactor, stir;
(4) drip directed agents in still, continue to stir 10-30 minute, make solution even fully
(5) at last D solution is splashed into fully, opening for feed can be closed, restir 20-30 minute can begin to heat up;
(6) at first rise to 120-125 ℃ by room temperature, kept constant temperature 35-40 hour with speed less than 20 ℃/hour;
(7) continue again can finish to rise to 155-160 ℃ of constant temperature 20-25 hour by 120-125 ℃ less than 15 ℃/hour speed;
(8) liquid in the still is shifted out in cooling, cooling;
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till pH value and be about about 8 and be placed in the baking oven, obtain the former powder of ZSM-5 molecular sieve with small crystal grains in 100-120 ℃ of oven dry 6-10 hour;
Described each constitutive molar ratio is:
Al
2O
3SiO
2Na
2O water
1??????????20-100????????5-15??????2500-5000
Directed agents and Al
2O
3, SiO
2, Na
2The volume ratio that O and water are respectively formed sum is:
Directed agents: (Al
2O
3+ SiO
2+ Na
2O+H
2O)=(5-20): 100
Described silicon source is: the water glass of modulus 2.8-3.2, silicon sol, white carbon black (SiO
2＞99wt%);
Described aluminium source is: Tai-Ace S 150, aluminum nitrate;
Described organic amine is: n-Butyl Amine 99, quadrol, ethamine, 1.6 hexanediamines;
Described directed agents is: aforesaid method synthetic directed agents;
Described mineral acid is: sulfuric acid, nitric acid, phosphoric acid;
Described mineral alkali is: hydroxide sodium, yellow soda ash;
Described water all adopts deionized water.
The present invention compared with prior art has following advantage:
1. synthesis cycle is short, only needs to finish in 50-80 hour, and degree of crystallinity height (more than 98%).
2. need be in the synthetic batching with salt, conservation.
3. replace amine template institute synthetic molecular sieve with special directed agents, directly carry out ion-exchange after can drying and do not need to carry out high-temperature roasting to decompose residual amine.
Embodiments of the invention are as follows:
Embodiment 1
The directed agents synthetic ratio
AL
2O
3SiO
2Na
2O n-Butyl Amine 99 H
2O
1????????????20?????????3.0??????????30???????3000
At first weight percent is consisted of SiO
222.69, Na
2O 7.27, H
2Water glass 300 gram of O 70.04 is formulated as A solution with deionized water 1319.1 grams, again Tai-Ace S 150 37.7 grams are added 1529.3 gram deionized waters and add 17.8 gram sulfuric acid and stir and then be B solution, fill process according to the following steps:
(1) A solution is packed in the synthesis reactor, stir;
(2) drip template n-Butyl Amine 99 139.3 and restrain in still, continue to stir 10 minutes, make solution even fully;
(3) at last B solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes;
Temperature-rise period is undertaken by following program:
(1) at first rises to 115 ℃ by room temperature, kept constant temperature 20 hours with 20 ℃/hour speed;
(2) speed that continues again with 15 ℃/hour rises to 150 ℃ by 115 ℃, and constant temperature can be finished in 1 hour;
(3) liquid in the still is shifted out in cooling, cooling;
(4) adopt natural sedimentation or centrifuging with solution separating, the upper strata that obtains is directed agents near transparent liquid portion.
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O?????H
2O
1????????????20??????????5???????????3800
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is:
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=5: 100
Charging
At first weight percent is consisted of: SiO
222.69, Na
2O 7.27, H
2Water glass 300 gram of O 70.04 is formulated as C solution with deionized water 1726.9 grams, 37.7 gram Tai-Ace S 150 is added 1937.0 gram deionized waters again and adds 6.8 gram sulfuric acid and stir and then be D solution, and charging is carried out according to the following steps:
(1) C solution is packed in the synthesis reactor, stir;
(2) drip 190.4 milliliters of directed agents in still, continue to stir 10 minutes, make solution even fully;
(3) at last D solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes;
Temperature-rise period is undertaken by following program:
(1) at first rises to 120 ℃ by room temperature, kept constant temperature 40 hours with 20 ℃/hour speed;
(2) continuing to rise to 160 ℃ of constant temperature with 15 ℃/hour speed by 120 ℃ again can finish in 20 hours;
(3) liquid in the still is shifted out in cooling, cooling;
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till pH value and be about about 8 and be placed in the baking oven in 120 ℃ of oven dry 8 hours, promptly obtaining median size is the ZSM-5 molecular screen primary powder of 0.036 μ m.
