CN104787777A - Highly-dispersed small grain ZSM-5 zeolite and preparation method thereof - Google Patents
Highly-dispersed small grain ZSM-5 zeolite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a highly-dispersed small grain ZSM-5 zeolite and a preparation method thereof. The ratio of silicate to aluminum of the zeolite is 20 to 150; the grain size of the zeolite is 50 to 500 nm. The method comprises the following steps: dissolving cellulose in a mixed solution of sodium hydroxide/urea/water, stirring to degrade, centrifuging to obtain a degradation solution A and standing; dissolving the sodium hydroxide, an aluminum salt and a template by using water to obtain an aluminum salt solution B; adding the degradation solution A into the aluminum salt solution B and mixing uniformly to enable the molar ratio of various components of the mixed solution to be that SiO2:Al2O3:H2O:the template is (20-150):1:(130-3,000):(1-20); then, adding the sodium hydroxide to regulate the pH value to be alkali; crystallizing a mixture of which the pH value is regulated; processing to obtain the ZSM-5 zeolite. The obtained ZSM-5 zeolite is uniform in grain size, and high in dispersibility.
Description
Technical field
The present invention belongs to Zeolite synthesis field, is specifically related to a kind of high dispersive ZSM-5 molecular sieve with small crystal grains and preparation method thereof.
Background technology
ZSM-5 molecular sieve (USP 3702886) is a kind of aluminosilicate zeolite molecular sieve developed by Mobil company of the U.S., belong to mesopore series zeolite, it has two-dimentional ten-ring channel system: being parallel to the axial ten-ring duct of a is that Z-shaped bends, turning, duct is about about 150 °, and aperture is
be parallel to the ten-ring duct linearly shape in c-axis direction, the aperture in oval duct is
this special pore passage structure and size, make it have good Shape-selective, there is the advantage that silica alumina ratio is adjustable, lipophilicity, thermostability and catalytic activity are high simultaneously, therefore become one of current most important molecular sieve catalytic material, be widely used in the catalytic fields such as refining of petroleum, Coal Chemical Industry and fine chemistry industry.
Compared with traditional large grain size ZSM-5 molecular sieve, little crystal grain has shorter micropore diffusion orifice throat length and larger external surface area, the aperture exposed is more, make reactant and product more effectively can pass in and out duct, be conducive to the contact probability of active sites in augmenting response thing and micropore, improve the activity of reaction; Meanwhile, shorten the evolving path of product, decrease the residence time of product in molecular sieve, inhibit the generation of secondary reaction, thus effectively increase object product, improve the selectivity of molecular sieve; In addition, high outer surface area makes little crystal grain have higher appearance carbon ability, improves the life-span of molecular sieve.
(the refining of petroleum such as Qin Guanlin, 1978,11:85) and (petrochemical complex such as Wang Zhongnan, 1983,12:744) adopt hydrothermal synthesis method, under low temperature (100-120 DEG C) condition, use tetrapropyl ammonium, ethamine and propylamine to synthesize ZSM-5 molecular sieve with small crystal grains as template, crystallization time is about 300 hours.Because the temperature of synthesis is lower, crystalline growth velocity is slow, and the cycle of synthesis is longer, is unfavorable for producing.
Verduijn J P (EP 0753482) etc. the and (Micropor.Mesopor.Mater.2000 such as Van Grieken R, 39 (1-2): 135) adopt clear liquid synthesis method, tetraethoxy (TEOS) is used to do silicon source, ZSM-5 molecular sieve with small crystal grains has been synthesized under without sodium or low sodium system, because the existence of sodium ion can reduce nucleation efficiencies, and crystal grain is obviously increased, but too low sodium content is unfavorable for that aluminium enters zeolite framework, the silica alumina ratio of synthetic zeolite is often higher.Use tetraethoxy silicone source, course of industrialization has problems.In addition, this synthetic system basicity is high, and product yield is low.Guo Hongchen etc. (CN 1699173A) use water glass to do silicon source, silica alumina ratio about 90 has been synthesized under the system higher containing sodium amount, the ZSM-5 molecular sieve with small crystal grains of about grain size 60nm, but the crystal morphology irregularity of zeolite product, especially agglomeration is more serious.
