CN103007983A - HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof - Google Patents
HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and a preparation method and application thereof. The preparation method of the HZSM-5 molecular sieve based catalyst comprises the steps of hydrolyzing an aluminium source in the ice water batch environment, removing alcohols in the synthesized liquid at a high temperature and preparing ZSM-5 molecular sieves by a single-template method or a double-temperature method. The HZSM-5 molecular sieve based catalyst prepared by the method provided by the invention has high crystallinity, small granularity and high mesoporous capacity; and the HZSM-5 molecular sieve based catalyst has the advantages of long stable phase and high oil phase product selectivity in the methanol to gasoline reaction.
Description
Technical field
The present invention relates to a kind of HZSM-5 molecular sieve catalyst for preparing gasoline by methanol and preparation method thereof, also relate to a kind of method that makes methyl alcohol and HZSM-5 molecular sieve catalyst of the present invention contact to prepare gasoline.
Background technology
As everyone knows, gasoline is the lifeblood of communications and transportation, and traditional preparation method is as raw material take oil.But under the promotion of the continuous high speed development of society, the social required quantity of gasoline grows with each passing day, and human constantly asking for causes petroleum resources day by day exhausted.At present, the whole world amount of consuming petroleum every day has reached 7,100 ten thousand barrels, almost annual increase by 2%.Scholarly forecast, with present depletion rate, existing petroleum based fuels can only be kept decades.Therefore, seek suitable oil replacement fuel and become the focus that various circles of society pay close attention to.Wherein, relatively abundant natural gas, coal and the bioenergy of reserves becomes the from now on primary selection in quite long one period.The energy feature of China is rich coal, oil starvation, weak breath.Therefore, relatively abundant coal resources just become the inevitable choice of China's energy.Yet, how to effectively utilize these energy, improve the productive rate of oil-phase product and selectively be the constantly emphasis places of effort of scientific circles.Preparing gasoline by methanol (MTG) is as the subsequent technique of these energy conversions, and the background at such society and economic needs becomes the focus that everybody pays close attention to day by day just.
The seventies in last century, Mobil company has developed preparing gasoline by methanol (MTG) technology.All the time, improve the selective of oil-phase product, the life-span of extending catalyst is the focus of preparing gasoline by methanol catalyst field research.Raising HZSM-5 molecular sieve catalyst oil-phase product optionally approach mainly comprises the granularity of introducing alien species and reducing molecular sieve.For example, H.A. Zaidi and K.K. Pant adopt infusion process to prepare the CuO/HZSM-5 molecular sieve catalyst, compare with parent HZSM-5 molecular sieve, and CuO/HZSM-5 molecular sieve catalyst degree of crystallinity obviously reduces; Specific area reduces, and is 254.6 m
2G
-1Pore volume reduces, and is 0.33 cm
3G
-1The introducing of CuO is thought by this research group, so that catalyst surface produces a kind of new activated centre, this is 38.7% so that oil-phase product selectively improves, but catalysqt deactivation is very fast, stationary phase almost nil (list of references Catalysis Today 96 (2004) 155 – 160).The people such as Ali A. Rownaghi adopt single template oil bath crystallization method to prepare the HZSM-5 molecular sieve catalyst that average grain diameter is 120 nm.Compare with common micron order HZSM-5 molecular sieve, the degree of crystallinity of nano-HZSM-5 zeolite catalyst improves; Specific area increases, and is 379 m
2G
-1Pore volume increases, and is 0.34 cm
3G
-1Weak acid and middle strong acid center disappear, and only strong acid center occurred at higher temperature.Oil-phase product selectively reaches 45.9 %, but phase stationary phase is shorter, only is 10 h.The main method that improves at present catalyst life has, and reduces two kinds of approach (list of references Catalysis Communications, 2011,14: 37-41) such as molecular sieve particle diameter and structure micropore-mesopore graded pore structure.The people such as Zhaoteng Xue adopt the method for silanization, through the hydrothermal crystallizing that reaching 5 days and obtain the micropore-mesopore gradient pore HZSM-5 molecular sieve catalyst that granularity is 23 nm, compare with common micropore HZSM-5 molecular sieve catalyst, the degree of crystallinity of gradient pore HZSM-5 molecular sieve catalyst obviously reduces; Specific area increases, and is 521 m
2G
-1, pore volume increases, and is 0.44 cm
3G
-1Granularity reduces to cause the outer aluminium of skeleton to increase, and L acid amount increases, and B acid amount reduces; Oil-phase product selectively higher be 30%, but catalysis is not long stationary phase, only is 20 h(list of references Microporous and Mesoporous Materials, and 2012, (151): 271-276).
