CN104307562B - A kind of preparing gasoline by methanol catalyst and preparation method thereof - Google Patents
A kind of preparing gasoline by methanol catalyst and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention relates to a kind of preparing gasoline by methanol catalyst and preparation method thereof, this catalyst with common aluminum source, silicon source synthesizing Si-Al than suitable fine grain ZSM-5 5 molecular sieve parent.First pretreated ZSM 5 molecular sieve parent through high-temperature calcination pretreatment regulation acidity, then is sufficiently mixed, extruded moulding by ZSM 5 molecular sieve parent with HY molecular sieve and binding agent, the material such as final load Ni, V, F, P.It is low that catalyst prepared by the present invention has production cost, the advantage that methanol conversion is high, activity is difficult to decay, product gasoline yield is high, octane number is high, heavy aromatics content is low.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparing gasoline by methanol catalyst and preparation method thereof.
Background technology
At present, the high speed development of World Economics causes the consumption of product oil the most all to increase, and without restriction the asking for of society causes petroleum resources the most exhausted.Data statistics, China consumes petroleum 4.39 hundred million tons for 2010, within 2011, consumes petroleum 4.7 hundred million tons, within 2012, consumes petroleum 4.93 hundred million tons.Annual about 200,000,000 tons of self-produced oil of China, within 2012, crude oil external dependence degree is 56.42%, for historic high.Scholarly forecast, calculates with the depletion rate in the whole world a few days ago, and existing petroleum resources can only maintain decades, and finding suitable oil replacement resource has become the magnificent mission that the whole society is extremely urgent.The energy resource structure feature of China is that coal enriches, oil starvation lacks gas.Therefore, the most domestic start this direction tilting transition of coal liquifaction, and wherein methanol dehydration synthetic gasoline is one of important step restricting this direction.
Methanol is considerable basis Organic chemical products and raw material.From coal preparing synthetic gas, methanol, China in Recent Years is faced with the crisis that methanol production capacity is seriously superfluous.According to statistics, 2008, China's methanol newly extended nearly 8,000,000 tons of production capacity, and speedup relatively raises up 33 percentage points for 2007, and whole nation methanol aggregated capacity exceedes 27,000,000 tons, increased nearly 40% compared with 2007.2010, the methanol output of China was 17,520,000 tons, increased by 169% than the Eleventh Five-Year Plan initial stage, average growth rate per annum is about 22%, the end of the year 2010, and China's methanol industry has enterprise 291, production capacity reaches 38,400,000 tons, increases by 3 times than the Eleventh Five-Year Plan initial stage, and average growth rate per annum reaches 32%.2012, China's methanol production capacity reached 51,490,000 tons/year, and Apparent con-sumption is only 36,220,000 tons/year, and production capacity surplus is serious.By in by the end of December, 2013, China's methanol yearly productive capacity 56290000 tons, relate to inefficacy production capacity 39.5 ten thousand tons, rough estimates China's methanol effective capacity in 2013 is 55,900,000 tons.The five-year, it is contemplated that newly-increased production capacity 43,620,000 tons, Chinese methanol production capacity was up to 100,000,000 tons in 2018.
At present, whole methanol industry immersal structure production capacity surplus crisis.The exploitation of Downstream Products of Methanol has great significance for development and the search for oil alternate resources of methanol industry.Although methanol can directly admix formation methanol gasoline in gasoline, but there is bigger drawback: one is that the calorific value of methanol is relatively low, two is that the moisture in fuel combination has large effect to the stability of fuel, three is that methanol is made to absorb moisture from air and cause engine stop to work when fuel uses, and four is that methanol has corrosiveness and rubber is had swelling action metal.Therefore, methanol conversion is prepared as gasoline and has more captivation more than being incorporated in gasoline.As far back as twentieth century seventies, Mobil company develops the technology of ZSM-5 catalyst and preparing gasoline by methanol, and this technology has successively developed fixed bed, fluid bed, the technique of calandria type fixed bed different reactor.Within 1979, Government Of New Zealand has built up first set preparing gasoline by methanol fixed bed industrialized unit, and operates successfully, but owing to oil price at that time is relatively low, methanol production is relatively costly, and plant running loses year after year, is finally stopped operating and removes.In recent years, the consumption day by day of petroleum resources and lack, the maturation of methanol production technology causes the surplus of production capacity, and this technology of preparing gasoline by methanol is mentioned by people again, and exploitation preparing gasoline by methanol can reach to solve the effect of the two problem simultaneously.