Because ZSM-5 molecular sieve is solid acid catalyst, acidic site is its active centre, and acidic site is produced by framework aluminum, it is generally acknowledged, the acidity of molecular sieve and the proportional relation of its silica alumina ratio.High silica alumina ratio ZSM-5 acid amount is little, and the active centre on unit catalyst is just few, and catalytic efficiency is low; And along with reaction is carried out, carbon distribution covers the activity that namely a little acidic site obviously can reduce catalyzer, shorten catalyst life.
Therefore, suitably reduce the silica alumina ratio of molecular sieve, contribute to improving reaction efficiency and catalytic life.But along with the reduction of silica alumina ratio, the ubiquitous agglomeration of little crystal grain will be more obvious.Reunion causes the minimizing of the effective surface sum active sites of small crystal grain molecular sieve, and reactive behavior, carbon accumulation resisting ability decline, and also can impact the dispersion of shaping of catalyst process Middle molecule sieve in matrix, have a strong impact on the catalytic performance of catalyzer.
At present, mostly adopt the method for hard template synthesis of nano ZSM-5, namely allow the crystallization process of molecular sieve carry out in the space limited, thus prevent little crystal grain from reuniting.(the Inorg.Chem.2000 such as Schmidt I, 39 (11): 2279) and (Chem.Mater.2003 such as Kim S S, 15 (8): 1664) by silicon source, aluminium source, template, alkali and water are mixed, be impregnated into again in porous carbon black and carry out crystallization, then template is removed in roasting, obtains the ZSM-5 molecular sieve of little crystal grain.Though this method can prepare the narrower molecular sieve of grain colony, not easily reunite, but require that mould material aperture must evenly, and will ensure that crystallization process to occur in template hole instead of surperficial, in addition, this special mesoporous material itself needs complicated preparation process, expensive, cause the nano molecular sieve cost of synthesis too high, hard template generally will be removed by the method for roasting, cannot second stage employ, therefore industrial applications will be subject to great restriction.
Summary of the invention
The present invention is directed to above-mentioned nanometer, submicron molecular sieve the problem such as easily to reunite, mainly solve low silica-alumina ratio small crystal grain ZSM-5 zeolite molecular sieve in conventional art, especially nanometer, submicron-scale, the crystal formation irregularity existed, the problem of easily reuniting, provide a kind of high dispersive ZSM-5 molecular sieve with small crystal grains and preparation method thereof.The method, by adding the Mierocrystalline cellulose of a small amount of degraded in synthetic system, the ZSM-5 molecular sieve with small crystal grains of preparation, especially has to the molecular sieve of low silica-alumina ratio that crystalline form is regular, good dispersity, the advantage of not easily reuniting.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of high dispersive ZSM-5 molecular sieve with small crystal grains, described molecular sieve silica alumina ratio is 20-150, and zeolite crystal particle diameter is 50-500nm.
According to ZSM-5 molecular sieve of the present invention, wherein preferred described zeolite crystal particle diameter is 100-300nm.
Molecular sieve silica alumina ratio provided by the present invention is low, crystalline form is regular, good dispersity, not easily reunites.
According to ZSM-5 molecular sieve of the present invention, the ZSM-5 molecular sieve described in the present invention is preferably prepared by the preparation method comprised the steps:
(1) cellulose dissolution is stirred degraded in the mixing solutions of sodium hydroxide/urea/water, centrifugally obtain degradation solution A;
(2) by sodium hydroxide, aluminium salt, template water dissolution, aluminum salt solution B is obtained;
(3) silicon source and degradation solution A are added in aluminum salt solution B mix, to make in mixture each component molar ratio with SiO
2: Al
2o
3: H
2o: template counts 20-150:1:130-3000:1-20, then add sodium hydroxide adjust ph to alkalescence;
(4) mixture after step (3) adjust ph is carried out crystallization, then obtain described ZSM-5 molecular sieve through aftertreatment.