Summary of the invention
The problem to be solved in the present invention is: the existing catalyst of preparing gasoline by methanol can't be taken into account the high selectivity of oil-phase product and the long-life of catalyst at present, simultaneously exist crystallization time longer aspect the preparation technology of catalyst, the problems such as degree of crystallinity descends, and technique is complicated.The objective of the invention is by selecting aluminium isopropoxide (AIP) to be the aluminium source, and hydrolysis aluminium source in ice-water bath, the hydrolysis rate in aluminium source and silicon source is complementary and removes at a certain temperature alcohol in the synthetic liquid, provide a kind of program simple, crystallization time is short, catalyst degree of crystallinity is higher, and the catalytic reaction of preparing gasoline by methanol is had effective catalyst of high oil phase selectivity of product and longer life and preparation method thereof simultaneously.
The invention provides a kind of preparation method of the HZSM-5 molecular sieve catalyst for preparing gasoline by methanol, said method comprising the steps of:
The preparation of I, synthetic liquid
The preparation of synthetic liquid one:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in the template TPAOH (TPAOH), be stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min and be the clear shape, then add successively silicon source and deionized water and obtain mixed liquor, this mixed liquor rotating speed with 600 ~ 650 r/min under room temperature is continued to stir a period of time, at last, mixed liquor is made synthetic liquid except alcohol 10 ~ 30 min under 80 ~ 90 ℃ of stirring conditions; The mole of described synthetic liquid consists of: SiO
2: Al
2O
3: TPAOH: H
2O=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30; Perhaps
The preparation of synthetic liquid two:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in the first template TPAOH (TPAOH), be stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min and be the clear shape, then add successively silicon source and deionized water and obtain mixed liquor, this mixed liquor rotating speed with 600 ~ 650 r/min under room temperature is continued to stir a period of time, the second template M is added drop-wise in the mixed liquor, after removing alcohol 10 ~ 30 min under 80 ~ 90 ℃ of stirring conditions, makes synthetic liquid; The mole of described synthetic liquid consists of: SiO
2: Al
2O
3: TPAOH: H
2O: M=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30: 0.035 ~ 0.095;
Synthesizing of II, molecular sieve:
The synthetic liquid one or two that step I is obtained joins in the stainless steel still, aged at room temperature 10-50 min, then at 140 ~ 180 ℃ of lower crystallization 30 ~ 96 h, solid product centrifugation, washing is extremely neutral, after 80-120 ℃ of lower drying, at 500-600 ℃ of lower roasting 5 h, obtain ZSM-5 molecular sieve;
The ammonium ion exchange of Ш, molecular sieve
The ammonium nitrate solution of preparation 0.5-1.5 mol/l, with the ZSM-5 molecular sieve of ammonium nitrate solution and Step II preparation according to volume mass than 10-30 ml: after the ratio of 1 g is mixed, centrifugation after carrying out ion-exchange 4-8h under 75 ~ 90 ℃; This process repeats 1-3 time; Then through washing, dry, calcination process, obtain the HZSM-5 molecular sieve catalyst.
Among the preparation method described above, used silicon source is ethyl orthosilicate (TEOS), Ludox or waterglass.The second used template M is polydiene propyl group polyquaternium-6(M100), polyquaternium-7(M550), alkyl dimethyl ammonium chloride (PDD-AM) or dimethyl-allyl ammonium chloride acrylamide copolymer (PDADMAC).
And among the described preparation method, best crystallization time in the Step II is 36 ~ 72 h, the concentration of ammonium nitrate solution is preferably 0.5mol/l among the Step II I, and ammonium nitrate solution mixes than the ratio of 15ml: 1g according to volume mass with the ZSM-5 molecular sieve of Step II preparation.