Preparing gasoline by methanol generally uses two sections of conversion process, first paragraph is methanol dehydration dimethyl ether-preparing, the mixture of first paragraph out dimethyl ether, unreacted methanol completely and water enters second segment and is filled with in the reactor of ZSM-5 catalyst, generates dry gas, liquefied gas and gasoline under the acidic catalyst effect of ZSM-5.
The restraining factors of technique for preparing gasoline by methanol are the ZSM-5 catalyst that second segment reacts, and its reason has two:
1) Acidity that ZSM-5 catalyst is suitable is difficult to control to.First the conversion on ZSM-5 of the mixture of first paragraph out dimethyl ether, unreacted methanol completely and water is belonging to acid site and is catalyzed the exothermic reaction of short-chain hydrocarbons processed, its reactivity is affected by molecular sieve acid catalysis, along with the difference of catalyst performance, product composition varies widely.The acidity of molecular sieve catalyst decides the distribution of methanol converted product, and the acidity adjusting zeolite molecular sieve the most under certain condition both can improve the stability of catalyst, can improve again the selectivity of product, i.e. reach the effect that oil is many, manufacture gas is few.
2) ZSM-5 catalyst is carried out acid regulation and can bring other problems.High-temperature vapor being usually taken and processes the acidity regulating catalyst, but the treatment temperature of these means is typically at about 600 DEG C, this can cause catalyst aperture to increase, and the above heavy aromatics of gasoline C10 of production increases.
Summary of the invention
The present invention relates to a kind of preparing gasoline by methanol catalyst and preparation method thereof, described method includes three parts:
(1) common aluminum source, silicon source and compound additive synthesis ZSM-5 molecular sieve parent are used；
(2) pretreatment of ZSM-5 molecular sieve parent and the preparation of preparing preparing gasoline by methanol catalyst precursor molecular sieve molded with binding agent and HY；
(3) preparing gasoline by methanol catalyst precursor is loaded modified.
Described preparation method, wherein, Part I concretely comprises the following steps:
Aluminum source and template stirring and dissolving in deionized water are formulated as solution a, by silicon source, NaOH and compound additive NaF and ZnSO4Stirring and dissolving is formulated as solution b in deionized water.Pour solution a into reactor, under the mixing speed of 200 ~ 400r/min, solution b is dropped in solution a, a small amount of crystal seed closed reactor is put into after dropping, it is warming up to 100 DEG C by room temperature with 5 DEG C/min again under the mixing speed of 500 ~ 700r/min, and constant temperature stirring 48 ~ 50h, it is warming up to 140 DEG C again with 5 DEG C/h, thermostatic crystallization 48h, last cooling down, after drawing off material, filtration washing to filtrate pH value is neutrality, filter cake is 100 ~ 120 DEG C of drying, then carries out ion exchange, obtains ZSM-5 molecular sieve parent.
Described preparation method, wherein, uses high-speed stirred crystallization, improves system heat transfer and mass transfer, accelerate nucleation, it is to avoid the generation of big crystal grain in Part I.Add compound additive NaF and ZnSO4, as electrolyte, utilize its electrostatic repulsion, prevent particle agglomeration.Add NaOH and make the aluminosilicate of System forming high concentration, control system ionic equilibrium state, promote that balance is carried out to ZSM-5 direction.
Described preparation method, wherein, in Part I, the mol ratio of each component is:
SiO2: Al2O3: template: NaOH:NaF:ZnSO4: H2O=25 ~ 120:1:10 ~ 20:3 ~ 8:35 ~ 50:0.1 ~ 1.2:2500 ~ 4000.
Described preparation method, wherein, used by Part IAluminumSource is one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate or aluminum isopropylate., silicon source used is one or more in Ludox, sodium silicate, tetraethyl orthosilicate, and template used is one or more in TPAOH, ethylenediamine, ethamine, n-butylamine.
