CN101954291A - Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof - Google Patents
Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a zinc isomorphism-substituted nano ZSM-5 molecular sieve catalyst and a preparation method thereof. In the method, solution of zinc amine or solution of zinc ammonia is taken as a zinc source, a one-pot method is adopted to directly make zinc atoms enter a framework of a molecular sieve, the prepared molecular sieve is a nano plate crystal with the dimension of 250nm*50nm*25nm, and the molecular sieve has the advantages of high yield, easy product separation, short preparation time and simple preparation method. When the molecular sieve serving as a catalyst is applied to methanol and ethanol aromatization reaction, the molecular sieve has the characteristics of high aromatic selectivity, high BTX proportion, long service life of the catalyst, stable catalytic performance, flexible technical operation, and the like.
Description
Technical field
The invention belongs to the catalysis material field, relate to molecular sieve type alcohols aromatized catalyst, be specifically related to a kind of catalyst that is used for catalysis methanol and ethanol aromatization.
Background technology
Aromatic hydrocarbons especially benzene,toluene,xylene (be called for short BTX) output and scale is the important Organic Chemicals that is only second to ethene and propylene.Its derivative is widely used in chemical products and fine chemicals such as fuel, petrochemical industry, chemical fibre, plastics and rubber.Along with the continuous development of society, the demand to aromatic hydrocarbons constantly increases in the world.To cause aromatic hydrocarbons mainly be holding at high price of benzene,toluene,xylene to the petroleum resources anxiety in recent years.Preparing aromatic hydrocarbons (MTA or ETA) by methyl alcohol or bio-ethanol is a useful process route, the deficiency that can utilize coal or biomass resource to remedy petroleum resources comes production Essential Chemistry product [referring to Wei Fei etc., aromatization of methanol process on the Ag/ZSM-5 catalyst, modern chemical industry, 2009,29:55].
For improving the yield and the life-span of MTA or ETA reaction, one uses metal-modified ZSM-5 catalyst such as zinc, gallium, silver.Be used for the metal of modification at bibliographical information, the price of zinc is cheap, catalytic activity is higher, can improve aromatics yield; And normally used commercial ZSM-5 molecular sieve all is micron-sized bulky grain, and inner duct is long in the molecular sieve, is unfavorable for the diffusion of product, easily makes low molecular weight hydrocarbon further react carbon distribution, causes catalysqt deactivation.People improve catalytic reaction activity and catalyst life aspect and have carried out number of research projects for improving the ZSM-5 performance.Present most improvement method for preparing catalyst is post-modification methods such as ion-exchange, dipping or mechanical mixture.
(1) ion-exchange prepares the Zn/ZSM-5 catalyst
Y.Ono etc. are with certain density zinc nitrate solution and NH
4-ZSM-5 exchanges 2 times down in 80 ℃, and after filtration, washing, the drying, with gained catalyst compressing tablet, fragmentation, screening are 16～32 purpose particles, is used for the MTA reaction behind the calcining 90min down in 580 ℃ again.Compare HZSM-5, its initial activity significantly improves: aromatics yield rises to 67.4% by 40.3%, but not mentioned catalyst life.[referring to: Yoshio Ono, Hiroshi Adachi and Yoko Senoda.Selective conversion of methanol into aromatic hydrocarbons over zinc-exchanged ZSM-5 zeolites.J.Chern.Soc., Faraday Trans.1,1988,84 (4): 1091].
(2) immersion process for preparing Zn/ZSM-5 catalyst
K.K.Pant etc. join HZSM-5 in the zinc nitrate solution for preparing by the excess solution infusion process, and the MTA reaction is used it in rotary evaporation, drying, roasting then again.At 400 ℃, 1atm, inlet amount W/F
A0(g
Cat.h/mol methanolfed)=4.138 o'clock, the aromatics yield of Zn/ZSM-5 (accounting for oil phase) 66.9%, conversion of methanol is 60%.If flood Cu simultaneously, aromatics yield can rise to 69.4% (accounting for oil phase), but the life-span is not long, methanol conversion will drop to 75.7% behind the 12h, does not fundamentally solve the problem of catalysqt deactivation, [referring to: H.A.Zaidi, K.K.Pant.Catalytic conversion of methanol to gasoline range hydrocarbons, Catalysis Today, 2004,96:155-160].