The present invention also provides a kind of HZSM-5 molecular sieve catalyst by the said method preparation, and the silica alumina ratio of described HZSM-5 molecular sieve catalyst is 18-54, and specific area is 361-468 m
2G
-1, pore volume is 0.27-0.50cm
3G
-1, average pore size is 6.25-7.98nm, particle mean size is that 23-33nm and relative crystallinity are 81.2-160%.
In addition, the present invention also provides a kind of method of preparing gasoline by methanol, and the HZSM-5 molecular sieve catalyst of the method for the invention preparation is contacted with methyl alcohol, catalysis methanol reaction gasoline processed, stationary phase 〉=the 35h of described catalyst, simultaneously oil-phase product selectively also up to about 30% or more than.
The reaction condition of the reaction of described catalysis methanol gasoline processed is: normal pressure, reaction temperature 350-420 ℃; Raw material adopts purity greater than the methanol solution of 99.5wt%; WHSV=3.2-8.5g/g
CatH
-1
Advantage of the present invention and good effect are:
Be the aluminium source by selecting aluminium isopropoxide (AIP), and be chosen in ice-water bath Water Under Xie Lvyuan, the hydrolysis rate in aluminium source and silicon source is complementary, and remove alcohol in the synthetic liquid under the uniform temperature, make the HZSM-5 molecular sieve catalyst degree of crystallinity that obtains higher, and the catalytic reaction of preparing gasoline by methanol is had high oil phase selectivity of product and longer life simultaneously;
. the present invention is simple to operate, and crystallization time is short, the shortest 30 h that only need; The catalyst relative crystallinity is higher, reaches as high as 160.0%; To the catalytic reaction of preparing gasoline by methanol, to oil-phase product selectively can reach 30% or more than; And the stationary phase of catalyst is more than 35 h; Wherein the stationary phase of catalyst the longest 70 h that reach, in the prior art stationary phase the longest catalyst, this catalyst selectively also maintains 30% to oil-phase product simultaneously.
Description of drawings
Accompanying drawing 1 is X-ray diffraction (XRD) figure of the present invention typical case HZSM-5 molecular sieve catalyst.
Accompanying drawing 2 is N of the present invention typical case HZSM-5 molecular sieve catalyst
2The adsorption-desorption curve map.
The NH of accompanying drawing 3 the present invention typical case HZSM-5 molecular sieve catalyst
3-TPD figure.
Accompanying drawing 4 is ESEM (SEM) figure of the present invention typical case HZSM-5 molecular sieve catalyst.
Accompanying drawing 5 is ESEM (TEM) figure of the present invention typical case HZSM-5 molecular sieve catalyst.
The specific embodiment
Below in conjunction with accompanying drawing, with the specific embodiment preparation method and the effect of a kind of HZSM-5 molecular sieve catalyst for preparing gasoline by methanol provided by the invention are made further detailed description.
Embodiment 1
The preparation of I, synthetic liquid one
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, and be stirred to mixed liquor with the rotating speed of 350 r/min and be the clear shape; Then add successively Ludox and deionized water.This moment, the mole of mixed liquor consisted of: SiO
2: 0.030Al
2O
3: 0.29TPAOH: 30H
2O.This mixed liquor is at room temperature continued to stir a period of time with the rotating speed of 600 r/min.Under 90 ℃ of stirring conditions, go out except pure 30 min at last, make synthetic liquid one.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid one that step I is obtained joins in the stainless steel still, aged at room temperature 10 min.Then carry out crystallization under 180 ℃, self pressure, the time is 30 h.After crystallization is complete, solid product centrifugation, washing is extremely neutral, in the 120 ℃ of lower dry evenings.Last 5 h that calcine in 600 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 1.5 mol/L, with the ZSM-5 molecular sieve (by mass calculation) of ammonium nitrate solution (by volume calculate) and Step II preparation according to 10 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 6 h under 75 ℃ the temperature.This process repeats 2 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 2
The preparation of I, synthetic liquid one
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, and be stirred to mixed liquor with the rotating speed of 420 r/min and be the clear shape; Then add successively Ludox and deionized water.This moment, the mole of mixed liquor consisted of: SiO
2: 0.025Al
2O
3: 0.25TPAOH: 20H
