CN102452666B - A kind of method of synthesizing IM-5 molecular sieve - Google Patents
A kind of method of synthesizing IM-5 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 48
- 230000008025 crystallization Effects 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000084 colloidal system Substances 0.000 claims abstract description 28
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000007529 inorganic bases Chemical class 0.000 claims abstract 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical group 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [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 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 4
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical group 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 19
- 238000010189 synthetic method Methods 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 14
- 239000012267 brine Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 13
- QJCLFTYUZCKBTH-UHFFFAOYSA-N [Br].CCCCC Chemical compound [Br].CCCCC QJCLFTYUZCKBTH-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- ISSUNVDQFLJNRZ-UHFFFAOYSA-N CCCCCC.[Br] Chemical compound CCCCCC.[Br] ISSUNVDQFLJNRZ-UHFFFAOYSA-N 0.000 description 1
- 241000283073 Equus caballus Species 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 propylene, butylene Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
一种合成IM-5分子筛的方法，包括：(1)将无机碱、铝源、模板剂溶于去离子水中，混合均匀；(2)向步骤(1)的混合溶液中加入硅源，加入或不加入添加剂，制成胶体或固液混合物，混合均匀；(3)将步骤(2)所得胶体或固液混合物移至晶化釜中，在120～200℃的温度下水热动态晶化1～10天，晶化结束后，冷却降温，所得混合液经洗涤、过滤、烘干即得到IM-5分子筛原粉；所述反应物的摩尔组成为SiO2∶Al2O3∶M2O∶R∶H2O＝60∶(0.3～6)∶(6～20)∶(0.6～18)∶(300～1800)，M2O为碱金属氧化物，R为模板剂。本发明提供的方法缩短了IM-5分子筛的晶化时间，原料配比范围较宽，提高了单釜收率，有利于工业放大。A method for synthesizing IM-5 molecular sieves, comprising: (1) dissolving inorganic base, aluminum source, and template in deionized water, and mixing uniformly; (2) adding silicon source to the mixed solution of step (1), adding Or do not add additives to make a colloid or a solid-liquid mixture, mix well; (3) move the colloid or solid-liquid mixture obtained in step (2) to a crystallization kettle, and hydrothermally dynamically crystallize at a temperature of 120-200°C for 1 ~ 10 days, after the crystallization is completed, cool down, and the obtained mixed solution is washed, filtered, and dried to obtain the original powder of IM-5 molecular sieve; the molar composition of the reactant is SiO 2 : Al 2 O 3 : M 2 O : R: H 2 O = 60: (0.3-6): (6-20): (0.6-18): (300-1800), M 2 O is an alkali metal oxide, and R is a template. The method provided by the invention shortens the crystallization time of the IM-5 molecular sieve, has a wide range of raw material proportioning, improves the yield of a single kettle, and is beneficial to industrial scale-up.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve, more particularly, relate to a kind of method of synthetic IM-5 molecular sieve.
Background technology
Molecular sieve plays a part more and more important in petrochemical industry.Along with the development of petrochemical complex and Fine Chemical Industry, in production process environmental requirement increasingly strict, the new catalytic material demand is also constantly increased.Wherein the ten-ring molecular sieve is due to its distinctive pore size and pore passage structure, and it is had a wide range of applications in the shape selective catalysis field.Only have the molecule that size and shape and molecular sieve pore passage are complementary just can enter molecular sieve pore passage, utilize the pore size of molecular sieve and the difference on pore passage structure, can realize to a certain extent " molecule screening ", make it have the ability of shape selective catalysis.The IM-5 molecular sieve is a kind of, and this molecular sieve has two-dimentional ten-ring pore canal system, limited short duct on the third dimension, and its pore canal system and ZSM-5 molecular sieve are quite similar, have good shape selectivity in the reactions such as aromatic disproportion, isomerization, alkylation.WO98/17581A1 discloses IM-5 molecular sieve and synthetic method thereof first, its synthetic method is for according to a certain ratio, water is joined in the blended solid sample that contains silicon source, template, be stirred to and obtain a kind of uniform mixture, then the mixed solution that sodium aluminate and caustic soda is dissolved into adds wherein, keep stirring, kept 15 minutes, then being transferred to one is equipped with in the teflon-lined autoclave, crystallization under certain condition, after filtration, washing, oven dry obtain the synthetic crude product of IM-5 molecular sieve.