According to ZSM-5 molecular sieve of the present invention, the mixing solutions of sodium hydroxide/urea/water is chilled to-20-0 DEG C in step (1) by the present invention in some preferred embodiments in advance, add Mierocrystalline cellulose again and stir degraded at such a temperature, after centrifugal, obtain degradation solution A.
The degree of crystallinity of superpolymer can be reduced like this, be conducive to cellulosic degree of depth swelling, can the dissolution equilibrium of accelerating fibers element.
According to ZSM-5 molecular sieve of the present invention, in some embodiments of the invention, the degradation solution A prepared places at-20-0 DEG C.
According to ZSM-5 molecular sieve of the present invention, in the mixing solutions of the sodium hydroxide/urea/water also in preferred steps (1), in this mixing solutions gross weight for 100%, sodium hydrate content is 3-10%, and urea content is 8-16%.
According to ZSM-5 molecular sieve of the present invention, Mierocrystalline cellulose described in step (1) can be the Mierocrystalline cellulose that commercially available routine uses, and it can be extract the Mierocrystalline cellulose from conventional plant; Be one or more in cotton linter pulp, bamboo pulp and wood pulp in preferred embodiments more of the present invention;
Wood pulp described in some of them more preferred embodiment is hardwood pulp or softwood pulp.
According to ZSM-5 molecular sieve of the present invention, the described aluminium salt of step (2) can be the aluminium salt that this area routine adopts, and the present invention is preferably one or more in Tai-Ace S 150, sodium metaaluminate and aluminum isopropylate.
According to ZSM-5 molecular sieve of the present invention, step (2) described template can be the template that this area routine uses, and the present invention is preferably one or more in n-Butyl Amine 99, quadrol and 4-propyl bromide.
According to ZSM-5 molecular sieve of the present invention, also the water of preferred steps (2) is deionized water.
According to ZSM-5 molecular sieve of the present invention, the sodium hydroxide concentration added in step (2) can be determined according to aluminium salt, and the amount adding sodium hydroxide ensures that aluminium salt dissolves completely.
According to ZSM-5 molecular sieve of the present invention, the add-on of degradation solution A is the 5-10% that described mixture adds the gross weight after sodium hydroxide in preferred steps (3).
According to ZSM-5 molecular sieve of the present invention, in order to better mix, be that silicon source and degradation solution A are added drop-wise in aluminum salt solution B in preferred steps (3).
According to ZSM-5 molecular sieve of the present invention, also add sodium hydroxide adjust ph to 10-14 in preferred steps (3).
According to ZSM-5 molecular sieve of the present invention, described in step (3), silicon source can be the silicon source of this area routine, and the present invention is preferably one or more in silicon sol, silochrom and white carbon black.
Be understandable that, in step of the present invention (3), silicon source and degradation solution A are added in aluminum salt solution B, wherein the addition sequence of silicon source and degradation solution A not special requirement, can or add silicon source and degradation solution A in aluminum salt solution B with any order simultaneously.
According to ZSM-5 molecular sieve of the present invention, crystallization described in preferred steps (4) is two sections of crystallization;
Wherein preferably first paragraph crystallization temperature is 80-110 DEG C further, crystallization time 10-40h; Second segment crystallization temperature is 150-180 DEG C, crystallization time 20-50h.
According to ZSM-5 molecular sieve of the present invention, wherein crystallization described in step (4) can also be one section of crystallization;
Wherein preferably one section of crystallization is specially: crystallization temperature 150-180 DEG C, and crystallization time is 30-60h.
