CN103007983B - 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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 methyl alcohol that makes and contact with HZSM-5 molecular sieve catalyst of the present invention the method preparing gasoline.
Background technology
As everyone knows, gasoline is the lifeblood of communications and transportation, and traditional preparation method take oil as raw material.But under the promotion of the continuous high speed development of society, the social required quantity of gasoline grows with each passing day, constantly asking for of the mankind 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 increases by 2% every year.Scholarly forecast, with current depletion rate, existing petroleum based fuels can only maintain decades.Therefore, the focus that suitable oil replacement fuel becomes various circles of society's concern is found.Wherein, the natural gas of reserves relative abundance, coal and bioenergy become the primary selection in quite long one period from now on.The energy feature of China is rich coal, oil starvation, weak breath.Therefore, the coal resources of relative abundance just become the inevitable choice of China's energy.But, how to effectively utilize these energy, improve the productive rate of oil-phase product and the selective emphasis place being scientific circles and constantly making great efforts.Preparing gasoline by methanol (MTG), as the subsequent technique of these energy conversions, becomes in the background of such society and economic needs the focus that everybody pays close attention to just day by day.
The seventies in last century, Mobil company develops 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 introduced alien species and reduce molecular sieve.Such as, H.A. Zaidi and K.K. Pant adopts infusion process to prepare CuO/HZSM-5 molecular sieve catalyst, and compared with parent HZSM-5 molecular sieve, CuO/HZSM-5 molecular sieve catalyst degree of crystallinity obviously reduces; Specific area reduces, and is 254.6 m
2g
-1; Pore volume reduces, and is 0.33 cm
3g
-1; The introducing of CuO is thought by this research group, catalyst surface is made to produce a kind of new activated centre, this makes the selective raising of oil-phase product, be 38.7%, but catalysqt deactivation is very fast, stationary phase almost nil (bibliography 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.Compared with common micro level HZSM-5 molecular sieve, the degree of crystallinity of nano-HZSM-5 zeolite catalyst improves; Specific area increases, and is 379 m
2g
-1; Pore volume increases, and is 0.34 cm
3g
-1; Weak acid and middle strong acid center disappear, and have only occurred strong acid center at higher temperature.Oil-phase product is selective reaches 45.9 %, but phase stationary phase is shorter, is only 10 h.The main method of current raising catalyst life has, and reduces two kinds of approach (bibliography 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, hydrothermal crystallizing through reaching 5 days obtains the micropore-mesopore gradient pore HZSM-5 molecular sieve catalyst that granularity is 23 nm, compared 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
-1; Granularity reduces to cause the outer aluminium of skeleton to increase, and L acid amount increases, and B acid amount reduces; Oil-phase product selective higher, be 30%, but catalysis is not long for stationary phase, is only 20 h(bibliography Microporous and Mesoporous Materials, 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 cannot take into account the high selectivity of oil-phase product and the long-life of catalyst at present, in the preparation technology of catalyst, there is crystallization time longer simultaneously, degree of crystallinity declines, the problems such as technique is more complicated.The object of the invention is by selecting aluminium isopropoxide (AIP) to be aluminium source, and in ice-water bath, be hydrolyzed aluminium source, the hydrolysis rate in aluminium source and silicon source is matched and removes the alcohol synthesized in liquid at a certain temperature, there is provided a kind of program simple, crystallization time is short, catalyst crystal degree is higher, has effective catalyst of high oil phase selectivity of product and longer life and preparation method thereof to the catalytic reaction of preparing gasoline by methanol 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:
I, the preparation of liquid is synthesized
