CN1648046A - Processfor preparing mordenite and beta zeolite mixed crystal material - Google Patents
Processfor preparing mordenite and beta zeolite mixed crystal material Download PDFInfo
- Publication number
- CN1648046A CN1648046A CN 200410000960 CN200410000960A CN1648046A CN 1648046 A CN1648046 A CN 1648046A CN 200410000960 CN200410000960 CN 200410000960 CN 200410000960 A CN200410000960 A CN 200410000960A CN 1648046 A CN1648046 A CN 1648046A
- Authority
- CN
- China
- Prior art keywords
- mordenite
- mixed crystal
- zeolite
- fluorochemical
- crystal material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000010457 zeolite Substances 0.000 title claims abstract description 46
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 235000010755 mineral Nutrition 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- -1 tetraethyl-ammonium halide Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009992 mercerising Methods 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005899 aromatization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- 208000012868 Overgrowth Diseases 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses the preparation process of mixed crystal material of mordenite and beta zeolite, and features that mordenite is used as crystal seed added into synthesis reaction of beta zeolite and through further hydrothermal crystallization the mixed crystal material is prepared. The mixed crystal material thus synthesized has adjustable mixed crystal ratio and even higher catalyst performance than the mixed crystal material obtain through mechanical mixing of mordenite and beta zeolite.
Description
Technical field
The invention relates to the preparation method of mixed crystal material, furtherly, the invention relates to the synthetic method of mercerising/β zeolite 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, β zeolite and mordenite are widely used two kinds of catalytic materials, and they itself exist many distinctive advantages and unsurmountable shortcoming.Have big one dimension straight hole passage and good heat-resisting, acidproof and isomerization performance as mordenite, but because its scarce limit on structure and aperture, easy coking and deactivation of the one-dimensional channels of mordenite and hydrothermal stability thereof are relatively poor, so be difficult to the catalyzed reaction of condition harshness.The β zeolite be have that good heat and hydrothermal stability, appropriateness are acid, acid acceptance unique have intersect the mesoporous molecular sieve of 12-membered ring's channel system, its catalyzed reaction shows the characteristics that hydrocarbon reaction is difficult for coking and long service life, and reactant and product there is certain shape feature of selecting, products distribution there is certain influence, but need strong acid catalyzed reaction strength of acid not enough, and its synthetic cost height to those.
Consider that mordenite and β zeolite 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 mercerising/β zeolite 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.
(Li Fuxiang, Wu Lan, Qin Menggeng etc. such as Li Fuxiang, Wu Lan, Qin Menggeng, mesopore MCM-41 molecular sieve is in the research of micro porous molecular sieve overgrowth on micro-pore zeolite ZSM-5, the chemistry of fuel journal, 1998,26 (2): 102-107) once designed mesopore-micropore molecular sieve composite material that a kind of plan is used for macromolecular reaction, so overgrowth on micro-pore zeolite ZSM-5 is studied to mesopore MCM-41 molecular sieve.
(volume such as Duan Qiwei such as the yellow upright people in 1998, Chen Haiying, the 9th national catalysis academic meeting paper collection, p500) with the organic formwork agent tetrapropyl amine bromide (TPBr) that synthesizes ZSM-5, keep inducing under stable temperature and the certain pH value condition amorphous aluminum silicide in the hole wall to carry out crystalline phase arranges in the mesopore duct, the even mesopore that existing aperture is bigger has the strongly-acid matrix material MCM-41/ZSM-5 of microporous crystal structure again.
The catalyzer ZSM/AlPO that people such as Chih-Hao Mark Tsang of ABB AB and Pel-shing Eugene Dal are extensively used two discussion
4Be synthesized together (Chih-Hao MarkTsang, Pel-shing Eugene Dal.Binary Molecular Sieves Having A Core andShell of Different Structures and Compositions.USA 5888921,1999).
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.
Do not see report so far about synthetic mercerising/β zeolite mixed crystal material method.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of mercerising/β zeolite mixed crystal material.
The synthetic method of mercerising provided by the invention/β zeolite mixed crystal material is characterized in that mordenite is added in the synthesis reaction mixture of β zeolite as crystal seed, forms through hydrothermal crystallizing.
