CN102502696A - Synthetic method of ZSM-5 zeolites - Google Patents

Synthetic method of ZSM-5 zeolites Download PDF

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CN102502696A
CN102502696A CN2011103645160A CN201110364516A CN102502696A CN 102502696 A CN102502696 A CN 102502696A CN 2011103645160 A CN2011103645160 A CN 2011103645160A CN 201110364516 A CN201110364516 A CN 201110364516A CN 102502696 A CN102502696 A CN 102502696A
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郭洪臣
刘春燕
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Dalian University of Technology
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Abstract

The invention belongs to the synthesis field of aluminosilicate ZMS (Zeolite Molecular Sieve), and relates to a synthetic method of ZSM-5 zeolite molecular sieves. ZSM-5 zeolites are high-silicon micro-porous zeolites with unique three-dimensional ten-membered ring crossing aperture passages, the diameters of the aperture passages are close to the sizes of benzene rings, and the ZSM-5 zeolites can be widely applied to petroleum refining, petrochemical industry and fine chemicals synthesis. Particularly, nano-sized ZSM-5 zeolites achieve larger external surface area and higher intracrystalline diffusion rate, and have higher activity and selectivity as well as strong coking deactivation-resisting capability in hydrocarbons catalysis conversion reactions. The synthetic method regulates the polymerization degrees of silicon sources and aluminum sources respectively by adding acid and alkali so as to obtain highly reactive reactants, and can rapidly achieve nucleus formation in large quantities in a system so as to obtain nano-sized zeolites. The synthetic method is not limited by the types of the silicon sources and the aluminum sources, has strong applicability to raw materials, changes the activity of the raw materials through simple regulation, and can rapidly synthesize products of the nano-sized ZSM-5 zeolites with well crystallinity under the dosage conditions of no template and low-cost templates.

Description

A kind of compound method of ZSM-5 zeolite
Technical field
The invention belongs to the synthetic field of aluminosilicate zeolite, relate to a kind of compound method of ZSM-5 zeolite.
Background technology
The ZSM-5 zeolite (USP 3702886) of U.S. Mobil oil company invention becomes a kind of very important shape selective catalysis material with its unique pore passage structure and good catalytic performance.Famous technology with the exploitation of ZSM-5 zeolite has: the Mobil intermediate distillates takes off cured technology (MDDW), and lubricating oil takes off cured technology (MLDW), catalytic reforming process; The selectoforming of gasoline and M-reforming process; By the Cyclar technology (LPG BTX) of the synthetic aromatic hydrocarbons of light hydrocarbons, Mobil-Badger synthesizing ethyl benzene technology, toluene gasifying process (MTDP); Xylene isomerization process (MVPI), preparing gasoline by methanol technology (MTG) and p-methyl-ethylbenzene synthesis technique (PET).
Following patent and document all relate to the application of ZSM-5 zeolite:
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Catal?Rev?Sci?Eng，23(1981)281-291；Stud?Sci?Catal，24(1985)39-46；Stud?Surf?Sci?Catal，24(1985)65-72；J?Catal，104(1987)484-489；Zeolites，7(1987)503-507；Appl?catal，23(1986)69-80；Appl?catal，35(1987)299-310；Appcatal，59(1990)311-331；Appcatal，42(1988)15-27；Appl?catal，54(1989)289-302；Appl?catal?A，55(1989)65-74；Appl?catal?A，82(1992)37-50；J?Catal，141(1993)548-565；J?Catal，16(1996)687-693；Zeolite，19(1997)161-168；Mieropor.Mesopor.Mater.34(2000)93-97；Appl?catal?A，161(1997)37-42；Appl?Catal?B，18(1998)233-240；
Because the ZSM-5 zeolite belongs to micro-pore zeolite, the duct size is less, so limited its application in the bulky molecular catalysis reaction to a certain extent.At present solution to this problem mainly contains two kinds, a kind ofly is in ZSM-5 zeolite micropore structure, to introduce meso-hole structure or is micropore with the crystallization of pore wall of mesoporous material, is formed with the transmission path that is beneficial to the macromolecular cpd diffusion; Another kind method is exactly synthetic superfine molecular sieves with nanoscale.Material with ZSM-5 zeolite Jie micropore composite structure can improve the diffusion of product; Remedied the deficiency of micro porous molecular sieve; For macromolecular reaction provides favourable sterie configuration, exist with problems such as hydrothermal stability are relatively low but its acidity is more weak always.And the crystal size of molecular sieve is reduced to nano level from micron order, performances such as its mass transfer, absorption and catalysis all can change.With micron order ZSM-5 zeolite facies ratio; The nano-ZSM-5 zeolite has the intracrystalline rate of diffusion of bigger outer surface area and Geng Gao; The duct is short; And there is a large amount of intracrystalline pores, improving the utilization ratio of catalyzer, strengthen the macromole conversion capability, reduce deep reaction, improving aspects such as selectivity and all show more superior performance, in some hydro carbons catalytic conversion reactions, show better active, selectivity and strong anti-coking deactivation ability.At present, the nano-ZSM-5 zeolite has been used as aromizing, the catalyzer of benzene alkylation, preparing gasoline by methanol processes such as (MTG).
Following patent and document all relate to the application of small-grain ZSM-5 zeolite:
US5780703 (nineteen ninety-five), US5401704 (nineteen ninety-five), US5689027 (nineteen ninety-five), US6123834 (1997), US6177374 (1997); US5981817 (1997), US5990365 (1997), WO9847840 (1998), US2001051754 (1999); US6261534 (1999), US6054040 (1999), US5961818 (1999), US5961818 (1999); US2002092797 (calendar year 2001), US6635792 (calendar year 2001), WO0244306 (calendar year 2001), US2003019792 (calendar year 2001); US6900365 (calendar year 2001), US2003038058 (2002), US2004182748 (2003), US6660896 (2003); US6504075 (2003), US7186871 (2003), US2005010074 (2004), US7199070 (2004); W0018089 (2004), US7723554 (2005), US2007112237 (2006), US7297831 (2006); US2009272672 (2007), US2007203377 (2007), CN101108363 (2007), US2008015105 (2007); US7691768 (2007), US2009036723 (2007) CN 101108363 (2007), US2010213101 (2010) J Catal, 187 (1999) 167-176; Appl catal A, 289 (2005) 2-9; Energy Fuel, 20 (2006) 1388-1391; Catal.Commun, 9 (2008); J Catal, 251 (2007) 258-270; Chem Mater, 21 (2009) 641-654; Catal.Commun, 10 (2008) 169-172; Catal.Commun, 10 (2009) 1582-1585; Mieropor.Mesopor.Mater.119 (2009) 18-22; Pet.Sci.Technol, 28 (2010) 219-224; The catalysis journal, 19 (1998) 234-237; The catalysis journal, 19 (1998) 432-435; The catalysis journal, 19 (1998) 53-57; Petrochemical complex, 29 (2000) 401-404; The Dalian University of Science & Engineering journal, 43 (2003) 571-577; The catalysis journal, 24 (2003) 585-589; Journal of Molecular Catalysis, 18 (2004) 109-114; The catalysis journal, 26 (2005) 216-222; The petrochemical complex Journal of Chinese Universities, 20 (2007) 32-32; The petrochemical complex Journal of Chinese Universities, 18 (2005) 20-23; Journal of Molecular Catalysis, 17 (2003) 140-145; The chemical industry journal, 58 (2007) 913-918; High chemical journal, 27 (2006) 929-934; The catalysis journal, 28 (2007) 567-571;
Because the huge applications potentiality that the nano-ZSM-5 zeolite all shows in numerous reactions make and produce the focus that nano-ZSM-5 becomes domestic and international research always.Existing a lot of about this respect synthetic report at present.
