CN103831127A - Catalyst for C4 hydrogenation aromatization and preparation method - Google Patents
Catalyst for C4 hydrogenation aromatization and preparation method Download PDFInfo
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Abstract
The invention belongs to the field of preparation of petrochemical engineering catalysts, and relates to a catalyst for C4 hydrogenation aromatization and a preparation method. A matrix of the catalyst is five-membered ring type silica-rich zeolite with a grain size of less than 500 nanometers. The preparation method comprises the steps: loading iron on a zeolite matrix by using ferric trichloride or ferric trichloride crystal when a template stripping agent is roasted by using hydrothermally synthesized zeolite raw powder, and treating a hydrogen type catalyst by using an acid solution after treating by using water vapor. The preparation method has the advantages that the preparation method of the catalyst is simple, and the dispersity of iron species in the catalyst is high. The catalyst is strong in carbon deposit resisting capacity and high in butene conversion rate in the mixed carbon four low-temperature hydrogen-contacting aromatization, and has a remarkable capacity of converting iso-butane.
Description
Technical field
The invention belongs to petrochemical catalyst preparation field, relate to a kind of catalyst and preparation method for carbon four hydroaromatizations.
Background technology
The a large amount of carbon 4 liquid gas of the device by-product such as steam cracking device and various catalytic cracking of oil plant.Various alkene in carbon 4 liquid gas are converted into the liquid fuel such as aromatic hydrocarbons or gasoline by aromatization, are that a standby valued liquefied gas utilizes method.
In open source literature and patent documentation, existing a large amount of reports about liquefied gas and other aromatization of low carbon hydrocarbon aspect.For example:
A kind of zeolite catalyst that can produce with carbon two～C 4 olefin high-octane rating aromatic type gasoline US4150062(1979) disclosing is metal ion-modified ZSM-5, ZSM-11, ZSM-12, ZSM-35 or ZSM-38 zeolite.In embodiment, describe the aromatization effect of a kind of potassium modified ZSM-5 in fixed bed reactors in detail.Wherein, in order to reduce the carbon distribution deactivation rate of catalyst, this patent adopts water as co-fed (water/olefin molar ratio is 0.5 ~ 15).
Aromatization of low carbon hydrocarbon catalyst CN1057476(1992) disclosing is containing zinc ZSM zeolite catalyst.In embodiment, describe a kind of Zn-Ti(SO in detail
4)
2the reaction effect of-ZSM-5 zeolite catalyst in fixed bed reactors: be that WHSV is 1～2h in raw liquefied petroleum gas charging air speed
-1, reaction temperature is under the condition of 500 ~ 550 DEG C, altogether said catalyst has been carried out the reaction evaluating of 1000 hours.But, in the reaction time of 1000 hours, need to regenerate altogether 6 times.In the one-time continuous reaction one way reaction evaluating of 168 hours, in product, the yield of benzene, toluene and dimethylbenzene (BTX) is finally down to 32% from 42.0% of beginning.
CN1154687(1997) disclose the passivating modified ZSM-5 zeolite catalyst of a kind of water vapour.In two reaction tower-type fixed bed single hop adiabatic reactors, with C 4 mixture be raw material, be 2.8h at charging air speed WHSV
-1, pressure is 0.5MPa, reaction temperature is under the condition of 530 DEG C, C in the time that reaction proceeds to 10 hours
6～C
9aromatics yield has reached 52.3wt%, C when successive reaction to 120 hour
6～C
9aromatics yield is down to 49wt%.
A kind of aromatized catalyst CN1232071(1999) disclosing is with ZSM-5 zeolite and γ-Al
2o
3for carrier, the catalyst through Steam treatment modification again after Zn and mishmetal modification.When to mix carbon four as raw material, in fixed bed reactors, be 530 DEG C in reaction temperature, reaction pressure is 0.2MPa, charging air speed WHSV is 0.65h
-1condition under, successive reaction 450 hours, the initial value of aromatics yield is 50wt%, is finally down to 43wt%.
A kind of catalyst CN1321728(2001) disclosing is with ZSM-5 zeolite and γ-Al
2o
3for carrier, after Zn and mishmetal modification, obtain through Steam treatment modification again.When charging is liquefied petroleum gas, reaction is normal pressure, 530～540 DEG C, and WHSV is 0.6 ± 0.1h
-1under condition, carry out continuously 16 days, the reaction conversion ratio of active princlple and the initial value of aromatics yield are respectively 85% and 40%, and end value is respectively 68% and 38%.