The preparation of synthesis liquid one:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in template TPAOH (TPAOH), being stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min is clear shape, then silicon source and deionized water acquisition mixed liquor is added successively, this mixed liquor is continued to stir a period of time with the rotating speed of 600 ~ 650 r/min under room temperature, finally, mixed liquor is synthesized liquid except alcohol 10 ~ 30 min is obtained under 80 ~ 90 DEG C of stirring conditions; Mole consisting of of described synthesis liquid: SiO
2: Al
2o
3: TPAOH: H
2o=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30; Or
The preparation of synthesis liquid two:
Under ice water bath environment, aluminium source aluminium isopropoxide (AIP) is joined in the first template TPAOH (TPAOH), being stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min is clear shape, then silicon source and deionized water acquisition mixed liquor is added successively, this mixed liquor is continued to stir a period of time with the rotating speed of 600 ~ 650 r/min under room temperature, second template M is added drop-wise in mixed liquor, except synthesis liquid obtained after alcohol 10 ~ 30 min under 80 ~ 90 DEG C of stirring conditions; Mole consisting of of described synthesis liquid: SiO
2: Al
2o
3: TPAOH: H
2o: M=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30: 0.035 ~ 0.095;
II, the synthesis of molecular sieve:
The synthesis liquid one or two obtained by step I joins in stainless steel still, aged at room temperature 10-50 min, then crystallization 30 ~ 96 h at 140 ~ 180 DEG C, by solid product centrifugation, washing to neutral, at 80-120 DEG C after drying, at 500-600 DEG C, roasting 5 h, obtains ZSM-5 molecular sieve;
The ammonium ion exchange of Ш, molecular sieve
The ammonium nitrate solution of preparation 0.5-1.5 mol/l, after ZSM-5 molecular sieve ammonium nitrate solution and Step II prepared mixes than the ratio of 10-30 ml: 1 g according to volume mass, carries out centrifugation after ion-exchange 4-8h at 75 ~ 90 DEG C; This process repeats 1-3 time; Then through washing, dry, calcination process, HZSM-5 molecular sieve catalyst is obtained.
In preparation method described above, silicon source used is ethyl orthosilicate (TEOS), Ludox or waterglass.Second template M used is polydiene propyl group polyquaternium-6(M100), polyquaternium-7(M550), alkyl dimethyl ammonium chloride (PDD-AM) or dimethylallylammonium chloride acrylamide copolymer (PDADMAC).
And in described preparation method, best crystallization time in Step II is 36 ~ 72 h, in Step II I, the concentration of ammonium nitrate solution is preferably 0.5mol/l, and ZSM-5 molecular sieve prepared by ammonium nitrate solution and Step II mixes according to the ratio of volume mass than 15ml: 1g.
The present invention also provides a kind of HZSM-5 molecular sieve catalyst prepared by said method, 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, and particle mean size is 23-33nm and relative crystallinity is 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 wherein making the method for the invention prepare contacts with methyl alcohol, catalysis methanol reaction gasoline processed, described catalyst stationary phase >=35h, simultaneously oil-phase product is selective also up to about 30% or more.
The reaction condition of the reaction of described catalysis methanol gasoline is: normal pressure, reaction temperature 350-420 DEG C; Raw material adopts purity to be 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:
By selecting aluminium isopropoxide (AIP) to be aluminium source, and select at ice-water bath Water Under Xie Lvyuan, the hydrolysis rate in aluminium source and silicon source is matched, and the alcohol under uniform temperature in removing synthesis liquid, make the HZSM-5 molecular sieve catalyst degree of crystallinity that obtains higher, and to the catalytic reaction of preparing gasoline by methanol, there is high oil phase selectivity of product and longer life simultaneously;
. the present invention is simple to operate, and crystallization time is short, the shortlyest only needs 30 h; Catalyst relative crystallinity is higher, reaches as high as 160.0%; To the catalytic reaction of preparing gasoline by methanol, reach 30% or more to oil-phase product is selective; And the stationary phase of catalyst is at 35 more than h; Wherein the longlyest reach 70 h the stationary phase of catalyst, be the catalyst that stationary phase in prior art is the longest, this catalyst also maintains 30% to the selective of oil-phase product simultaneously.
Accompanying drawing explanation
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
2adsorption-desorption curve map.
The NH of accompanying drawing 3 the present invention typical case HZSM-5 molecular sieve catalyst
3-TPD schemes.
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.
