CN1565970A - Synthetic method for ZSM-5/mordenite mixed crystal material - Google Patents
Synthetic method for ZSM-5/mordenite mixed crystal material Download PDFInfo
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Abstract
The invention discloses a synthetic method for ZSM-5/mordenite mixed crystal material, wherein ZSM-5 molecular sieve is charged into the synthesized reaction mixture of mordenite as seed crystal, and said material is prepared through water thermal crystallization. The invention realizes low making cost and more ideal catalyzing performance.
Description
Technical field
The invention relates to the synthetic method of mixed crystal material, furtherly, the invention relates to the synthetic method of ZSM-5/ mordenite mixed crystal material.
Background technology
Along with to the improving constantly of the specification of quality of Chemicals, the catalytic performance of zeolite catalysis material is also had higher requirement.People have arrived certain degree of depth for the exploration of single structure zeolite, for the performance that makes the zeolite catalysis material has more improvement, are fit to industrial application better, and the mixed crystal catalytic material of exploring multiple structure type is a new approach.
In oil refining and petrochemical industry, ZSM-5 molecular sieve and mordenite are widely used two kinds of catalytic materials, and they itself exist many distinctive advantages and unsurmountable shortcoming.As special pore passage structure of ZSM-5 molecular sieve and good heat and hydrothermal stability, make it have unique catalytic performance, but its aromizing performance is bad; Mordenite has big one dimension straight hole passage and good heat-resisting, acidproof and isomerization performance, but because easy coking and deactivation of one-dimensional channels and hydrothermal stability thereof are relatively poor, so be difficult to the catalyzed reaction of condition harshness.
Consider that ZSM-5 and mordenite microcosmic mix the interaction that may exist, utilize they separately advantage and overcome its shortcoming, may have some characteristic that is beneficial to catalyzed reaction.Therefore, synthesizing in oil refining and petrochemical industry of ZSM-5/ mordenite mixed crystal material has very important significance for theories and practical significance.
Synthetic about the mixed crystal material of different types of structure has following document to report.
At Microporous Mater.1996, reported the synthetic of FAU/MCM-41 mixed crystal catalyzer among the 6:287..In Chem.Commun.1997:2281, reported the synthetic of composite catalyst MCM-41/MFI mixed crystal system and characterized.
At J.Mater.Chem, 2001,11 (7), the Beta/MCM-41 synthetic method of 1886-1890. report is to use tetraethyl ammonium hydroxide and cetyl trimethylammonium bromide, by two step crystallization hydrothermal methods.
At " several molecular sieves change the control and the single crystalline optimization of brilliant and mixed crystal and synthesize " (catalysis journal, in July, 2002, Vol.23 (4)) in, reported with hexamethylene imine and made template, under the certain situation of ratio of components, temperature of reaction and reaction times, ZSM 5 to MCM 22, the influence of ZSM 35 and mordenite molecular sieve Cheng Jing.Simultaneously, this article has also been inquired into the influence of the adding of crystal seed to the product crystalline phase.By the conditioned reaction temperature and time,, can synthesize the controlled ZSM35/MCM of ratio 22 mixed crystal, ZSM 5/ZSM 35 mixed crystal and ZSM 35/ mordenite mixed crystal in specific temperature and time interval.
In European patent EP 999182A1, disclose and used organic formwork agent dimethyl-diphenylamine by adding the synthetic method of the synthetic EUO mixed crystal of crystal seed.
Do not see report so far about synthetic ZSM-5 molecular sieve/mordenite mixed crystal material method.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of ZSM-5/ mordenite mixed crystal material.
The synthetic method of ZSM-5/ mordenite mixed crystal material provided by the invention is characterized in that the ZSM-5 molecular sieve is added in the synthesis reaction mixture of mordenite as crystal seed, forms through hydrothermal crystallizing.
More particularly, synthetic method provided by the invention is according to (1～3.5) Na
2O: Al
2O
3: (0～10) NaF: (8～30) SiO
2: (240～600) H
2The mole of O is formed, silicon source, aluminium source, mineral alkali, fluorochemical, deionized water are mixed, form mordenite building-up reactions system, again according to 1～80%, preferred 2～60% of mordenite building-up reactions system butt weight, add the ZSM-5 molecular sieve, continue to be stirred to evenly synthetic and recovery product under the conventional hydrothermal crystallizing condition in encloses container.