Above-mentioned preparation condition is the key factor generating and being suitable for preparing gasoline by methanol ZSM-5 molecular sieve with small crystal grains parent.
Described preparation method, wherein, ion-exchange process used by Part I is: employing ion exchange liquid is one or more in ammonium nitrate, ammonium sulfate or ammonium chloride, the concentration of exchange liquid is 0.5 ~ 1mol/L, 1g preparing gasoline by methanol catalyst precursor consumes the consumption 5 ~ 20mL of ion exchange liquid, exchange temperature is 60 ~ 120 DEG C, exchanges duration 3 ~ 8h, and exchange times is 2 ~ 6 times.Repeatedly in exchange, the catalyst after exchange washing directly carries out exchange next time without calcining every time, until carrying out 120 DEG C after last exchange to dry 2 ~ 5h, then 550 DEG C of calcining 2h.
Described preparation method, wherein, in Part II, the pretreatment of ZSM-5 molecular sieve parent is:
Molecular sieve parent is 2 ~ 5h, 2 ~ 5h at 500 ~ 550 DEG C, 2 ~ 8h calcine by steps at 700 ~ 900 DEG C at 350 DEG C, in order to regulate acidity.
Described preparation method, wherein, in Part II, the preparation method of preparing gasoline by methanol catalyst precursor is:
By the ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, molecular sieve and bonding agent and HY molecular sieve, with weight ratio 6 ~ 9:2.5 ~ 4:0.5 ~ 1, dry 2 ~ 5h at latter 350 DEG C, 2 ~ 5h at 500 ~ 550 DEG C at 120 DEG C.
Described preparation method, wherein, in Part III, the loaded modified step of preparing gasoline by methanol catalyst precursor is:
Preparing gasoline by methanol catalyst precursor uses step impregnation, first presoma is placed in the solution of nickel nitrate, ammonium fluoride and phosphoric acid dipping 4 ~ 12h, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, finally impregnate 4 ~ 12h in ammonium metavanadate solution again, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, load percentage meter is 0.8% ~ 3.6 %, V with NiO2O5Be 0.5% ~ 1.5%, F be 0.1% ~ 0.8%, P be 0.2 ~ 1.0%, obtain preparing gasoline by methanol catalyst.
The essence of the reaction of preparing gasoline by methanol is that methanol molecules converts on ZSM-5 catalyst, belong to typical acid catalyzed reaction, so this catalyst must have a certain amount of acid site, but too much acid amount or or the reaction that cracking can be caused again to produce manufacture gas of high acid strength occur, very few acid amount or too low acid strength can cause again gasoline selective relatively low, there is also the phenomenon that the octane number produced is relatively low.Therefore, acid amount and the acid strength of various method modulation molecular sieves are generally used.
Molecular sieve catalysts carrying out the usual high-temperature vapor of acid regulation process, these means can cause catalyst aperture to increase, and the above heavy aromatics of gasoline C10 of production increases.
The innovative point that the present invention has has 4 points:
The first, compound additive NaF and ZnSO is used when synthesizing ZSM-5 molecular sieve4, prepare the molecular sieve of little crystal grain.
The second, adding a small amount of HY molecular sieve when prepared by catalyst, it can play the effect that suppression heavy aromatics generates when methanol synthesized gasoline.
3rd, the present invention uses segmented high-temperature calcining that molecular sieve parent carries out the catalyst low cost that pretreatment is prepared to the method regulating Acidity, improve the distribution of oil product hydrocarbon product, there is higher gasoline selective, manufacture gas is few, in manufacture gas, higher composition is liquefied gas simultaneously, by-product value is high, and suitable acid mass-energy reduces or slows down knot carbon.
4th, the present invention has loaded tetra-kinds of elements of Ni, V, F, P, and on the one hand they promote dimethyl ether and unreacted methanol dehydration ability, and the opposing party can regulate again acidity, reduces highly acid center.
Catalyst single pass life and the cycle lie prepared according to the present invention are the longest, and feed throughput is big, and air speed can accomplish 2.5h-1, can be applied not only to two-step method preparing gasoline by methanol technique, apply also for one-step method preparing gasoline by methanol technique.