It is synthesis of nano ZSM-5 zeolite in the system of template that following patent and open source literature all relate at quaternary ammonium hydroxide and quaternary ammonium salt:
U.S. Pat 3926782 (1975) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: on the basis of patent US3702886 with TPAOH; 4-propyl bromide or both mixtures are as structure directing agent; Crystallization process adopts violent stirring to reach high mass transfer velocity, at 75～205 ℃ of following crystallization 1 hour～obtained in 6 days, the ZSM-5 zeolite of 5～100nm.Molar ratio is SiO 2/ Al 2O 3=15～300, Na 2O/SiO 2=0.14～2, TPA +/ (TPA ++ Na +)=0.4～0.9, H 2O/OH -=10～300.But the essence of this method is rely on to use expensive quaternary ammonium salt and quaternary ammonium hydroxide to do the purpose that template and two kinds of means of violent stirring reach synthesis of nano ZSM-5 zeolite.
European patent EP 0173901 (1985) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: with raw mix 80 ℃ of following pre-treatment 6 hours; Then with the pre-treatment thing with 15% ratio with newly join raw mix 175 ℃ of following crystallization 8 hours; Can obtain silica alumina ratio and be 60 ZSM-5 zeolite; Grain-size is about 100～300nm, quaternary amines template (TPA, consumption (mol ratio R:SiO TEA) 2) can be decreased to 0.05.Molar ratio is SiO 2/ Al 2O 3=40～80, (Si+Al)/H 2O=0.06～0.09, R/SiO 2＜0.4, H 2O/OH -=50～70.80 ℃ of following pre-treatment of 6 hours in this method are equivalent to prepare directed agents with the aged method, and still need use expensive quaternary amines template to reach the purpose of synthesis of nano ZSM-5 zeolite.
U.S. Pat 4606900 (1986) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: on the basis of patent US3702886; In the reaction system that contains a large amount of template, add the amorphous silicon alumina gel directed agents for preparing in advance with tetrapropyl quaternary ammonium salt or quaternary ammonium hydroxide; Crystallization rate can be accelerated on the one hand, percent crystallinity can be improved on the other hand.This method can obtain the ZSM-5 zeolite of 100nm～100um through the amount of control amorphous silicon alumina gel crystallization accelerator.The molar ratio of patent is SiO 2/ Al 2O 3＞5, Na 2O/SiO 2=2 * 10 -10～2, TPA/SiO 2=0.01～2.0, H 2O/OH -=0.7～3000.This method is to rely on directed agents and expensive quaternary amines template to reach the purpose of synthesis of nano ZSM-5 zeolite.
World patent WO 9703019 (1997) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: with Tai-Ace S 150, silicon sol, ammoniacal liquor and TPAOH is raw material, adopts the clear liquid synthesis method to synthesize nano-ZSM-5.A certain proportion of Tai-Ace S 150 and silicon sol are joined in the TPAOH aqueous solution of ebullient 20% continuously, and reflux conditions stirred 10 minutes down, obtained clear liquid, was cooled to room temperature.Clear liquid is placed the matrass that reflux cooler is housed, 80 ℃ of backflows.The molar ratio of patent is SiO 2/ Al 2O 3=8～10, K 2O/Al 2O 3=0.25～0.5, (TMA) 2O/SiO 2=0.05, H 2O/Al 2O 3=80～100.The characteristics of this method are to adopt compound method under stillness of night normal pressure and the low temperature, and need to adopt expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Zeolites, 14 (1994) 643-649 have introduced the compound method of a kind of ZSM-5.This method is that silicon source, 4-propyl bromide are that template, sodium hydroxide are that alkali source, aluminum nitrate are the aluminium source with silicon sol or the silicon that from GEOTHERMAL WATER, obtains, and dynamic crystallization under 433K obtains the ZSM-5 zeolite aggregate of 30～50nm.This method is that dependence is stirred and expensive 4-propyl bromide is the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Zeolites, 15 (1995) 611-619 have introduced the method for the synthetic ZSM-5 zeolite of a kind of clear liquid method.This method is that raw material has synthesized nano-ZSM-5 with Tai-Ace S 150, tetraethyl silicate, ammoniacal liquor and TPAOH.At first; Prepare tetrapropyl aluminium under certain condition with ammoniacal liquor and Tai-Ace S 150, TPAOH; Make tetraethyl silicate hydrolysis 10～24h in the TPAOH aqueous solution then, again with the tetrapropyl aluminium of preparation under intensive stirs, join in the hydrolyzed solution of tetraethyl orthosilicate; Mixed clear liquid is 98 ℃ of refluxed, and synthesizing grain-size is the nano-ZSM-5 zeolite of 130～230nm.The essence of this method is employing stillness of night method, stirring is synthetic and low temperature is synthetic, and expensive tetrapropyl hydrogen-oxygen ammonium is the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Micropor.Mesopor.Mater, 39 (2000) 135-147 have introduced the compound method of a kind of ZSM-5.This method is a raw material with TEOS and aluminum isopropylate, and TPAOH is that template adopts no sodium clear liquid method to synthesize the ZSM-5 zeolite that elementary crystal grain is 10～100nm under higher basicity.The feed molar proportioning is 1Al 2O 3: 60SiO 2: 21.4TPAOH: 650H 2O at 170 ℃ of following crystallization 48h, finds that the existence of sodium ion has reduced the crystallization velocity of ZSM-5 zeolite, causes crystal grain obviously to increase.What this method adopted is the synthetic purpose of using expensive tetrapropyl hydrogen-oxygen ammonium to reach synthesis of nano ZSM-5 zeolite as methods such as template that reaches of high basicity, the stillness of night.
Open source literature Micropor.Mesopor.Mater, 57 (2003) 83-92 have introduced a kind of method for preparing the ZSM-5 zeolite based on the two-step approach synthesis program.This method is at first synthesized total silicon zeolite (silicalile-1) under the condition that does not add the aluminium source.With the total silicon zeolite is that crystal seed, Tai-Ace S 150 are that aluminium source, silicon oxide are that silicon source, TPAOH are template, adopts clear liquid synthetic method, and 80 ℃ of following normal pressures, backflow synthesize the ZSM-5 that grain-size is 100～300nm.The advantage of this method is the concentration through crystal seed in the adjustment mother liquor, can the better controlled grain-size.Its essence is that the combined method that adopts stillness of night colloid, low temperature crystallized and expensive TPAOH to do template reaches the purpose of synthesis of nano ZSM-5 zeolite.
Open source literature Langmuir, 20 (2004) 8301～8306 have introduced the compound method of a kind of ZSM-5.This method adopts the clear liquid method to obtain the small-grain ZSM-5 zeolite aggregate of 100～600nm at 165 ℃ of following crystallization 120h.Silica alumina ratio=40, TPAOH/Si=0.36, the use of organic formwork agent helps to form rapidly a large amount of nucleus.But this method requires the content of sodium ion in the raw material extremely low owing to be that no sodium synthesizes, and this requires highly to raw material, and correspondingly cost is also high.Its essence is and adopt stillness of night method and expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Micropor.Mesopor.Mater, 75 (2004) 41-49 have introduced the compound method of a kind of ZSM-5.It is template that this method adopts expensive TPAOH, and TEOS is a raw material, and sec.-propyl aluminium is aluminium source crystallization more than 12 days under 70～90 ℃ of low temperature, obtains the glomerocryst be made up of the ZSM-5 zeolite of 10～20nm, silica alumina ratio＜60, and TPAOH/Si is about 0.36.Because this method low temperature suppressed the crystalline growth, obtain causing yield very low nanocrystalline the time.Its essence is and adopt low temperature crystallized and expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Open source literature Catalysis Today, 116 (2006) 82～87 have introduced the method for a kind of synthetic ZSM-5.This method in the gelling system of WHITE CARBON BLACK and sodium metaaluminate, respectively with TMAH, tetraethyl-hydrogenation ammonium; TPAOH, TBAH are template, obtain 159.9nm in 45 hours 230 ℃ of following crystallization; 76.3nm, the ZSM-5 zeolite of 55.8nm and 87.2nm.This method adopts is that the expensive tetrapropyl hydrogen-oxygen ammonium of high Gentle is that method such as template reaches the synthetic purpose of receiving the ZSM-5 zeolite.