2O.This mixed liquor is at room temperature continued to stir a period of time with the rotating speed of 630 r/min.Under 85 ℃ of stirring conditions, go out except pure 25 min at last, make synthetic liquid one.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid one that step I is obtained joins in the stainless steel still, aged at room temperature 20 min.Then carry out crystallization under 175 ℃, self pressure, the time is 36 h.After crystallization is complete, solid product centrifugation, washing is extremely neutral, in the 100 ℃ of lower dry evenings.Last 5 h that calcine in 500 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, with the ZSM-5 molecular sieve (by mass calculation) of ammonium nitrate solution (by volume calculate) and Step II preparation according to 20 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 5 h under 85 ℃ the temperature.This process repeats 2 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 3
The preparation of I, synthetic liquid one
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, and be stirred to mixed liquor with the rotating speed of 550 r/min and be the clear shape; Afterwards, add successively ethyl orthosilicate and deionized water.This moment, the mole of mixed liquor consisted of: SiO
2: 0.017Al
2O
3: 0.20TPAOH: 15H
2O.This mixed liquor is at room temperature continued to stir a period of time with the rotating speed of 620 r/min.Under 80 ℃ of stirring conditions, remove at last pure 14 min, make synthetic liquid one.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid one that step I is obtained joins in the stainless steel still, and then aged at room temperature 30 min carry out crystallization under 170 ℃, self pressure, and the time is 72 h.After crystallization was complete, solid product is centrifugal, washing was to neutral, in the 110 ℃ of lower dry evenings.Last 5 h that calcine in 550 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
[0042] ammonium nitrate solution of preparation 0.5 mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared is according to 15 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 4 h under 80 ℃ the temperature.This process repeats 3 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 4
The preparation of I, synthetic liquid one
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, be stirred to mixed liquor with the rotating speed of 450 r/min and be the clear shape; Then add successively waterglass and deionized water.The mole of mixed liquor consists of: SiO
2: 0.010Al
2O
3: 0.17TPAOH: 10H
2O.Then this mixed liquor rotating speed with 650 r/min under room temperature is continued to stir a period of time.Under 85 ℃ of stirring conditions, remove at last pure 10 min, make synthetic liquid one.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid one that step I is obtained joins in the stainless steel still, and then aged at room temperature 50 min carry out crystallization under 140 ℃, self pressure, and the time is 96 h.After crystallization is complete, solid product centrifugation, washing is extremely neutral, in the 80 ℃ of lower dry evenings.Last 5 h that calcine in 550 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared is according to 30 ml: after the ratio of 1 g is mixed, after carrying out ion-exchange 8 h under 90 ℃ the temperature, through centrifugal, separate,, washing, drying and roasting, obtain the HZSM-5 molecular sieve catalyst.
The preparation of I, synthetic liquid two
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, after being stirred to mixed liquor and being the clear shape with the rotating speed of 400 r/min; Then add successively Ludox and deionized water.This mixed liquor after stirring a period of time with the rotating speed of 600 r/min under the room temperature, slowly is added drop-wise to polyquaternium-6(M100) and continues in the mixed liquor to stir.At last mixed liquor is removed pure 30 min under 85 ℃ of stirring conditions, make synthetic liquid two.At this moment, the mole of synthetic liquid two consists of: SiO
2: 0.030Al
2O
3: 0.29TPAOH: 10H
2O: 0.035 M100.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid two that step I is obtained joins in the stainless steel still, and then aged at room temperature 50 min carry out crystallization under 140 ℃, self pressure, and the time is 60 h.After crystallization was complete, solid product is centrifugal, washing was to neutral, in the 80 ℃ of lower dry evenings.Last 5 h that calcine in 500 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 1.5 mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared is according to 10 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 8 h under 75 ℃ the temperature.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 6
The preparation of I, synthetic liquid two