A kind of aromatized catalyst CN1340601(2002) disclosing, it is characterized in that, taking ZSM-5 zeolite as parent, first impregnating metal ion (Zn), introduce the second modification component VA or group vib metal to prevent the loss of Zn, catalyst is passivating modified with carrying out water vapour after binding agent moulding again again.When to mix carbon four as raw material, react at 530 DEG C, 0.2MPa, WHSV is 0.65h
-1while carrying out under condition, the initial value of aromatics yield is 50wt%, and the result of successive reaction after 450 hours is 43wt%.
CN 1341699(2002) disclose a kind of aromatized catalyst, be Zn-Ni-ZSM-5 zeolite.When mixing carbon four 500 DEG C of fixed bed reactors neutral temperatures, pressure 0.5～1MPa, WHSV is 1.0～1.5h
-1when under condition, charging is reacted, while reacting 40 hours, liquid is received as 60.37wt%, and total arenes yield is 57.30wt%; While reacting 120 hours, liquid is incorporated to 47.80wt%, and total arenes yield is down to 45.34wt%.
CN101429452 (2007) has disclosed a kind of method of producing high-knock rating gasoline.It is characterized in that, catalytically cracked gasoline is contacted with catalyst on aromatization reactor with C4 mixed material and carry out aromatization production high-knock rating gasoline.
CN101530813 (2008) has disclosed the preparation method of the molecular sieve catalyst of carbon 4 liquid gas aromatization reaction.This invention catalyst is mainly for the conversion of butylene in carbon 4 liquid gas raw material.The feature of its Kaolinite Preparation of Catalyst is, by the ZSM5/ZSM11 cocrystallization molecular sieve extruded catalyst precursor that contains rare earth, first to process and carry out ammonium exchange, high-temperature water vapor processing and zinc supported modification again with strong base solution.
In CN1586721, a kind of method of preparing aromatization of low carbon hydrocarbon catalyst is disclosed.Its principal character is, selects nano-ZSM-5 zeolite molecular sieve as catalyst Precursors, notes protecting the diffusion smoothness of microporous molecular sieve in the time that catalyst is carried out to modification simultaneously.No matter the aromatized catalyst of preparing based on the method is at non-hydrogen or facing under the reaction condition of hydrogen and all show superpower anti-carbon deactivation.But catalyst prepared by the method is not high to the aromatization activity of iso-butane.
People were in the time of development liquefied gas through aromatization catalyst in the past, major concern be the anti-carbon deactivation of catalyst and the selective and productive rate of principal product aromatic hydrocarbons, be seldom concerned about the byproduct methane ethane of aromatisation and have neither part nor lot in the purposes of the butane of aromatization.Liquid (the C including aromatic hydrocarbons of the various aromatized catalysts of having reported in carbon 4 liquid gas aromatization reaction
5above product) yield is generally no more than 60%.Product yield is low is the key that affects aromatization technology economy.Can strengthen to a certain extent butane and participate in the degree of aromatization although carry out aromatization at the temperature higher than 500 DEG C, high temperature aromatization is by the carbon distribution inactivation of accelerator activator inevitably and increase and devalue the growing amount of byproduct methane and ethane.
Therefore,, in order to improve the economy of aromatization technology, aromatization should be conceived to the comprehensive utilization of resource to the conversion of the lower carbon number hydrocarbons such as liquefied gas.
Taking carbon 4 liquid gas resource as example: allow aromatization carry out at low temperatures, only by various butylene higher activity in carbon 4 liquid gas (as 1-butylene, cis-butene-2, trans-butene-2 and isobutene) be converted into aromatic hydrocarbons, just can effectively limit the generation of devaluation byproduct methane ethane.The butane that can not react at low temperatures, and follow when butylene is by hydrogen transfer reaction aromatisation at low temperatures the propane (still belonging to liquefied gas) of generation can be as the raw material of preparing ethylene by steam cracking.This is one can make full use of carbon 4 liquid gas resource, has much the aromatization mode of attraction.