Embodiment 2
1. directed agents synthetic ratio
AL
2O
3SiO
2Na
2O quadrol H
2O
1????????????40?????????6.0????????25??????????2500
Water glass 500 grams that at first will form with embodiment 1 are formulated as A solution with deionized water 711.8 grams, Tai-Ace S 150 31.43 gram being added 1062.2 gram deionized waters adds 29.4 gram nitric acid and stirs and then be B solution again, fill process is with embodiment 1, and the amount of template quadrol is 77.8 grams.
Temperature-rise period is with embodiment 1.
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O???H
2O
1????????????80??????????8?????????3800
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is:
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=10: 100
Charging:
Water glass 800 grams that at first will form with embodiment 1 are formulated as C solution with deionized water 459.2 grams, 25.2 gram Tai-Ace S 150 being added 1019.3 gram deionized waters adds 63.5 gram sulfuric acid and stirs then and to be D solution again, the charging program is with embodiment 1, and directed agents need add 220 milliliters.
Temperature-rise period is with routine embodiment 1.
To synthesize liquid and carry out can washing after the solid-liquid separation, and be washed till pH value and be about about 8 and be placed in the baking oven in 105 ℃ of oven dry 10 hours, obtaining median size is the former powder of ZSM-5 molecule of 0.059 μ m.
Embodiment 3
1. directed agents synthetic ratio
AL
2O
3SiO
2Na
2O 1.6 hexanediamine H
2O
1????????????65?????????7.8????????40??????????3800
Water glass 600 gram that at first will form with embodiment 1 is formulated as A solution with deionized water 771.9 grams, aluminum nitrate 23.2 grams is added 1192.2 gram deionized waters again and adds 43.1 gram sulfuric acid and stir and then be B solution, and fill process is carried out according to the following steps:
(1) A solution is packed in the synthesis reactor, stir;
(2) drip in template 1.6 hexanediamines, 181.3 grams and the still, continue to stir 10 minutes, make solution even fully;
(3) at last B solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes;
Temperature-rise period is undertaken by following program:
(1) at first rises to 118 ℃ by room temperature, kept constant temperature 23 hours with 20 ℃/hour speed;
(2) continuing to be warming up to 148 ℃ of constant temperature with 15 ℃/hour speed by 118 ℃ again can finish in 1 hour;
(3) cool off, lower the temperature, liquid in the still is shifted out;
(4) adopt natural sedimentation or centrifugal separation with solution separating, the upper strata that obtains is directed agents near transparent liquid portion.
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O?????H
2O
1????????????200?????????12?????????5000
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=16: 100
Charging
At first with white carbon black (SiO
2＞99%) 229.2 grams are formulated as C solution with deionized water 849.6 gram repeated hydrogenation sodium oxides 4.5 grams, 12.6 gram Tai-Ace S 150 are added 849.6 gram deionized waters again and add 94.5 gram sulfuric acid and stir and then be D solution, and charging is carried out according to the following steps:
(1) C solution is packed in the synthesis reactor, stir;
(2) drip 270 milliliters of directed agents in still, continue to stir 20 minutes, make solution even fully;
(3) at last D solution is splashed into, opening for feed can be closed, restir can begin to heat up in 30 minutes
Temperature-rise period is with embodiment 2.
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till PH and be about about 8 and be placed in the baking oven in 115 ℃ of oven dry 10 hours, promptly obtaining crystal grain is the ZSM-5 molecular screen primary powder of 0.085 μ m.
Embodiment 4
1. directed agents synthetic ratio
AL
2O
3SiO
2Na
2O n-Butyl Amine 99 H
2O
1?????????????85??????????10??????36????????3880
Water glass 600 gram that at first will form with embodiment 1 is formulated as A solution with deionized water 510.3 grams, aluminum nitrate 17.8 grams is added 930.3 gram deionized waters again and adds 43.6 gram sulfuric acid and stir and then be B solution, and fill process is with example 1.The template n-Butyl Amine 99 adds 78.6 grams.
Temperature-rise period is with embodiment 3
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O????H
2O
1?????????????60??????????15????????2500
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is:
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=16: 100
Charging
Water glass 600 gram that at first will form with embodiment 1 is formulated as C solution with deionized water 429.8,25.2 gram Tai-Ace S 150 is added 849.6 gram deionized waters again and adds 13.7 gram phosphoric acid and stir and then be D solution, and charging is carried out according to the following steps:
(1) C solution is packed in the synthesis reactor, begin to stir (300 rev/mins of kinds);
(2) drip 280 milliliters of directed agents in still, continue to stir 10 minutes, make solution even fully;
(3) at last D solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes.