Chinese patent CN1715186 (application number 200410048354.X, 2004) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: be with SiO 2/ Al 2O 3Mol ratio 20～600, granularity are the aqueous solution of 20～300 purpose alumino silica gel particles and organic formwork agent, carry out hydrothermal crystallizing then, and filtration, dry, roasting obtain product at last.This method can make the ZSM-5 zeolite that silica alumina ratio is 15～200, elementary crystal grain particle is 100～500nm.Molar ratio is SiO 2/ Al 2O 3=20～600, Na 2O/SiO 2=0.25～1, R/SiO 2=0.01～0.2, H 2O/SiO 2=2～15, R is the quaternary ammonium salt template.The characteristics of this method are that the requirement synthetic system does not have the purpose that sodium and quaternary ammonium salt template reach synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1730391 (application number 200510016885.5,2005 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: synthesis of nano yardstick ZSM-5 zeolite under microwave action.At first be added to the water TPAOH and silicon source, under agitation add aluminium source prepare silicon aluminate solution after mixing; The direct microwave of reaction soln 3～180 minutes is synthetic, or 3～30 minutes heating backs of microwave were 150～190 ℃ of crystallization 1～3 day; Spinning or filtration after the crystallization, washing is dry, obtains nano level ZSM-5 zeolite, and its grain size is adjustable in 50～300nm scope, and molar ratio is (0～10) Al 2O 3: (20～30) SiO 2: (100～1500) H 20: (4～45) TPAOH.The essence of this method is to rely on microwave and expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1915819 (application number 200510028781.6,2005 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: before crystallization, in the crystallization mother liquor, adding is the silicon source with tetraethoxy, silicon sol or white carbon black in advance, and TPAOH or 4-propyl bromide are the crystal seed directed agents of template preparation.Directed agents has produced a large amount of ZSM-5 primary structure and secondary structure unit in its preparation weathering process, in the synthetic crystallization process of back, as the nucleus of ZSM-5 zeolite crystallization growth, obtain the ZSM-5 zeolite crystal of 100nm.The molar ratio of patent is XNa 2O: YAl 2O 3: 100SiO 2: ZH 2O, wherein, X=4～36, Y=0～3, Z=1400～6000, the crystal seed guiding dosage preferable range of adding is 1.0～10% of a crystallization mother liquor weight.The essence of this method is to rely on crystal seed directed agents and expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1958453 (application number 200610097462.5,2006 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopting silicone grease or silane is raw material, and 4-propyl bromide is a template, obtains the ZSM-5 zeolite of 100～400nm.The wherein silicon source time hydrolysis in acidic conditions PH＜6.0 in advance, hydrolysis temperature is 20～40 ℃, hydrolysis time is 6～24 hours.Molar ratio is SiO 2/ Al 2O 3=20～200, Na 2O/SiO 2=0.15～0.6, R/SiO 2=0.001～0.02, H 2O/SiO 2=0.1258～3.The essence of this method is to rely on low water silicon than doing the purpose that template reaches synthesis of nano ZSM-5 zeolite with expensive 4-propyl bromide.
Chinese invention patent CN101733143 (application number 200810043970.4,2008 years) has disclosed the method for the synthetic ZSM-5 zeolite of a kind of fractional crystallization.Its technical characterictic is: the sial mixed gel was worn out 4～10 hours down prior to 90～110 ℃, be warming up to 120～150 ℃ again, crystallization 6～30 hours.The lower basicity and the water yield are selected in requirement for use, when guaranteeing the solution alkali concn, make reaction mixture in crystallization process, keep hypersaturated state, thereby help a large amount of formation of low temperature crystallized stage molecular sieve nucleus.The ZSM-5 nucleus that the high temperature crystallization helps forming is grown fast, obtains the ZSM-5 zeolite less than 300nm.Molar ratio is SiO 2/ Al 2O 3=400～1500, Na 2O/SiO 2=0.2～2, R/SiO 2=0.02～2, H 2O/SiO 2=10～35.The essence of this method is the purpose that the combined method that adopts low temperature aging, low wash water, fractional crystallization and expensive TPAOH to do template reaches synthesis of nano ZSM-5 zeolite.
The open source literature Chinese Journal of Inorganic Chemistry, 19 (2003) 396 have introduced the compound method of a kind of ZSM-5.This method is template with the 4-propyl bromide, and silicon sol is the silicon source, and Tai-Ace S 150 is that aluminium source crystallization 1～9d under 100～150 ℃ of crystallization temperatures obtains the nano-ZSM-5 zeolite.This method requires in synthetic system, to add an amount of an alkali metal salt, an alkali metal salt and Al 2O 3Ratio in 40～120 scopes, the particle diameter of ZSM-5 zeolite is dropped to about 60nm.The essence of this method is the purpose that the combined method that adopts low temperature aging, add an alkali metal salt and use expensive TPAOH to do template reaches synthesis of nano ZSM-5 zeolite.
Open source literature petrochemical complex Journal of Chinese Universities, 18 (2005) 20～23 have introduced the compound method of a kind of ZSM-5.This method is template with the TPAOH, and aluminum isopropylate is the aluminium source, and water glass is the silicon source, adopts moistened surface method synthesis of nano ZSM-5 zeolite.Aluminum isopropylate and TPAOH solution are mixed according to certain ratio, stir, clarify fully until solution with magnetic stirring apparatus.Above-mentioned settled solution is joined in a certain amount of silica gel, and the limit edged stirs, until the silica gel complete wetting.Wetting silica gel is completely added in the crystallizing kettle, obtain the ZSM-5 zeolite of 100nm at 170 ℃ of following crystallization 2～4d.The essence of this method is to adopt dampening and expensive TPAOH to do the purpose that template reaches synthesis of nano ZSM-5 zeolite.
Quaternary ammonium hydroxide and quaternary ammonium salt are that a kind of cost is high, produce the molecular sieve synthesis material of high pollution, highly toxic chemical exhaust when removing, and a large amount of uses can make the synthetic cost of molecular sieve significantly increase.In order to reduce the synthetic cost of molecular sieve, Many researchers attempts replacing TPAOH synthesis of nano ZSM-5 zeolite with other template, is aided with salt, low temperature aging means such as stirring simultaneously.
Following patent and open source literature have all related to the method with non-quaternary amines template synthesis of nano ZSM-5 zeolite:
U.S. Pat 4151189 (1979) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: on the basis of patent US3702886, use instead contain 2-9 carbon atom primary amine as template, synthesized the small-grain ZSM-5 zeolite in 24 hours～500 hours 75～300 ℃ of following crystallization.This method is not used expensive quaternary ammonium salt or quaternary ammonium hydroxide, and only introduces a spot of alkali metal cation.Molar ratio is SiO 2/ Al 2O 3=10～40, Na 2O/SiO 2=0.14～2, R/ (R+Na +)=0.4～0.9, H 2O/OH -=10～300, R is a template.The characteristics of this method are that less salt, low silica-alumina ratio reach synthesis of nano ZSM-5 zeolite.
U.S. Pat 4526879 (1985) has disclosed the method for the synthetic ZSM-5 of a kind of low sodium.Its technical characterictic is: use composite mould plate agent to substitute quaternary ammonium hydroxide and quaternary ammonium salt, obtained the ZSM-5 zeolite that crystal grain is 50nm～20um in 3 hours～30 days 180～350 ℃ of following crystallization.Composite mould plate agent is alkylamine and alkyl halide, controls the crystal size size through the ratio that changes both.Molar ratio is SiO 2/ Al 2O 3=20～200, M/SiO 2=0.01～2.0, R/SiO 2=0.1～1.0, H 2O/SiO 2=15～60.R is a template, and M is basic metal or earth alkali metal.The characteristics of this method are the purposes that low sodium, high temperature and use alkylamine reach synthesis of nano ZSM-5 zeolite.