The IM-5 molecular sieve has good thermostability and hydrothermal stability, catalytic performance is good, has a wide range of applications in catalyzed reaction, for example the disclosed a kind of catalyzer of US5989410, be that the hydrogenation/dehydrogenation metallic element is loaded on the IM-5 molecular sieve, this catalyzer can effectively improve the paraffin pour point.The molecular sieve that the disclosed catalytic cracking catalyst of US6007698 comprises comprises IM-5 molecular sieve and USY molecular sieve, and this catalyzer is used for the heavy oil feedstock catalytic cracking process, can effectively improve the reaction mass transformation efficiency, simultaneously high yield propylene, butylene.
Synthetic report about the IM-5 molecular sieve is less, WO98/17581A1 discloses several synthetic methods of IM-5, comprise and adopt 1, two (N-crassitude) the pentane bromine salt or 1 of 5-, two (N-crassitude) the hexane bromine salt of 6-are as template, and crystallization synthesized pure phase IM-5 molecular sieve in 8～13 days under 160～170 ℃ of conditions.
synthesizing of IM-5 and NU-88 molecular sieve, characterize and catalysis characteristics (Synthesis, characterization, and catalytic properties of zeolites IM-5 and NU-88.Journal of Catalysis 2003:215 151～170) and IM-5: the shape slective cracking molecular sieve of a kind of high thermal stability and hydrothermal stability (IM-5:A Highly Thermal and Hydrothermal Shape-Selective Cracking Zeolite. (Journal of Catalysis 2002:206, 125～133) also reported respectively the synthetic method of IM-5 molecular sieve in and comparatively at large set forth its synthesising law: in the synthetic method of having reported, only have employing white carbon black (Aerosil 130/200) can successfully synthesize the IM-5 molecular sieve of pure phase as the silicon source, and synthesis cycle is longer, mostly need 10 to 14 days.During the IM-5 Zeolite synthesis, the ratio range of raw material is very narrow, and particularly sodium-silicon-rate only can synthesize pure IM-5 molecular sieve near 0.73, changes a little stray crystals such as will generating MOR, ZSM-12 and ANA mutually, and synthetic narrow range is unfavorable for that industry amplifies.The system water-content of IM-5 Zeolite synthesis is too high, and water silicon ratio is not less than 40, causes single still yield low, and only can synthesize in little reactor (50ml left and right), amplifies difficulty.
Due to less to the study on the synthesis of IM-5 molecular sieve, there is no so far the relevant report solution to the problems described above.Therefore explore effective synthesizing mean, widen the proportioning raw materials scope, shorten generated time, improve single still yield, seek suitable amplification method significant.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, provides that a kind of proportioning raw materials is wider, crystallization time is short, single still yield is high, is easy to amplify the IM-5 Zeolite synthesis method of production.
A kind of method of synthetic IM-5 molecular sieve comprises the following steps:
(1) mineral alkali, aluminium source, template are dissolved in deionized water, mix;
(2) add the silicon source in the mixing solutions of step (1), add or do not add additive, mix, make colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in crystallizing kettle, the hydro-thermal dynamic crystallization is 1～10 day at the temperature of 120～200 ℃, crystallization cools after finishing, and the gained mixed solution namely obtains the IM-5 molecular screen primary powder through washing, filtration, oven dry;
Described reactant mole consist of SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.3～6): (6～20): (0.6～18): (300～1800), M
2O is alkalimetal oxide, and R is template.
Preferred reactant mole consists of: SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.5～4): (6～19.5): (3～12): (600～1200).
The beneficial effect of method provided by the invention is:
The method of a kind of synthetic IM-5 molecular sieve provided by the invention can shorten the crystallization time of IM-5 molecular sieve effectively, widens the ratio range of raw material, improves single still yield.Present method in water-content, has added different additives in reducing building-up process, make generated time obtain further shortening.The synthetic method of IM-5 molecular sieve provided by the invention is easier to amplify and produces, and can realize that the crystallization in 2 liters of reactors is synthetic.
Description of drawings
Fig. 1 is the IM-5 molecular sieve X-ray diffractogram (XRD) of report in Comparative Examples 1.
Fig. 2 is the X-ray diffractogram (XRD) of the synthetic IM-5 molecular sieve of embodiment 11.
Fig. 3 is the scanning electron microscope shape appearance figure (SEM) of the synthetic IM-5 molecular sieve of embodiment 11.
