CN100522812C - Method for preparing ZSM-5/mercerization zeolite symbiosis molecular screen - Google Patents
Method for preparing ZSM-5/mercerization zeolite symbiosis molecular screen Download PDFInfo
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Abstract
The invention relates to a method of preparing a symbiotic molecular sieve of ZSM-5/mordenite, which aims at solving the problems of high synthesis cost and serious environmental pollution caused by adding templates in the synthesis process of the molecular sieve in prior art. By adding crystal seed which contains ZSM-5 and mordenite precursors in the synthesis process of the molecular sieve and controlling the mole composition and PH value of the synthetic solution of the molecular sieve precursors, the symbiotic molecular sieve consisting of ZSM-5 and mordenite can be prepared without using templates, which well solved the problems. The symbiotic molecular sieve can be used in the industrial production of ethylene and propylene by using naphtha catalytic cracking.
Description
Technical field
The present invention relates to a kind of preparation method of ZSM-5/ mercerization zeolite symbiosis molecular screen.
Background technology
Ethylene, propylene has critical role as the tap of petrochemical industry in the national economic development.Be raw material mainly at present, adopt steam cracking technology production with petroleum naphtha (or ethane).But the required very high temperature of reaction of this technology, energy consumption is big, needs expensive high temperature material preparation feedback device and annex.Operational cycle is short, and the boiler tube life-span is low, and product yield is low.Catalytic cracking reaction prepares ethene, and then to have temperature of reaction low, product yield height, the advantage of reduced investment.In Kai Fa the preparing ethylene propylene from catalytic pyrolysis catalyzer, maximum is to adopt ZSM-5 molecular sieve or mordenite as catalyzer now.But the aperture is evenly single separately owing to two kinds of molecular sieves, can not deal with complicated component separately, and they is to the catalytic performance difference of same reaction thing.The composite molecular screen that contains two kinds of components then can be handled molecular diameter complex component not of uniform size, also can bring into play their concerted catalysis effect.Existing report synthetic coexisting molecular sieve, building-up process all needs to add organic amine as template, synthetic cost price height, organic amine is poisoned big to human body, reclaim difficulty, adopts the method for roasting to remove usually, and required energy consumption is big, and environmental pollution is serious.
Document CN1565967A, CN1565970A report adopts ZSM-5 molecular sieve or mordenite as crystal seed, adds respectively in the resulting solution of mordenite or ZSM-5 molecular sieve, has synthesized the mixed crystal material of ZSM-5 and mordenite.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanically mixing, but needs to add different crystal seeds in the building-up process as inductor, also needs to add fluorochemical in addition.
Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve composition, is used for heavy oil upgrading.Synthetic method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carry out the crystallization of fs then, after the crystallization 3～300 hours, the acidity-basicity ph value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out subordinate phase, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining, but the building-up process of molecular sieve needs the segmentation crystallization, and the pH value also will be regulated in the centre, and synthetic method is also comparatively complicated.
Document CN03133557.8 has reported and has synthesized the symbiotic structure molecular sieve with TON and two kinds of structures of MFI under the static conditions, this molecular sieve has added a spot of crystal seed and salt in the preparation gelation process, control crystallization parameter can obtain the molecular sieve of two kinds of crystal formation different ratioss, silica alumina ratio obtains the reaction process that coexisting molecular sieve of the present invention can be used for mixture such as petroleum fractions greater than 50 on the lattice of molecular sieve.Building-up process of the present invention also needs to add template and salt.
Document CN1583562 has reported a kind of double-micropore zeolites molecular sieve and preparation method, it is characterized in that adopting orderly synthesis method, tentatively synthesizes y-type zeolite by certain material proportion earlier; After it is mixed with the tetraethylammonium bromide solution that is dissolved with ammoniacal liquor, adding a certain amount of silicon sol at last more fully stirs and makes it even, in 130～140 ℃ of following crystallization 4～7 days, obtain having the symbiosis zeolite molecular sieve of the two microvoid structures of Y/ β, this method is also similar with the segmentation crystallization, also need use template.