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, after being stirred to mixed liquor and being the clear shape with the rotating speed of 350 r/min; Then add successively waterglass and deionized water.This mixed liquor after stirring a period of time with the rotating speed of 600 r/min under the room temperature, slowly is added drop-wise to polyquaternium-7(M550) and continues in the mixed liquor to stir.At last mixed liquor is removed pure 10 min under 90 ℃ of stirring conditions, make synthetic liquid two.At this moment, the mole of synthetic liquid two consists of: SiO
2: 0.010Al
2O
3: 0.20TPAOH: 30 H
2O: 0.095 M550.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid two that step I is obtained joins in the stainless steel still, and then aged at room temperature 30 min carry out crystallization under 180 ℃, self pressure, and the time is 30 h.After crystallization was complete, solid product is centrifugal, washing was to neutral, in the 110 ℃ of lower dry evenings.Last 5 h that calcine in 550 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
The ammonium nitrate solution of preparation 1.0mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared are according to 20 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 6 h under 90 ℃ the temperature.This process repeats 2 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 7
The preparation of I, synthetic liquid two
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, after being stirred to mixed liquor and being the clear shape with the rotating speed of 550 r/min; Then add successively ethyl orthosilicate and deionized water.After stirring a period of time with the rotating speed of 620 r/min under the room temperature, diallyl dimethyl ammoniumchloride (PDD-AM) slowly is added drop-wise to and continues in the mixed liquor to stir with this mixed liquor.At last mixed liquor is removed pure 14 min under 80 ℃ of stirring conditions, make synthetic liquid two.At this moment, the mole of synthetic liquid two consists of: SiO
2: 0.017Al
2O
3: 0.20TPAOH: 15H
2O: 0.070 PDD-AM.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid two that step I is obtained joins in the stainless steel still, aged at room temperature 30 min.Then carry out crystallization under 170 ℃, self pressure, the time is 72 h.After crystallization was complete, solid product is centrifugal, washing was to neutral, in the 120 ℃ of lower dry evenings.Last 5 h that calcine in 550 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 0.5 mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared is according to 15 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 4 h under 80 ℃ the temperature.This process repeats 3 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Embodiment 8
The preparation of I, synthetic liquid two
Under ice water bath environment, aluminium isopropoxide is joined in the TPAOH that mass fraction is 25wt% (TPAOH) solution, after being stirred to mixed liquor and being the clear shape with the rotating speed of 550 r/min; Then add successively Ludox and deionized water.This mixed liquor after stirring a period of time with the rotating speed of 620 r/min under the room temperature, slowly is added drop-wise to dimethyl-allyl ammonium chloride acrylamide copolymer (PDADMAC) and continues in the mixed liquor to stir.At last mixed liquor is removed pure 14 min under 80 ℃ of stirring conditions, make synthetic liquid two.At this moment, the mole of synthetic liquid two consists of: SiO
2: 0.025Al
2O
3: 0.22TPAOH: 16H
2O: 0.055 PDADMAC.
Synthesizing of II, molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthetic liquid two that step I is obtained joins in the stainless steel still, aged at room temperature 25 min.Then carry out crystallization under 150 ℃, self pressure, the time is 58 h.After crystallization was complete, solid product is centrifugal, washing was to neutral, in the 90 ℃ of lower dry evenings.Last 5 h that calcine in 600 ℃ Muffle furnace make ZSM-5 molecular sieve.
The ammonium ion exchange of III, molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, the ZSM-5 molecular sieve (by mass calculation) that ammonium nitrate solution (by volume calculate) and Step II are prepared is according to 30 ml: after the ratio of 1 g is mixed, centrifugal after carrying out ion-exchange 5 h under 75 ℃ the temperature.This process repeats 3 times.Then washing, dry, roasting obtain the HZSM-5 molecular sieve catalyst.
Comparative Examples 1
Method according to embodiment 3 prepares the HZSM-5 molecular sieve catalyst, and different is: do not use ice-water bath to be hydrolyzed at ambient temperature the aluminium source.
Characterize example 1
HZSM-5 molecular sieve catalyst to embodiment 1-8 and Comparative Examples 1 carries out X-ray diffraction (XRD) evaluation
Adopt Rigaku D/max2500 type powder x-ray diffraction instrument (XRD) that the crystal of catalyst is observed, the sign condition is: adopt CuK α radiation, tube voltage is 40 KV, and tube current is 40 mA, sweep limits 2 θ=5 ~ 35o, sweep speed is 8 o/min.The relative crystallinity of each catalyst is as shown in table 1.