In method provided by the invention, in the formation of the building-up reactions system of said mordenite, the addition sequence of raw material there is no special requirement, but wherein preferred raw material addition sequence is after earlier silicon source solution, Sodium Fluoride, deionized water being mixed, under agitation add aluminium source solution again and become glue, add mineral alkali at last and stir evenly.
In method provided by the invention, said silicon source, aluminium source, fluorochemical and inorganic alkali source there is no special requirement, raw material that in the prior art can synthesizing flokite can be applied to the present invention, for example, said aluminium source is selected from least a in the group that pseudo-boehmite, sodium aluminate or Tai-Ace S 150 forms; Described silicon source is water glass and/or silicon sol; Described fluorochemical is alkali-metal fluorochemical or Neutral ammonium fluoride or its mixture, in alkali-metal fluorochemical, and preferred fluorinated sodium; Said mineral alkali is selected from least a in the group that sodium hydroxide, potassium hydroxide or ammoniacal liquor forms.
In the method provided by the invention, said conventional hydrothermal crystallizing condition generally is 120～200 ℃ and descended 5～120 hours.
Method provided by the invention has the following advantages:
(1) because ZSM-5 be linear relationship (accompanying drawing 1) as crystal seed adding ratio fashionable and in mixed crystal material substantially, so the ratio of ZSM-5 and mordenite can be regulated easily by the metering to adding ZSM-5 crystal seed in the mixed crystal material.
(2) compare with the method for synthetic other molecular sieve mixed crystal material in the prior art, method of the present invention is not used organic formwork agent, and therefore synthetic cost is low.
(3) compare with the mixed crystal material that mordenite obtains with mechanically mixing ZSM-5, interact because ZSM-5 wherein and mordenite microcosmic mix or exist, specific surface area and pore volume drop-out value should be little than the mechanically mixing molecular sieve behind the hydrothermal aging.Identical at two kinds of zeolite proportions, for example respectively account under the situation of 50 weight %, the invention provides method synthetic mixed crystal material in the little performance evaluation that all is better than mechanical mixed crystal material in anti-of carbon 14 pure hydrocarbon pulse micro-inverses, o-Xylol pulse micro-inverse and light oil.
Description of drawings
Fig. 1 is the graph of a relation of ZSM-5 content in 1～4 synthetic mixed crystal material of embodiment with the ZSM-5 crystal seed that is added.
Fig. 2 is the XRD figure that embodiment 1～4 adds the different amount ZSM-5 molecular sieve synthetic mixed crystal material A1 of institute, A2, A3, A4 and Comparative Examples 1 synthetic mordenite DB-1, among the figure, ▲ be the mordenite characteristic peak, is the ZSM-5 characteristic peak.
Embodiment
Following example will give further instruction to method provided by the invention, but therefore not limit the present invention.
Among the embodiment, the raw materials used chemically pure reagent that is in synthesizing.
In the mixed crystal material, the relative content of ZSM-5 and mordenite is by XRD spectra, and target K value method is measured in adding:
If to be measured in the heterogeneous sample is a mutually, the quality and the massfraction that participate in diffraction are respectively Wa and wa, and establishing each total amount W that participates in diffraction mutually of sample again is unit mass (W=1), then Wa=W*wa=wa.
Internal standard substance (phase) s that in sample, adds known content, establish its composite sample promptly add s mutually the massfraction in the sample of back be ws, the massfraction of a in composite sample is wa`, and wa`=wa (1-ws) is then arranged
Have for composite sample
Ia/Is＝(Ca/Cs)*(ρs/ρa)*(w`a/ws)
Make K
s a=(Ca/Cs) * (ρ s/ ρ a) then has Ia/Is=K
s a* (w`a/ws) *
Formula * is the fundamental equation of K value, K
s aBe called the K value of a phase (phase to be measured) to s phase (internal standard substance).The diffraction lines are selected mutually if a is with s, then K
s aBe constant.
K
s aThe measuring of value: preparation w`a: ws=1: 1 two-phase biased sample (can think in pure a phase sample, to add the composite sample of the s phase of equivalent).At this moment, by * K is arranged
s a=Ia/Is promptly gets K so measure Ia/Is
s aValue.