Fig. 4 is the transmission electron microscope shape appearance figure (TEM) of the synthetic IM-5 molecular sieve of embodiment 11.
Embodiment
Synthetic method provided by the present invention can adopt different silicon sources and the aluminium source synthetic, template is 1, the salt of two (N-crassitude) pentanes of 5-also can add appropriate other additive or crystal seed, according to the synthetic IM-5 molecular sieve of the method for conventional hydrothermal crystallizing.
The method of synthetic IM-5 molecular sieve provided by the invention comprises the following steps:
(1) mineral alkali, aluminium source, template are dissolved in deionized water, mix;
(2) add the silicon source in the mixing solutions of step (1), add or do not add additive, mix, make colloid or solidliquid mixture;
(3) step (2) gained colloid or solidliquid mixture are moved in crystallizing kettle, the hydro-thermal dynamic crystallization is 1～10 day at the temperature of 140～200 ℃, crystallization cools after finishing, and the gained mixed solution namely obtains the IM-5 molecular screen primary powder through washing, filtration, oven dry;
Wherein, described reactant mole consists of SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.3～6): (6～20): (0.6～18): (300～1800), M
2O is alkalimetal oxide, and R is template.
Preferred reactant mole consists of: SiO
2: Al
2O
3: M
2O: R: H
2O=60: (0.5～4): (6～19.5): (3～12): (600～1200).
In method provided by the invention, step (1) can be at room temperature be dissolved in the mineral alkali of certain proportioning, aluminium source, template in deionized water together, mix with the method that stirs, also can be dissolved in respectively the mineral alkali of certain proportioning, aluminium source, template in deionized water, be prepared into respectively solution, then the solution for preparing is mixed, the present invention is not limited in this respect.After solution prepares, preferred standing for some time, more preferably standing more than 30 minutes.
In step (1), described silicon source is selected from one or more in soft silica, water glass, silicon sol, solid oxidation silicon, solid silicone, diatomite, white carbon black and tetraethoxy, is preferably silicon sol and/or solid silicone.
Described aluminium source is selected from one or more in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum phosphate, aluminum chloride, aluminum nitrate, aluminium hydroxide, aluminum oxide and pseudo-boehmite, is preferably one or more in sodium metaaluminate, aluminum nitrate and aluminum chloride.
Described mineral alkali is NaOH or KOH, is preferably NaOH.
Described template is the salt of two (N-crassitude) pentanes of 1,5-, is preferably two (N-crassitude) the pentane bromine salt of 1,5-.
In method provided by the invention, add the silicon source in the solution that makes in the step (1) in step (2), the process that adds is preferred slowly drips silicon source solution, can react plastic after making silicon source solution add solution with very slow speed.Can add or not add additive in method provided by the invention, more preferably add additive, additive can with the common dissolving of other materials or plastic after add the solid state additive, with the SiO that adds
2Weight be benchmark, the add-on of additive is SiO
2The 1-20wt% of weight.
Described additive is selected from crystal seed, the synthetic precursor of IM-5, NaBr, NaNO
3And NaClO
4In one or more, one or more in the synthetic precursor of crystal seed, IM-5 and NaBr more preferably.
Wherein, described crystal seed is the IM-5 molecular sieve after roasting.The synthetic precursor of described IM-5 is the extract of IM-5 colloid crystallization pilot process.
In method provided by the invention, in step (3), the colloid of step (2) gained or solidliquid mixture are moved to and carry out hydrothermal crystallizing in crystallizing kettle, described hydrothermal crystallizing is the usual manner of hydrothermal crystallizing in prior art, comprises static hydrothermal crystallization or Dynamic Hydrothermal crystallization.Hydrothermal crystallizing in method provided by the invention refers at hydrothermal crystallizing 1～10 day at the temperature of 120～200 ℃ and under autogenous pressure, preferably hydrothermal crystallizing at the temperature of 140～180 ℃ and under autogenous pressure 3～5 days.Crystallization cools after finishing, and the gained mixed solution is namely obtained the IM-5 molecular screen primary powder through washing, filtration, oven dry.Wherein, washing, filtration, oven dry are the mode of various routines in this area, and the present invention is not limited in this respect.Preferably dry under 80 ℃ and spend the night, obtain the IM-5 molecular screen primary powder.