Table 1: the relative crystallinity of catalyst
| Numbering | Granularity/nm | Relative crystallinity/% |
| Embodiment 1 | 27 | 110.7 |
| Embodiment 2 | 33 | 160.0 |
| Embodiment 3 | 23 | 127.7 |
| Embodiment 4 | 31 | 118.6 |
| |
25 | 88.3 |
| Embodiment 6 | 30 | 90.3 |
| Embodiment 7 | 30 | 81.2 |
| Embodiment 8 | 30 | 88.0 |
| Comparative Examples 1 | 31 | 100 |
Characterize example 2
HZSM-5 molecular sieve catalyst to 1-8 embodiment and Comparative Examples 1 carries out N
2Adsorption-desorption is estimated.
Adopt Micromeritics ASAP 2020 type automatic absorbing instrument to measure specific area, pore volume and the pore-size distribution of catalyst.The sign condition is: take High Purity Nitrogen as adsorbing medium, liquid nitrogen is cold-trap, and adsorption temp is-196.5 ℃, and relative pressure is 0 ~ 0.995.Characterization result is as shown in table 2.
Table 2: the pore structure character of catalyst
Characterize example 3
HZSM-5 molecular sieve catalyst to 1-8 embodiment and Comparative Examples 1 carries out NH
3-TPD characterizes.
Employing is weighed first the dynamic in-situ analyzer of TP-5000 type the Acidity of catalyst mensuration is measured.The sign condition is: the loading amount of catalyst is 0.10 g, and sample purges 1 h under the Ar compression ring border under 500 ℃; Be down to afterwards 50 ℃ of absorption NH
3, adsorb saturated laggard Ar and walk surely to baseline, be warming up to 700 ℃ with the speed of 8 °/min afterwards and finish desorption.The ratio of acid amount represents that by the ratio of the right peak area in corresponding temperature peak characterization result is as shown in the table.
Table 3: the Acidity of catalyst
| Catalyst | T Weak acid/℃ | T Middle strong acid/℃ | T Strong acid/℃ | S Weak acid : S Middle strong acid : S Strong acid |
| Embodiment 1 | 120 | 190 | 410 | 312 : 405 : 478 |
| Embodiment 2 | 120 | 180 | 400 | 190 : 540 : 400 |
| Embodiment 3 | 130 | 190 | 400 | 226 : 614 : 469 |
| Embodiment 4 | 130 | 200 | 425 | 300 : 450 : 515 |
| |
130 | 200 | 430 | 476 : 400 : 600 |
| Embodiment 6 | 130 | 190 | 420 | 390 : 410 : 575 |
| Embodiment 7 | 120 | 190 | 400 | 254 : 390 : 527 |
| Embodiment 8 | 120 | 200 | 400 | 154 : 612 : 550 |
| Comparative Examples 1 | 120 | 190 | 400 | 450 : 380 : 717 |
Catalytic reaction evaluation Example 1
Preparing gasoline by methanol catalysis experiment is carried out at miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 350 ℃, and raw material adopts the methanol solution of 99.5 wt%, WHSV=3.2 g/g
CatH
-1The catalytic result of embodiment is as shown in table 4.
Table 4: evaluating catalyst result
Catalytic reaction evaluation Example 2
Preparing gasoline by methanol catalysis experiment is carried out at miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 370 ℃, and raw material adopts the methanol solution of 99.5 wt%, WHSV=5.6 g/g
CatH
-1The catalytic result of embodiment is as shown in table 5.
Table 5: evaluating catalyst result
Catalytic reaction evaluation Example 3
Preparing gasoline by methanol catalysis experiment is carried out at miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 420 ℃, and raw material adopts the methanol solution of 99.5 wt%, WHSV=8.5 g/g
CatH
-1The catalytic result of embodiment is as shown in table 6.