U.S. Pat 5268162 (1993) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt repeatedly the method for the aging nucleation of alternating temperature, using 1,3 dimethyl-urea is organic directed agents, and synthesizing Si-Al is than the ZSM-5 zeolite that is 25～40, the about 100～500nm of granularity.Molar ratio is SiO 2/ Al 2O 3=25～50, Na 2O/SiO 2=0.2～0.3, SO 4 2-/ SiO 2=0.15～0.25, R/SiO2=0.05, H 2O/SiO 2=20～300.The characteristics of this method are to rely on alternating temperature aging and use the special template agent to be issued to the purpose of synthesis of nano ZSM-5 zeolite at low silica-alumina ratio.
U.S. Pat 6180550 (calendar year 2001) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: raw material is a kind of amorphous silicon aluminum, adopts Tri N-Propyl Amine to make template, and adds crystal seed, makes the ZSM-5 zeolite less than 500nm 100～200 ℃ of following crystallization.Molar ratio is SiO 2/ Al 2O 3=15～20, M/SiO 2=0.15～0.2, R/SiO 2=0～0.4, H 2O/SiO 2=8～20.M is basic metal or earth alkali metal.The characteristics of this method are to rely on crystal seed, an alkali metal salt to be issued to the purpose of synthesis of nano ZSM-5 zeolite at low silica-alumina ratio.
Open source literature Journal of the Indian chemical society, 83 (2006) 686-691 have introduced the method for a kind of synthetic ZSM-5.This method is a template with the quadrol, uses 1.85Na 2O: 0.25Al 2O 3: 15.2SiO 2: 19.7C 2DN: 592H 2O fills a prescription in 177 ℃ of following crystallization 6～10 days, synthesizes the spherical ZSM-5 zeolite that crystal formation perfection, crystal grain are about 500nm.The characteristics of this method are that crystallization time is long.
Chinese invention patent CN1240193 (application number 99102700.0,1999 years) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: be template with the n-Butyl Amine 99, water glass, Tai-Ace S 150 and sodium hydroxide are raw material, through the grain-size that the amount that changes crystallization time, temperature and an alkali metal salt is regulated molecular sieve, obtain the ZSM-5 zeolite of 10～500nm.Molar ratio is SiO 2/ Al 2O 3=20～100, Na 2O/SiO 2=0.04～0.1, R/SiO 2=0.15～0.5, H 2O/SiO 2=40～200.The essence of this method is to rely on the measure of adding an alkali metal salt and low temperature aging to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese patent CN1417121 (application number 02155482.X, 2004) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt directing agent method synthesizing small crystal grain ZSM-5-5 zeolite.Concrete method is by a certain percentage directed agents to be processed in silicon source and template, aluminium source, mineral acid, deionized water; By a certain percentage silicon source and template, aluminium source, mineral acid, deionized water are configured to crystallization mother liquor again, in mother liquor, add the directed agents that accounts for TV 5～10%.120 ℃ of following constant temperature 20～25 hours, 155～165 ℃ of following crystallization prepared the ZSM-5 zeolite about 100nm in 20～25 hours.The mol ratio of directed agents each component is SiO 2: Al 2O 3: Na 2O: organic amine: mineral acid: H 2O=40～80: 1: (7～15): (25～40): (3.0～7.5): (2000～4000).Molar ratio is SiO 2: Al 2O 3: Na 2O: organic amine: mineral acid: H 2O=20～100: 1: 7～15: 2～4: 0.5～8.5: 2000～4000.Organic amine is n-Butyl Amine 99, quadrol, ethamine or 1, the 6-hexanediamine.The essence of this method is to rely on directed agents and low temperature aging to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101837298 (application number 201010171630.7,2010 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: the sial weight ratio of ZSM-5 zeolite is 10～200, and particle diameter is 60～100nm, and the preparation method of this molecular sieve is following: with alkyl alcohol, alkylamine and aromatic amine are formed ternary organic template agent; The silicon source is dissolved in ternary organic template agent and water is made into A liquid; The aluminium source is dissolved in organic acid and water obtains B liquid; Under the vigorous stirring state, B liquid is added in the A liquid, be mixed with colloidal solution, the synthesis reactor of packing into reaction and crystallization are cooled to room temperature, and water promptly gets the small-grain ZSM-5 zeolite after with synthetic product washing, drying.Molar ratio is Na 2O: SiO 2: Al 2O 3: H 2O: ternary organic template agent=5～18: 20～150: 1: 700～3500:: 0.05～100.The essence of this method is to rely on stirring and polynary template to reach the purpose of synthesis of nano ZSM-5 zeolite.
Open source literature chemistry journal, 12 (1978) 85-87 have introduced the compound method of a kind of ZSM-5.It is template that this method adopts n-Butyl Amine 99, ethamine or tripropyl amine, and water glass is the silicon source, and Tai-Ace S 150 is that static crystallization were descended 12 hours at 105 ℃ in the aluminium source, obtains the ZSM-5 zeolite less than 100nm in 38 hours 125 ℃ of crystallization again.But this method must add NaCl when synthetic, and makes NaCl/Al 2O 3Mol ratio is in 30～60 scopes, the too high or too low small-grain ZSM-5 zeolite that all can not get.The essence of this method is to rely on interpolation an alkali metal salt and low temperature aging to be issued to the purpose of synthesis of nano ZSM-5 zeolite at low silica-alumina ratio.
The open source literature refining of petroleum, 12 (1983) 744-748 have introduced the compound method of a kind of ZSM-5.This method is template with the n-Butyl Amine 99, and water glass is the silicon source, and Tai-Ace S 150 is the aluminium source, and sodium hydroxide is alkali source obtains 100nm and 700nm 100～130 ℃ of following crystallization ZSM-5 zeolite.Through adding inorganic salt modulation zeolite particle diameter, find that the content that increases NaCl can make its crystal grain be decreased to about 70 nanometers.The essence of this method is to rely on interpolation NaCl and low temperature aging to be issued to the purpose of synthesis of nano ZSM-5 zeolite at low silica-alumina ratio.
In addition, there is the scholar to adopt space constraint method synthesis of nano ZSM-5.The growth that the space constraint method is come restriction molecule sieve crystal grain by means of the hole of gac nano-scale, but the zeolite product of pure phase just can be obtained after needing after synthetic the gac oxidation removed, and complex manufacturing and cost are high.
The following discloses document has related to the method for space constraint method synthesis of nano ZSM-5 zeolite:
Open source literature Chem.Commum, (1999) 673-674 have introduced the method for the synthetic ZSM-5 zeolite of a kind of space constraint method.This method is a template with TPAOH, is the silicon source with TEOS, growth total silicon nano-ZSM-5 zeolite in the pore structure of carbon black matrix.But it is bigger that this method synthetic nano zeolite is influenced by the pore size distribution of inert media, to having relatively high expectations of inertia mesoporous material; Must guarantee that also synthetic liquid gets into the mesoporous inside of inert media fully, reduces the residual quantity outside the hole; The inert media large usage quantity, and need take roasting method to remove, increased cost.
Open source literature Chem Mater, 15 (2003) 1664-1668 have introduced the compound method of a kind of ZSM-5.This method with raw materials mix such as aluminum isopropylate, tetraethyl silicate, water, TPAOH and ethanol after, be impregnated on the gluey charcoal template, then 180 ℃ of following crystallization 48h.570 ℃ of following roasting 8h remove gluey charcoal, synthesize the ZSM-5 that the homogeneous grain-size is 13nm, 22nm, 42nm and 90nm.This method synthetic grain-size homogeneous, but cost is higher.