Summary of the invention
Technical problem to be solved by this invention is to have now in the technology of synthesizing coexisting molecular sieve to need to add template, the molecular sieve cost is higher, the more serious technical problem of environmental pollution in the building-up process provides a kind of preparation method of new ZSM-5/ mercerization zeolite symbiosis molecular screen.This side has in legal system is equipped with the process of coexisting molecular sieve does not need to add template, synthetic cost is low, the environmental pollution degree is low, and the ZSM-5/ mercerization zeolite symbiosis molecular screen that makes in this way preparation is used for petroleum naphtha and splits catalysis and separate the preparing ethylene and propylene reaction, and the higher ethylene, propylene yield and the advantage of feed stock conversion are arranged.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of ZSM-5/ mercerization zeolite symbiosis molecular screen, with at least a in the oxide sol of metasilicate, silicate or silicon is the silicon source, with at least a in meta-aluminate or the aluminium salt be the aluminium source, above-mentioned raw materials is made solution by required proportioning, regulator solution pH value is between 9～14, obtained the ZSM-5/ mercerization zeolite symbiosis molecular screen of crystal grain diameter between 0.2～20 micron in 10～100 hours at 100～200 ℃ of following hydrothermal crystallizings, wherein the mole proportioning of solution is: SiO
2: (0.0033～0.1) Al
2O
3: (0.04～0.3) Na
2O: (30～200) H
2O: (0.005～0.2) crystal seed, seed molecule amount are by the silicon dioxide molecules amount, and described crystal seed is SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that contains ZSM-5 and the mordenite presoma amorphous substance in 1～500 nanometer, and the presoma ratio that contains the ZSM-5 molecular sieve by weight percentage in the crystal seed is 85～99%.
In the technique scheme, do not use template in the ZSM-5/ mercerization zeolite symbiosis molecular screen preparation process; The ZSM-5/ mercerization zeolite symbiosis molecular screen crystal grain diameter preferable range of preparation is between 0.4～10 micron; The pH value preferable range of solution is 10.5～13.5; The crystallization temperature preferable range is 120～180 ℃; The crystallization time preferable range is 12～40 hours.The mole proportion optimization scope of solution is: SiO
2: (0.01～0.083) Al
2O
3: (0.1～0.2) Na
2O: (40～100) H
2O: (0.01～0.1) crystal seed.Used crystal seed preferred version is SiO
2/ Al
2O
3Mol ratio is 20～100 the crystal grain that contains ZSM-5 and the mordenite presoma amorphous substance in 1～200 nanometer, and containing ZSM-5 molecular sieve precursor ratio preferable range by weight percentage in the crystal seed is 85～99%.In the ZSM-5/ mercerization zeolite symbiosis molecular screen by weight percentage ZSM-5 molecular sieve content preferable range be 1～99%, more preferably scope is 20～98%; The SiO of ZSM-5/ mercerization zeolite symbiosis molecular screen
2/ Al
2O
3The mol ratio preferable range is 10～100, and more preferably scope is 12～40.
The raw material that the coexisting molecular sieve of the present invention preparation uses is: be the silicon source with at least a in metasilicate, silicate or the silicon sol, with at least a in aluminium salt or the aluminate is the aluminium source, with sodium hydroxide is the sodium source, and the pH value of regulating synthetic system with diluted acid is 9～14.Agents useful for same is commercially available chemically pure reagent, wherein the SiO in the silicon sol
2Content is 40 weight %.
The present invention is owing to adopted SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that contains ZSM-5 and mordenite presoma at the amorphous substance of 1～500 nanometer as crystal seed, regulate the pH value scope that is fit to ZSM-5 molecular sieve and the two growth of mordenite, silica alumina ratio and the crystallization temperature that control is fit to the two growth, under hydrothermal condition, the ZSM-5 molecular sieve crystal seed that in mixed sols, induces and the amount of mordenite crystal seed have been controlled, and controlled the temperature and time of the two grain growth, generated crystal grain diameter and be small-grain ZSM-5/mercerization zeolite symbiosis molecular screen of 0.5～10 micron.With owing to do not use template in the building-up process, therefore the synthetic cost of ZSM-5/ mercerization zeolite symbiosis molecular screen is reduced greatly, exempted the discharging of the serious organic waste water of environmental pollution simultaneously in the building-up process, alleviated pollution to environment.