More particularly, synthetic method provided by the invention is according to the aluminium source: (15～100) silicon source: (0～100) mineral alkali: (1.5～30) template: (0～20) fluorochemical: (270～3200) water: the mole of the β zeolite synthesis reaction system of (0～20) mineral acid is formed, mix with aluminium source, silicon source mineral alkali or acid, template, fluorochemical, deionized water with as the mordenite of crystal seed, synthetic and recovery product under the conventional hydrothermal crystallizing condition in encloses container, wherein, in the mole composition formula, the aluminium source is with Al
2O
3Meter, silicon source are with SiO
2Meter, the weight of said mordenite as crystal seed is 2～100%, preferred 5～80% of β zeolite synthesis reaction system butt weight.
In method provided by the invention, the addition sequence of raw material there is no special requirement, but wherein preferred raw material addition sequence is earlier mineral alkali or acid, template, fluorochemical, deionized water to be mixed, and adds mordenite, under agitation adds aluminium source, silicon source again.
In method provided by the invention, said aluminium source, silicon source, fluorochemical, template and raw materials such as mineral alkali, mineral acid there is no special requirement, the raw material that can synthesize the β zeolite in the prior art 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; Said silicon source is water glass and/or silicon sol; Said fluorochemical is alkali-metal fluorochemical or Neutral ammonium fluoride or its mixture, and in alkali-metal fluorochemical, preferred fluorinated sodium; Said mineral alkali is selected from least a in the group that sodium hydroxide, potassium hydroxide or ammoniacal liquor forms, and said mineral acid is sulfuric acid or hydrochloric acid; Said template is selected from tetraethyl-oxyammonia or tetraethyl-ammonium halide or tetrapropyl oxyammonia or two or three mixture wherein.
In the method provided by the invention, said conventional hydrothermal crystallizing condition generally is 100 ℃～200 ℃ crystallization 3～7 days.
Method provided by the invention has the following advantages:
(1) since mercerising as crystal seed add fashionable and ratio in mixed crystal material substantially for increasing progressively trend (accompanying drawing 1), so the ratio of mordenite and β zeolite can be regulated easily by the metering to adding mordenite crystal seed in the mixed crystal material.
(2) compare with the mixed crystal material that the β zeolite obtains with the mechanically mixing mordenite, interact because mordenite wherein and β zeolite microcosmic mix or exist.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 all is better than mechanical mixed crystal material in normal hexane catalytic cracking aromizing, aromatization of methanol, m-xylene disproportionation reaction performance evaluation.
Description of drawings
Fig. 1 is the graph of a relation of mordenite content in 1～4 synthetic mixed crystal material of embodiment with the mordenite crystal seed that is added.
Fig. 2 is the XRD figure that embodiment 1～4 adds the different amount mordenite synthetic mixed crystal material A1 of institute, A2, A3, A4 and Comparative Examples 1 synthetic β zeolite DB-1 and Comparative Examples 2 synthetic mordenite DB-2.
Embodiment
Following example will give further instruction to method provided by the invention, but therefore not limit the present invention.
Among the embodiment, synthetic raw materials used in tetraethyl-oxyammonia, silicon sol be technical grade, other is SILVER REAGENT.
In the mixed crystal material, the relative content of mordenite and β zeolite carries out quantitative analysis by XRD spectra.
Earlier respectively preparation to contain the mordenite mass percent be 20%, 40%, 50%, 60%, 80% the mixed mercerising/β zeolite of machinery, it is carried out XRD analysis, diffracted intensity with its characteristic peak is the x axle, is the y axle with its mass percent, makes working curve.Institute's synthetic mercerising/β zeolite mixed crystal is also carried out XRD analysis, to the working curve of being done, find out its corresponding mass percent, can obtain the mass percent of mercerising in mercerising/β zeolite mixed crystal by its diffracted intensity.
Comparative Examples 1
Synthesizing of this Comparative Examples explanation β zeolite.