Open source literature petrochemical complex Journal of Chinese Universities, 18 (2005) 17～19 have introduced the compound method of a kind of ZSM-5.This method adopts mesoporous carbon to receive the material pipe for inertial base, is raw material with tetraethoxy, n-Butyl Amine 99, the vitriol oil, sodium hydroxide, absolute ethyl alcohol.Obtain the nano-ZSM-5 molecular sieve that mean grain size is 27nm through restriceted envelope size method at 170 ℃ of following crystallization 4～5d.This method is carried out on the hydrothermal method basis, relates to crystallization in the hole of matrix, limits the size of grain-size with the hole dimension of carbon base body.But still find the grain fineness number wider distribution of institute's synthesis of nano molecular sieve, have of the crystal grain existence of a certain amount of grain-size greater than the matrix hole size.
Former study shows that though use organic formwork agent can synthesize purity and the very high zeolite of degree of crystallization, the price of template itself but is a costliness very, and there is the pollution problem to environment in process.And use organic formwork agent synthetic ZSM-5 zeolite to need high-temperature roasting, to remove organism contained in the zeolite cavity, removed template method produces atmospheric pollution again.In view of the many disadvantages of using organic amine, it is on the inorganic method that Many researchers are just transferred to non-organic amine template to sight, and the process of synthetic ZSM-5 zeolite has been carried out a large amount of systematic studyes.
Following patent and open source literature have all related to the method for inorganic method synthesis of nano ZSM-5 zeolite:
U.S. Pat 5240892 (1993) has disclosed the method for the synthetic ZSM-5 zeolite of a kind of inorganic method high-density.Its technical characterictic is: do not use organic formwork agent; Earlier water-soluble silicate (like water glass) is processed non-water-soluble deposition silica gel with mineral acid precipitation agent deposition; Precipitating silica gel with this is that the silicon source is prepared into the solid content that contains silicon source, aluminium source, alkali and water and is at least 35% heavy reaction mixture, then this reaction mixture is being stirred and is being lower than the ZSM-5 zeolite that crystallization under 250 ℃ the condition obtains 5～20nm granularity.Molar ratio is SiO 2/ Al 2O 3=25～50, Na 2O/SiO 2=0.22, H 2O/SiO 2=5.This method is that employing deposition silica gel is the silicon source, relies on low wash water and stirs crystallization is issued to synthesis of nano ZSM-5 zeolite at low silica-alumina ratio purpose.
Open source literature Materials Letters, 59 (2005) 3827-3430 have introduced the compound method of a kind of ZSM-5.This method is a raw material with silicon sol, sodium metaaluminate and sodium hydroxide under the condition of not using organic formwork agent, and ratio of components is 12Na 2O: 100SiO 2: 2Al 2O 3: 2500H 2O.The aging at normal temperatures 12h of feed liquid, 180 ℃ of following crystallization 24h synthesize the ZSM-5 that grain-size is about 15nm.The essence of this method is to rely on low temperature aging to reach the purpose of synthesis of nano ZSM-5 zeolite, but the zeolite crystal size that obtains is inhomogeneous not high with percent crystallinity, also exists stray crystal to equate.
Open source literature Journal of Materials Processing Technology, 206 (2005) 445 have introduced a kind of method of not having template synthesis of nano ZSM-5 zeolite, but this method can only synthesize specific silica alumina ratio (SiO 2/ Al 2O 3Be 50) the nano-ZSM-5 zeolite, work as SiO 2/ Al 2O 3Mol ratio was greater than or less than 50 o'clock, and stray crystal phases such as mordenite all appear in the crystallization product that obtains, and can't prepare the pure phase nanometer ZSM-5 zeolite of high-crystallinity.
Chinese invention patent CN1067226 (application number 92103601.9,1992 years) has disclosed the method for a kind of synthetic ZSM-5.Its technical characterictic is: with a kind of specific surface that contains is 100～250m 2The nucleus that contains of/g partial crystallization forms slurries and raw materials mix post-heating, can obtain containing specific surface area greater than 250m 2The product slurry of the particulate zeolite of/g.Be actually through preparing a kind of grain fineness number of preparatory crystallization slurry mixture control molecular sieve, in the hope of reaching the purpose of producing particulate zeolite.Molar ratio is SiO 2/ Al 2O 3=20～50, Na 2O/SiO 2=0.2～0.4, SO 4 2-/ SiO 2=0.1～0.3, H 2O/SiO 2=40～200.The essence of this method is to rely on directed agents to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN1303816 (application number 00109593.5,2003 year) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt directing agent method quickly synthesizing small crystal grain ZSM-5-5 zeolite, comprise directed agents preparation, synthetic two steps of molecular sieve.The preparation of the first step directed agents; After at first silicon source and vaal water being processed A solution the organic amine template is added according to ratio of components; Under agitation again the aluminium source is splashed into homogeneous reaction; Regulate potential of hydrogen and carry out the temperature programming processing, approaching transparent part in the synthetic fluid is isolated be directed agents then.The building-up process of molecular sieve is identical with directed agents, just the organic amine template in the proportioning raw materials is replaced by directed agents, and crystallization process needed to accomplish in 65～75 hours, obtained the ZSM-5 zeolite of median size 100nm.Molar ratio is Na 2O: SiO 2: Al 2O 3: H 2O: organic amine=3～10: 20～100: 1: 2500～5000: 25～40.The essence of this method is to rely on directed agents to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101041442 (application number 200710087075.8,2007 years) has disclosed a kind of method of not having the synthetic ZSM-5 zeolite of template.Its technical characterictic is: introduced ultrasonic technology and carried out the crystallization pre-treatment.With silicon source, aluminium source and mineral acid is raw material, having or not having in the presence of the crystal seed silica-alumina gel was carried out ultrasonication 0.5～3 hour in 70 ℃, makes the feed composition thorough mixing form a large amount of nucleus, obtains the ZSM-5 zeolite of 100～500nm.The molar ratio of patent is SiO 2/ Al 2O 3=20～150, Na 2O/SiO 2=0.25～1, H 2O/SiO 2=40～200.The essence of this method is to rely on ultrasonic technology and low temperature aging to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN101643219 (application number 200910072747,2009 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: the crystal seed of preparatory crystallization is joined in the gelling system of no template synthesis of nano ZSM-5 zeolite, in 160～180 ℃ of following crystallization 24 hours, be cooled to room temperature with product centrifuging, washing, drying, roasting., obtain the nanoscale height accumulative ZSM-5 zeolite of silica alumina ratio 60～160.The molar ratio of patent: 7.2～19.2Na 2O: 1Al 2O 3: (60～160) SiO 2: (1500～4000) H 2O.The essence of this method is to rely on crystal seed to reach the purpose of synthesis of nano ZSM-5 zeolite.
Chinese invention patent CN 101654259 (application number 200910172206.1,2009 years) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt twin columns method preparation gel, soon silicon source, aluminium source are added drop-wise to identical speed simultaneously and prepare gel in the high speed agitator.Take by weighing silicon source solution 300-500 part by weight, the concentration that joins the parts by weight that measure and be 200-300 part is in 10% the NaOH aqueous solution, adds parts by weight and be 350 parts pure water and high-speed stirring 2 hours, forms translucent milky white solution; Take by weighing aluminium source solution 30-60 part by weight, adding the parts by weight that measure is in 1200 parts of pure water, and stirring at room 2 hours forms clear solution; Then silicon source and aluminium source are added dropwise in the high speed agitator with the interpolation speed that 100-300ml/ divides simultaneously, drip with continued and stirred 1 hour, form the oyster white homogeneous gel.Gel is processed high-crystallinity, highly purified small-grain ZSM-5 zeolite 140 ℃～240 ℃ following crystallization 1～100 hour.Its elementary crystal grain can reach 20～30nm, and the silica alumina ratio basically identical of each crystal grain.This method need not introduced organic formwork agent, its essence is to rely on the twin columns method under the condition of high-speed stirring, to prepare burden and crystallization reaches the purpose of synthesis of nano ZSM-5 zeolite, but complicated operating process.