Temperature-rise period is undertaken by following program
(1) at first rises to 120 ℃ by room temperature, kept constant temperature 40 hours with 20 ℃/hour speed;
(2) continuing to rise to 160 ℃ of constant temperature with 15 ℃/hour speed by 120 ℃ again can finish in 20 hours;
(3) liquid in the still is shifted out in cooling, cooling;
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till pH value and be about about 8 and be placed in the baking oven in 110 ℃ of oven dry 8 hours, promptly obtaining crystal grain is the ZSM-5 molecular screen primary powder of 0.097 μ m.
Embodiment 5
1. directed agents synthetic ratio
AL
2O
3SiO
2Na
2O ethamine H
2O
1?????????????100????????8.0?????????36??????4000
Water glass 800 gram that at first will form with embodiment 1 is formulated as A solution with deionized water 527.7 grams, and again Tai-Ace S 150 20.1 grams are added 1087.7 gram deionized waters and add 67.5 gram sulfuric acid and stir and then be B solution,
(1) A solution is packed in the synthesis reactor, stir;
(2) drip template ethamine 89.18 and restrain in still, continue to stir 10 minutes, make solution even fully.
(3) at last B solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes.
Temperature-rise period is fully with embodiment 4, and the liquid that synthesizes is inserted it in encloses container without centrifugation, takes 24 hours method of natural subsidence to separate, and obtains supernatant liquid and is directed agents.
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O?????H
2O
1???????????100?????????8.3???????4500
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is:
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=10: 100
Charging
Water glass 800 gram that at first will form with embodiment 1 is formulated as C solution with deionized water 663.8 grams, 20.1 gram Tai-Ace S 150 is added 1223.6 gram deionized waters again and adds 68.9 gram sulfuric acid and stir and then be D solution, and charging is carried out according to the following steps:
(1) C solution is packed in the synthesis reactor, stir;
(2) drip 249 milliliters of directed agents in still, continue to stir 10 minutes, make solution even fully;
(3) at last D solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes;
Temperature-rise period is undertaken by following program
(1) at first rises to 122 ℃ by room temperature, kept constant temperature 38 hours with 20 ℃/hour speed;
(2) continuing to rise to 158 ℃ of constant temperature with 15 ℃/hour speed by 122 ℃ again can finish in 25 hours;
(3) liquid in the still is shifted out in cooling, cooling;
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till PH and be about about 8 and be placed in the baking oven in 120 ℃ of oven dry 10 hours, promptly obtaining crystal grain is the ZSM-5 molecular screen primary powder of 0.108 μ m.
Embodiment 6
1. directed agents and embodiment 2 are identical
2. molecular sieve is synthetic
AL
2O
3????SiO
2????Na
2O?????H
2O
1??????????150???????8.3?????????3890
Directed agents and AL
2O
3, SiO
2, Na
2O and H
2The volume ratio of O is:
Directed agents: (AL
2O
3+ SiO
2+ Na
2O+H
2O)=20: 100
Charging
At first weight percent is consisted of SiO
280%, H
2Silicon sol 283.8 gram of O 20% adds yellow soda ash 22.6 grams and is formulated as C solution with deionized water 824.8 grams, 17.7 gram Tai-Ace S 150 is added 881.5 gram deionized waters again and adds 96.3 gram sulfuric acid and stir and then be D solution, and charging is carried out according to the following steps:
(1) C solution is packed in the synthesis reactor, stir;
(2) drip 354 milliliters of directed agents in still, continue to stir 10 minutes, make solution even fully;
(3) at last D solution is splashed into, opening for feed can be closed, restir can begin to heat up in 20 minutes;
Temperature-rise period is fully with embodiment 5.Obtain liquid and carry out can washing after the solid-liquid separation, be washed till pH value and be about about 8 and be placed in the baking oven in 120 ℃ of oven dry 6-10 hour, obtaining average crystal grain is the ZSM-5 molecular screen primary powder of 0.091 μ m.
The catalyst reaction activity rating
Above-mentioned synthetic small crystal grain molecular sieve is prepared as catalyzer through ion-exchange, washing and drying, after adding the caking agent kneading and compacting, carried out the reactive behavior evaluation of methyl alcohol system hydrocarbon (MTG) on the 1ml fixed-bed reactor, the catalyzer result of result who obtains and the preparation of common directed agents all is listed in the table below:
| The catalyzer numbering | Average product grain diameter (μ m) | Yield (gram oil/gram catalyzer) |
| Example 1 | ????0.036 | ????93.15 |
| Example 2 | ????0.059 | ????81.42 |
| Example 3 | ????0.035 | ????89.24 |
| Example 4 | ????0.097 | ????71.12 |
| Example 5 | ????0.105 | ????65.36 |
| Example 6 | ????0.091 | ????68.41 |
| ????P-D-28* | ????2.130 | ????40.21 |
The molecular sieve catalyst of * common directed agents preparation.