Detailed description of the invention
Below in conjunction with accompanying drawing, by detailed description of the invention, the preparation method of a kind of HZSM-5 molecular sieve catalyst for preparing gasoline by methanol provided by the invention and effect are further described in detail.
embodiment 1
I, the preparation of liquid one is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, and to be stirred to mixed liquor with the rotating speed of 350 r/min be clear shape; Then Ludox and deionized water is added successively.Now mole the consisting of of mixed liquor: 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.Finally go out except alcohol 30 min under 90 DEG C of stirring conditions, obtained synthesis liquid one.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid one obtained by step I joins in stainless steel still, aged at room temperature 10 min.Then 180 DEG C, carry out crystallization under pressure itself, the time is 30 h.After crystallization, by solid product centrifugation, washing to neutral, a dry evening at 120 DEG C.Finally in the Muffle furnace of 600 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 1.5 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 10 ml: 1 g with ZSM-5 molecular sieve (by mass) prepared by Step II, centrifugal carry out ion-exchange 6 h at the temperature of 75 DEG C after.This process repeats 2 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 2
I, the preparation of liquid one is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, and to be stirred to mixed liquor with the rotating speed of 420 r/min be clear shape; Then Ludox and deionized water is added successively.Now mole the consisting of of mixed liquor: 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.Finally go out except alcohol 25 min under 85 DEG C of stirring conditions, obtained synthesis liquid one.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid one obtained by step I joins in stainless steel still, aged at room temperature 20 min.Then 175 DEG C, carry out crystallization under pressure itself, the time is 36 h.After crystallization, by solid product centrifugation, washing to neutral, a dry evening at 100 DEG C.Finally in the Muffle furnace of 500 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 20 ml: 1 g with ZSM-5 molecular sieve (by mass) prepared by Step II, centrifugal carry out ion-exchange 5 h at the temperature of 85 DEG C after.This process repeats 2 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 3
I, the preparation of liquid one is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, and to be stirred to mixed liquor with the rotating speed of 550 r/min be clear shape; Afterwards, ethyl orthosilicate and deionized water is added successively.Now mole the consisting of of mixed liquor: 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.Finally under 80 DEG C of stirring conditions, remove alcohol 14 min, obtained synthesis liquid one.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid one obtained by step I joins in stainless steel still, aged at room temperature 30 min, then 170 DEG C, carry out crystallization under pressure itself, the time is 72 h.After crystallization, solid product is centrifugal, washing extremely neutrality, a dry evening at 110 DEG C.Finally in the Muffle furnace of 550 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
[0042] ammonium nitrate solution of 0.5 mol/L is prepared, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 15 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, centrifugal carry out ion-exchange 4 h at the temperature of 80 DEG C after.This process repeats 3 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 4
I, the preparation of liquid one is synthesized
Under ice water bath environment, joined by aluminium isopropoxide in TPAOH (TPAOH) solution that mass fraction is 25wt%, being stirred to mixed liquor with the rotating speed of 450 r/min is clear shape; Then waterglass and deionized water is added successively.Mole consisting of of mixed liquor: SiO
2: 0.010Al
2o
3: 0.17TPAOH: 10H
2o.Then this mixed liquor is continued to stir a period of time with the rotating speed of 650 r/min under room temperature.Finally under 85 DEG C of stirring conditions, remove alcohol 10 min, obtained synthesis liquid one.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid one obtained by step I joins in stainless steel still, aged at room temperature 50 min, then 140 DEG C, carry out crystallization under pressure itself, the time is 96 h.After crystallization, by solid product centrifugation, washing to neutral, a dry evening at 80 DEG C.Finally in the Muffle furnace of 550 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 30 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, carry out ion-exchange 8 h at the temperature of 90 DEG C after, through centrifugal, be separated, washing, dry and roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 5
I, the preparation of liquid two is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, be stirred to after mixed liquor is clear shape with the rotating speed of 400 r/min; Then Ludox and deionized water is added successively.After this mixed liquor is stirred a period of time with the rotating speed of 600 r/min under room temperature, by polyquaternium-6(M100) be slowly added drop-wise in mixed liquor and continue to stir.Finally mixed liquor is removed alcohol 30 min under 85 DEG C of stirring conditions, obtained synthesis liquid two.Now, mole consisting of of liquid two is synthesized: SiO