Chinese invention patent CN 102001680 (application number 201010588177.X, 2010) has disclosed a kind of method of synthetic ZSM-5 zeolite.Its technical characterictic is: adopt two-step approach to prepare presoma, do not have promptly that template agent method prepares liquid stock and the agitation and dropping legal system is equipped with mixed glue solution; In glue, add 1～10% crystal seed, obtain the zeolite of 50～100nm 100～200 ℃ of following crystallization.It is with the NaOH in the reactor drum, NaAlO that no template agent method prepares mixing solutions 2Stirred 2-4 hour with the rotating speed of deionized water with PM 200-300, bath temperature is 60-90 ℃, obtains the mixing solutions that mixes; NaOH, NaAlO 2With the mass ratio of deionized water be 10: (3-6): (320-380).It is when mixing solutions is proceeded to stir that the agitation and dropping legal system is equipped with mixed glue solution, in solution, slowly drips silicon sol by volumetric ratio, acquisition mixed glue solution when silicon sol drips after; The volumetric ratio of said mixing solutions and silicon sol is 200: (115-135).The essence of this method is to rely on crystal seed and low temperature aging to reach the purpose of synthesis of nano ZSM-5 zeolite.
The open source literature Industrial Catalysis, 16 (2008) 20～23 have introduced the compound method of a kind of ZSM-5.This method is a raw material with silicon sol and Tai-Ace S 150, in not introducing the hydro-thermal synthetic system of organic formwork agent, adds self-control crystal seed directed agents and obtains the ZSM-5 zeolite less than 100nm.Prepared crystal seed directed agents be total silicon Silicalite-1 zeolite nano particle, zeolite is elementary or the SiO of secondary structure unit 2And the mixed colloidal solution of template TPAOH.The preparation method is to be raw material with TPAOH (TPAOH) solution with positive tetraethyl orthosilicate (TEOS), according to n (TPA) 2O: n (SiO 2): n (EtOH): n (H 2O)=and 1: 5.5: 22: 0 mixes, and stirred overnight under the room temperature makes at the aging certain hour of certain temperature then.The essence of this method is to rely on nanometer crystal seed directed agents to reach the purpose of synthesis of nano ZSM-5 zeolite.
More than inorganic method successfully overcome the variety of issue that organic formwork agent exists, but the synthetic ZSM-5 zeolite sial of inorganic method is lower, in most cases percent crystallinity is relatively poor relatively, product performance are not as synthesizing with the organic formwork agent method.
From patent documentation, synthesis of nano ZSM-5 zeolite is still a challenge at present.Though it is a lot of to relate to the report of this respect; Get up to use nothing more than directed agents, nanometer crystal seed, tensio-active agent, inorganic salt but sum up; Or use the inertia mesoporous material that hard template is provided, or when crystallization, adopt stirring, methods such as microwave, ultrasonic and two-part crystallization.Technique effect receives raw material type, and synthetic ratio and crystallization condition influence are very big.
Zeolite is to be reacted in strong alkali solution by silicate and aluminate, and crystallization generates.As the silicon source and the aluminium source that generate the main starting material of zeolite, multi-silicate radical ion and aluminate ion with different polymerization degree under different acid-base conditions exist, and panoramic zeolite molecular sieve is formed by these structural unit assemblings.We are through discovering, the polymerization state in silicon source and aluminium source has material impact to synthetic nano zeolite.
This is because the silicon source that zeolite synthesis is commonly used can be divided into SiO 2Micelle (silicon sol, solid silicone and amorphous Si O 2Powder) and soluble silicate (water glass, water glass).SiO 2Micelle is a kind of polymer that is formed by connecting silicon-oxy tetrahedron, following depolymerization behavior can take place under the condition of soda acid obtain oligomeric attitude and monomeric silicate:
For soluble silicate; It exists with silicate hydrate root negatively charged ion in the aqueous solution; The silicate ion and the big height of relative molecular mass that can generate oligomeric attitude gather the attitude silicate ion, and height gathers the attitude silicate ion, and depolymerization behavior as above also can take place under the condition of soda acid.That is to say that the aggregation problem in silicon source extensively is present in the various raw materials of synthesis of molecular sieve, the polymerization degree of regulating the silicon source improves that molecular sieve is synthetic to have a universal significance.
On the other hand, pseudo-boehmite, sodium metaaluminate, homemade white lake, mineral acid aluminium salt and aluminum isopropylate are the aluminium commonly used sources in the zeolite synthesis.In basic soln, the main existence form of aluminate ion is Al (OH) 4 -(Na in the solution when alkaline concentration is increased to a certain degree 2The concentration of O is greater than 25%), Al (OH) 4 -Just dewater and be transformed into AlO 2 -Anionic form.Its dehydration has dual mode:
First kind
Figure BDA0000108989890000132
Second kind
Figure BDA0000108989890000133
In acidic solution, aluminium is with Al 3+The form of hydrated ion exists.Acidity is big more, and this hydrated ion is stable more.
So silicon source and aluminium source that height gathers attitude can obtain oligomeric attitude and monomeric silicate and aluminate by stepwise hydrolysis under the condition of soda acid.
In general, the hydrothermal crystallizing synthetic zeolite is via following three phases: silicon source and the reaction of aluminium source generate silica-alumina gel, gel nucleation and crystal growth.Nucleation is the key of whole crystallization process, no matter be homogeneous nucleation or heterogeneous nucleation, a large amount of nucleation will make the reactive behavior species that shortage is enough in the reaction system supply with crystal growth with " nutritive ingredient ", thus the restriction crystalline size.In addition, the size of crystal grain and distribution are decided by nucleation rate and crystalline growth velocity, accelerate nucleation rate and also can cause synthesizing superfine particulate molecular sieve.The silicon source of oligomeric attitude and aluminium source help generating uniform silica-alumina gel, reduce gel and reset the time, cause a large amount of nucleations, thereby it are synthetic to help nano zeolite.
Therefore, when synthetic ZSM-5 zeolite, in silicon source and aluminium source, adding a certain amount of acid or alkali makes it depolymerize to oligomeric attitude or monomeric high reactivity silicate and aluminate, is an important channel that obtains nano zeolite and little crystal grain zeolite.
Summary of the invention
The invention provides a kind of use soda acid and regulate the polymerizable raw material degree respectively, the method for quickly synthesizing nano ZSM-5 zeolite.This method and existing methods difference are, need in building-up process, not introduce expensive template, also need not prepare directed agents with loaded down with trivial details step, need not add inorganic salt, and be strong to adaptability to raw material.The key of control crystal size is the polymerization degree of raw material.Concrete technical scheme of the present invention is:
The first step:, divide two kinds of situation to carry out with the polymerization degree that acid, alkali are regulated silicon source and aluminium source respectively;
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
A is scattered in the silicon source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source with alkali, and the depolymerization time is 5min～100h, adds organic formwork agent again, obtains solution A;
Described silicon source is a kind of and any mixture in silicon sol, water glass, WHITE CARBON BLACK, the solid silicone; Described alkali is with sodium hydroxide, Pottasium Hydroxide, and a kind of and any mixture in the ammoniacal liquor provides; Described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, the ethanol.
B is scattered in the aluminium source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source with acid solution, and the depolymerization time is 5min～100h, obtains solution B.
Described aluminium source is a kind of and any mixture in boehmite, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, white lake, the aluminum isopropylate; A kind of and any mixture in the optional sulfuric acid of said acid solution, phosphoric acid, nitric acid, the hydrochloric acid.
When above preparation solution A, do not add template and can also synthesize the ZSM-5 zeolite, this does not influence the depolymerization in silicon source.Next alkali mole number that is used for the depolymerization of silicon source must equal to be used for the sour mole number of aluminium source depolymerization, cancels out each other to guarantee acid-alkali, does not influence the pH value of gel.
(2) with the polymerization degree in mineral acid adjusting silicon source,, pre-treatment is carried out in silicon source and aluminium source with the polymerization degree that mineral alkali is regulated the aluminium source.
A is scattered in the silicon source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source with acid solution, and the depolymerization time is 5min～100h, adds organic formwork agent again, obtain solution A ';
A kind of and any mixture in the optional silicon sol in described silicon source, water glass, WHITE CARBON BLACK, the solid silicone; A kind of and any mixture in the optional sulfuric acid of said acid solution, phosphoric acid, nitric acid, the hydrochloric acid; Described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, the ethanol.