According to ZSM-5 molecular sieve of the present invention, aftertreatment described in step (4) can adopt the post-processing operation of this area routine, such as can comprise at least one in filtration, washing and drying.
The preparation method of the ZSM-5 molecular sieve described in any one of the present invention, described method comprises the steps:
(1) cellulose dissolution is stirred degraded in the mixing solutions of sodium hydroxide/urea/water, centrifugally obtain degradation solution A, leave standstill;
(2) by sodium hydroxide, aluminium salt, template water dissolution, aluminum salt solution B is obtained;
(3) silicon source and degradation solution A are added in aluminum salt solution B mix, to make in mixture each component molar ratio with SiO
2: Al
2o
3: H
2o: template counts 20-150:1:130-3000:1-20, then add sodium hydroxide adjust ph to alkalescence;
(4) mixture after step (3) adjust ph is carried out crystallization, then obtain described ZSM-5 molecular sieve through aftertreatment.
Wherein the present invention can be more specifically:
(1) use the dynamic sodium hydroxide/urea/water mixed solution of precooling to carry out low temperature to Mierocrystalline cellulose and stir degraded, centrifugally obtain degradation solution A, and low-temperature storage;
(2) sodium hydroxide, aluminium salt, template Q deionized water dissolving are obtained, aluminum salt solution B;
(3) silicon source and degradation solution A are added drop-wise in aluminum salt solution B lentamente simultaneously, make the mol ratio of total composition of mixture be SiO
2: Al
2o
3: H
2o:Q=20-150:1:130-3000:1-20, then to add NaOH adjust ph be 10-14;
(4) reaction mixture is through two sections of crystallization: first paragraph crystallization temperature is 80-110 DEG C, and crystallization time is 10-40 hour; Second segment crystallization temperature is 150-180 DEG C, and crystallization time is 20-50 hour.
In sum, the invention provides a kind of high dispersive ZSM-5 molecular sieve with small crystal grains and preparation method thereof.Technical scheme tool of the present invention has the following advantages:
The invention provides the synthetic method that a kind of silica alumina ratio is the ZSM-5 molecular sieve with small crystal grains of 20-150, the high molecular polymer that the method is produced by cellulose degradation is adsorbed on nano grain surface, change Particle surface charge distribution, increase intergranular steric hindrance, thus play dispersion effect, simultaneously by controlling the composition of solution, solve the crystal formation irregularity that low silica-alumina ratio ZSM-5 molecular sieve with small crystal grains in the past exists well, the shortcomings such as easy reunion, gained ZSM-5 molecular sieve homogeneous grain size, size between 50-500nm, good dispersity.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 product.
Fig. 2 is the SEM figure of comparative example 1 product.
Fig. 3 is the SEM figure of embodiment 1 product.
Fig. 4 is the Laser particle-size distribution figure of embodiment 1 product.
Fig. 5 is the SEM figure of embodiment 4 product.
Fig. 6 is the Laser particle-size distribution figure of embodiment 4 product.
Fig. 7 is the SEM figure of embodiment 5 product.
Fig. 8 is the Laser particle-size distribution figure of embodiment 5 product.
Fig. 9 is the SEM figure of embodiment 7 product.
Fig. 2,3,5,7,9 all adopts FEI QUANTA-200 scanning electronic microscope, observes intuitively the surface topography of molecular sieve and grain size.
Fig. 4,6,8 adopts Malvern Mastersizer 2000 laser particle analyzer, utilizes the light scattering phenomenon of particle to carry out sreen analysis, carries out statistical measurement to the size-grade distribution of whole sample.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Embodiment 1
Get NaOH 6g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-20 DEG C of environment and refrigerate 2 hours; Get cotton linter pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 18g, sodium metaaluminate 4g, 4-propyl bromide 40g, dissolve with deionized water 150g; Get silicon sol 250g and degradation solution 30g, be added drop-wise in aluminum salt solution lentamente simultaneously, then to add NaOH adjust ph be 14; Installed to by reaction mixture in reactor, crystallization 36h hour at 100 DEG C, be then warmed up to 170 DEG C, crystallization 24 hours, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 100nm, SiO
2/ Al
2o
3be 30.As shown in Figure 1, as shown in Figure 3, size-grade distribution as shown in Figure 4 for SEM figure for its XRD figure spectrum.