0.5g Sodium Fluoride, 23.6g 15% tetraethyl-oxyammonia solution (technical grade) and 15.9mL deionized water are mixed, under agitation add the 0.7g sodium aluminate again, be stirred to evenly, add 15.7g silicon sol (technical grade) again, continue to be stirred to evenly, move into reactor then, in 14 5 ℃ of crystallization 5 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the β zeolite powder, numbering DB-1.
Comparative Examples 2
The explanation of this Comparative Examples is as the preparation of the mordenite of crystal seed.
69.6g water glass (modulus 3, down together) and 59.5g water are mixed, under agitation add 13.3g Tai-Ace S 150 (Al again
2(SO
4)
318H
2O) become glue, continue to be stirred to evenly, add 2.3g sodium hydroxide at last and stir evenly, move into reactor then, in 160 ℃ of crystallization 72 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 mordenite, numbering DB-2.
Comparative Examples 3
The mixed crystal material of this Comparative Examples obtains through mechanically mixing.
The mixed crystal material of this Comparative Examples obtains Comparative Examples 1 synthetic β zeolite and Comparative Examples 2 synthetic mordenites through mechanically mixing, wherein β zeolite and mordenite respectively account for 50 heavy %, and this contrast material is numbered DB-3.
Embodiment 1
1.0g mordenite crystal seed, 0.5g Sodium Fluoride, 23.6g 15% tetraethyl-oxyammonia solution and 15.9mL deionized water are mixed, under mechanical stirring, add the 0.7g sodium aluminate again, be stirred to evenly, add the 15.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 145 ℃ of crystallization 5 days, 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, be numbered A1.
Embodiment 2
2.0g mordenite crystal seed, 0.5g Sodium Fluoride, 23.6g 15% tetraethyl-oxyammonia solution and 15.9mL deionized water are mixed, under mechanical stirring, add the 0.7g sodium aluminate again, be stirred to evenly, add the 15.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 145 ℃ of crystallization 5 days, 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, be numbered A2.
Embodiment 3
3.0g mordenite crystal seed, 0.5g Sodium Fluoride, 23.6g 15% tetraethyl-oxyammonia solution and 15.9mL deionized water are mixed, under mechanical stirring, add the 0.7g sodium aluminate again, be stirred to evenly, add the 15.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 145 ℃ of crystallization 5 days, 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, be numbered A3.
Embodiment 4
4.5g mordenite crystal seed, 0.5g Sodium Fluoride, 23.6g 15% tetraethyl-oxyammonia solution and 15.9mL deionized water are mixed, under mechanical stirring, add the 0.7g sodium aluminate again, be stirred to evenly, add the 15.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 145 ℃ of crystallization 5 days, 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, be numbered A4.
Embodiment 5
2.5g mordenite crystal seed, 29.5g 15% tetraethyl-oxyammonia solution, 2.2g 20% sulphuric acid soln and 13.5mL deionized water are mixed, under mechanical stirring, add the 0.5g sodium aluminate again, be stirred to evenly, add the 19.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 140 ℃ of crystallization 6 days, 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, be numbered A5.
Embodiment 6
1.0g mordenite crystal seed, 0.4g Neutral ammonium fluoride, 19.6g 15% tetraethyl-oxyammonia solution, 6.2mL strong aqua and 5.2mL deionized water are mixed, under mechanical stirring, add the 0.7g sodium aluminate again, be stirred to evenly, add the 19.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 120 ℃ of crystallization 7 days, 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, be numbered A6.
Embodiment 7
0.5g mordenite crystal seed, 15.7g 15% tetraethyl-oxyammonia solution and 5.4mL deionized water are mixed, under mechanical stirring, add 0.7g Tai-Ace S 150 again, be stirred to evenly, add the 19.7g silicon sol again, continue to be stirred to evenly, move into reactor then, in 155 ℃ of crystallization 5 days, 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, be numbered A7.
The mordenite of embodiment 8～10 explanations method preparation provided by the invention and the catalytic perfomance of β zeolite mixed crystal material.
Embodiment 8
The dimethylbenzene disproportionation reaction pulse micro-inverse evaluation result of present embodiment explanation mixed crystal material.
Sample loading amount 0.1g is at 400 ℃ of down logical N
2Pre-thermal activation used m-xylene as probe molecule, pulse sample introduction 0.3 μ L after 30 minutes.