(3) mechanical mixing prepares the Zn/ZSM-5 catalyst
G.J.Hutchings etc. put the H-ZSM-5 and the ZnO of equivalent grinding a period of time together, then the powder of gained are made bead, and screening is that 0.6～1.0 millimeter particle is used for the MTA reaction.At 400 ℃, air speed 1.3h
-1, reaction time 30min, He the dilution condition under, the catalytic activity of Zn/ZSM-5 and H-ZSM-5 are more or less the same: the former aromatics yield is 13.6%, latter's aromatics yield 11.4%; As seen, not obvious by the Zn/ZSM-5 catalyst aromatization effect of mechanical mixing preparation, there is not prospects for commercial application.[referring to: David Freeman, Richard P.K.Wells, Graham J.Hutchings.Methanol to hydrocarbons:enhanced aromatic formation using composite group 13oxide/H-ZSM-5catalysts, Catalysis Letters, 2002,82 (3-4): 217].
The size of the Zn/ZSM-5 catalyst by exchange, dipping or mechanical mixing preparation depends primarily on the grain size of selected ZSM-5 molecular sieve, and one is all at micron order; And there is Zn shortcoming pockety on molecular sieve in the catalyst by above-mentioned three kinds of methods preparation, and particularly the dispersiveness of Zn is poorer on the catalyst of mechanical mixing preparation.This will cause that these catalyst have that the aromatisation performance is bad in MTA, ETA reaction, poor stability, short defective of life-span.
Directly preparation Zn-MFI, Zn-ZSM-5 molecular sieve can allow zinc be evenly distributed in the molecular sieve crystal.There is seminar to report that some directly prepare the ZSM-5 catalyst method that contains zinc both at home and abroad, for example: G.Giordano etc. have directly prepared the Zn-MFI molecular sieve [referring to S.Kowalak, E.Szymkowiak, I.Lehmann, G.Giordano.Catalytic properties of MFI zincosilicate, Studies in Surface Science and Catalysis, 2001,135:4645-4654], but the granule size of molecular sieve all is a micron order, Zn instability in the molecular sieve, the Zn during heating in the molecular sieve can partly be released.After by ion-exchange Al being incorporated into the Zn-MFI molecular sieve, use it for the decomposition reaction of 2-propyl alcohol, catalytic activity increases, but still undesirable, and the conversion ratio of 2-propyl alcohol still is no more than 10%; Use short-chain alkyl amine such as S.Valange are done the mineralising reagent preparation, characterized the Zn-MFI molecular sieve [referring to S.Valange, B.Onida, F.Geobaldo, E.Garrone, Z.Gabelica.Preparation and characterization of Zn-MFI zeolitesusing short chain alkylamines as mineralizing agents, Studies in Surface Science and Catalysis, 2002,142A:215-222], this zeolite crystal is big and thick, crystallization time is long: obtain pure Zn-MFI crystal, crystallization time took more than 6 days; Liu Zhongmin etc. are with [Zn (NH
3)
4]
2+Be the zinc source, alabastrine Zn-ZSM-5 molecular sieve that n-butylamine is the direct hydrothermal preparation of template agent [referring to: Ligang Wang, Shiyun Sang, Shuanghe Meng, Ying Zhang, Yue Qi, Zhongmin Liu.Direct synthesis of Zn-ZSM-5with novel morphology, Materials Letters, 2007,61 (8-9): 1675-1678], the length of this molecular sieve is 6～8 microns, crystallization time takes 5 days.
Summary of the invention
Task of the present invention provides a kind of alcohols aromatized catalyst.
Another task of the present invention provides the preparation method of this alcohols aromatized catalyst.
Another task of the present invention provides the application of this alcohols aromatized catalyst.