Embodiment 2
Get NaOH 7g, add deionized water 80g wherein, make it fully dissolve, then add urea 12g, after stirring and dissolving, be put in-20 DEG C of environment and refrigerate 2 hours; Get cotton linter pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 20g, aluminum isopropylate 6.8g, 4-propyl bromide 40g, dissolve with deionized water 250g; Get white carbon black 100g and degradation solution 30g, be added drop-wise in aluminum salt solution lentamente simultaneously, then to add NaOH adjust ph be 14; Installed to by reaction mixture in reactor, crystallization 36h hour at 100 DEG C, be then warmed up to 170 DEG C, crystallization 24 hours, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 70nm, SiO
2/ Al
2o
3be 40.
Embodiment 3
Get NaOH 6g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-20 DEG C of environment and refrigerate 2 hours; Get cotton linter pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 20g, sodium metaaluminate 2g, 4-propyl bromide 40g, dissolve with deionized water 250g; Get silochrom 100g and degradation solution 30g, be added drop-wise in aluminum salt solution lentamente simultaneously, then to add NaOH adjust ph be 14; Installed to by reaction mixture in reactor, crystallization 36h hour at 100 DEG C, be then warmed up to 170 DEG C, crystallization 24 hours, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 100nm, SiO
2/ Al
2o
3be 50.
Embodiment 4
Get NaOH 6g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-15 DEG C of environment and refrigerate 2 hours; Get bamboo pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-5 DEG C of preservations.Get sodium hydroxide 18g, sodium metaaluminate 2g, n-Butyl Amine 99 20g, dissolve with deionized water 250g; Get silochrom 100g and degradation solution 30g, be added drop-wise in aluminum salt solution lentamente simultaneously, then to add NaOH adjust ph be 14; Installed to by reaction mixture in reactor, crystallization 36h hour at 100 DEG C, be then warmed up to 170 DEG C, crystallization 24 hours, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 150nm, SiO
2/ Al
2o
3be 50.Its SEM schemes as shown in Figure 5, and size-grade distribution as shown in Figure 6.
Embodiment 5
Get NaOH 6g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-20 DEG C of environment and refrigerate 2 hours; Get bamboo pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 18g, Tai-Ace S 150 6g, quadrol 18g, dissolve with deionized water 400g; Get silochrom 100g and degradation solution 30g to be added drop-wise in aluminum salt solution lentamente, then to add NaOH adjust ph be 13 simultaneously; Installed to by reaction mixture in reactor, crystallization 48h hour at 170 DEG C, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 300nm, SiO
2/ Al
2o
3be 100.Its SEM schemes as shown in Figure 7, and size-grade distribution as shown in Figure 8.
Embodiment 6
Get NaOH 6g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-20 DEG C of environment and refrigerate 2 hours; Get hardwood pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 18g, Tai-Ace S 150 4g, quadrol 18g, dissolve with deionized water 400g; Get silochrom 100g and degradation solution 30g to be added drop-wise in aluminum salt solution lentamente, then to add NaOH adjust ph be 13 simultaneously; Installed to by reaction mixture in reactor, crystallization 48h hour at 170 DEG C, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 300nm, SiO
2/ Al
2o
3be 140.