Chromatographic instrument is a HP5890 II type, is furnished with fid detector.The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
The sodium type is converted into the process of Hydrogen: take off amine under the first temperature programming condition, take by weighing then a certain amount of oneself take off the mixed crystal of amine, add the NH of 1 mol
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 1 hour, exchange at every turn, oven dry is put into muffle furnace at last and was kept 4 hours down in 540 ℃.
Dimethylbenzene disproportionation reaction activity and products distribution see Table 1.
Table 1
| Catalyzer | Transformation efficiency/% | Benzene/% | Toluene/% | M-xylene/% | P-Xylol/% | O-Xylol/% | (benzene+toluene)/% | The dimethylbenzene total amount |
| ??DB-1 | ????90.50 | ????8.47 | ????37.18 | ????9.50 | ????26.40 | ????10.04 | ????45.65 | ??45.94 |
| ??DB-2 | ????91.66 | ????11.56 | ????35.76 | ????8.34 | ????25.78 | ????7.86 | ????47.32 | ??41.98 |
| ??A3 | ????91.20 | ????8.16 | ????30.92 | ????8.80 | ????27.70 | ????12.47 | ????39.08 | ??48.97 |
| ??DB-3 | ????91.54 | ????9.84 | ????32.51 | ????8.46 | ????28.07 | ????11.17 | ????42.35 | ??47.7 |
As shown in Table 1, when 400 ℃ of temperature of reaction, the mordenite of the inventive method preparation and β zeolite mixed crystal material are than mixed crystal material low 3.27 percentage points on (benzene+toluene) total amount of mechanically mixing, and the total amount of dimethylbenzene has improved 1.27, and the o-Xylol amount exceeds 1.3 percentage points; And purer β zeolite of its selectivity for o-Xylol (DB-1) and pure silk geolyte (DB-2) are all good.
Embodiment 9
The reactivity worth of mixed crystal material in the aromatization of methanol 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, use methyl alcohol as probe molecule, pulse sample introduction 0.3 μ L.
The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
Aromatization of methanol reactive behavior and products distribution see Table 2.
Table 2
| Catalyzer | Transformation efficiency/% | Benzene/% | Toluene/% | M-xylene/% | P-Xylol/% | O-Xylol/% | (benzene+toluene)/% | Dimethylbenzene total amount/% | The aromatic hydrocarbons total amount |
| DB-3 | ?59.38 | ??1.21 | ??5.9 | ????1.14 | ??3.72 | ??0.99 | ??7.11 | ??5.85 | ?12.96 |
| A3 | ?58.84 | ??2.17 | ??10.76 | ????1.82 | ??5.81 | ??1.37 | ??12.93 | ??9.00 | ?21.93 |
As shown in Table 2, the mordenite of the inventive method preparation and β zeolite mixed crystal material do not have significant difference than the mixed crystal material of mechanically mixing on transformation efficiency, but good to the selectivity of aromatic hydrocarbons, particularly toluene and p-Xylol.
The reactivity worth of mixed crystal material in normal hexane catalytic cracking aromizing pulse micro-inverse is estimated of the inventive method preparation.
Experimental technique: sample loading amount 0.1g, at 450 ℃ of down logical N
2Behind the pre-thermal activation 30min, use normal hexane as probe molecule, pulse sample introduction 0.3 μ L.
The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
Normal hexane cracking aromatization activity and aromatic hydrocarbons distribution reaction result see Table 3.
Table 3
| Catalyzer | Transformation efficiency/% | Benzene/% | Toluene/% | M-xylene/% | P-Xylol/% | O-Xylol/% | ??BTX ??/％ |
| ??A3 | ??94.70 | ??2.25 | ??5.45 | ????0.52 | ????1.71 | ????0.21 | ??10.14 |
| ??DB-3 | ??72.72 | ??1.44 | ??2.39 | ????- | ????0.35 | ????- | ??4.18 |
As shown in Table 3, the mordenite and the β zeolite mixed crystal material of the inventive method preparation are better than mixed crystal material cracking, the aromatization activity of mechanically mixing.