But, want the comprehensive utilization that realizes liquefied gas according to above-mentioned idea industrial, to ensure that on the one hand the alkene in liquefied gas raw material transforms as far as possible completely in aromatization, to prevent causing steam cracking tube coking too fast because olefin(e) centent is too high as the residue alkane of steam crack material; Also to ensure on the other hand to there is acceptable just different ratio as the residue butane of steam crack material.Generate in the technique of ethene and propylene at steam cracking, the productive rate that normal butane generates ethylene, propylene is high, and the productive rate of iso-butane generation ethylene, propylene is low.Unfortunately, in the catalytic cracking carbon 4 liquid gas as carbon 4 liquid gas important sources, the content of iso-butane is far above normal butane, and its ratio can reach 3/1.
CN1781886A(2006) disclosed a kind of method of catalytic-ally cracking butane.It is characterized in that, taking the mixture of iso-butane and normal butane as raw material, nitrogen buffer gas, adopting ZSM-23 zeolite is catalyst, at 500～650 DEG C, carry out catalytic cracking, the conversion ratio of butane can reach more than 87%, and the overall selectivity of ethene, propylene and butylene can reach 45%.In general, under the high temperature of 500～650 DEG C, zeolite molecular sieve solid acid, because acidity is strong, not only can make iso-butane cracking, also can make normal butane cracking, therefore, can not be used for addressing the above problem under such catalyst and reaction condition.Moreover iso-butane and normal butane react and certainly lead to a large amount of methane ethane accessory substances under the high temperature of 500～650 DEG C.CN101362669A(2007) disclosed the catalysis conversion method of a kind of preparing ethylene, propylene and aromatic hydrocarbons.It is characterized in that, the hydrocarbon raw material of different cracking performances contacts with catalytic cracking catalyst, at 550～800 DEG C, and weight (hourly) space velocity (WHSV) 0.1～800h
-1, reaction pressure 0.10～1.0MPa under the condition that the weight ratio of water vapour and raw material is 0.15～1.0, carries out cracking reaction in fluidized-bed reactor, obtains ethene, propylene and aromatic hydrocarbons object product.This patent is mentioned the ethane, propane and the butane that generate as steam crack material.But, under the condition of this fluid catalystic cracking, in carbon 4 liquid gas, not only contain butylene, and butane is taking iso-butane as main.This patent does not relate to the just different problem that compares of adjusting butane.Open source literature Appl.Catal.A:Gen.278 (2004) 111-121 has studied iso-butane at Mo
2aromatisation rule on C/ZSM-5 catalyst, has mentioned load Mo on ZSM-5
2c can promote dehydrogenation and the aromatisation of iso-butane.But, Mo
2c only just shows catalytic activity under the high temperature more than 500 DEG C.
Because the ZSM-5 zeolite of iron content is at N
2in SCR (SCR) reaction of O oxidation Benzene to phenol and NOx, all have good catalytic performance, therefore existing many patent documentations and open source literature have been reported the method for introducing ferro element in ZSM-5 zeolite so far.For example:
CN1353087A(2000) disclosed a kind of method of synthesizing containing the ZSM-5 zeolite of Fe.It is characterized in that, the thermal synthesis of FeZSM-5 zeolite water has adopted the Y zeolite raw material of iron exchange.In ZSM-5 zeolite is synthetic, use the Y zeolite of iron content as Fe source.The synthetic ZSM-5 zeolite containing Fe adopts ethamine, TPAOH or 4-propyl bromide template.
CN1557707A(2004) disclosed a kind of synthetic method containing Fe-ZSM-5 zeolite.It is characterized in that, the Hydrothermal Synthesis of Fe-ZSM-5 zeolite has adopted diatomite material, introduces assorted former Fe with diatomite, uses 4-propyl bromide template, and product has microballoon pattern.
CN101121526A(2006) disclosed a kind of method of synthesizing containing the Fe-ZSM-5 zeolite of nanoscale.It is characterized in that, the Hydrothermal Synthesis of Fe-ZSM-5 zeolite adopts two sections of variable temperature crystallization methods, and taking TPAOH, 4-propyl bromide or n-butylamine as template, Fe is by before zeolite crystallization, and inorganic acid and inorganic molysite wiring solution-forming are introduced.Product grains degree is less than 100 nanometers.
In open source literature J.Cata.213 (2003) 251-271, relate to a kind of based on FeCl
3chemical vapour deposition (CVD) prepare the method for Fe/ZSM-5.
Open source literature Micro.Meso.Mater.80 (2005) 279-289 has related to immersion in a kind of ferric trichloride and acetylacetone,2,4-pentanedione solution and has carried out ion-exchange, and under vacuum condition, dipping solid is dried to the method for preparing Fe zeolite.The document has also related separately to a kind of ferrous chloride and ferrous chloride crystal carries out the method for solid ionic exchange system for Fe zeolite under dry air and nitrogen atmosphere.