Claims (6)
1. method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve is characterized in that step is as follows:
A. the preparation method of directed agents:
(1) half of silicon source and total water amount is mixed with A solution;
(2) with second half wiring solution-forming of aluminium source and total water amount, be adjusted to contained Na in the solution with mineral acid or husband's machine alkali
+Volumetric molar concentration is 0.027-2.223M, then is B solution;
(3) A solution is packed in the synthesis reactor, stir;
(4) drip organic amine in still, continue to stir 10-30 minute, make solution even fully;
(5) at last B solution is splashed into fully, opening for feed can be closed, restir 20-30 minute can begin to heat up;
(6) at first rise to 115-125 ℃ by room temperature, kept constant temperature 15-20 hour with speed less than 20 ℃/hour;
(7) continue again can finish to rise to 150-155 ℃ of constant temperature 1-2 hour by 115-125 ℃ less than 15 ℃/hour speed;
(8) liquid in the still is shifted out in cooling, cooling;
(9) adopt centrifugal settling method or centrifugal separation with solution separating, the upper strata that obtains is directed agents near transparent liquid portion.
Each above-mentioned constitutive molar ratio is:
Al
2O
3SiO
2Na
2O organic amine water
1????????20-100???????3-10???????25-40?????2500-5000
B. molecular sieve is synthetic:
(1) half of silicon source and total water amount is mixed with C solution;
(2), be adjusted to Na in the solution with mineral acid or mineral alkali with half wiring solution-forming of aluminium source and total water amount
+Volumetric molar concentration is 0.045-3.335M, then is D solution;
(3) C solution is packed in the synthesis reactor, stir;
(4) drip directed agents in still, continue to stir 10-30 minute, make solution even fully
(5) at last D solution is splashed into fully, opening for feed can be closed, restir 20-30 minute can begin to heat up;
(6) at first rise to 120-125 ℃ by room temperature, kept constant temperature 35-40 hour with speed less than 20 ℃/hour;
(7) continue again can finish to rise to 155-160 ℃ of constant temperature 20-25 hour by 120-125 ℃ less than 15 ℃/hour speed;
(8) liquid in the still is shifted out in cooling, cooling;
Aforesaid liquid is carried out can washing after the solid-liquid separation, be washed till pH value and be about about 8 and be placed in the baking oven, obtain the former powder of ZSM-5 molecular sieve with small crystal grains in 100-120 ℃ of oven dry 6-10 hour.
Described each constitutive molar ratio is:
Al
2O
3SiO
2Na
2O water
1???????20-100???????5-15??????2500-5000
Directed agents and Al
2O
3, SiO
2, Na
2The volume ratio that O and water are respectively formed sum is:
Directed agents: (Al
2O
3+ SiO
2+ Na
2O+H
2O)=(25-40): 100
Above-mentioned water all is deionized water.
2. a kind of method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve as claimed in claim 1 is characterized in that described aluminium source is Tai-Ace S 150, aluminum nitrate.
3. a kind of method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve as claimed in claim 1 is characterized in that described mineral acid is sulfuric acid, nitric acid, phosphoric acid.
4. a kind of method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve as claimed in claim 1 is characterized in that described mineral alkali is sodium hydroxide, yellow soda ash.
5. a kind of method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve as claimed in claim 1 is characterized in that described silicon source is that modulus is water glass, silicon sol, the white carbon black of 2.8-3.2.
6. a kind of method of utilizing directed agents quickly synthesizing small crystal grain ZSM-5-5 molecular sieve as claimed in claim 1 is characterized in that described organic amine is n-Butyl Amine 99, quadrol, ethamine, 1.6 hexanediamines.
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| CN100455511C (en) * | 2006-11-10 | 2009-01-28 | 南京工业大学 | Method for synthesizing small-grain ZSM-5 zeolite molecular sieve |
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| CN100471825C (en) * | 2006-09-15 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Technology of preparing hydrocarbons produce from methanol by one-step method |
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| CN1056818C (en) * | 1997-01-10 | 2000-09-27 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
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2000
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| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
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| CN107697928A (en) * | 2012-12-21 | 2018-02-16 | 埃克森美孚化学专利公司 | Small crystals ZSM 5, it is synthesized and purposes |
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| CN104787777A (en) * | 2015-03-20 | 2015-07-22 | 中国石油天然气股份有限公司 | High-dispersion small-crystal-grain ZSM-5 molecular sieve and preparation method thereof |
| CN106000452A (en) * | 2016-06-28 | 2016-10-12 | 唐山境界实业有限公司 | Catalyst of aromatic mixture prepared through methanol conversion and preparation method and application |
| CN109384247A (en) * | 2018-11-06 | 2019-02-26 | 黄山学院 | A kind of preparation method of ZSM-5 zeolite molecular sieve |
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