After the ZSM-5/ mordenite molecular sieve compressing tablet that makes, grinding, screening, it is 12 millimeters fixed-bed reactor that cut-off footpath 20～40 purpose particles are put into diameter, is used for the reaction of naphtha catalytic pyrolysis preparing ethylene propylene, is distributed as C with component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, and the raw material physical index sees Table 1.In reaction pressure is 0.001MPa～0.5MPa, and range of reaction temperature is 600～700 ℃, and weight space velocity is 0.25～4 hour
-1, water/petroleum naphtha weight ratio is to carry out the catalyzer examination under 1: 1～4: 1 the condition, and its ethylene, propylene total recovery can reach 58%, and yield has been obtained better technical effect.
Table 1 feed naphtha index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| Normal paraffin % (weight %) in the alkane | >32.5 |
| Naphthenic hydrocarbon % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
Description of drawings
Fig. 1 be X-ray diffraction (XRD) collection of illustrative plates of synthetic coexisting molecular sieve;
Fig. 2 is scanning electron microscope (SEM) collection of illustrative plates with template synthetic coexisting molecular sieve.
Fig. 3 is without the scanning electron microscope of template synthetic coexisting molecular sieve (SEM) collection of illustrative plates.
Wherein, curve 1 is not add template synthetic ZSM-5/ mercerization zeolite symbiosis molecular screen among Fig. 1, and curve 2 is to add template synthetic ZSM-5/ mercerization zeolite symbiosis molecular screen.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Getting 1137 gram Starsos is dissolved in the 1800 gram deionized waters.In addition 89 gram Tai-Ace S 150 are dissolved in the 350 gram deionized waters, add in the sodium silicate solution under stirring.The mixed evenly back of solution is stirred and is added 100 gram quadrols down, is stirred to evenly, and regulating the pH value with 30% sulphuric acid soln is 10.5, continues then to be stirred to evenly, carries out conventional hydrothermal crystallizing 15 hours under 160 ℃.After product washs after filtration, in 130 ℃ dry 4 hours down, 550 ℃ of following roastings 3 hours promptly get crystal seed required for the present invention, remember and make M1 that the presoma ratio that contains the ZSM-5 molecular sieve by weight percentage in the crystal seed is about 95%.
[embodiment 2]
Method and content according to embodiment 2 is provided change the sodium metaaluminate add-on into 133.4 grams, make crystal seed required for the present invention, are designated as M2, and the presoma ratio that contains the ZSM-5 molecular sieve by weight percentage in the crystal seed is about 85%.
[comparative example 1]
This contrast has been used with catalyzer and has been added the method that template prepares the catalyzer close with physico-chemical property of the present invention.
Get 540 gram silicon sol and be dissolved in 90 milliliters of sodium hydroxide solutions adding 3 mol under the 1500 gram deionized water for stirring to evenly.Again 28.8 gram sodium metaaluminates are added in 900 ml deionized water and be stirred to evenly in the aforementioned solution of dissolving back adding.Under agitation add 22 gram crystal seed M1 and 96 gram n-Butyl Amine 99s then.After continuing to stir, this ZSM-5 synthetic system under 180 ℃, carried out conventional hydro-thermal synthetic 40 hours.Product wash after filtration the back 130 ℃ dry 3 hours down, 550 ℃ of following roastings 3 hours.Take out product and in 1000 milliliters 10 weight % ammonium nitrate solutions, under 90 ℃, carry out ammonium exchange 2 hours.Product after filtration, washing, 130 ℃ carry out down an ammonium exchange again after dry 2 hours.Washing after filtration,, 130 ℃ down after dry 3 hours 550 ℃ of following roastings 5 hours.Promptly get to contrast and use catalyzer, note is made C1.Catalyzer XRD figure spectrum shows and contains two kinds of things of ZSM-5 and mordenite in the molecular sieve mutually as shown in Figure 1.With the XRD quantitative analysis as can be known, ZSM-5 and mordenite content are respectively 98% and 2%.Stereoscan photograph shows that the sieve particle diameter is about 3 microns as shown in Figure 2.After the molecular sieve compressing tablet that makes, grinding, screening, cut-off footpath 20～40 purpose particles are dosed the lab scale fixed-bed reactor that are used for naphtha catalytic pyrolysis preparing ethylene, propylene for 30 milliliters, are distributed as C with component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, is 0.02MPa in reaction pressure, and temperature of reaction is 650 ℃, and weight space velocity is 1 hour
-1, water/petroleum naphtha weight ratio is to carry out catalyzer examination, appraisal result such as table 3 under 3: 1 the condition.