Realize that technical scheme of the present invention is:
This alcohols aromatized catalyst provided by the invention, it is the nano-ZSM-5 molecular sieve that the Alusil and the zinc isomorphous synthetic through hydrothermal crystallizing after zinc amine aqueous solution or zinc ammonia solution mix and that ion-exchange obtains are replaced, silicon source in the described Alusil is a Ludox, and the template agent in the described Alusil is the TPAOH (TPAOH) or 4-propyl bromide (TPABr) aqueous solution; Described Alusil obtains by following preparation method: earlier alkali source is joined in the silicon source, stir, add the aluminium source, stir, add the template agent again, stir, obtain Alusil, Si in the gained Alusil: Al: OH
-: TPA
+: H
2The mol ratio of O is 1: (0.01～0.05): (0.08～0.3): (0.05～0.50): (30～60); Described silicon source is a Ludox, and the molar concentration that contains Si is 0.5～12mol/L; Described alkali source is the aqueous solution of NaOH or potassium hydroxide, contains OH
-Molar concentration be 0.3～3mol/L; Described aluminium source is sodium metaaluminate, aluminum sulfate or aqueous solution of aluminum nitrate, and the molar concentration that contains Al is 0.05～1mol/L; Described template agent is the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr), contains TPA
+Molar concentration be 0.1～3mol/L.Described zinc amine aqueous solution or zinc ammonia solution obtain by following preparation method: with zinc salt solution and amine aqueous solution or ammonia spirit preparation zinc amine aqueous solution or zinc ammonia solution, making the mol ratio of amine in the solution or ammonia and zinc is (1～10): 1; The concentration of used zinc amine aqueous solution or zinc ammonia solution (by the cubage of zinc) is 0.08～1mol/L; Zinc salt in the described zinc salt solution is zinc nitrate, zinc sulfate or zinc chloride; Amine in the described amine aqueous solution is methylamine, ethamine, ethylenediamine, dimethylamine or diethylamine.
The preparation method of the nano-ZSM-5 molecular sieve alcohols aromatized catalyst that this zinc isomorphous provided by the invention replaces may further comprise the steps:
(1) preparation of Alusil
Earlier alkali source is joined in the silicon source, stir, add the aluminium source, stir, add the template agent again, stir, obtain Alusil, Si in the gained Alusil: Al: OH
-: TPA
+: H
2The mol ratio of O is 1: (0.01～0.05): (0.08～0.3): (0.05～0.50): (30～60);
(2) preparation of zinc amine aqueous solution or zinc ammonia solution
With zinc salt solution and amine aqueous solution or ammonia spirit preparation zinc amine aqueous solution or zinc ammonia solution, it is characterized in that the mol ratio of amine in this solution or ammonia and zinc is (1～10): 1; The concentration of this zinc amine aqueous solution or zinc ammonia solution (by the cubage of zinc) is 0.08～1mol/L;
(3) hydrothermal crystallizing is synthetic
Zinc amine aqueous solution that step (2) is made or zinc ammonia solution join in the reaction Alusil that step (1) makes, and stirring obtains the crystallization raw material, and the mol ratio of Si and Zn is 1 in the crystallization raw material: (0.005～0.04); With the crystallization raw material teflon-lined stainless steel hydrothermal reaction kettle of packing into, at 100～200 ℃ of crystallization 6～72h; Reactant mixture behind the hydrothermal crystallizing obtains white powder through filtration, washing, the drying of routine behind 550 ℃～600 ℃ calcining 5h;
(4) ion-exchange
Sodium ion in the white powder is exchanged into ammonium ion or amine ion, method of operating is: the white powder that obtains is carried out ion-exchange at 80 ℃ of ammonium nitrate solutions with 0.8mol/L, exchange altogether 3 times, obtained the nano-ZSM-5 molecular sieve that the zinc isomorphous replaces, alcohols aromatized catalyst promptly of the present invention in 5 hours 550 ℃～600 ℃ calcinings then.