The beneficial effect of the synthetic method of IM-5 molecular sieve provided by the invention is:
The problems such as crystallization time length, proportioning raw materials narrow range, the single still yield that method provided by the invention has existed when having solved the synthetic IM-5 molecular sieve of prior art is low, amplification difficulty.Because present method has reduced the system water-content, improve material concentration, thereby shortened widely the crystallization time of IM-5 molecular sieve, single still yield also is improved thereupon.Adopt simultaneously this method can effectively suppress the generation of stray crystal phase, can access pure phase in proportioning raw materials scope that can be wider and get the IM-5 molecular sieve, be conducive to industry and amplify.Adopt present method to successfully synthesize pure IM-5 molecular sieve in 2 liters of stainless steel cauldrons.
Below by example in detail the present invention, but the present invention is not therefore subject to any restriction.
In embodiment and Comparative Examples, the specification of all ingredients used and source are as follows:
NaOH, NaBr, AlCl
3And Al (NO
3)
39H
2O is analytical pure, is produced by the Beijing Chemical Plant;
Two (N-crassitude) the pentane bromine salt brine solutions of 1,5-, solid content is 43.79wt%, by Guangzhou, Fine Chemical Works production is arranged greatly;
Two (N-crassitude) the pentane villaumite salt brine solutions of 1,5-, solid content 45.28wt% has greatly Fine Chemical Works production by Guangzhou;
Alkaline silica sol, SiO
2Solid content 30wt% is produced by Beijing flying dragon equine trade company limited;
Solids crude piece silica gel, SiO
2Solid content 92.5wt% is produced by Qingdao Marine Chemical Co., Ltd.;
Silica gel microball, SiO
2Solid content 90.13wt% is produced by Qingdao Marine Chemical Co., Ltd.;
Pseudo-boehmite, solid content 66.3wt% is produced by Chang Ling catalyzer branch office of limited-liability company of China Petrochemical Industry.
Comparative Examples 1
Comparative Examples 1 explanation documents 1 (synthetic, the sign of IM-5 and NU-88 molecular sieve and catalysis characteristics; Synthesis, characterization, and catalytic properties of zeolites IM-5 and NU-88.Journal of Catalysis 2003:215 151～170) in the synthetic method of disclosed IM-5 molecular sieve.
Salt and NaOH, Al (NO with two (N-crassitude) pentanes of 1,5-
3)
39H
2(98%, Junsei), (Aerosil 200, Degussa) are mixed and made into colloid with deionized water, mole the consisting of of reaction mixture: SiO for white carbon black for O
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 21.9: 9: 2400.Gained mixture stirring at room 24 hours is transferred to the colloid that makes in 45ml teflon-lined crystallizing kettle, and in rotating crystallization under 160 ℃ after 14 days, rotating speed is 100rpm.Stop crystallization, product namely obtains the IM-5 molecular sieve after washing, filtration, oven dry.
The X-ray diffractogram (XRD) of gained IM-5 molecular sieve is seen accompanying drawing 1
Comparative Examples 2
Comparative Examples 2 explanation documents 2 (IM-5: the shape slective cracking molecular sieve of a kind of high thermal stability and hydrothermal stability; IM-5:A Highly Thermal and Hydrothermal Shape-Selective Cracking Zeolite.Journal of Catalysis 2002:206,125～133) disclosed IM-5 Zeolite synthesis method in.
(Aerosil 200, Degussa) in joining the aqueous solution of two (N-crassitude) the pentane bromine salt of 1,5-under the condition that stirs, and then add respectively sodium aluminate (CarloErba, 56%Al with the white carbon black of aequum
2O
3), the aqueous solution of NaOH (Prolabo, 98%), NaBr (Scharlau, 99%), make colloid, mole the consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 17: 6: 10: 2400.Gained mixture stirring at room 30 minutes was transferred to the colloid that makes in the teflon-lined crystallizing kettle, in 175 ℃ of lower crystallization 10 days.Stop crystallization, product namely obtains the IM-5 molecular sieve after washing, filtration, oven dry.
Embodiment 1
The synthetic method of embodiment 1 explanation IM-5 molecular sieve provided by the invention.
(1) sodium metaaluminate (NaAlO
2) preparation of solution
Take 194g NaOH and be dissolved in approximately in the 500ml deionized water, add 153g pseudo-boehmite (solid content 66.3%), boiling 30min obtains clear solution.Gained liquid is made into 1L solution while hot, and is cooling standby.