The present invention also provides for molecular sieve catalyst specific surface area 359 ~ 523m prepared by said method2, pore volume is 0.28 ~ 0.56cm3·g-1, aperture is 4.18 ~ 5.03nm, intensity ＞ 120N/cm.This preparation method is simple and practical, easily operated, be prone to produce in a large number simultaneously.
Accompanying drawing explanation
Accompanying drawing 1 is ZSM-5 molecular sieve X-ray diffraction (XRD) figure of the embodiment of the present invention 1
Accompanying drawing 2 is ZSM-5 molecular sieve scanning electron microscope (SEM) figure of the embodiment of the present invention 1
Accompanying drawing 3 is ZSM-5 molecular sieve X-ray diffraction (XRD) figure of the embodiment of the present invention 2
Accompanying drawing 4 is ZSM-5 molecular sieve scanning electron microscope (SEM) figure of the embodiment of the present invention 2
Accompanying drawing 5 is ZSM-5 molecular sieve X-ray diffraction (XRD) figure of the embodiment of the present invention 3
Accompanying drawing 6 is ZSM-5 molecular sieve scanning electron microscope (SEM) figure of the embodiment of the present invention 3
Accompanying drawing 7 is X-ray diffraction (XRD) figure of the ZSM-5 molecular sieve of comparative example 1 of the present invention
Accompanying drawing 8 is ZSM-5 molecular sieve scanning electron microscope (SEM) figure of comparative example 1 of the present invention.
Detailed description of the invention
By following case study on implementation, the present invention is described further, but the content not thereby limited the invention.
Embodiment 1:
Aluminum nitrate and n-butylamine stirring and dissolving in deionized water are formulated as solution a, by tetraethyl orthosilicate, NaOH and NaF and ZnSO4Compound additive stirring and dissolving in deionized water be formulated as solution b, pour solution a into reactor, under the mixing speed of about 200r/min, solution b is dropped in solution a, a small amount of crystal seed closed reactor is put into after adding, it is warming up to 100 DEG C by room temperature with 5 DEG C/min again under the mixing speed of about 700r/min, and constant temperature stirring 48 ~ 50h, it is warming up to 140 DEG C again with 5 DEG C/h, thermostatic crystallization 48h, last cooling down, it is neutrality that material draws off rear filtration washing to filtrate pH value, and filter cake is 100 DEG C of drying.The mol ratio of each component is: SiO2: Al2O3: n-butylamine: NaOH:NaF:ZnSO4: H2O=25:1:20:8:35:1.2:4000.The ammonium nitrate exchange liquid using concentration to be 1mol/L again carries out sodium ion exchange, and 1g preparing gasoline by methanol catalyst precursor consumes the consumption 5mL of ion exchange liquid, and exchange temperature is 60 DEG C, exchanges duration 8h, 120 DEG C of drying again after exchanging 6 times.Molecular sieve parent calcines 2h, 500 DEG C of calcining 5h, 900 DEG C of calcining 2h calcine by steps through 350 DEG C after drying, and X-ray diffraction (XRD) figure of molecular sieve is shown in Fig. 1, and scanning electron microscope (SEM) figure of molecular sieve is shown in Fig. 2.By the ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, molecular sieve and kieselguhr bonding agent and HY molecular sieve, with weight ratio 6:4:0.5 extruded moulding, are dried rear 350 DEG C of calcining 2h, 500 DEG C of calcining 5h, are obtained preparing gasoline by methanol presoma for 120 DEG C.Preparing gasoline by methanol catalyst precursor uses step impregnation, first presoma is placed in the solution of nickel nitrate, ammonium fluoride and phosphoric acid dipping 12h, load gauge with NiO for 0.8%, F is 0.1%, P is 1.0%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, impregnate 4h in ammonium metavanadate solution the most again, and load gauge is with V2O5It is 0.15%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h.