According to the * formula, contrast the intensity and interior mark intensity mutually of determinand phase, and ws is known, then so can get w`a.
Comparative Examples 1
Synthesizing of this Comparative Examples explanation mordenite.
Reaction paste ratio: 2.3Na
2O: Al
2O
3: 13SiO
2: 320H
2O
Raw material: 13.3g Tai-Ace S 150 (Al
2(SO
4)
318H
2O)
69.6g water glass (modulus 3, together following)
2.3g sodium hydroxide
59.5g???H
2O
Water glass and water are mixed, under mechanical stirring, add alum liquor again and become glue, add sodium hydroxide again, continue to be stirred to evenly, move into reactor then, in 160 ℃ of crystallization 72 hours, crystallization finishes back cooling rapidly, and washing is after filtration put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mordenite, numbering DB-1.
Comparative Examples 2
Synthesizing of this Comparative Examples explanation ZSM-5 molecular sieve.
Reactant ratio: 7Na
2O: Al
2O
3: 50SiO
2: 2000H
2O
Raw material: 13.3g alum liquor
26.8g water glass
4.7g 20% sulphuric acid soln
37.4g???????H
2O
Water glass and deionized water are mixed, under mechanical stirring, slowly add alum liquor again and become glue, add sulphuric acid soln again, the back that stirs fast adds 0.30g NaZSM-5 crystal seed, and is again that its violent stirring is even, move into reactor then, in the cooling rapidly after 48 hours of 165 ℃ of crystallization, after filtration, wash to pH=8～9, in baking oven in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of ZSM-5, numbering DB-2.
Comparative Examples 3
The mixed crystal material of this Comparative Examples obtains Comparative Examples 1 synthetic mordenite and Comparative Examples 2 synthetic ZSM-5 molecular sieves through mechanically mixing, wherein mordenite and ZSM-5 respectively account for 50 heavy %, and this contrast material is numbered DB-3.
Embodiment 1
Raw material: 4.8g Tai-Ace S 150
25.1g water glass
21.5g???H
2O
0.8g sodium hydroxide
Experimentation: water glass and water are mixed, add Tai-Ace S 150 again and become glue under mechanical stirring, continue to be stirred to evenly, add sodium hydroxide again, gained mordenite reaction system proportioning is 2.3Na
2O: Al
2O
3: 13SiO
2: 320H
2O, the back adding Comparative Examples that stirs 2 synthetic ZSM-5 zeolite seed crystal 0.5g, continue to be stirred to evenly, move into reactor then, in 170 ℃ of crystallization 64 hours, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A1.
Embodiment 2
Raw material: 4.8g Tai-Ace S 150
25.1g water glass
21.5g???H
2O
0.8g sodium hydroxide
Experimentation: water glass and water are mixed, under mechanical stirring, add Tai-Ace S 150 again and become glue, continue to be stirred to evenly, the repeated hydrogenation sodium oxide, gained mordenite reaction system proportioning is 2.3Na
2O: Al
2O
3: 13SiO
2: 320H
2O, the back adding Comparative Examples that stirs 2 synthetic ZSM-5 zeolite seed crystal 1.5g, continue to be stirred to evenly, move into reactor then, in 170 ℃ of crystallization 64 hours, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A2.
Embodiment 3
Raw material: 4.8g Tai-Ace S 150
25.1g water glass
21.5g???H
2O
0.8g sodium hydroxide
Experimentation: water glass and water are mixed, under mechanical stirring, add Tai-Ace S 150 again and become glue, continue to be stirred to evenly, the repeated hydrogenation sodium oxide, gained mordenite reaction system proportioning is 2.3Na
2O: Al
2O
3: 13SiO
2: 320H
2O, the back adding Comparative Examples that stirs 2 synthetic ZSM-5 zeolite seed crystal 2.5g, continue to be stirred to evenly, move into reactor then, in 170 ℃ of crystallization 64 hours, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A3.