Embodiment 7
Get NaOH 5g, add deionized water 80g wherein, make it fully dissolve, then add urea 10g, after stirring and dissolving, be put in-10 DEG C of environment and refrigerate 2 hours; Get softwood pulp 4g, put into above-mentioned NaOH/ urea/aqueous solution and degrade, centrifugally obtain degradation solution, be put in-10 DEG C of preservations.Get sodium hydroxide 16g, sodium metaaluminate 4g, 4-propyl bromide 40g, dissolve with deionized water 500g; Get silochrom 100g and degradation solution 40g, be added drop-wise in aluminum salt solution lentamente simultaneously, then to add NaOH adjust ph be 12.5; Installed to by reaction mixture in reactor, crystallization 20h hour at 100 DEG C, be then warmed up to 170 DEG C, crystallization 24 hours, products obtained therefrom after filtration, washing, after drying, average crystal grain size is at about 500nm, SiO
2/ Al
2o
3be 100.Its SEM schemes as shown in Figure 9.
Comparative example 1
This comparative example is ZSM-5 molecular sieve with small crystal grains prepared by the method provided according to CN 200810019849.8.Concrete preparation method is as follows: get tetraethoxy 0.28mol (60g), add deionized water 5.6mol (100.8g) wherein, it is made fully to dissolve, then vitriol oil 2g is added, the pH to 1.0 of regulator solution, add Tai-Ace S 150 0.0068mol (4.5g) again, 4-propyl bromide 0.027mol (7.2g), ZSM-5 zeolite crystal seed 0.5g, stir at 20 DEG C and be fully hydrolyzed 6h, add 0.0125mol (0.5g) NaOH solid, regulate crystallization liquid pH=10, stir, be encapsulated into high pressure water heating kettle, static crystallization 15h at 180 DEG C, products therefrom is through washing, filter, dry, the former powder of ZSM-5 zeolite is obtained after roasting.This zeolite powder is ZSM-5 through XRD analysis structure, and its silica alumina ratio is that 27, SEM schemes as shown in Figure 2, and grain size is 100-200nm.
Claims (10)
1. a high dispersive ZSM-5 molecular sieve with small crystal grains, is characterized in that, described molecular sieve silica alumina ratio is 20-150, and zeolite crystal particle diameter is 50-500nm, and wherein preferred described zeolite crystal particle diameter is 100-300nm.
2. ZSM-5 molecular sieve according to claim 1, is characterized in that, described ZSM-5 molecular sieve is prepared by the preparation method comprised the steps:
(1) cellulose dissolution is stirred degraded in the mixing solutions of sodium hydroxide/urea/water, centrifugally obtain degradation solution A; Preferred described Mierocrystalline cellulose adds the 3-6% that weight is mixing solutions weight; Preferred described Mierocrystalline cellulose is one or more in cotton linter pulp, bamboo pulp and wood pulp; More preferably described wood pulp is hardwood pulp or softwood pulp;
(2) by sodium hydroxide, aluminium salt, template water dissolution, aluminum salt solution B is obtained; Preferred described aluminium salt is one or more in Tai-Ace S 150, sodium metaaluminate and aluminum isopropylate; Preferred described template is one or more in n-Butyl Amine 99, quadrol and 4-propyl bromide;
(3) silicon source and degradation solution A are added in aluminum salt solution B mix, to make in mixture each component molar ratio with SiO
2: Al
2o
3: H
2o: template counts 20-150:1:130-3000:1-20, then add sodium hydroxide adjust ph to alkalescence; Preferred described silicon source is one or more in silicon sol, silochrom and white carbon black;
(4) mixture after step (3) adjust ph is carried out crystallization, then obtain described ZSM-5 molecular sieve through aftertreatment.
3. ZSM-5 molecular sieve according to claim 2, is characterized in that, step (1) is that the mixing solutions of sodium hydroxide/urea/water is chilled to-20-0 DEG C in advance, adds Mierocrystalline cellulose and stirs degraded at such a temperature, obtain degradation solution A after centrifugal.
4. ZSM-5 molecular sieve according to claim 2, it is characterized in that, in the mixing solutions of the sodium hydroxide/urea/water in step (1), in this mixing solutions gross weight for 100%, sodium hydrate content is 3-10%, and urea content is 8-16%.