The HZSM-5 molecular sieve catalyst prepared according to the present embodiment uses TCD detector to be measured its Acidity.Sign condition is: loaded catalyst 0.10g, sample at 500 DEG C, high-purity N2Atmosphere encloses purging 1h, then is cooled to 50 DEG C of absorption NH3, adsorb saturated after be passed through high-purity N2Until baseline stability, it is warming up to 700 DEG C with the rate program of 5 DEG C/min and completes desorption.The ratio of acid amount is represented by the ratio of the peak area corresponding to relevant temperature peak, and it the results are shown in Table embodiment 1 in 1.The molecular sieve catalyst prepared according to the present embodiment, use it for miniature fixed-bed reactor and carry out preparing gasoline by methanol Catalysis experiments, reaction condition is: reaction pressure is 2.0MPa, reaction temperature is 380 ~ 400 DEG C, and raw material uses the methanol of content >=99.5%, and liquid air speed is 2.0h-1, prepared product slates is shown in Table embodiment 1 in 2.
Embodiment 2:
Sodium metaaluminate and TPAOH stirring and dissolving in deionized water are formulated as solution a, by sodium silicate, NaOH and NaF and ZnSO4Compound additive stirring and dissolving in deionized water be formulated as solution b, pour solution a into reactor, under the mixing speed of about 300r/min, solution b is dropped in solution a, a small amount of crystal seed closed reactor is put into after adding, it is warming up to 100 DEG C by room temperature with 5 DEG C/min again under the mixing speed of about 500r/min, and constant temperature stirring 48 ~ 50h, it is warming up to 140 DEG C again with 5 DEG C/h, thermostatic crystallization 48h, last cooling down, it is neutrality that material draws off rear filtration washing to filtrate pH value, and filter cake is 110 DEG C of drying.The mol ratio of each component is: SiO2: Al2O3: TPAOH: NaOH:NaF:ZnSO4: H2O=70:1:15:8:40:1:3500.The ammonium chloride exchange fluid using concentration to be 0.8mol/L again carries out sodium ion exchange, 1g preparing gasoline by methanol catalyst precursor consumes the consumption 15mL of ion exchange liquid, exchange temperature is 80 DEG C, exchange duration 4h, seeing Fig. 3 through 350 DEG C of calcining 2h, 500 DEG C of calcining 2h, X-ray diffraction (XRD) figures of 700 DEG C of calcining 3h calcine by steps molecular sieves after 120 DEG C of drying molecular sieve parents are dried again after exchanging 2 times, scanning electron microscope (SEM) figure of molecular sieve is shown in Fig. 4.By the ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, molecular sieve and boehmite bonding agent and HY molecular sieve are with weight ratio 8.5:3:0.8 extruded moulding, dry rear 350 DEG C of calcining 2h, 550 DEG C of calcining 3h, obtain preparing gasoline by methanol presoma for 120 DEG C.Preparing gasoline by methanol catalyst precursor uses distribution dipping, first presoma is placed in the solution of nickel nitrate, ammonium fluoride and phosphoric acid dipping 8h, load gauge with NiO for 2.4%, F is 0.4%, P is 0.6%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, impregnate 8h in ammonium metavanadate solution the most again, and load gauge is with V2O5It is 1.1%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h.
The HZSM-5 molecular sieve catalyst prepared according to the present embodiment uses TCD detector to be measured its Acidity, and the condition that characterizes is with embodiment 1, and it the results are shown in Table embodiment 2 in 1.The molecular sieve catalyst prepared according to the present embodiment, uses it for miniature fixed-bed reactor and carries out preparing gasoline by methanol Catalysis experiments, and reaction condition is same embodiment 1, and prepared product slates is shown in Table embodiment 2 in 2.