[embodiment 3]
Get 540 gram silicon sol and be dissolved in 90 milliliters of sodium hydroxide solutions adding 3 mol under the 1500 gram deionized water for stirring to evenly.Again 28.8 gram sodium metaaluminates are added in 900 ml deionized water and be stirred to evenly in the aforementioned solution of dissolving back adding.Under agitation add 22 gram crystal seed M1 then.This ZSM-5 synthetic system pH value that the back regulates this synthetic system with diluted acid that continues to stir is 11.5.Under 180 ℃, carried out conventional hydro-thermal synthetic 40 hours.Product washs the back after filtration and carry out ammonium exchange 2 hours in 1000 milliliters 10 weight % ammonium nitrate solutions under 90 ℃.Product after filtration, washing, 130 ℃ carry out down an ammonium exchange again after dry 2 hours.Washing after filtration,, 130 ℃ down after dry 3 hours 550 ℃ of following roastings 5 hours.Promptly get catalyzer provided by the invention, note is made H1.Catalyzer XRD figure spectrum shows and contains two kinds of things of ZSM-5 and mordenite in the molecular sieve mutually that the XRD quantitative analysis results shows that ZSM-5 and mordenite weight percentage are respectively 98% and 2% as shown in Figure 1.Stereoscan photograph shows that the sieve particle diameter is about 5 microns as shown in Figure 2.After the molecular sieve compressing tablet that makes, grinding, screening, cut-off footpath 20～40 purpose particles are dosed the lab scale fixed-bed reactor that are used for naphtha catalytic pyrolysis preparing ethylene, propylene for 30 milliliters, are distributed as C with component
4～C
10The petroleum naphtha of hydrocarbon is a raw material, in normal pressure, and 650 ℃ of temperature of reaction, weight space velocity 1 hour
-1, carry out the catalyzer examination under water/condition of 3: 1 of petroleum naphtha weight ratio, appraisal result such as table 3.
[embodiment 4～5]
The method and the content that are provided according to embodiment 3 change the sodium metaaluminate add-on into 39.4 grams and 19.7 gram raw materials respectively and form mole proportionings and be respectively: SiO
2: 0.067Al
2O
3: 0.1Na
2O: 82H
2O: 0.1M1 and SiO
2: 0.033Al
2O
3: 0.1Na
2O: 82H
2O: 0.1M1.The pH value of regulating two parts of solution is 13.5 and 11, and other condition and step are constant, make coexisting molecular sieve provided by the present invention respectively, are designated as H4 and H5.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 6]
Method and content according to embodiment 3 is provided change the sodium metaaluminate add-on into 14.76 grams, and crystal seed is used M2 instead, and the mole proportioning that raw material is formed is: SiO
2: 0.025Al
2O
3: 0.1Na
2O: 82H
2O: 0.1M2.Other condition and step are constant, make coexisting molecular sieve provided by the present invention, are designated as H6.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 7～8]
Method and content according to embodiment 2 is provided change 3 mol aqueous sodium hydroxide solution add-ons into 480 milliliters and 120 milliliters, and the mole proportioning that raw material is formed is: SiO
2: 0.049Al
2O
3: 0.2Na
2O: 82H
2O: 0.1M1 and SiO
2: 0.049Al
2O
3: 0.05Na
2O: 82H
2O: 0.1M1 regulates the pH value and is respectively 13.3 and 10.5, and other condition and step are constant, make composite molecular screen provided by the present invention, are designated as H7 and H8.The physical index such as the table 2 of the composite molecular screen of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 9～11]