Claims (11)
1, the preparation method of a kind of mordenite and β zeolite mixed crystal material is characterized in that mordenite is added in the synthesis reaction mixture of β zeolite as crystal seed, forms through hydrothermal crystallizing.
2, according to the method for claim 1, it is characterized in that according to the aluminium source: (15～100) silicon source: (0～100) mineral alkali: (1.5～30) template: (0～20) fluorochemical: (270～3200) water: the mole of the β zeolite synthesis reaction system of (0～20) mineral acid is formed, mix with aluminium source, silicon source mineral alkali or acid, template, fluorochemical, deionized water with as the mordenite of crystal seed, synthetic and recovery product under the conventional hydrothermal crystallizing condition in encloses container, wherein, in the mole composition formula, the aluminium source is with Al
2O
3Meter, silicon source are with SiO
2Meter, the weight of said mordenite as crystal seed is 2～100% of β zeolite synthesis reaction system butt weight.
3, according to the method for claim 2, be earlier mineral alkali or acid, template, fluorochemical, deionized water to be mixed, add mordenite, under agitation add aluminium source, silicon source again.
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, said mineral acid is selected from sulfuric acid or hydrochloric acid.
10, according to the method for claim 2, said template is meant tetraethyl-oxyammonia or tetraethyl-ammonium halide or tetrapropyl oxyammonia or its mixture.
11, according to the method for claim 2, the add-on of said mordenite is 5～80% of a β zeolite synthesis reaction system butt weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000960 CN1276873C (en) | 2004-01-19 | 2004-01-19 | Processfor preparing mordenite and beta zeolite mixed crystal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000960 CN1276873C (en) | 2004-01-19 | 2004-01-19 | Processfor preparing mordenite and beta zeolite mixed crystal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1648046A true CN1648046A (en) | 2005-08-03 |
| CN1276873C CN1276873C (en) | 2006-09-27 |
Family
ID=34866954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410000960 Expired - Lifetime CN1276873C (en) | 2004-01-19 | 2004-01-19 | Processfor preparing mordenite and beta zeolite mixed crystal material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1276873C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386261C (en) * | 2006-04-06 | 2008-05-07 | 辽宁石油化工大学 | Synthetic process of Beta zeolite and MAPO-5 two-structure molecular sieve |
| CN102039153B (en) * | 2009-10-13 | 2012-06-27 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/Magadiite coexisting material catalyst |
| CN102039163B (en) * | 2009-10-13 | 2012-07-18 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/MCM-22 symbiotic molecular sieve catalyst |
| CN102039167B (en) * | 2009-10-13 | 2012-07-25 | 中国石油化工股份有限公司 | Method for preparing adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst |
| CN102039173B (en) * | 2009-10-13 | 2012-07-25 | 中国石油化工股份有限公司 | Binderless ZSM-5/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof |
| CN102039166B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst |
| CN102039164B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst |
| CN102039171B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst |
| CN101992124B (en) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | Binder-free mordenite/beta zeolite coexisting molecular sieve catalyst and preparation method thereof |
| CN102039162B (en) * | 2009-10-13 | 2012-09-05 | 中国石油化工股份有限公司 | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof |
| CN103011191A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Mordenite and beta zeolite core-shell molecular sieve and preparation method thereof |
| CN103058220A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of BETA-MOR symbiotic molecular sieve |
| CN103121690A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| JP2019099451A (en) * | 2017-11-29 | 2019-06-24 | 日揮触媒化成株式会社 | Manufacturing method of zeolite |
-
2004
- 2004-01-19 CN CN 200410000960 patent/CN1276873C/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386261C (en) * | 2006-04-06 | 2008-05-07 | 辽宁石油化工大学 | Synthetic process of Beta zeolite and MAPO-5 two-structure molecular sieve |
| CN101992124B (en) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | Binder-free mordenite/beta zeolite coexisting molecular sieve catalyst and preparation method thereof |