Embodiment 3:
Aluminum isopropylate. and ethylenediamine stirring and dissolving in deionized water are formulated as solution a, by Ludox, NaOH and NaF and ZnSO4Compound additive stirring and dissolving in deionized water be formulated as solution b, pour solution a into reactor, under the mixing speed of about 400r/min, solution b is dropped in solution a, a small amount of crystal seed closed reactor is put into after adding, it is warming up to 100 DEG C by room temperature with 5 DEG C/min again under the mixing speed of about 600r/min, and constant temperature stirring 48 ~ 50h, it is warming up to 140 DEG C again with 5 DEG C/h, thermostatic crystallization 48h, last cooling down, it is neutrality that material draws off rear filtration washing to filtrate pH value, and filter cake is 120 DEG C of drying.The mol ratio of each component is: SiO2: Al2O3: ethylenediamine: NaOH:NaF:ZnSO4: H2O=120:1:10:3:50:0.1:2500.The ammonium sulfate exchange liquid using concentration to be 0.5mol/L again carries out sodium ion exchange, and 1g preparing gasoline by methanol catalyst precursor consumes the consumption 20mL of ion exchange liquid, and exchange temperature is 120 DEG C, exchanges duration 3h, 120 DEG C of drying again after exchanging 5 times.Molecular sieve parent is shown in Fig. 5 through 350 DEG C of calcining 5h, 500 DEG C of calcining 2h, X-ray diffraction (XRD) figures of 700 DEG C of calcining 8h calcine by steps molecular sieves after drying, and scanning electron microscope (SEM) figure of molecular sieve is shown in Fig. 6.By the ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, molecular sieve and Alumina gel bonding agent and HY molecular sieve, with weight ratio 9:2.5:1 extruded moulding, are dried rear 350 DEG C of calcining 5h, 500 DEG C of calcining 2h, are obtained preparing gasoline by methanol presoma for 120 DEG C.Preparing gasoline by methanol catalyst precursor uses distribution dipping, first presoma is placed in the solution of nickel nitrate, ammonium fluoride and phosphoric acid dipping 4h, load gauge with NiO for 3.6%, F is 0.5%, P is 0.2%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, impregnate 12h in ammonium metavanadate solution the most again, and load gauge is with V2O5It is 0.5%, 120 DEG C of dry 4h, 550 DEG C of calcining 4h.
The HZSM-5 molecular sieve catalyst prepared according to the present embodiment uses TCD detector to be measured its Acidity, and the condition that characterizes is with embodiment 1, and it the results are shown in Table embodiment 3 in 1.The molecular sieve catalyst prepared according to the present embodiment, uses it for miniature fixed-bed reactor and carries out preparing gasoline by methanol Catalysis experiments, and reaction condition is shown in Table embodiment 3 in 2 with embodiment 1, prepared product slates.
Comparative example 1:
The preparation method of catalyst and appreciation condition are with embodiment 2, except that be not added with NaF and ZnSO in the sieve parent synthesis of this example Middle molecule4Compound additive, i.e. the mol ratio of feed components is: SiO2: Al2O3: TPAOH: NaOH:H2O=70:1:15:8:3500.X-ray diffraction (XRD) figure of molecular sieve is shown in Fig. 7, and scanning electron microscope (SEM) figure of molecular sieve is shown in Fig. 8.The Determination of Acidity that the HZSM-5 molecular sieve catalyst prepared according to the present embodiment is adopted the results are shown in Table comparative example 1 in 1, and prepared product slates is shown in Table comparative example 1 in 2.
Comparative example 2:
The preparation method of catalyst and appreciation condition are with embodiment 2, except that not to molecular sieve parent high-temperature calcination pretreatment in this example.The Determination of Acidity of the HZSM-5 molecular sieve catalyst prepared according to the present embodiment the results are shown in Table comparative example 2 in 1, and prepared product slates is shown in Table comparative example 2 in 2.
Comparative example 3:
The preparation method of catalyst agent and appreciation condition are with embodiment 2, except that when shaping of catalyst without HY molecular sieve in this example, will ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, molecular sieve and boehmite bonding agent are with weight ratio 8.5:0.8 extruded moulding.The HZSM-5 acidic zeolite prepared according to the present embodiment measures fruit and is shown in Table comparative example 3 in 1, and prepared product slates is shown in Table comparative example 3 in 2.
Comparative example 4:
The preparation method of catalyst and appreciation condition, with embodiment 2, except that it is loaded modified not carry out catalyst in this example, does not i.e. load after extruded moulding, but are directly evaluated.The HZSM-5 molecular sieve catalyst Determination of Acidity prepared according to the present embodiment the results are shown in Table comparative example 4 in 1, and prepared product slates is shown in Table comparative example 4 in 2.