According to method and the content that embodiment 2 is provided, change the consumption of deionized water, the mole proportioning that raw material is formed is respectively: SiO
2: 0.098Al
2O
3: 0.1Na
2O: 43H
2O: 0.1M1, SiO
2: 0.098Al
2O
3: 0.1Na
2O: 30H
2O: 0.1M1 and SiO
2: 0.098Al
2O
3: 0.1Na
2O: 100H
2Other condition of O: 0.1M1 and step are constant, make composite molecular screen provided by the present invention, are designated as H9, H10 and H11.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 12～13]
The method and the content that are provided according to embodiment 3 change the amount of the crystal seed M1 that adds into 33 grams and 2.2 grams respectively, and raw material is formed a mole proportioning and is respectively: SiO
2: 0.098Al
2O
3: 0.1Na
2O: 82H
2O: 0.153M1.SiO
2∶0.098Al
2O
3∶0.1Na
2O∶82H
2O∶0.01M1。
Other condition and step are constant, make coexisting molecular sieve provided by the present invention, are designated as H12 and H13.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 14～16]
Method and content according to embodiment 3 is provided change the hydro-thermal synthesis temperature into 200 ℃, 160 ℃ and 120 ℃, and other condition and step are constant, make coexisting molecular sieve provided by the present invention, are designated as H14, H15 and H16.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
[embodiment 17～19]
According to method and the content that embodiment 3 is provided, prepare three parts of solution, regulate the pH value then and be respectively 11,10.5 and 12, change the hydro-thermal generated time into 14,24,48 hours, other condition and step are constant, make coexisting molecular sieve provided by the present invention, are designated as H17, H18 and H19.The physical index such as the table 2 of the coexisting molecular sieve of XRD and SEM test.Carry out catalyzer examination, appraisal result such as table 3 according to the method for embodiment 3.
The physical index of table 2 coexisting molecular sieve
| Sample | Average crystal grain diameter size (micron) | ZSM-5 content (weight %) | Mordenite content (weight %) |
| H3 | 5 | 97.3 | 2.7 |
| H4 | 10 | 81.5 | 18.5 |
| H5 | 2 | 98.5 | 1.5 |
| H6 | 3 | 94.4 | 5.6 |
| H7 | 8 | 85.1 | 14.9 |
| H8 | 0.5 | 97.5 | 2.5 |
| H9 | 5 | 96.9 | 3.1 |
| H10 | 7 | 96.2 | 3.8 |
| H11 | 2 | 98.4 | 2.6 |
| H12 | 0.4 | 99.0 | 1.0 |
| H13 | 4 | 95.7 | 4.3 |
| H14 | 12 | 95.5 | 4.5 |
| H15 | 2 | 98.3 | 1.7 |
| H16 | 0.8 | 98.7 | 1.3 |
| |
2 | 97.7 | 2.3 |
| |
1 | 98.1 | 1.9 |
| H19 | 4 | 96.2 | 3.8 |
The catalytic performance of table 3 coexisting molecular sieve
| Sample | Yield of ethene (weight %) | Propene yield (weight %) | Ethylene, propylene total recovery (weight %) |
| H3 | 30.45 | 26，27 | 56.72 |
| H4 | 31.07 | 21.59 | 52.66 |
| H5 | 30.53 | 27.14 | 57.67 |
| H6 | 30.24 | 26.03 | 56.37 |
| H7 | 27.76 | 25.42 | 53.18 |
| H8 | 31.23 | 27.46 | 58.69 |
| H9 | 30.24 | 26.19 | 56.43 |
| H10 | 28.73 | 26.27 | 55.00 |
| H11 | 30.64 | 26.49 | 57.13 |
| H12 | 33.67 | 24.79 | 58.46 |
| H13 | 32.21 | 23.87 | 56.08 |
| H14 | 28.34 | 21.79 | 50.13 |
| H15 | 33.57 | 23.65 | 57.22 |
| H16 | 33.01 | 25.44 | 58.45 |
| H17 | 32.54 | 23.69 | 56.23 |
| H18 | 32.53 | 25.12 | 57.65 |
| H19 | 30.71 | 25.32 | 56.03 |
Claims (8)
