CN101954291B - 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
- Publication number
- CN101954291B CN101954291B CN201010291061XA CN201010291061A CN101954291B CN 101954291 B CN101954291 B CN 101954291B CN 201010291061X A CN201010291061X A CN 201010291061XA CN 201010291061 A CN201010291061 A CN 201010291061A CN 101954291 B CN101954291 B CN 101954291B
- Authority
- CN
- China
- Prior art keywords
- zinc
- aqueous solution
- preparation
- solution
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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; Deficiency that coal capable of using or biomass resource remedy petroleum resources comes production Essential Chemistry article [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, is prone to make low molecular weight hydrocarbon further to 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 through 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 processed 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 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%; It is thus clear that, not obvious through 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 through 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 through 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 in MTA, ETA reaction that the aromatisation performance is bad, poor stability, short defective of life-span.
Directly preparation Zn-MFI, Zn-ZSM-5 molecular sieve can let zinc be evenly distributed in the molecular sieve crystal.Have both at home and abroad seminar reported some directly preparation contain ZSM-5 catalyst methods of zinc, 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, and the Zn in the molecular sieve is unstable, and the Zn during heating in the molecular sieve can partly be released out.After through 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, have been 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, and 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, and alabastrine Zn-ZSM-5 molecular sieve that n-butylamine is the hot preparation of template Direct Water [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; Be with Alusil and the substituted nano-ZSM-5 molecular sieve of the zinc isomorphous synthetic through hydrothermal crystallizing after zinc amine aqueous solution or zinc ammonia solution mix and that ion-exchange obtains; Silicon source in the said Alusil is a Ludox, and the template in the said 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 template 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 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: prepare zinc amine aqueous solution or zinc ammonia solution with zinc salt solution and amine aqueous solution or ammonia spirit, 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 substituted nano-ZSM-5 molecular sieve alcohols of this zinc isomorphous provided by the invention aromatized catalyst 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 template 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 substituted nano-ZSM-5 molecular sieve of the zinc isomorphous, 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 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; Described 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) be 40～60 purpose particles with prepared catalyst through compressing tablet, fragmentation, screening, then the gained particle installed in the Continuous Flow fixed bed reactors, with nitrogen 380～500 ℃ of following activation half an hour;
(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 after in storage tank, collecting 1-24h, then through being separated into oil phase and water, oil phase is separated promptly obtaining aromatic hydrocarbons again.
The substituted nano-ZSM-5 molecular sieve alcohols of the zinc isomorphous aromatized catalyst that " one kettle way " fast provided by the invention directly prepares at methyl alcohol, has excellent catalytic performance in the reaction of alcohol catalysis conversion for preparing arene.
The present invention compares prior art and has following advantage:
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, productive rate height, the product easy separation of molecular sieve, preparation time is short, the preparation method is simple.3, molecular sieve provided by the invention is applied in methyl alcohol, the ethanol aromatization, and arenes selectivity is high, and the BTX ratio is high, and catalyst life is long, and catalytic performance is stable.4, in catalyst applications of the present invention in the technology of methyl alcohol (or ethanol) aromatisation, raw material liq body air speed WHSV can be at 0.2～4.0h
-1Interior adjustment, reaction pressure can be adjusted in 0.1～2MPa, and the technological operation flexibility is high.5, use the catalytic reaction technology of catalyst of the present invention only to need a segment process, practice thrift cost.6, do not use carrier gas in the catalytic reaction technology of use catalyst of the present invention, practice thrift 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 can be found out that by Fig. 1 the catalyst grain shape of the present invention's preparation is a laminated structure, and 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, but the catalyst of knowledge capital invention preparation is the ZSM-5 molecular sieve.[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 with the absworption peak of 207nm, know that zinc exists with the substituted form of the isomorphous in the catalyst that the present invention prepares.[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
Below in conjunction with embodiment the present invention is described further; 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 the restriction to protection domain of the present invention, the technical staff in this field 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 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 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 are 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, with nitrogen 430 ℃ of following activation half an hour.
(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 entering gas-chromatography is carried out on-line analysis.
(5) liquid product takes out after in storage tank, collecting a period of time; Be oil phase and water through extract and separate then; Oil phase gets into gas-chromatography and analyzes, and the result shows and mainly contains aromatic hydrocarbons in the oil phase, is main with benzene,toluene,xylene (abbreviating BTX as) again in the aromatic hydrocarbons.Analysis result is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 is seen 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 that Nankai University buys from Tianjin, and all the other steps are identical with embodiment 4, and analysis result is seen 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 that Nankai University buys from Tianjin, and raw material changes ethanol into, and all the other steps are identical with embodiment 4, and analysis result is seen table 2.