J.Catal.254, has related to two kinds of methods that solid ionic exchange system is processed for Fe zeolite with to the iron zeolite preparing in 383-396 (2008).A kind of method is to adopt the NH that silica alumina ratio is 25
4zSM-5, mixes with a certain amount of ferric trichloride with purity oxygen after the roasting temperature of 823K, then by mixture constant temperature 2 hours under the condition of helium atmosphere, 598K.Then the molecular sieve of processing is processed at the temperature of the atmosphere 473K of air with the water of 0.5VOL%.Finally, under the atmosphere of oxygen, with the heating rate of 8K/min, temperature is risen to 823K from room temperature, constant temperature two hours, obtains Fe/ZSM-5 catalyst.Another is that method is above made to catalyst Fe/ZSM-5 under helium atmosphere, 1173K roasting 2h.Successively twice roasting temperature at the atmosphere 823K of pure oxygen of the method, solid ionic exchange under helium atmosphere, step complexity, cost are higher, and ferric trichloride mixes with ammonia zeolite and carries out solid ionic and be mixed after catalyst, for N
2o is oxidized Benzene to phenol, does not have the high aromatisation conversion ratio of iso-butane activity.
In open source literature Appl.Catal.A:Gen.295 (2005) 106-115, relate to and a kind ofly prepared Fe-ZSM-5 catalyst and use it for catalysis benzyl chloride and benzene generates the method for diphenyl-methane by solution impregnation.
In open source literature React Kinet Catal Lett (2009) 97:19-26, relate to the modification of the ferric nitrate solution dipping of a kind of use and prepared Fe/H-ZSM-5 catalyst and used it for ethanol dehydration the method for producing carbon three above alkene.
Open source literature Catal.Commun.7 (2006) 199-203 has related to the modification of the ferric nitrate solution dipping of a kind of use and has prepared FeHZSM-5 zeolite catalyst, and catalyst is used for to the method for catalyzing iso-butane alkane cracking ethylene preparation propylene.Under the high temperature of said cracking reaction more than 600 DEG C, carry out, the productive rate of total olefin can reach more than 60%, but reaction generates the dry gas accessory substances such as a large amount of methane and ethane.Be understood that, under the high temperature more than 600 DEG C, also can there is similar reaction in normal butane.And what iso-butane cracking reaction activated is carbon-carbon bond.
Although the preparation of iron content ZSM-5 zeolite can use the methods such as Hydrothermal Synthesis, solion exchange, nonaqueous solvents ion-exchange, gas solid precipitation to realize; but the program complexity that these methods have, have need inert gas shielding; the needs that also have use the special material that is unfavorable for environment and equipment, otherwise the decentralization variation of iron species on catalyst.In addition, the preparation of the iron content ZSM-5 zeolite of having reported, the overwhelming majority is the SCR object for NOx, or the hydroxylating object of benzene, current preparation method's report of also not finding to be directed to the iron content ZSM-5 zeolite that passes through aromatization selective conversion butylene and iso-butane under normal butane exists.
Summary of the invention
The object of this invention is to provide a kind of catalyst and preparation method for carbon four aromatisation.Aromatized catalyst prepared by the present invention, by the carbon-hydrogen link of activation iso-butane, facilitate iso-butane aromatisation, be applicable to fixed bed reactors, whole butylene in carbon 4 liquid gas and part iso-butane are transformed, obtain the high octane gasoline component that is rich in aromatic hydrocarbons and propane, the butane liquefied gas (high-quality ethylene cracking material) with suitable normal butane iso-butane ratio simultaneously.
Object of the present invention realizes by following method: catalyst preparation process at least comprises:
By dry, not yet remove organic formwork agent, grain size is that the former powder of the na-pretreated zeolite with MFI structure of 10～500 nanometers, silica alumina ratio mixes with ferric trichloride or ferric trichloride crystal, carry out temperature-programmed calcination and remove organic formwork agent, sintering temperature scope is 300～600 DEG C, calcination atmosphere is air atmosphere, and roasting time is 3～24 hours; The na-pretreated zeolite powder of taking off organic formwork agent and load has iron and aluminium oxide are dried and roasting after with the mixing of butt weight ratio 1:9～9:1, moulding, and roasting condition is 500～600 DEG C, 3～8 hours, then exchange through ammonium salt, make hydrogen type catalyst; Then at 400～800 DEG C of temperature, with the above-mentioned hydrogen type catalyst of steam treatment 5 minutes～200 hours, at 1 DEG C～80 DEG C, with inorganic acid solution, the catalyst after to above-mentioned steam treatment carries out the acid treatment of 0.5～200 hour, then through washing, dry, roasting, makes finished catalyst.