1, a kind of preparation method of ZSM-5/ mercerization zeolite symbiosis molecular screen, with at least a in the oxide sol of metasilicate, silicate or silicon is the silicon source, with at least a in meta-aluminate or the aluminium salt is the aluminium source, above-mentioned raw materials is made solution by required proportioning, regulator solution pH value is between 9～14, obtained the ZSM-5/ mercerization zeolite symbiosis molecular screen of crystal grain diameter between 0.2～20 micron in 10～100 hours at 100～200 ℃ of following hydrothermal crystallizings, wherein the mole proportioning of solution is: SiO
2: (0.0033～0.1) Al
2O
3: (0.04～0.3) Na
2O: (30～200) H
2O: (0.005～0.2) crystal seed, seed molecule amount are by the silicon dioxide molecules amount, and described crystal seed is SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that contains ZSM-5 and the mordenite presoma amorphous substance in 1～500 nanometer, and the ratio that contains ZSM-5 molecular sieve presoma by weight percentage in the crystal seed is 80～99.5%.
2,, it is characterized in that ZSM-5/ mercerization zeolite symbiosis molecular screen crystal grain diameter is between 0.4～10 micron according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 1; The pH value of solution is 10.5～13.5; Crystallization temperature is 120～180 ℃; Crystallization time is 12～40 hours.
3,, it is characterized in that the mole proportioning of solution is: SiO according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 1
2: (0.01～0.083) Al
2O
3: (0.1～0.2) Na
2O: (40～100) H
2O: (0.01～0.1) crystal seed.
4,, it is characterized in that used crystal seed is SiO according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 1
2/ Al
2O
3Mol ratio is 20～100 the crystal grain that contains ZSM-5 and the mordenite presoma amorphous substance in 1～200 nanometer, and the presoma ratio that contains the ZSM-5 molecular sieve by weight percentage in the crystal seed is 85～99%.
5,, it is characterized in that in the coexisting molecular sieve that the ZSM-5 molecular sieve content is 1～99.5% by weight percentage according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 1.
6,, it is characterized in that in the coexisting molecular sieve that the ZSM-5 molecular sieve content is 20～98% by weight percentage according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 5.
7,, it is characterized in that the SiO of coexisting molecular sieve according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 1
2/ Al
2O
3Mol ratio is 10～100.
8,, it is characterized in that the SiO of coexisting molecular sieve according to the preparation method of the described ZSM-5/ mercerization zeolite symbiosis molecular screen of claim 7
2/ Al
2O
3Mol ratio is 12～40.
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| CN102838128B (en) * | 2011-06-23 | 2014-08-20 | 中国石油化工股份有限公司 | Mordenite/ZSM-5 intergrowth molecular sieve and synthesis method thereof |
| CN103803580B (en) * | 2012-11-07 | 2015-12-02 | 中国石油化工股份有限公司 | Isomorphous ZSM-5 composite molecular screen of a kind of nucleocapsid structure and preparation method thereof |
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| JP7145002B2 (en) * | 2017-11-29 | 2022-09-30 | 日揮触媒化成株式会社 | Method for producing zeolite |
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| CN110615443B (en) * | 2019-10-30 | 2021-05-04 | 常州工学院 | Method for synthesizing MOR/ZSM-5 composite zeolite monolith |
| CN115501907B (en) * | 2021-06-23 | 2024-01-12 | 中国石油化工股份有限公司 | ZSM-5/mordenite composite phase full-crystallization molecular sieve catalyst, preparation and application thereof |
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