Silicon source described in the above-mentioned steps (1) is a Ludox; Described alkali source is the aqueous solution of NaOH or potassium hydroxide; Described aluminium source is sodium metaaluminate, aluminum sulfate or aqueous solution of aluminum nitrate; Described template agent is the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr).The molar concentration that described Ludox as the silicon source contains Si is 0.5～12mol/L; Describedly contain OH as the NaOH of alkali source or the aqueous solution of potassium hydroxide
-Molar concentration be 0.3～3mol/L; The molar concentration that described sodium metaaluminate as the aluminium source, aluminum sulfate or aqueous solution of aluminum nitrate contain Al is 0.05～1mol/L; It is described that agent is that the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr) contains TPA as template
+Molar concentration be 0.1～3mol/L.
Zinc salt in the zinc salt solution described in the above-mentioned steps (2) is zinc nitrate, zinc sulfate or zinc chloride; Amine in the described amine aqueous solution is methylamine, ethamine, ethylenediamine, dimethylamine or diethylamine.
Use alcohols aromatized catalyst provided by the invention to carry out the technology of alcohols aromatisation, comprise the steps:
(1) is 40～60 purpose particles with prepared catalyst through compressing tablet, fragmentation, screening, then the gained particle installed in the Continuous Flow fixed bed reactors, activate half an hour down at 380～500 ℃ with nitrogen;
(2) with constant-flux pump material benzenemethanol or ethanol being pumped in the fixed bed reactors, is 0.1～2.0Mpa at operating pressure, and operating temperature is 380～500 ℃, and the raw material liq air speed is 0.2～4.0h
-1React under the condition;
(3) the fixed bed reactors exit gas separates through cooling off laggard promoting the circulation of qi liquid, obtains gas-phase product and liquid product;
(4) gas-phase product mainly contains C
1～C
5Various light hydrocarbons;
(5) liquid product takes out collect 1-24h in storage tank after, then through being separated into oil phase and water, oil phase is separated promptly obtaining aromatic hydrocarbons again.
The nano-ZSM-5 molecular sieve alcohols aromatized catalyst that the zinc isomorphous that " one kettle way " fast provided by the invention directly prepares replaces at methyl alcohol, has excellent catalytic performance in the reaction of alcohol catalysis conversion for preparing arene.
The present invention has following advantage compared to existing technology:
1, the molecular sieve zinc atom of the present invention's preparation enters into the framework of molecular sieve structure, and the molecular sieve of preparation is the thick nano-sheet crystal of about 25nm.2, adopt one kettle way directly to introduce zinc, the productive rate height of molecular sieve, product separate easily, preparation time is short, the preparation method is simple.3, molecular sieve provided by the invention is applied in methyl alcohol, the ethanol aromatization, the arenes selectivity height, and BTX ratio height, catalyst life is long, and catalytic performance is stable.4, be applied in the technology of methyl alcohol (or ethanol) aromatisation at catalyst of the present invention, raw material liq body air speed WHSV can be at 0.2～4.0h
-1The interior adjustment, reaction pressure can be adjusted in 0.1～2MPa, technological operation flexibility height.5, use the catalytic reaction technology of catalyst of the present invention only to need a segment process, save cost.6, do not use carrier gas in the catalytic reaction technology of use catalyst of the present invention, save cost, help the recycling of light hydrocarbons tail gas, environmental pollution is few.
Description of drawings
The SEM figure of the molecular sieve catalyst of Fig. 1: embodiment 1 preparation, as seen from Figure 1, the catalyst grain shape of the present invention's preparation is a laminated structure, crystal particle scale approximately is 250nm * 50nm * 25nm, has nanoscale.
The XRD figure of the catalyst of Fig. 2: embodiment 1 preparation, 2 θ=7.9 ° from Fig. 2,8.8 °, 23.1 °, 23.9 °, 24.4 ° of characteristic diffraction peaks of locating, the catalyst of the present invention's preparation is the ZSM-5 molecular sieve as can be known.[referring to: Minkee Choi, Kyungsu Na, Jeongnam Kim, Yasuhiro Sakamoto, Osamu Terasaki Ryong, Ryoo.Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts, Nature, 2009,46:246-249]
The UV, visible light spectrogram of the molecular sieve catalyst of Fig. 3: embodiment 1 preparation from Fig. 3 228 and the absworption peak of 207nm, knows that in the catalyst of the present invention's preparation, zinc exists with the form of isomorphous replacement.[referring to: Ligang Wang, Shiyun Sang, Shuanghe Meng, Ying Zhang, Yue Qi, Zhongmin Liu, Direct synthesis of Zn-ZSM-5with novel morphology, Materials Letters, 2007,61:1675-1678]
Fig. 4: oil-phase product gas chromatographic analysis figure, the oil phase main component is benzene,toluene,xylene, trimethylbenzene.