Embodiment 4
Raw material: 4.8g Tai-Ace S 150
25.1g water glass
21.5g???H
2O
0.8g sodium hydroxide
Experimentation: water glass and water are mixed, under mechanical stirring, add Tai-Ace S 150 again and become glue, continue to be stirred to evenly, the repeated hydrogenation sodium oxide, gained mordenite reaction system proportioning is 2.3Na
2O: Al
2O
3: 13SiO
2: 320H
2O, the back adding Comparative Examples that stirs 2 synthetic ZSM-5 zeolite seed crystal 3.5g, continue to be stirred to evenly, move into reactor then, in 170 ℃ of crystallization 64 hours, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A4.
Embodiment 5
Raw material: 2.5g Tai-Ace S 150
25.1g water glass
1.3g?????NaF
22.6g????H
2O
Experimentation: water glass, Sodium Fluoride and water are mixed, add alum liquor again and become glue under mechanical stirring, mordenite reaction system proportioning is 8NaF: Al
2O
3: 25SiO
2: 600H
2O, the back that stirs adds Comparative Examples 2 synthetic ZSM-5 zeolite 1.0g, continues to be stirred to evenly, moves into reactor, in 175 ℃ of crystallization 48 hours, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A5.
Embodiment 6
Raw material: 4.3g Tai-Ace S 150
25.7g water glass
33.6g???H
2O
Experimentation: water glass adding alum liquor becomes glue with water under mechanical stirring, and mordenite reaction system proportioning is 1.5Na
2O: Al
2O
3: 15SiO
2: 450H
2O, 2 synthetic ZSM-5 of the back adding Comparative Examples that stirs molecular sieve 4.0g, continue to be stirred to evenly, add sulphuric acid soln, move into reactor then, in 165 ℃ of crystallization 84 hours, crystallization finishes back cooling rapidly, and washing is after filtration put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A6.
Embodiment 7
Raw material: 2.7g Tai-Ace S 150
10.9g water glass
0.7g sodium hydroxide
29.1g???H
2O
Experimentation: under mechanical stirring, water glass adds Tai-Ace S 150 and becomes glue with water, and mordenite reaction system proportioning is 2Na
2O: Al
2O
3: 10SiO
2: 500H
2O, 2 synthetic ZSM-5 of the back adding Comparative Examples that stirs molecular sieve 1.5g, continue to be stirred to evenly, add sodium hydroxide and stir evenly, move into reactor then, in 155 ℃ of crystallization 120 hours, crystallization finishes back cooling rapidly, and washing is after filtration put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal material, be numbered A7.
The catalytic perfomance of embodiment 8～10 explanations method synthetic mixed crystal material provided by the invention.
Embodiment 8
The pure hydrocarbon pulse micro-inverse evaluation result of present embodiment explanation mixed crystal material.
Sample loading amount 0.4g is at 450 ℃ of down logical N
2Pre-thermal activation used n-tetradecane as probe molecule, pulse sample introduction 0.2～0.3 μ L after 30 minutes.
Chromatographic instrument is HP5890 II, is furnished with fid detector.The product analysis condition: (chromatogram column temperature is from 30 ℃ of temperature programmings to 200 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 250 ℃ of injector temperatures to select OV-1 for use.
The sodium type is converted into the process of Hydrogen: take by weighing a certain amount of sodium type mixed crystal, add 1 mole NH then
4Cl solution (15 milliliters/gram zeolite) heat in 96～100 ℃ of water-baths, and constantly stirring makes it exchange evenly, need to keep finish back suction filtration and be washed to no chlorine, twice of repeated exchanged of exchange 30 minutes, exchange at every turn, oven dry is put into muffle furnace at last and was kept 4 hours down in 540 ℃.
Before the reaction, mixed crystal material is through 800 ℃, 100%H
2O atmosphere burin-in process 4h.
The hydrocarbon cracking activity sees Table 1.
Table 1
| Numbering | ????n(SiO 2)/ ????n(Al 2O 3) | ??nC 14Transformation efficiency % |
| ????DB-1 | ????11 | ????13 |
| ????DB-2 | ????33 | ????81 |
| ????DB-3 | ????22 | ????45 |
| ????A3 | ????23 | ????66 |
As shown in Table 1, method synthetic mixed crystal material of the present invention shows higher cracking activity.
Embodiment 9
Isomerization and the disproportionation reaction performance of mixed crystal material in the o-Xylol pulse micro-inverse is estimated of present embodiment explanation the inventive method preparation.