(2) 2.95g NaOH is dissolved in the 25.57g deionized water, then adds the NaAlO of preparation in 4.01g step (1)
2The aqueous solution and 27.40g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, make colloid, continue to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 13.5: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 160 ℃ after 6 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
The synthetic method of embodiment 2 explanation IM-5 molecular sieves provided by the invention.
1.65g NaOH is dissolved in the 24.66g deionized water, then adds the NaAlO of preparation in 12.04g embodiment 1 step (1)
2The aqueous solution and 18.27g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, then add SiO
2IM-5 molecular sieve after the roasting of the 5wt% of weight is made colloid as crystal seed (seed), continues to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H2O=60: 3: 13.5: 6: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 160 ℃ after 5 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 3
The synthetic method of embodiment 3 explanation IM-5 molecular sieves provided by the invention.
2.88g NaOH and 2.06g NaBr are dissolved in the 21.95g deionized water, then add the 2.01g NaAlO of preparation in embodiment 1 step (1)
2The aqueous solution, 36.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, make colloid, continue to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 0.5: 12: 6: 12: 1200, water silicon ratio was 20: 1.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 160 ℃ after 4 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 4
The synthetic method of embodiment 4 explanation IM-5 molecular sieves provided by the invention.
1.99g NaOH is dissolved in the 21.74g deionized water, then adds the NaAlO of preparation in 4.01g embodiment 1 step (1)
2The aqueous solution and 27.40g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and add 12.97g solids crude piece silica gel in mixing solutions, make solidliquid mixture.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 9.9: 6: 600, water silicon ratio is 10: 1.The solidliquid mixture that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 160 ℃ after 8 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
The synthetic method of embodiment 5 explanation IM-5 molecular sieves provided by the invention.
With 4.00g NaOH and 0.45g AlCl
3Be dissolved in the 32.72g deionized water, then add 20.61g1, two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, make colloid, continue to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 0.5: 15: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 140 ℃ after 10 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 6
The synthetic method of embodiment 6 explanation IM-5 molecular sieves provided by the invention.
With 4.80g NaOH and 0.89g AlCl
3Be dissolved in the 91.65g deionized water, then add 27.47g1, two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and add the 13.31g silica gel microball in mixing solutions, make solidliquid mixture.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 18: 9: 1800, water silicon ratio is 30: 1.The solidliquid mixture that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 180 ℃ after 6 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 7
The synthetic method of embodiment 7 explanation IM-5 molecular sieves provided by the invention.
With 3.12g NaOH, 2.06g NaBr and 3.75g Al (NO
3)
39H
2O is dissolved in the 27.29g deionized water, then adds 16.44g 1, and two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and add 12.97g solids crude piece silica gel in mixing solutions, make solidliquid mixture.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 11.7: 6: 5: 900, water silicon ratio was 15: 1.The solidliquid mixture that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 180 ℃ after 4 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 8
The synthetic method of embodiment 8 explanation IM-5 molecular sieves provided by the invention.
2.05g NaOH is dissolved in the 14.39g deionized water, then adds the NaAlO of preparation in 12.04g embodiment 1 step (1)
2The aqueous solution and 36.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, then add SiO
2Synthetic precursor after the 10wt% roasting of weight is made colloid, continues to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 3: 15: 12: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 160 ℃ after 3 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 9
The synthetic method of embodiment 8 explanation IM-5 molecular sieves provided by the invention.
With 3.36g NaOH, 2.06g NaBr and 3.75gAl (NO
3)
39H
2O is dissolved in the 31.10g deionized water, then adds 20.61g 1, and two (N-crassitude) the pentane villaumite salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 40g alkaline silica sol, then add SiO
2IM-5 molecular sieve after the 5wt% roasting of weight is made colloid as crystal seed, continues to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: NaBr: R: H
2O=60: 1.5: 12.6: 6: 9: 1200.The colloid that makes is transferred in 50ml teflon-lined autoclave, in rotating crystallization under 180 ℃ after 3 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
The effect of the synthetic IM-5 molecular sieve of embodiment 2 liters of crystallization devices of 10 explanation employings provided by the invention.
49.76g NaOH is dissolved in the 643.70g deionized water, then adds the NaAlO of preparation in 100.35g embodiment 1 step (1)
2The aqueous solution and 319.71g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and add 324.32g solids crude piece silica gel in mixing solutions, make solidliquid mixture.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 9.9: 4: 600, water silicon ratio is 10: 1.The solidliquid mixture that makes is transferred in 2L stainless steel crystallizing kettle, in rotating crystallization under 160 ℃ after 4 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Embodiment 11
The effect of the synthetic IM-5 molecular sieve of embodiment 2 liters of crystallization devices of 11 explanation employings provided by the invention.