Fig. 5: gas-phase product gas chromatographic analysis figure, the gas phase main component is C
1～C
5Various light hydrocarbons.
The specific embodiment
The invention will be further described below in conjunction with embodiment; be necessary to be pointed out that at this; following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: one of Preparation of catalysts scheme of the present invention
The crystallization material molar ratio is SiO
2: 0.02Al
2O
3: 0.14NaOH: 0.20TPAOH: 0.01ZnO: 30H
2O
(1) preparation of Alusil
Take by weighing 2.8g NaOH and be dissolved in the 40ml water, it is in 30% the Ludox that the sodium hydrate aqueous solution of preparation slowly is added drop-wise to the 100g mass fraction, stirs 10min under the room temperature; Slowly drip the sodium aluminate solution 60ml of 0.33mol/L again, stir 20min under the room temperature; Slowly add the 81.2g mass fraction again and be 20% the TPAOH aqueous solution, stir 30min under the room temperature and obtain Alusil.
(2) preparation of zinc ammonia solution
Taking by weighing the 1.48g zinc nitrate hexahydrate and be dissolved in the 20ml water, is that 25% ammoniacal liquor coordination obtains the zinc ammonia solution with the zinc salt solution and the 1.40g mass fraction of preparation.
(3) hydrothermal crystallizing
The zinc ammonia solution that step (2) is made joins in the Alusil that step (1) makes, and stirring obtains the crystallization raw material, with the crystallization raw material teflon-lined stainless steel hydrothermal reaction kettle of packing into, at 175 ℃ of crystallization 24h; Reactant mixture behind the hydrothermal crystallizing obtains white powder through filtration, washing, the drying of routine behind 550 ℃ of calcining 5h.
(4) ion-exchange
The white powder that obtains is carried out ion-exchange at 80 ℃ of ammonium nitrate solutions with 0.8mol/L, exchange altogether 3 times, obtain the alcohols aromatized catalyst at 550 ℃ of calcining 5h then.
Embodiment 2: two of Preparation of catalysts scheme of the present invention
The crystallization material molar ratio is SiO
2: 0.005Al
2O
3: 0.08NaOH: 0.05TPAOH: 0.04ZnO: 40H
2O
(1) preparation of Alusil
Take by weighing 1.6g NaOH and be dissolved in the 40ml water, it is in 25% the waterglass that the sodium hydrate aqueous solution of preparation slowly is added drop-wise to the 274g mass fraction, stirs 10min under the room temperature; Slowly drip the aluminum sulfate solution 60ml of 0.04mol/L again, stir 20min under the room temperature; Slowly add the 20.3g mass fraction again and be 20% TPAOH, stir 30min under the room temperature and obtain Alusil.
(2) preparation of zinc amine aqueous solution
Taking by weighing the 5.74g white vitriol and be dissolved in the 20ml water, is that 40% methyl amine aqueous solution coordination obtains the zinc amine aqueous solution with the zinc salt solution and the 6.20g mass fraction of preparation.
All the other steps are identical with embodiment 1.
Embodiment 3: three of Preparation of catalysts scheme of the present invention
The crystallization material molar ratio is SiO
2: 0.025Al
2O
3: 0.3KOH: 0.5TPABr: 0.005ZnO: 60H
2O
(1) preparation of Alusil
Take by weighing 8.4g potassium hydroxide and be dissolved in the 120ml water, the potassium hydroxide aqueous solution of preparing slowly is added drop-wise in the 104g ethyl orthosilicate, stir 10min under the room temperature; Slowly drip the aluminum nitrate solution 180ml of 0.14mol/L again, stir 20min under the room temperature; Slowly adding 200ml concentration again is the 4-propyl bromide solution of 1.25mol/L, stirs 30min under the room temperature and obtains Alusil.