Table 6: evaluating catalyst result
Claims (1)
1. preparation method who is used for the HZSM-5 molecular sieve catalyst of preparing gasoline by methanol said method comprising the steps of:
The preparation of I, synthetic liquid
The preparation of synthetic liquid one:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in the template TPAOH (TPAOH), be stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min and be the clear shape, then add successively silicon source and deionized water and obtain mixed liquor, this mixed liquor rotating speed with 600 ~ 650 r/min under room temperature is continued to stir a period of time, at last, mixed liquor is made synthetic liquid except alcohol 10 ~ 30 min under 80 ~ 90 ℃ of stirring conditions; The mole of described synthetic liquid consists of: SiO
2: Al
2O
3: TPAOH: H
2O=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30; Perhaps
The preparation of synthetic liquid two:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in the first template TPAOH (TPAOH), be stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min and be the clear shape, then add successively silicon source and deionized water and obtain mixed liquor, this mixed liquor rotating speed with 600 ~ 650 r/min under room temperature is continued to stir a period of time, the second template M is added drop-wise in the mixed liquor, after removing alcohol 10 ~ 30 min under 80 ~ 90 ℃ of stirring conditions, makes synthetic liquid; The mole of described synthetic liquid consists of: SiO
2: Al
2O
3: TPAOH: H
2O: M=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30: 0.035 ~ 0.095;
Synthesizing of II, molecular sieve:
The synthetic liquid one or two that step I is obtained joins in the stainless steel still, aged at room temperature 10 ~ 50 min, then at 140 ~ 180 ℃ of lower crystallization 30 ~ 96 h, solid product centrifugation, washing is extremely neutral, after 80 ~ 120 ℃ of lower dryings, at 500-600 ℃ of lower roasting 5 h, obtain ZSM-5 molecular sieve;
The ammonium ion exchange of Ш, molecular sieve
The ammonium nitrate solution of preparation 0.5 ~ 1.5 mol/l, with the ZSM-5 molecular sieve of ammonium nitrate solution and Step II preparation according to volume mass than 10-30 ml: after the ratio of 1 g is mixed, centrifugation after carrying out ion-exchange 4 ~ 8 h under 75 ~ 90 ℃; This process repeats 1-3 time; Then through washing, dry, calcination process, obtain the HZSM-5 molecular sieve catalyst.
2. be used for as claimed in claim 1 the preparation method of the catalyst of preparing gasoline by methanol, it is characterized in that used silicon source is ethyl orthosilicate (TEOS), Ludox or waterglass.
3. such as the preparation method of claims 1 or 2 described catalyst for preparing gasoline by methanol, it is characterized in that the second used template M is polyquaternium-6(M100), polyquaternium-7(M550), diallyl dimethyl ammoniumchloride (PDD-AM) or dimethyl-allyl ammonium chloride acrylamide copolymer (PDADMAC).
4. such as the preparation method of claims 1 or 2 described catalyst for preparing gasoline by methanol, it is characterized in that: the best crystallization time in the Step II is 36 ~ 72 h.
5. such as the preparation method of claims 1 or 2 described catalyst for preparing gasoline by methanol, it is characterized in that: the concentration of ammonium nitrate solution is 0.5mol/l among the Step II I, and ammonium nitrate solution mixes than the ratio of 15ml: 1g according to volume mass with the ZSM-5 molecular sieve of Step II preparation.
6. HZSM-5 molecular sieve catalyst of arbitrary described method preparation according to claim 1-5, the silica alumina ratio of described HZSM-5 molecular sieve catalyst is 18-54, specific area is 361-468 m
2G
-1, pore volume is 0.27-0.50cm
3G
-1, average pore size is 6.25-7.98nm, particle mean size is that 23-33nm and relative crystallinity are 81.2-160%.
7. the method for a preparing gasoline by methanol, the HZSM-5 molecular sieve catalyst of the arbitrary described method preparation of claim 1-5 is contacted with methyl alcohol, catalysis methanol reaction gasoline processed, it is characterized in that: stationary phase 〉=35 h of described catalyst, simultaneously oil-phase product selectively also up to 30% or more than.
8. method as claimed in claim 7, the reaction condition of the reaction of described catalysis methanol gasoline processed is: normal pressure, reaction temperature 350-420 ℃; Raw material adopts purity greater than the methanol solution of 99.5wt%; WHSV=3.2-8.5 g/g
CatH
-1
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| CN103506150A (en) * | 2013-10-18 | 2014-01-15 | 中国科学院上海高等研究院 | Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst |
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