Embodiment 4,5,6 and Comparative Examples 1 can be found out in the comparison sheet 1, and the catalyst of the present invention's preparation all has the catalytic activity height in the aromatization of methanol reaction, and aromatics yield is high, good stability, the advantage that the life-span is long; Can be found out that by embodiment in the table 14 and 7 temperature is bigger to the influence of reaction, along with reaction temperature increases, aromatics yield increases, but catalyst stability has decline slightly; Can find out that by embodiment in the table 14 and 8 pressure is little to the catalytic activity influence, therefore pressure operation wider range of reaction; Can find out that by embodiment in the table 14 and 9 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.
Table 1 aromatization of methanol reaction result
Annotate: "-" expression reaction result approaches 0, down together.
Table 2 ethanol aromatization result
Claims (8)
1. alcohols aromatized catalyst, it is that the silicon source in the said Alusil is a Ludox with Alusil and the substituted nano-ZSM-5 molecular sieve of the zinc isomorphous synthetic through hydrothermal crystallizing after zinc amine or zinc ammonia solution mix and that ion-exchange obtains; Template in the said Alusil is the TPAOH (TPAOH) or 4-propyl bromide (TPABr) aqueous solution, and described Alusil obtains by following preparation method: earlier alkali source is joined in the silicon source, stir; Add the aluminium source; Stir, add template 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 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: prepare zinc amine aqueous solution or zinc ammonia solution with zinc salt solution and amine aqueous solution or ammonia spirit, 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 is 0.08～1mol/L by the cubage of zinc; 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.
2. the preparation method of the substituted nano-ZSM-5 molecular sieve 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 template 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: prepare zinc amine aqueous solution or zinc ammonia solution with zinc salt solution and amine aqueous solution or ammonia spirit, 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 is 0.08～1mol/L by the cubage of zinc;
(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 substituted nano-ZSM-5 molecular sieve of the zinc isomorphous, alcohols aromatized catalyst promptly of the present invention at 550 ℃～600 ℃ calcining 5h then.
3. preparation method according to claim 2 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 is the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr).
4. preparation method according to claim 2 is characterized in that the zinc salt in the described zinc salt solution of step (2) is zinc nitrate, zinc sulfate or zinc chloride.
5. preparation method according to claim 2 is characterized in that the amine in the described amine aqueous solution of step (2) is methylamine, ethamine, ethylenediamine, dimethylamine or diethylamine.
6. preparation method according to claim 3 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; Described is that the aqueous solution of TPAOH (TPAOH) or 4-propyl bromide (TPABr) contains TPA as template
+Molar concentration be 0.1～3mol/L.
7. a technology of using the described alcohols aromatized catalyst of claim 1 to carry out the alcohols aromatisation comprises the steps:
(1) be 40～60 purpose particles with prepared catalyst through compressing tablet, fragmentation, screening, then the gained particle installed in the Continuous Flow fixed bed reactors, with nitrogen 380～500 ℃ of following activation half an hour;
(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 after in storage tank, collecting 1-24h, then through being separated into oil phase and water, oil phase is separated promptly obtaining aromatic hydrocarbons again.
8. the application of the described alcohols aromatized catalyst of claim 1 in the catalyzing alcohols aromatisation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010291061XA CN101954291B (en) | 2010-09-26 | 2010-09-26 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010291061XA CN101954291B (en) | 2010-09-26 | 2010-09-26 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101954291A CN101954291A (en) | 2011-01-26 |
| CN101954291B true CN101954291B (en) | 2012-07-04 |
Family
ID=43482024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010291061XA Expired - Fee Related CN101954291B (en) | 2010-09-26 | 2010-09-26 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101954291B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795638B (en) * | 2012-08-06 | 2013-12-25 | 黑龙江大学 | Preparation method of nanometer Zn/Al ZSM-5 molecular sieve |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2495017C1 (en) * | 2012-03-28 | 2013-10-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ имени М.В. Ломоносова) | Method for simultaneous production of aromatic hydrocarbons and divinyl |
| CN103372456A (en) * | 2012-04-13 | 2013-10-30 | 上海中科高等研究院 | Molecular sieve based catalyst and preparation and application thereof |
| CN103820181A (en) * | 2012-11-16 | 2014-05-28 | 东莞市久能二甲醚应用技术专利有限公司 | Method and device for converting methanol into natural gas |
| CN104107707A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof |
| CN104107710A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof |
| CN103241746B (en) * | 2013-05-02 | 2015-06-17 | 西南化工研究设计院有限公司 | In-situ synthetic method of modified molecular sieve for preparing ethylene by transforming ethanol |