(2) preparation of zinc amine aqueous solution
Take by weighing the 0.34g anhydrous zinc chloride and be dissolved in the 20ml water, the zinc salt solution and the coordination of 0.45g ethylamine of preparing obtained the zinc amine aqueous solution.
All the other steps are identical with embodiment 1.
Embodiment 4: the aromatization of methanol active testing of the catalyst of embodiment 1 preparation
(1) catalyst with embodiment 1 preparation is 40～60 purpose particles through compressing tablet, fragmentation, screening, then the gained particle is installed in the Continuous Flow fixed bed reactors, activates half an hour with nitrogen down at 430 ℃.
(2) with constant-flux pump material benzenemethanol being pumped in the fixed bed reactors, is 0.1Mpa at operating pressure, and operating temperature is 430 ℃, and the raw material liq air speed is 0.4h
-1React under the condition;
(3) the fixed bed reactors exit gas separates through cooling off laggard promoting the circulation of qi liquid, obtains gas-phase product and liquid product;
(4) gas-phase product enters gas-chromatography and carries out on-line analysis.
(5) liquid product takes out collect a period of time in storage tank after, be oil phase and water through extract and separate then, oil phase enters gas-chromatography analysis, and the result shows and mainly contain aromatic hydrocarbons in the oil phase, in the aromatic hydrocarbons again based on benzene,toluene,xylene (abbreviating BTX as).Analysis result sees Table 1, and the productive rate of each material refers to that all carbon molal quantity in the material accounts for the percentage of total carbon molal quantity in the charging in the analysis result.
Embodiment 5: the aromatization of methanol active testing of the catalyst of embodiment 2 preparations
Catalyst system therefor is the catalyst of embodiment 2 preparations, and all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Embodiment 6: the aromatization of methanol active testing of the catalyst of embodiment 3 preparations
Catalyst system therefor is the catalyst of embodiment 3 preparations, and all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Embodiment 7: temperature is to the aromatization of methanol activity influence of the catalyst of embodiment 1 preparation
Change the operating temperature among the embodiment 4 into 500 ℃, all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Embodiment 8: pressure is to the aromatization of methanol activity influence of the catalyst of embodiment 1 preparation
Change the operating pressure among the embodiment 4 into 1MPa, all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Embodiment 9: air speed is to the aromatization of methanol activity influence of the catalyst of embodiment 1 preparation
Change the methyl alcohol WSHV among the embodiment 4 into 2h
-1, all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Embodiment 10: the ethanol aromatization activity test of the catalyst of embodiment 1 preparation
Change the raw material among the embodiment 4 into ethanol, ethanol conversion calculates according to the conversion of ethylene that the dehydration back produces, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Embodiment 11: the ethanol aromatization activity test of the catalyst of embodiment 2 preparations
Catalyst system therefor is the catalyst of embodiment 2 preparations, and raw material is an ethanol, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Embodiment 12: the ethanol aromatization activity test of the catalyst of embodiment 3 preparations
Catalyst system therefor is the catalyst of embodiment 3 preparations, and raw material is an ethanol, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Embodiment 13: temperature is to the ethanol aromatization activity influence of the catalyst of embodiment 1 preparation
Change the operating temperature among the embodiment 4 into 380 ℃, raw material changes ethanol into, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Embodiment 14: pressure is to the ethanol aromatization activity influence of the catalyst of embodiment 1 preparation
Change the operating pressure among the embodiment 4 into 2MPa, raw material changes ethanol into, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Embodiment 15: air speed is to the ethanol aromatization activity influence of the catalyst of embodiment 1 preparation
Change the feed ethanol WSHV among the embodiment 4 into 4h
-1, all the other steps are identical with embodiment 4, and analysis result sees Table 2.
Comparative Examples 1: the aromatization of methanol active testing of commercial H-ZSM-5 molecular sieve
Catalyst system therefor is the commercial H-ZSM-5 molecular sieve of buying from Tianjin Nankai University, and all the other steps are identical with embodiment 4, and analysis result sees Table 1.