| CN102039173B (en) * | 2009-10-13 | 2012-07-25 | 中国石油化工股份有限公司 | Binderless ZSM-5/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof |
| CN102039162B (en) * | 2009-10-13 | 2012-09-05 | 中国石油化工股份有限公司 | Binderless ZSM-5/beta zeolite symbiotic molecular sieve catalyst and preparation method thereof |
| CN102039163B (en) * | 2009-10-13 | 2012-07-18 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/MCM-22 symbiotic molecular sieve catalyst |
| CN102039166B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst |
| CN102039164B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst |
| CN102039171B (en) * | 2009-10-13 | 2012-08-01 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst |
| CN102039153B (en) * | 2009-10-13 | 2012-06-27 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/Magadiite coexisting material catalyst |
| CN102039167B (en) * | 2009-10-13 | 2012-07-25 | 中国石油化工股份有限公司 | Method for preparing adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst |
| CN103011191A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Mordenite and beta zeolite core-shell molecular sieve and preparation method thereof |
| CN103011191B (en) * | 2011-09-22 | 2015-04-08 | 中国石油化工股份有限公司 | Mordenite and beta zeolite core-shell molecular sieve and preparation method thereof |
| CN103058220A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of BETA-MOR symbiotic molecular sieve |
| CN103058220B (en) * | 2011-10-24 | 2014-08-20 | 中国石油化工股份有限公司 | Preparation method of BETA-MOR symbiotic molecular sieve |
| CN103121690A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| CN103121690B (en) * | 2011-11-18 | 2015-01-07 | 中国石油化工股份有限公司 | Method for synthetizing mordenite by utilizing vapor phase process |
| JP2019099451A (en) * | 2017-11-29 | 2019-06-24 | 日揮触媒化成株式会社 | Manufacturing method of zeolite |
| JP7145002B2 (en) | 2017-11-29 | 2022-09-30 | 日揮触媒化成株式会社 | Method for producing zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1276873C (en) | 2006-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1647856A (en) | Method for preparing ZSM-5 and beta zeolite mixed crystal material | |
| CN1176020C (en) | MFI structure molecular sieve containing phosphorus and transition metal | |
| CN1276873C (en) | Processfor preparing mordenite and beta zeolite mixed crystal material | |
| CN1393403A (en) | Fractional crystallization synthesis method of medium-micropore composite molecular sieve composition | |
| CN101898151B (en) | Three-crystalline phase composite molecular sieve and preparation method thereof | |
| CN1435374A (en) | Combined molecular sieve and preparation method thereof | |
| CN100453460C (en) | High molecule polymer template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN1785808A (en) | Preparation method of high-silica-alumina-ratio small-grain NaY molecular sieve | |
| CN1308238C (en) | Double microporous zeolite molecular sieves and preparing method thereof | |
| CN100429148C (en) | Method for growing mesoporous molecular sieve by attaching crystals on surface of microporous molecular sieve | |
| CN1171788C (en) | Synthesis method of medium-micropore composite molecular sieve composition | |
| CN101444748B (en) | Beta/ZSM-5 compound borosilicate molecular sieve and preparation method thereof | |
| CN1049406C (en) | Phosphorus and RE containing molecular sieve with MFI structure | |
| CN1785807A (en) | High-silica-alumina-ratio small-crystal-grain NaY molecular sieve | |
| CN1072031C (en) | Preparation method for penta-basic cyclic molecular sieve composite | |
| CN1715186A (en) | Process for preparing small crystal ZSM-5 zeolite | |
| CN100386261C (en) | Synthetic process of Beta zeolite and MAPO-5 two-structure molecular sieve | |
| CN1296276C (en) | Synthetic method for ZSM-5/mordenite mixed crystal material | |
| CN1296275C (en) | Process for preparing mordenite/ZSM-5 mixed crystal material | |
| CN1042201C (en) | Cracking catalyst of rich producing olefines | |
| CN1157465C (en) | Catalytic cracking catalyst for preparing light oil with high yield and its preparing process | |
| CN103964466B (en) | 5 molecular sieves of a kind of ZSM and preparation method thereof | |
| CN1020039C (en) | Synthesis of mercerized zeolite with high silicon content | |
| CN1769249A (en) | Method for catalytically isomerizing aromatic compound | |
| CN1353087A (en) | Process for preparing ZSM-5 molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060927 |
|
| CX01 | Expiry of patent term |