B is scattered in the aluminium source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source with alkali, and the depolymerization time is 5min～100h, obtain solution B '.
A kind of and any mixture in the optional pseudo-boehmite in described aluminium source, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, white lake, the aluminum isopropylate; Described alkali lye provides with a kind of and any mixture in sodium hydroxide, Pottasium Hydroxide, the ammoniacal liquor.
Equally, when above preparation solution A, do not add template and can also synthesize the ZSM-5 zeolite, this does not influence the depolymerization in silicon source.Next sour mole number that is used for the depolymerization of silicon source must equal to be used for the alkali mole number of aluminium source depolymerization cancels out each other to guarantee acid-alkali, does not influence the pH value of gel.
Second step: with the synthetic ZSM-5 zeolite in silicon source and aluminium source of depolymerization
(1) preparation gel
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente or B ' solution that depolymerization is obtained under agitation is added drop-wise in A ' solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=10～1000, Na 2O/SiO 2=0.05～0.3, R/SiO 2=0～1.0, H 2O/SiO 2=10～50, crystal seed/SiO 2=0～20wt%, R are template.
(2) gel crystallization
With prepared gel hydrothermal crystallizing under optimum conditions, the solid that crystallization goes out through filter, washing, dry, roasting, obtain the nano-ZSM-5 zeolite.
Described crystallization condition is 80～200 ℃ of crystallization temperatures; Crystallization time 1～400 hour.Crystallization can be carried out under static state, but in order to make the crystallization product homogeneous grain diameter, recommends to adopt and stir.Stirring is advisable to reach to mix, can continuously stirring, also can intermittently stir.
The invention has the beneficial effects as follows: reduce the polymerization degree in silicon source and aluminium source respectively through adding soda acid, obtain highly active reactant, can obtain nano zeolite through a large amount of nucleus that produce in system.Need in building-up process, not introduce expensive template, need not prepare directed agents yet, need not add inorganic salt etc. with loaded down with trivial details step.The present invention is not limited to the kind in silicon source and aluminium source, and is strong to adaptability to raw material, and it is active to change raw material through simple adjustment, can and hang down the quick good nano-ZSM-5 zeolite product of synthetic crystallization degree under the cheap template consumption condition in no template.
Embodiment
Below through embodiment the present invention is described further, but therefore do not limit content of the present invention.
Comparative Examples 1: with the synthetic ZSM-5 zeolite in silicon source and aluminium source of not depolymerization
With 104g silicon sol (technical grade, SiO 2>=30wt%) be scattered in the 40g deionized water, add 14.86g n-Butyl Amine 99 solution (technical grade) then, fully stirred 1 hour under the room temperature, process A liquid; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, fully stirs 1 hour under the room temperature, processes B liquid.Then, B solution under agitation is added drop-wise in the A solution lentamente, processes even gel, and add the pH value that 2.78g NaOH solid is regulated gel, continue stir about 1h.The molar ratio of each material is: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26, the even gel that makes is transferred in the synthesis reactor, about 20 hours of 170 ℃ of following crystallization, be cooled to room temperature, filter, washing.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 97%, granularity is 25um.
Comparative Examples 2
Repeat Comparative Examples 1, but in gel, add the 1g crystal seed, crystal seed/SiO 2=3.2wt%.Then obtained ZSM-5 zeolite product in about 6 hours 170 ℃ of following crystallization, granularity is 4um.Its relative crystallinity is 95.2%.
Comparative Examples 3
Repeat Comparative Examples 1, but in gel, add 18.5g Na 2SO 4Then obtained ZSM-5 zeolite product in 16 hours 170 ℃ of following crystallization, granularity is 25um.Its relative crystallinity is 96.4%.
Embodiment 1
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
With 104g silicon sol (technical grade, SiO 2>=30wt%) be scattered in the 40g deionized water, add then and stir abundant hydrolysis 1 hour under the 6.95g NaOH solid room temperature, add 14.86g n-Butyl Amine 99 solution (technical grade) again, process A solution; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, stirs abundant hydrolysis 1 hour then under the vitriol oil room temperature of Dropwise 5 g 98%, processes B solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 20 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 78.2%, granularity be an accumulative nano zeolite highly.
Embodiment 2
Repeat embodiment 1, but with adding 9.035g NaOH solid, Al in (1) silicon sol 2O 3The middle vitriol oil that adds 7.819g 98% obtains ZSM-5 zeolite product, and its relative crystallinity is 75.2%, and granularity is a height accumulative nano zeolite.
Embodiment 3
Repeat embodiment 1, but with adding 13.205g NaOH solid, Al in (1) silicon sol 2O 3The middle vitriol oil that adds 13.031g98% obtains ZSM-5 zeolite product, and its relative crystallinity is 77.7%, and granularity is a height accumulative nano zeolite.
Embodiment 4
Repeat embodiment 1, but with adding 23.63g NaOH solid, Al in (1) silicon sol 2O 3The middle vitriol oil that adds 26.062g 98% obtains ZSM-5 zeolite product, and its relative crystallinity is 75.6%, and granularity is a height accumulative nano zeolite.
Embodiment 5
Repeat embodiment 4, but do not add organic formwork agent.Corresponding preparing gel step is following:
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
With 104g silicon sol (technical grade, SiO 2>=30wt%) be scattered in the 40g deionized water, add then and stir abundant hydrolysis 1 hour under the 23.63g NaOH solid room temperature, process A solution; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, drips then to stir abundant hydrolysis 1 hour under the vitriol oil room temperature of 26.062g 98%, processes B solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 84 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 60.2%, granularity be an accumulative nano zeolite highly.
Embodiment 6
Repeat embodiment 5, but with adding 1g crystal seed, crystal seed/SiO in (2) gel 2=3.2wt%, the product crystalline phase that obtained in about 18 hours 170 ℃ of following crystallization is the ZSM-5 zeolite, and its relative crystallinity is 80.2%, and granularity is a height accumulative nano zeolite.
Embodiment 7
Repeat embodiment 1, but regulate the silicon source and regulate the aluminium source with alkali with mineral acid.Corresponding preparing gel step is following:
(1) regulates the polymerization degree in silicon source with mineral acid, the polymerization degree of regulating the aluminium source with mineral alkali.
With 104g silicon sol (technical grade, SiO 2>=30wt%) be scattered in the 40g deionized water, stir abundant hydrolysis 1 hour then under the vitriol oil room temperature of Dropwise 5 g 98%, add 14.86g n-Butyl Amine 99 solution (technical grade) again, process A ' solution; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, adds then to stir abundant hydrolysis 1 hour under the 6.95g NaOH room temperature, processes B ' solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
B ' solution that depolymerization is obtained under agitation is added drop-wise in A ' solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 20 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 78.4%, granularity be an accumulative nano zeolite highly.
Embodiment 8
Repeat embodiment 7, but with the vitriol oil that drips 13.031g98% in (1) silicon sol, Al 2O 3The middle 13.205g NaOH solid that adds obtains ZSM-5 zeolite product, and its relative crystallinity is 76.5%, and granularity is a height accumulative nano zeolite.
Embodiment 9
Repeat embodiment 7, but with the vitriol oil that drips 26.062g 98% in (1) silicon sol, to Al 2O 3The middle 23.63gNaOH solid that adds obtains ZSM-5 zeolite product, and its relative crystallinity is 75.6%, and granularity is a height accumulative nano zeolite.
Embodiment 10
Repeat embodiment 1, but with adding 1g crystal seed, crystal seed/SiO in (2) gel 2=3.2wt%, the product crystalline phase that obtained in about 6 hours 170 ℃ of following crystallization is the ZSM-5 zeolite, and its relative crystallinity is 78.2%, and granularity is a height accumulative nano zeolite.