Comparative Examples 2: the ethanol aromatization activity test of commercial H-ZSM-5 molecular sieve
Catalyst system therefor is the commercial H-ZSM-5 molecular sieve of buying from Tianjin Nankai University, and raw material changes ethanol into, and all the other steps are identical with embodiment 4, and analysis result sees Table 2.
In the comparison sheet 1 embodiment 4,5,6 and Comparative Examples 1 as can be seen, the catalyst of the present invention preparation all has the catalytic activity height in the aromatization of methanol reaction, aromatics yield height, good stability, the advantage that the life-span is long; By embodiment in the table 14 and 7 as can be seen, temperature is bigger to the influence of reaction, and along with reaction temperature increases, aromatics yield increases, but catalyst stability has decline slightly; By embodiment in the table 14 and 8 as can be seen, pressure is little to the catalytic activity influence, therefore pressure operation wider range of reaction; By embodiment in the table 14 and 9 as can be seen, when handling the methyl alcohol of same amount, air speed is also little to the influence of catalytic activity, but the opereating specification of air speed is also bigger.
In the comparison sheet 2 embodiment 10,11,12 and Comparative Examples 2 as can be seen, the catalyst of the present invention preparation also all has the catalytic activity height in the ethanol aromatization, aromatics yield height, good stability, the advantage that the life-span is long; Temperature is bigger to the influence of reaction as can be seen by embodiment in the table 2 10 and 13, and along with reaction temperature reduces, aromatics yield reduces; By embodiment in the table 2 10 and 14 as can be seen, pressure is little to the catalytic activity influence, therefore pressure operation wider range of reaction; By embodiment in the table 2 10 and 15 as can be seen, when handling the ethanol of same amount, air speed is also little to the influence of catalytic activity, but the opereating specification of air speed is also bigger.
Table 1 aromatization of methanol reaction result
Annotate: "-" expression reaction result approaches 0, down together.
Table 2 ethanol aromatization result
Claims (9)
1. alcohols aromatized catalyst, it is the nano-ZSM-5 molecular sieve that the Alusil and the zinc isomorphous synthetic through hydrothermal crystallizing after zinc amine or zinc ammonia solution mix and that ion-exchange obtains are replaced, silicon source in the described Alusil is a Ludox, and the template agent in the described Alusil is the TPAOH (TPAOH) or 4-propyl bromide (TPABr) aqueous solution.
2. alcohols aromatized catalyst according to claim 1 is characterized in that:
Described Alusil obtains by following preparation method: earlier alkali source is joined in the silicon source, stir, add the aluminium source, stir, add the template agent again, stir, obtain Alusil, Si in the gained Alusil: Al: OH
-: TPA
+: H
2The mol ratio of O is 1: (0.01～0.05): (0.08～0.3): (0.05～0.50): (30～60); Described silicon source is a Ludox, and the molar concentration that contains Si is 0.5～12mol/L; Described alkali source is the aqueous solution of NaOH or potassium hydroxide, contains OH
-Molar concentration be 0.3～3mol/L; Described aluminium source is sodium metaaluminate, aluminum sulfate or aqueous solution of aluminum nitrate, and the molar concentration that contains Al is 0.05～1mol/L; Described template agent is the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr), contains TPA
+Molar concentration be 0.1～3mol/L;
Described zinc amine aqueous solution or zinc ammonia solution obtain by following preparation method: with zinc salt solution and amine aqueous solution or ammonia spirit preparation zinc amine aqueous solution or zinc ammonia solution, making the mol ratio of amine in the solution or ammonia and zinc is (1～10): 1; The concentration of used zinc amine aqueous solution or zinc ammonia solution (by the cubage of zinc) is 0.08～1mol/L; Zinc salt in the described zinc salt solution is zinc nitrate, zinc sulfate or zinc chloride; Amine in the described amine aqueous solution is methylamine, ethamine, ethylenediamine, dimethylamine or diethylamine.