2: 0.030Al
2o
3: 0.29TPAOH: 10H
2o: 0.035 M100.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid two obtained by step I joins in stainless steel still, aged at room temperature 50 min, then 140 DEG C, carry out crystallization under pressure itself, the time is 60 h.After crystallization, solid product is centrifugal, washing extremely neutrality, a dry evening at 80 DEG C.Finally in the Muffle furnace of 500 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 1.5 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 10 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, centrifugal carry out ion-exchange 8 h at the temperature of 75 DEG C after.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 6
I, the preparation of liquid two is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, be stirred to after mixed liquor is clear shape with the rotating speed of 350 r/min; Then waterglass and deionized water is added successively.After this mixed liquor is stirred a period of time with the rotating speed of 600 r/min under room temperature, by polyquaternium-7(M550) be slowly added drop-wise in mixed liquor and continue to stir.Finally mixed liquor is removed alcohol 10 min under 90 DEG C of stirring conditions, obtained synthesis liquid two.Now, mole consisting of of liquid two is synthesized: SiO
2: 0.010Al
2o
3: 0.20TPAOH: 30 H
2o: 0.095 M550.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid two obtained by step I joins in stainless steel still, aged at room temperature 30 min, then 180 DEG C, carry out crystallization under pressure itself, the time is 30 h.After crystallization, solid product is centrifugal, washing extremely neutrality, a dry evening at 110 DEG C.Finally in the Muffle furnace of 550 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
The ammonium nitrate solution of preparation 1.0mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 20 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, centrifugal carry out ion-exchange 6 h at the temperature of 90 DEG C after.This process repeats 2 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 7
I, the preparation of liquid two is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, be stirred to after mixed liquor is clear shape with the rotating speed of 550 r/min; Then ethyl orthosilicate and deionized water is added successively.After this mixed liquor is stirred a period of time with the rotating speed of 620 r/min under room temperature, diallyl dimethyl ammoniumchloride (PDD-AM) is slowly added drop-wise in mixed liquor and continues to stir.Finally mixed liquor is removed alcohol 14 min under 80 DEG C of stirring conditions, obtained synthesis liquid two.Now, mole consisting of of liquid two is synthesized: SiO
2: 0.017Al
2o
3: 0.20TPAOH: 15H
2o: 0.070 PDD-AM.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid two obtained by step I joins in stainless steel still, aged at room temperature 30 min.Then 170 DEG C, carry out crystallization under pressure itself, the time is 72 h.After crystallization, solid product is centrifugal, washing extremely neutrality, a dry evening at 120 DEG C.Finally in the Muffle furnace of 550 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 0.5 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 15 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, centrifugal carry out ion-exchange 4 h at the temperature of 80 DEG C after.This process repeats 3 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
embodiment 8
I, the preparation of liquid two is synthesized
Under ice water bath environment, aluminium isopropoxide is joined in TPAOH (TPAOH) solution that mass fraction is 25wt%, be stirred to after mixed liquor is clear shape with the rotating speed of 550 r/min; Then Ludox and deionized water is added successively.After this mixed liquor is stirred a period of time with the rotating speed of 620 r/min under room temperature, dimethylallylammonium chloride acrylamide copolymer (PDADMAC) is slowly added drop-wise in mixed liquor and continues to stir.Finally mixed liquor is removed alcohol 14 min under 80 DEG C of stirring conditions, obtained synthesis liquid two.Now, mole consisting of of liquid two is synthesized: SiO
2: 0.025Al
2o
3: 0.22TPAOH: 16H
2o: 0.055 PDADMAC.
II, the synthesis of molecular sieve
Adopt hydrothermal crystallization method to synthesize, the synthesis liquid two obtained by step I joins in stainless steel still, aged at room temperature 25 min.Then 150 DEG C, carry out crystallization under pressure itself, the time is 58 h.After crystallization, solid product is centrifugal, washing extremely neutrality, a dry evening at 90 DEG C.Finally in the Muffle furnace of 600 DEG C, calcine 5 h, obtained ZSM-5 molecular sieve.
III, the ammonium ion exchange of molecular sieve
Prepare the ammonium nitrate solution of 1.0 mol/L, after ammonium nitrate solution (by volume calculating) is mixed according to the ratio of 30 ml: 1 g with the ZSM-5 molecular sieve (by mass) that Step II is prepared, centrifugal carry out ion-exchange 5 h at the temperature of 75 DEG C after.This process repeats 3 times.Then washing, dry, roasting, obtain HZSM-5 molecular sieve catalyst.
comparative example 1
HZSM-5 molecular sieve catalyst is prepared according to the method for embodiment 3, unlike: do not use ice-water bath to be hydrolyzed aluminium source at ambient temperature.