| CN104437595B (en) * | 2013-09-24 | 2018-01-09 | 中国石油化工股份有限公司 | Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof |
| CN104549444B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application |
| CN104607235B (en) * | 2015-01-13 | 2017-02-22 | 大连理工大学 | Preparation method of Zn-ZSM-5 and application of Zn-ZSM-5 in preparing propylene via propane dehydrogenation |
| CN110857218A (en) * | 2018-08-23 | 2020-03-03 | 国家能源投资集团有限责任公司 | Nano-flake ZSM-5 molecular sieve and preparation method and application thereof |
| CN109967118B (en) * | 2019-05-05 | 2020-07-21 | 北京化工大学 | In-situ modification method of HZSM-5 molecular sieve catalyst for preparing aromatic hydrocarbon through methanol conversion |
| CN111056559A (en) * | 2019-12-30 | 2020-04-24 | 大连理工大学 | Preparation method of flaky Zn/ZSM-5 molecular sieve for methanol aromatization |
| CN112044466A (en) * | 2020-07-29 | 2020-12-08 | 华东理工大学 | Method for preparing high-value aromatic hydrocarbon by aromatization of MTP (methanol to propylene) byproduct |
| CN113751055A (en) * | 2021-09-24 | 2021-12-07 | 大连理工大学 | In-situ preparation method of high-stability molecular sieve loaded metal catalyst |
| CN113943008B (en) * | 2021-12-01 | 2023-06-23 | 南宁师范大学 | Preparation method of ZSM-5 molecular sieve |
| CN114656328B (en) * | 2022-04-09 | 2023-05-23 | 江苏昌吉利新能源科技有限公司 | Production process of ultralow-moisture chloro-n-butane |
| CN115646538B (en) * | 2022-11-08 | 2024-04-16 | 中国矿业大学 | Encapsulation bimetal constructed b-axial ZSM-5 molecular sieve and application thereof in catalyzing MTA reaction |
| CN116477637A (en) * | 2023-03-28 | 2023-07-25 | 浙江工业大学 | Transition metal atom pre-occupying-secondary hydrothermal isomorphous substituted molecular sieve and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1023633C (en) * | 1992-10-15 | 1994-02-02 | 大庆石油学院 | Gallium, zinc, platinum modified HZSM-5 catalyst for low-carbon chain hydrocarbon aromatization |
| US5961818A (en) * | 1997-02-20 | 1999-10-05 | Council Of Scientific And Industrial Research | Process for the production of LPG and high octane aromatic hydrocarbons from non-economically viable petroleum feed stock |
| CN101322942B (en) * | 2008-07-29 | 2010-09-29 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN101628242B (en) * | 2009-08-10 | 2011-12-14 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof |
-
2010
- 2010-09-26 CN CN201010291061XA patent/CN101954291B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795638B (en) * | 2012-08-06 | 2013-12-25 | 黑龙江大学 | Preparation method of nanometer Zn/Al ZSM-5 molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101954291A (en) | 2011-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101954291B (en) | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof | |
| US10960387B2 (en) | Catalyst and method for direct conversion of syngas to light olefins | |
| CN107840778B (en) | Method for preparing aromatic hydrocarbon by carbon dioxide hydrogenation | |
| AU2011232735C1 (en) | A high-selectivity catalyst for the production of high-quality gasoline fractions from syngas and its preparation method | |
| CN108970600B (en) | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas | |
| CN103537315A (en) | Catalyst for preparation of aromatic hydrocarbons from methanol and preparation method thereof | |
| WO2008116104A1 (en) | A precursor of a catalytic structure, a catalytic structure, a method of fabricating the same, and a system and a method for using the same | |
| CN103664440B (en) | Methanol conversion produces the method for aromatic hydrocarbons | |
| CN105502433B (en) | A kind of preparing gasoline by methanol catalyst nano Zn ZSM 5 preparation method | |
| CN110280302B (en) | Catalyst for converting methane into aromatic hydrocarbon and preparation method and application thereof | |
| Tian et al. | Methanol aromatization over Zn-modified HZSM-5 catalysts derived from ZIF-8 | |
| CN102910647B (en) | The Catalysts and its preparation method of a kind of methyl alcohol and/or dimethyl ether conversion preparing aromatic hydrocarbon and application | |
| CN105597815A (en) | ZSM-5/ZnVPI-8 composite structure molecular sieve catalyst | |
| CN110903843A (en) | Method for preparing isoparaffin by catalytic hydrogenation of carbon dioxide | |
| CN103418426B (en) | Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof | |
| CN107661773B (en) | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas | |
| WO2018219364A1 (en) | Catalyst, and method for direct conversion of syngas to prepare liquid fuel and to produce light olefins | |
| CN111346666B (en) | Catalyst and method for preparing liquid fuel with high aromatic hydrocarbon content by directly converting synthesis gas | |
| CN103212434B (en) | Catalyst for preparing dimethylbenzene by converting methanol and preparation method of catalyst | |
| CN104549444B (en) | The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application | |
| Qu et al. | Zeolite-encaged Ultrasmall Pt-Zn Species with Trace Amount of Pt for Efficient Propane Dehydrogenation | |
| CN109701630A (en) | Coupled catalyst system for the direct producing light olefins of synthesis gas | |
| CN104307562B (en) | A kind of preparing gasoline by methanol catalyst and preparation method thereof | |
| Doluda et al. | Modified Zeolites in Methanol to Hydrocarbons Transformation. | |
| CN112973779A (en) | Post-treatment method of ZSM-22 molecular sieve and application of post-treatment method in preparation of liquid fuel by synthesis gas one-step method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20120926 |