3. the preparation method of the nano-ZSM-5 molecular sieve that replaces of the zinc isomorphous may further comprise the steps:
(1) preparation Alusil: earlier alkali source is joined in the silicon source, stir, add the aluminium source, stir, add the template agent again, stir, obtain Alusil, Si in the gained Alusil: Al: OH
-: TPA
+: H
2The mol ratio of O is 1: (0.01～0.05): (0.08～0.3): (0.05～0.50): (30～60);
(2) preparation zinc amine aqueous solution or zinc ammonia solution:, it is characterized in that the mol ratio of amine in this solution or ammonia and zinc is (1～10): 1 with zinc salt solution and amine aqueous solution or ammonia spirit preparation zinc amine aqueous solution or zinc ammonia solution; The concentration of this zinc amine aqueous solution or zinc ammonia solution (by the cubage of zinc) is 0.08～1mol/L;
(3) hydrothermal crystallizing is synthetic: zinc amine aqueous solution that step (2) is made or zinc ammonia solution join in the reaction Alusil that step (1) makes, and stirring obtains the crystallization raw material, and the mol ratio of Si and Zn is 1 in the crystallization raw material: (0.005～0.04); With the crystallization raw material teflon-lined stainless steel hydrothermal reaction kettle of packing into, at 100～200 ℃ of crystallization 6～72h; Reactant mixture behind the hydrothermal crystallizing obtains white powder through filtration, washing, the drying of routine behind 550 ℃～600 ℃ calcining 5h;
(4) ion-exchange: the white powder that obtains is carried out ion-exchange at 80 ℃ of ammonium nitrate solutions with 0.8mol/L, exchange altogether 3 times, obtain the nano-ZSM-5 molecular sieve that the zinc isomorphous replaces, alcohols aromatized catalyst promptly of the present invention at 550 ℃～600 ℃ calcining 5h then.
4. preparation method according to claim 3 is characterized in that the described silicon of step (1) source is a Ludox; Described alkali source is the aqueous solution of NaOH or potassium hydroxide; Described aluminium source is sodium metaaluminate, aluminum sulfate or aqueous solution of aluminum nitrate; Described template agent is the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr).
5. preparation method according to claim 3 is characterized in that the zinc salt in the described zinc salt solution of step (2) is zinc nitrate, zinc sulfate or zinc chloride.
6. preparation method according to claim 3 is characterized in that the amine in the described amine aqueous solution of step (2) is methylamine, ethamine, ethylenediamine, dimethylamine or diethylamine.
7. preparation method according to claim 4 is characterized in that the molar concentration that described Ludox as the silicon source contains Si is 0.5～12mol/L; Describedly contain OH as the NaOH of alkali source or the aqueous solution of potassium hydroxide
-Molar concentration be 0.3～3mol/L; The molar concentration that described sodium metaaluminate as the aluminium source, aluminum sulfate or aqueous solution of aluminum nitrate contain Al is 0.05～1mol/L; It is described that agent is that the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr) contains TPA as template
+Molar concentration be 0.1～3mol/L.
8. a technology of using claim 1 or 2 described alcohols aromatized catalysts to carry out the alcohols aromatisation comprises the steps:
(1) is 40～60 purpose particles with prepared catalyst through compressing tablet, fragmentation, screening, then the gained particle installed in the Continuous Flow fixed bed reactors, activate half an hour down at 380～500 ℃ with nitrogen;
(2) with constant-flux pump material benzenemethanol or ethanol being pumped in the fixed bed reactors, is 0.1～2.0Mpa at operating pressure, and operating temperature is 380～500 ℃, and the raw material liq air speed is 0.2～4.0h
-1React under the condition;
(3) the fixed bed reactors exit gas separates through cooling off laggard promoting the circulation of qi liquid, obtains gas-phase product and liquid product;
(4) gas-phase product mainly contains C
1～C
5Various light hydrocarbons;
(5) liquid product takes out collect 1-24h in storage tank after, then through being separated into oil phase and water, oil phase is separated promptly obtaining aromatic hydrocarbons again.
9. claim 1 or 2 application of described alcohols aromatized catalyst in the catalyzing alcohols aromatisation.
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