5. ZSM-5 molecular sieve according to claim 2, is characterized in that, the add-on of degradation solution A is the 5-10% that described mixture adds the gross weight after sodium hydroxide in step (3).
6. ZSM-5 molecular sieve according to claim 2, is characterized in that, is to be added drop-wise in aluminum salt solution B in silicon source and degradation solution A in step (3).
7. ZSM-5 molecular sieve according to claim 2, is characterized in that, adds sodium hydroxide adjust ph to 10-14 in step (3).
8. ZSM-5 molecular sieve according to claim 2, is characterized in that, crystallization described in step (4) is one section of crystallization or two sections of crystallization; Preferably one section of crystallization is: crystallization temperature 150-180 DEG C, and crystallization time is 30-60h; Preferably two sections of crystallization are: first paragraph crystallization temperature is 80-110 DEG C, crystallization time 10-40h; Second segment crystallization temperature is 150-180 DEG C, crystallization time 20-50h.
9. ZSM-5 molecular sieve according to claim 2, is characterized in that, aftertreatment described in step (4) comprises at least one in filtration, washing and drying.
10. the preparation method of the ZSM-5 molecular sieve described in claim 2 ~ 9 any one, is characterized in that, described method comprises the steps:
(1) cellulose dissolution is stirred degraded in the mixing solutions of sodium hydroxide/urea/water, centrifugally obtain degradation solution A, leave standstill;
(2) by sodium hydroxide, aluminium salt, template water dissolution, aluminum salt solution B is obtained;
(3) silicon source and degradation solution A are added in aluminum salt solution B mix, to make in mixture each component molar ratio with SiO
2: Al
2o
3: H
2o: template counts 20-150:1:130-3000:1-20, then add sodium hydroxide adjust ph to alkalescence;
(4) mixture after step (3) adjust ph is carried out crystallization, then obtain described ZSM-5 molecular sieve through aftertreatment.
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| CN105000574A (en) * | 2015-07-24 | 2015-10-28 | 中科合成油技术有限公司 | HZSM-5 molecular sieve with special appearance and preparation method and application thereof |
| CN105565339A (en) * | 2016-03-02 | 2016-05-11 | 中国科学院山西煤炭化学研究所 | Preparation method of small-crystalline-grain ZSM-22 (Zeolite Socony Mobil-22) molecular sieve |
| CN107285339A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | A kind of high silica ZSM-5 molecular sieve and its preparation method and application |
| CN107459047A (en) * | 2016-06-06 | 2017-12-12 | 中国科学院青岛生物能源与过程研究所 | A kind of molecular sieve preparation method based on hemicellulose |
| CN109694088A (en) * | 2017-10-23 | 2019-04-30 | 惠生工程（中国）有限公司 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN112520754A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof |
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| CN105565339A (en) * | 2016-03-02 | 2016-05-11 | 中国科学院山西煤炭化学研究所 | Preparation method of small-crystalline-grain ZSM-22 (Zeolite Socony Mobil-22) molecular sieve |
| CN107285339A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | A kind of high silica ZSM-5 molecular sieve and its preparation method and application |
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| CN109694088A (en) * | 2017-10-23 | 2019-04-30 | 惠生工程（中国）有限公司 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN112520754A (en) * | 2019-09-19 | 2021-03-19 | 中国石油化工股份有限公司 | Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof |
| CN112520754B (en) * | 2019-09-19 | 2022-12-09 | 中国石油化工股份有限公司 | Aluminum-rich ZSM-5 molecular sieve and synthesis method thereof |
| CN115231587A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Nano ZSM-5 molecular sieve and preparation method and application thereof |
| CN115231587B (en) * | 2021-04-22 | 2024-01-30 | 中国石油化工股份有限公司 | Nano ZSM-5 molecular sieve and preparation method and application thereof |
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