Our research work shows, face in appropriateness under the condition of hydrogen, carry out the zeolite molecular sieve aromatized catalyst (as ZSM-5) with MFI structure of modification with a small amount of ferro element, in low temperature aromatization reaction, except keeping conversion of olefines ability, also show very significantly iso-butane aromatization activity.The catalytic capability of this low temperature conversion iso-butane is because of the activity of hydrogen atom on tertiary carbon in iso-butane molecule, and as non-skeleton elements but high degree of dispersion in the special catalysis dehydrogenation effect of the iron species on zeolite molecular sieve surface.Owing to there is no tertiary carbon atom in normal butane molecule, so in butylene and iso-butane aromatization process, normal butane does not participate in reaction substantially.This just provides a kind of by catalyst modification, selective conversion iso-butane, the effective way of the just different ratio of the residue butane of raising carbon 4 liquid gas aromatization reaction.
Our research work shows, aromatized catalyst is depended critically upon and in catalyst, introduced iron species and addition and method by the activity of dehydrogenation selective conversion iso-butane under the condition of butylene low temperature aromatization.The iron ion of applying its high degree of dispersion of preparation method of the present invention is also conducive to iso-butane and transforms through dehydrogenation.
That zeolite powder in the present invention refers to is dry, not yet remove organic formwork agent, grain size is the zeolite powder that the sodium type of 10～500 nanometers has MFI structure.The zeolite powder with MFI structure of removed template method is not mixed with the material that contains ferric trichloride or ferric trichloride crystal, through subsequent step, processing can make valence state, the attachment state etc. of iron ion can ensure the aromatisation conversion ratio of butylene in carbon four aromatization process, and also centering iso-butane aromatisation has good activity simultaneously.
As everyone knows, ZSM-5, ZSM-11, ZSM-8 belong to MFI structure, have similar catalytic performance.Particularly, in common Hydrothermal Synthesis, ZSM-5 zeolite and ZSM-11 zeolite inseparable mixed crystal often.Therefore, the present invention is applicable to ZSM-5, ZSM-11 or the ZSM-8 zeolite that grain size is 10～500 nanometers completely, or the former any mixed crystal.In order to utilize the short intrinsic anti-carbon inactivation advantage in small crystal grain molecular sieve duct, the preferred grain size of the present invention is that the ZSM-5 zeolite of 50～400 nanometers is catalyst Precursors.
Inorganic acid solution of the present invention can be selected the mixed acid solution of hydrochloric acid, nitric acid or sulfuric acid and above inorganic acid thereof, and the hydrogen proton concentration scope in acid solution is preferably 0.001 mol/L～5.0 mol/L, preferably 0.1 mol/L～1.0 mol/L.
It is general conditions of the prior art that ammonium salt solution of the present invention carries out ion-exchange condition, as can be the ammonium ion solution of 0.1～1.0 mol/L and exchanges 1～15 time according to 1～100 liquid-solid volume ratio containing zeolite granular by concentration, with dry after deionized water washing, roasting, obtain hydrogen type catalyst, sintering temperature is preferably 500～600 DEG C, and the time is preferably 3～8 hours.
Ammonium ion in the ammonium ion solution adding when exchange of the present invention is preferably by ammonium nitrate, and the ammonium salts such as ammonium chloride, ammonium acetate or ammonium carbonate provide.
The more specifically technical step that the present invention recommends is as follows:
Adopt hydrothermal synthesis method to prepare the former powder of na-pretreated zeolite, preferably synthetic grain size is the ZSM-5 zeolite parent of 10～500 nanometers, or other has zeolite and the mixed crystal thereof of MFI structure.