characterize example 1
X-ray diffraction (XRD) evaluation is carried out to the HZSM-5 molecular sieve catalyst of embodiment 1-8 and comparative example 1
Rigaku D/max2500 type Powder X-ray Diffractometer (XRD) crystal to catalyst is adopted to observe, 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 |
| Embodiment 5 | 25 | 88.3 |
| Embodiment 6 | 30 | 90.3 |
| Embodiment 7 | 30 | 81.2 |
| Embodiment 8 | 30 | 88.0 |
| Comparative example 1 | 31 | 100 |
characterize example 2
N is carried out to the HZSM-5 molecular sieve catalyst of 1-8 embodiment and comparative example 1
2adsorption-desorption is evaluated.
Adopt the specific area of Micromeritics ASAP 2020 type automatic absorbing instrument mensuration catalyst, pore volume and pore-size distribution.Sign condition is: take High Purity Nitrogen as adsorbing medium, and liquid nitrogen is cold-trap, and adsorption temp is-196.5 DEG C, 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
NH is carried out to the HZSM-5 molecular sieve catalyst of 1-8 embodiment and comparative example 1
3-TPD characterizes.
First power TP-5000 type dynamic in-situ analyzer is adopted to measure the Acidity that catalyst measures.Sign condition is: the loading amount of catalyst is 0.10 g, and sample is at 500 DEG C, and Ar compression ring purges 1 h under border; Be down to 50 DEG C of absorption NH afterwards
3, adsorb saturated laggard Ar and walk surely to baseline, be warming up to 700 DEG C with the speed of 8 °/min afterwards and complete desorption.The ratio of acid amount is represented by the ratio of the right peak area in corresponding temperature peak, and 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 |
| Embodiment 5 | 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 example 1 | 120 | 190 | 400 | 450 : 380 : 717 |
catalytic reaction evaluation Example 1
Preparing gasoline by methanol Catalysis experiments carries out on miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 350 DEG C, and raw material adopts the methanol solution of 99.5 wt%, WHSV=3.2 g/g
cath
-1.The 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 experiments carries out on miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 370 DEG C, and raw material adopts the methanol solution of 99.5 wt%, WHSV=5.6 g/g
cath
-1.The 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 experiments carries out on miniature fixed-bed reactor, and reaction condition is: normal pressure, reaction temperature are 420 DEG C, and raw material adopts the methanol solution of 99.5 wt%, WHSV=8.5 g/g
cath
-1.The catalytic result of embodiment is as shown in table 6.
Table 6: evaluating catalyst result
Claims (7)
1., for a preparation method for the HZSM-5 molecular sieve catalyst of preparing gasoline by methanol, said method comprising the steps of:
I, the preparation of liquid is synthesized
Under ice water bath environment, aluminium source aluminium isopropoxide is joined in the first template TPAOH, being stirred to mixed liquor with the rotating speed of 300 ~ 550 r/min is clear shape, then silicon source and deionized water acquisition mixed liquor is added successively, this mixed liquor is continued to stir a period of time with the rotating speed of 600 ~ 650 r/min under room temperature, second template M is added drop-wise in mixed liquor, except synthesis liquid obtained after alcohol 10 ~ 30 min under 80 ~ 90 DEG C of stirring conditions; Mole consisting of of described synthesis liquid: SiO
2: Al
2o
3: TPAOH: H
2o: M=1:0.010 ~ 0.030: 0.15 ~ 0.29: 10 ~ 30: 0.035 ~ 0.095; Wherein said second template M is diallyl dimethyl ammoniumchloride or dimethylallylammonium chloride acrylamide copolymer;
II, the synthesis of molecular sieve:
The synthesis liquid obtained by step I joins in stainless steel still, aged at room temperature 10 ~ 50 min, then crystallization 30 ~ 96 h at 140 ~ 180 DEG C, by solid product centrifugation, washing to neutral, at 80 ~ 120 DEG C after drying, at 500-600 DEG C, roasting 5 h, obtains ZSM-5 molecular sieve;
The ammonium ion exchange of Ш, molecular sieve
The ammonium nitrate solution of preparation 0.5 ~ 1.5 mol/l, after ZSM-5 molecular sieve ammonium nitrate solution and Step II prepared mixes than the ratio of 10-30 ml: 1 g according to volume mass, carries out centrifugation after ion-exchange 4 ~ 8 h at 75 ~ 90 DEG C; This process repeats 1-3 time; Then through washing, dry, calcination process, HZSM-5 molecular sieve catalyst is obtained;
The silica alumina ratio of described HZSM-5 molecular sieve catalyst is 18-54, and specific area is 395-468 m
2g
-1, pore volume is 0.27-0.50cm
3g
-1, average pore size is 6.25-7.98nm, and particle mean size is 23-33nm and relative crystallinity is 81.2-160%, and described catalyst in the reaction of catalysis methanol gasoline stationary phase>=35h, simultaneously oil-phase product is selective also up to 30% or more.