36.88g NaOH is dissolved in the 319.65g deionized water, then adds the NaAlO of preparation in 50.18g embodiment 1 step (1)
2The aqueous solution and 342.54g 1, two (N-crassitude) the pentane bromine salt brine solutions of 5-mix, and under the condition that stirs, slowly drip the 500g alkaline silica sol, then add SiO
2IM-5 molecular sieve after the 5wt% roasting of weight is made colloid as crystal seed, continues to stir 2 hours.Mole consisting of of reaction mixture: SiO
2: Al
2O
3: Na
2O: R: H
2O=60: 1: 13.5: 9: 1200, water silicon ratio is 20: 1.The colloid that makes is transferred to 2L stainless steel crystallizing kettle, in rotating crystallization under 160 ℃ after 3 days, stops crystallization, product is after washing, filtering, and 80 ℃ of oven dry are spent the night and namely obtained the IM-5 molecular sieve.
Synthetic molecular sieve is carried out X diffraction analysis (XRD) and scanning electron microscope is taken pictures, the results are shown in Figure 2-4.X diffraction analysis instrument is Japan reason D/MAX-III A type diffractometer, and test condition is the Cu target, K α radiation, and tube voltage is 35KV, tube current is 35mA.
Scanning electron microscope is taken pictures (SEM), and instrument is the Quanta 200F of FEI Co. type scanning electron microscope, acceleration voltage 20.0KV.
The transmission electron microscope photo instrument is the TECNAIG of FEI Co.
2F20, acceleration voltage 200KV.
By accompanying drawing 2 as seen, method provided by the invention can at low water silicon ratio, in larger crystallization device, utilize shorter crystallization time to synthesize the IM-5 molecular screen primary powder.By accompanying drawing 3 and accompanying drawing 4 as seen, synthetic IM-5 molecular sieve crystal pattern is for long bar-shaped, uniform crystal particles, and better crystallinity degree exists without amorphous substance.
Claims (10)
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| CN103483137B (en) * | 2012-06-11 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of ethylbenzene conversion is the method for benzene and paraxylene |
| CN103708491B (en) * | 2012-09-28 | 2015-07-29 | 中国石油化工股份有限公司 | The method of synthesis IM-5 molecular sieve |
| CN103693654B (en) * | 2012-09-28 | 2018-07-31 | 中国石油化工股份有限公司 | A method of synthesis IM-5 molecular sieves |
| CN103723740B (en) * | 2012-10-12 | 2015-06-17 | 中国石油化工股份有限公司 | Synthesis method of IM-5 molecular sieve |
| CN103466652B (en) * | 2013-09-03 | 2015-04-15 | 山西大学 | IM-5 molecular sieve and preparation method for catalyst thereof |
| CN106608638B (en) * | 2015-10-26 | 2019-04-16 | 中国石油化工股份有限公司 | A method of preparing multi-stage porous Y type molecular sieve |
| CN107020145B (en) * | 2016-01-29 | 2020-11-13 | 中国石油化工股份有限公司 | Mesoporous IM-5 molecular sieve and preparation method thereof |
| CN107151022B (en) * | 2016-03-02 | 2020-03-24 | 中国石油化工股份有限公司 | Mesoporous P-IM-5 molecular sieve, and preparation method and application thereof |
| CN107032368B (en) * | 2017-04-13 | 2019-08-06 | 上海交通大学 | A kind of MTW zeolite nanorod with intergrowth structure and its preparation method |
| CN107324356A (en) * | 2017-06-28 | 2017-11-07 | 中国石油天然气集团公司 | One kind is mesoporous to select type molecular sieve and preparation method thereof |
| CN109574032B (en) * | 2017-09-29 | 2020-12-04 | 中国石油化工股份有限公司 | Synthetic method of IM-5 molecular sieve |
| CN109592697B (en) * | 2017-09-30 | 2022-07-12 | 中国石油化工股份有限公司 | IM-5 molecular sieve and its synthesis method |
| CN110407226B (en) * | 2018-04-26 | 2021-04-06 | 中国石油化工股份有限公司 | Method for synthesizing NU-88 molecular sieve |
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