Embodiment 11
Repeat embodiment 1, but change the depolymerization temperature in (1) silicon source and aluminium source into 20 ℃ and 100 ℃ respectively, the product crystalline phase that obtains is the ZSM-5 zeolite, and its relative crystallinity is respectively 77.2%, 76.8%.
Embodiment 12
Repeat embodiment 1, but change the depolymerization time in (1) silicon source and aluminium source into 20min, 48h and 100h respectively, the product crystalline phase that obtains is the ZSM-5 zeolite, and its relative crystallinity is respectively 79.3%, 76.7%, and 77.8%.
Embodiment 13
Repeat embodiment 3, but change (1) silicon source into WHITE CARBON BLACK silicon-dioxide, corresponding preparing gel step is following:
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
The 31.2g WHITE CARBON BLACK is scattered in the 40g deionized water, adds then and stir abundant hydrolysis 1 hour under the 13.205g NaOH solid room temperature, add 14.86g n-Butyl Amine 99 solution (technical grade) again, process A solution; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, drips then to stir abundant hydrolysis 1 hour under the vitriol oil room temperature of 13.031g98%, processes B solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 20 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 80%, granularity be an accumulative nano zeolite highly.
Embodiment 14
Repeat embodiment 1, but change (1) silicon source into water glass, corresponding preparing gel step is following:
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
With 120.5g water glass (SiO 225.88%, NaO 28.21%, technical grade) be scattered in the 40g deionized water, add then and stir abundant hydrolysis 1 hour under the 6.95g NaOH solid room temperature, add 14.86g n-Butyl Amine 99 solution (technical grade) again, process A solution; With 2.3gAl 2O 3Powder (pseudo-boehmite) is scattered in the 100g deionized water, drips then to stir abundant hydrolysis 1 hour under the vitriol oil room temperature of 20.8g 98%, processes B solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 20 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 85.6%, granularity be an accumulative nano zeolite highly.
Embodiment 15
Repeat embodiment 14, difference aluminium source is Tai-Ace S 150 (Al 2O 315.8%, technical grade), corresponding preparing gel step is following:
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid.
With 120.5g water glass (SiO 225.88%, NaO 28.21%, technical grade) be scattered in the 40g deionized water, add then and stir abundant hydrolysis 1 hour under the 6.95g NaOH solid room temperature, add 14.86g n-Butyl Amine 99 solution (technical grade) again, process A solution; With 10.9g Tai-Ace S 150 (Al 3O 215.8.%, technical grade) be scattered in the 100g deionized water, drip then under the vitriol oil room temperature of 15g98% and stir abundant hydrolysis 1 hour, process B solution.
(2) synthesize the ZSM-5 zeolite with the silicon source and the aluminium source of depolymerization.
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente, processes even gel.Gel mixture has following mole and forms: SiO 2/ Al 2O 3=30, NaOH/SiO 2=0.12, NBA/SiO 2=0.39, H 2O/SiO 2=26.The gel that makes is transferred in the synthesis reactor,, be cooled to room temperature, filter, washing about 16 hours of 170 ℃ of following crystallization.Filter cake use x-ray powder diffractions to record wherein 110 ℃ of down dry backs the relative crystallinity of ZSM-5 zeolite is 85.6%, granularity be an accumulative nano zeolite highly.
Embodiment 16
Repeat embodiment 1, but change (2) gel crystallization temperature into 120 ℃, 130 ℃, 140 ℃ respectively, 150 ℃; 160 ℃, 180 ℃, 190 ℃; Corresponding gel crystallization time 72 hours, 62 hours, 56 hours respectively, 42 hours, 36 hours, 16 hours and 12 hours, the product crystalline phase that obtains was the ZSM-5 zeolite; Its relative crystallinity is respectively 74.3%, 73.9%, 74.5%, 76.3%, 78.9%, 84.5%, 84.3%, and granularity is a height accumulative nano zeolite.
Embodiment 17
Repeat embodiment 15, but change (1) template n-Butyl Amine 99 into methylamine (31.05g) ethamine (13.47g) respectively, diethylamine (73.14g); Tri N-Propyl Amine (59.11g); Isopropylamine (59.11g), about 24 hours of 170 ℃ of following crystallization, the product crystalline phase that all obtains was the ZSM-5 zeolite; Its relative crystallinity is respectively 75.2%, 74.3%, 73.9%, 74.5%, 76.5%, and granularity is a height accumulative nano zeolite.

Claims (5)

1. the compound method of a ZSM-5 zeolite is characterized in that following steps:
The first step: pre-treatment is carried out in silicon source, aluminium source, divided two kinds of situation to carry out;
(1) regulates the polymerization degree in silicon source with mineral alkali, the polymerization degree of regulating the aluminium source with mineral acid;
A is scattered in the silicon source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source with alkali, and the depolymerization time is 5min～100h, adds organic formwork agent again, obtains solution A;
B is scattered in the aluminium source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source with acid solution, and the depolymerization time is 5min～100h, obtains solution B;
(2) regulate the polymerization degree in silicon source with mineral acid, the polymerization degree of regulating the aluminium source with mineral alkali;
A is scattered in the silicon source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of silicon source with acid solution, and the depolymerization time is 5min～100h, adds organic formwork agent again, obtain solution A ';
B is scattered in the aluminium source in the water, stirs and keeps 20 ℃～100 ℃ temperature, makes the depolymerization of aluminium source with alkali, and the depolymerization time is 5min～100h, obtain solution B '.
Second step: with the synthetic ZSM-5 zeolite in silicon source and aluminium source of depolymerization;
The B solution that depolymerization is obtained under agitation is added drop-wise in the A solution lentamente or B ' solution that depolymerization is obtained under agitation is added drop-wise in A ' solution lentamente, processes even gel; Then gel is transferred to and carried out hydrothermal crystallizing in the synthesis reactor, the solid that crystallization goes out obtains the nano-ZSM-5 zeolite through filtration, washing, dry, roasting.
2. a kind of ZSM-5 synthesis method of zeolite molecular sieve according to claim 1 is characterized in that described silicon source is a kind of and any mixture in silicon sol, water glass, WHITE CARBON BLACK, the solid silicone; Described aluminium source is a kind of and any mixture in boehmite, Tai-Ace S 150, aluminum chloride, aluminum nitrate, sodium metaaluminate, white lake, the aluminum isopropylate.
3. a kind of ZSM-5 synthesis method of zeolite molecular sieve according to claim 1 is characterized in that a kind of and any mixture in the optional sulfuric acid of described mineral acid, phosphoric acid, nitric acid, the hydrochloric acid; Described alkali is with a kind of and any mixture in sodium hydroxide, Pottasium Hydroxide, the ammoniacal liquor.
4. a kind of ZSM-5 synthesis method of zeolite molecular sieve according to claim 1 is characterized in that described template is a kind of and any mixture in methylamine, ethamine, propylamine, n-Butyl Amine 99, quadrol, tripropyl amine, the ethanol.
5. a kind of ZSM-5 synthesis method of zeolite molecular sieve according to claim 1 is characterized in that the crystallization temperature scope is 80～200 ℃; Crystallization time is 1～400 hour; The silica-alumina gel mixture has following mole and forms: SiO 2/ Al 2O 3=10～1000, Na 2O/SiO 2=0.05～0.3, R/SiO 2=0～1.0, H 2O/SiO 2=10～50, crystal seed/SiO 2=0～20wt%, R are template.
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CN115108564B (en) * 2021-03-23 2024-05-31 中国石油天然气股份有限公司 Preparation method of MFI structure molecular sieve with high silicon-aluminum ratio
CN114229865A (en) * 2021-12-10 2022-03-25 成都理工大学 Seed crystal-free rapid aging crystallization synthesis method of ZSM-5 micro mesoporous molecular sieve
CN115925437A (en) * 2022-12-08 2023-04-07 上海绿强新材料有限公司 Integral honeycomb molecular sieve for removing VOCs (volatile organic compounds), and preparation and application thereof
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