2., as claimed in claim 1 for the preparation method of the catalyst of preparing gasoline by methanol, it is characterized in that silicon source used is ethyl orthosilicate, Ludox or waterglass.
3. the preparation method of the catalyst for preparing gasoline by methanol as described in claims 1 or 2, is characterized in that: the best crystallization time in Step II is 36 ~ 72 h.
The preparation method of the catalyst for preparing gasoline by methanol 4.4. as described in claims 1 or 2, it is characterized in that: in Step II I, the concentration of ammonium nitrate solution is 0.5mol/l, ZSM-5 molecular sieve prepared by ammonium nitrate solution and Step II mixes according to the ratio of volume mass than 15ml: 1g.
5.5. according to a HZSM-5 molecular sieve catalyst prepared by the arbitrary described method of claim 1-4, the silica alumina ratio of described HZSM-5 molecular sieve catalyst is 18-54, and specific area is 395-468 m
2g
-1, pore volume is 0.27-0.50cm
3g
-1, average pore size is 6.25-7.98nm, and particle mean size is 23-33nm and relative crystallinity is 81.2-160%.
6.6. the method for a preparing gasoline by methanol, the HZSM-5 molecular sieve catalyst wherein making the arbitrary described method of claim 1-4 prepare contacts with methyl alcohol, catalysis methanol reaction gasoline processed, it is characterized in that: described catalyst stationary phase >=35 h, simultaneously oil-phase product is selective also up to 30% or more.
7.7. method as claimed in claim 6, the reaction condition of described catalysis methanol gasoline reaction is: normal pressure, reaction temperature 350-420 DEG C; Raw material adopts purity to be greater than the methanol solution of 99.5wt%; WHSV=3.2-8.5 g/g
cath
-1.
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| CN103506150B (en) * | 2013-10-18 | 2016-01-20 | 中国科学院上海高等研究院 | The catalyst of preparing gasoline by methanol and method for making thereof and application is used for by steam modification |
| CN104843740B (en) * | 2014-02-13 | 2017-12-12 | 中国科学院过程工程研究所 | A kind of molecular sieves of ZSM 5 and preparation method thereof |
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| WO2016086362A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing multilevel pore zsm-5 zeolite |
| CN106542545B (en) * | 2015-09-23 | 2018-11-16 | 中国石油天然气股份有限公司 | A kind of step hole ZSM-5 zeolite and preparation method thereof |
| CN106423256A (en) * | 2016-09-19 | 2017-02-22 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of liquid fuel, preparation method and application |
| CN109133091B (en) * | 2017-06-27 | 2020-05-19 | 中国石油化工股份有限公司 | Preparation and forming method of mesoporous ZSM-5 zeolite |
| CN107551993A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of method that heavy metals sorbing material is prepared using Organic Ingredients |
| CN108529646A (en) * | 2018-05-29 | 2018-09-14 | 广东工业大学 | A kind of method of modifying of ZSM-5 molecular sieve and application |
| CN110882717B (en) * | 2019-12-03 | 2022-08-16 | 新榕能源(福建)有限公司 | Simple synthesis method and application of catalyst for preparing oil from methanol under normal pressure |
| CN114471672B (en) * | 2020-10-26 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for alkylation of benzene and ethylene and preparation method and application thereof |
| CN112551542B (en) * | 2021-02-05 | 2021-07-30 | 福州大学 | Single crystal cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN114751424B (en) * | 2022-05-23 | 2024-03-01 | 中国平煤神马能源化工集团有限责任公司 | Fe-ZSM-5 molecular sieve and preparation method and application thereof |
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