Experimental technique: sample loading amount 0.1g, at 450 ℃ of down logical N
2Behind the pre-thermal activation 30min, pulse sample introduction 0.2～0.3 μ L.
The product analysis condition: (chromatogram column temperature is from 30 ℃ of temperature programmings to 200 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 250 ℃ of injector temperatures to select OV-1 for use.
Isomerization and disproportionation reaction activity see Table 2.
Table 2
| The mixed crystal material numbering | ????A3 | Comparative Examples DB-3 | |
| Product quality divides rate/% | Between the small molecule hydrocarbon benzene toluene+p-Xylol 1,3,5 trimethylbenzenes 1,2,4 trimethylbenzenes 1,2,3 trimethylbenzenes | ????0.09 ????4.39 ????24.01 ????33.49 ????3.98 ????14.50 ????2.16 | ????0.10 ????4.24 ????23.34 ????33.35 ????3.87 ????12.83 ????1.86 |
| Transformation efficiency/% | ????82.62 | ????79.59 | |
As shown in Table 2, method synthetic mixed crystal material reactive behavior provided by the invention is higher than the mixed crystal material of mechanically mixing.
Embodiment 10
The little anti-performance evaluation result of present embodiment explanation light oil.
Investigate the inventive method synthetic mixed crystal material A3 and mechanically mixing material DB-3 hydrothermal aging (800 ℃, 100%H
2O handles 4h) after the little anti-performance of light oil.
Appreciation condition is: the huge port solar oil is a raw material, agent-oil ratio 1.92, carrier gas flux 30mL/min, inlet amount 1.56g/70s, 460 ℃ of temperature of reaction.
Reaction result sees Table 3.
Table 3
| The mixed crystal material numbering | ????A3 | Comparative Examples DB-3 |
| Transformation efficiency/% | ????23 | ????19 |
Claims (9)
1, a kind of synthetic method of ZSM-5/ mordenite mixed crystal material is characterized in that the ZSM-5 molecular sieve is added in the synthesis reaction mixture of mordenite as crystal seed, forms through hydrothermal crystallizing.
2,, it is characterized in that according to (1～3.5) Na according to the method for claim 1
2O: Al
2O
3: (0～10) NaF: (8～30) SiO
2: (240～600) H
2The mole of O is formed, silicon source, aluminium source, mineral alkali, fluorochemical, deionized water are mixed, form the building-up reactions system of mordenite, again according to 1～80% of mordenite building-up reactions system butt weight, add the ZSM-5 molecular sieve, continue to be stirred to evenly synthetic and recovery product under the conventional hydrothermal crystallizing condition in encloses container.
3, according to the method for claim 2, the building-up reactions system of said mordenite is that silicon source solution, Sodium Fluoride, deionized water are mixed, under agitation add aluminium source solution again and become glue, adds mineral alkali at last and stirs evenly and obtain.
4, according to the method for claim 2, said aluminium source is selected from least a in the group that pseudo-boehmite, sodium aluminate and Tai-Ace S 150 forms.
5, according to the method for claim 2, described silicon source is water glass and/or silicon sol.
6, according to the method for claim 2, described fluorochemical is alkali-metal fluorochemical or Neutral ammonium fluoride or its mixture.
7, according to the method for claim 6, wherein alkali-metal fluorochemical is a Sodium Fluoride.
8, according to the method for claim 2, said mineral alkali is selected from least a in the group that sodium hydroxide, potassium hydroxide and ammoniacal liquor forms.
9, according to the method for claim 2, the add-on of said ZSM-5 is 2～60% of a mordenite building-up reactions system butt weight.
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| CN101190418B (en) * | 2006-11-21 | 2010-10-27 | 中国石油化工股份有限公司 | Method for preparing fine grain ZSM-5/mordenite composite molecular sieve |
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Family Cites Families (2)
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| RO117093B1 (en) * | 1995-12-08 | 2001-10-30 | Inst Nat De Cercetare Pentru R | Isomerization process of xylenes containing ethylbenzene |
| RO112692B1 (en) * | 1996-08-19 | 2002-07-30 | Omv Petrom S.A. | Zeolitic catalyst for the isomerization of ethylbenzene-containing xylols and process for preparing the same |
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2003
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