The Acidity of table 1 HZSM-5 molecular sieve catalyst
The product slates of the preparation of table 2 HZSM-5 molecular sieve catalyst
Claims (4)
1. the preparation method of a preparing gasoline by methanol catalyst, it is characterised in that: the method includes three parts:
(1) common aluminum source, silicon source and compound additive synthesis ZSM-5 molecular sieve parent are used；
The synthetic method of described ZSM-5 molecular sieve parent is: aluminum source and template stirring and dissolving in deionized water are formulated as solution a, silicon source, NaOH and compound additive stirring and dissolving in deionized water is formulated as solution b；Pour solution a into reactor, under the mixing speed of 200 ~ 400r/min, solution b is dropped in solution a, a small amount of crystal seed closed reactor is put into after dropping, it is warming up to 100 DEG C by room temperature with 5 DEG C/min again under the mixing speed of 500 ~ 700r/min, and constant temperature stirring 48 ~ 50h, it is warming up to 140 DEG C again with 5 DEG C/h, thermostatic crystallization 48h, last cooling down, after drawing off material, filtration washing to filtrate pH value is neutrality, filter cake is 100 ~ 120 DEG C of drying, then carries out ion exchange, obtains ZSM-5 molecular sieve parent；
Described compound additive is NaF and ZnSO4, the mol ratio of each component is: SiO2: Al2O3: template: NaOH:NaF:ZnSO4: H2O=25 ~ 120:1:10 ~ 20:3 ~ 8:35 ~ 50:0.1 ~ 1.2:2500 ~ 4000；
(2) pretreatment of ZSM-5 molecular sieve parent and molecular sieve molded with bonding agent and HY prepare preparing gasoline by methanol catalyst precursor；
The pretreatment of described ZSM-5 molecular sieve parent is: molecular sieve parent is 2 ~ 5h, 2 ~ 5h at 500 ~ 550 DEG C, 2 ~ 8h calcine by steps at 700 ~ 900 DEG C at 350 DEG C, in order to regulate acidity；
The preparation method of described preparing gasoline by methanol catalyst precursor is: by the ZSM-5 molecular sieve parent after high-temperature calcination through smashing to 200 mesh, then with bonding agent and HY molecular sieve with weight ratio 6 ~ 9:2.5 ~ 4:0.5 ~ 1 extruded moulding, after 120 DEG C dry, 2 ~ 5h is calcined in 350 DEG C, then at 500 ~ 550 DEG C, calcine 2 ~ 5h, obtain the presoma of preparing gasoline by methanol catalyst；
(3) preparing gasoline by methanol catalyst precursor is loaded modified；
The described loaded modified step of preparing gasoline by methanol catalyst precursor is: preparing gasoline by methanol catalyst precursor uses step impregnation, first presoma is placed in the solution of nickel nitrate, ammonium fluoride and phosphoric acid dipping 4 ~ 12h, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, finally impregnate 4 ~ 12h in ammonium metavanadate solution again, 120 DEG C of dry 4h, 550 DEG C of calcining 4h, load percentage meter is 0.8% ~ 3.6 %, V with NiO2O5Be 0.5% ~ 1.5%, F be 0.1% ~ 0.8%, P be 0.2 ~ 1.0%, obtain preparing gasoline by methanol catalyst.
The most in accordance with the method for claim 1, it is characterized in that: aluminum source used is one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate or aluminum isopropylate., silicon source used is one or more in Ludox, sodium silicate, tetraethyl orthosilicate, and template used is one or more in TPAOH, ethylenediamine, ethamine, n-butylamine.
The most in accordance with the method for claim 1, it is characterised in that exchange operations step is:
Employing ion exchange liquid is one or more in ammonium nitrate, ammonium sulfate or ammonium chloride, the concentration of exchange liquid is consumption 5 ~ 20mL that 0.5 ~ 1mol/L, 1g preparing gasoline by methanol catalyst precursor consumes ion exchange liquid, and exchange temperature is 60 ~ 120 DEG C, exchange duration 3 ~ 8h, exchange times is 2 ~ 6 times；Repeatedly in exchange, the catalyst after exchange washing directly carries out exchange next time without calcining every time, until carrying out 120 DEG C after last exchange to dry 2 ~ 5h.
The most in accordance with the method for claim 1, it is characterised in that: bonding agent used is one or more in Ludox, Alumina gel, alumina gel, kieselguhr, boehmite.
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