Preparing grain size with hydrothermal synthesis method is that the zeolite method of the above-mentioned MFI of the having structure of 10～500 nanometers illustrates in many patent documentations and open source literature, method such as disclosed in following patent documentation and open source literature: U.S.Pat.No.3702886, U.S.Pat.No.3709979, U.S.Pat.No.3781226, U.S.Pat.No.3926782, U.S.Pat.No.4205053, U.S.Pat.No.4289607, U.S.Pat.No.5405596, U.S.Pat.No.1334243, EP173901, EP130809, Dani sh Patent PR 173, 486, GB1334243A, Chem.Mater 5 (1993) 452, Zeolites 14(1994) 557, Zeolites 14 (1994) 643, J.Catal.145 (1994) 243, Mater.Res.Soc.Symp.Proc.371 (1995) 21, Aangew.Chem.Int.Ed.Engl.34 (1995) 73, Chem.Mater.7 (1995) 920, Colloid Interface Sci.170(1995) 449, Micropor.Mater.5 (1996) 381, Zeolites 18 (1997) 97, J.Phys.Chem.B 101 (1997) 10094, Micropor.Mesopor.Mater.22 (1998) 9, Micropor.Mesopor.Mater.25 (1998) 434, Chem.Comm.673 (1999), Micropor.Mesopor.Mater.31 (1999) 141, Micropor.Mesopor.Mater.31 (1999) 241, Micropor.Mesopor.Mater.39 (2000) 393, Inorg.Chem.39 (2000) 2279, Micropor.Mesopor.Mater.50 (2001) 121-128, Micropor.Mesopor.Mater.43 (2001) 51-59, Mater.Sci.Eng.C 19 (2002) 111-114.Go out according to existing method Hydrothermal Synthesis ZSM-5 zeolite or other MFI zeolite sample that the said grain size of the present invention is 10～500 nanometers, adopt respectively X-ray polycrystal powder diffraction approach and scanning (transmission) electron microscope method to confirm zeolite structured and zeolite grain size.
First former na-pretreated zeolite powder is made to hydrogen type catalyst according to the following steps:
(1) by dry former na-pretreated zeolite dried bean noodles, ferric trichloride or ferric trichloride crystal are mixed with the dry former powder of na-pretreated zeolite, the temperature range of temperature-programmed calcination is 300～600 DEG C, and calcination atmosphere is air atmosphere, and roasting time is 3～24 hours.Adopt temperature programming method can prevent that organic compound combustion is too violent, thereby avoid the inner hot-spot of zeolite crystal, destroy zeolite crystal structure, and in the time of temperature-programmed calcination removed template method on zeolite load iron.Drying condition is general conditions, as being: 90 DEG C～120 DEG C of temperature, air atmosphere, 3～12 hours;
Described temperature-programmed calcination can carry out in Muffle furnace, and the temperature-rising method of recommendation can be: rise to 270～330 DEG C from 20 DEG C～30 DEG C heating rates with 0.8～4 DEG C/min, constant temperature 0.5～30 hour; Be warming up to 380～400 DEG C with same heating rate again, constant temperature 0.5～30 hour; Be warming up to 470～530 DEG C with same heating rate again, constant temperature 0.5～30 hour; Be warming up to 540～600 DEG C with same heating rate again, constant temperature 8～40 hours.
(2) there is the na-pretreated zeolite powder of iron to mix with aluminium oxide and moulding the also load of taking off organic formwork agent, as added 8%～12%(percentage by weight) inorganic acid preferably rare nitric acid knead, carry out compressing tablet or extrusion or shoot out or roller forming with rule method.After moulding, will be dried and roasting containing zeolite granular.Dry available general conditions, concrete drying condition can be described above.Recommend the optimum condition of roasting to be: air atmosphere, 500～600 DEG C, 3～8 hours.Sintering temperature is too low, can have influence on stability and the mechanical strength of catalyst granules, if contrary sintering temperature is too high, will change catalyst crystal structure.
(3) zeolite granular of moulding, roasting is exchanged through ammonium salt, make hydrogen type catalyst.Ammonium salt is exchanged for the general method in this area, comprise: at 20 DEG C～30 DEG C, exchange liquid (ammonium concentration optimum range is 0.1～1.0 mol/L) and exchange containing zeolite granular with ammonium ion solution, liquid-solid volume ratio is 1～100, exchange times is 1～5 time, and be 0.5～10 hour each swap time; After each exchange, outwell raffinate, add fresh exchange liquid; After all ammonium exchange work completes, outwell raffinate, with dry after deionized water washing, roasting.Dry, all available prior aries of roasting condition, concrete drying condition can be as previously mentioned.The optimum condition of roasting is: air atmosphere, 500～600 DEG C, 3～8 hours.
On above-mentioned basis of preparing hydrogen type catalyst, process and obtain aromatized catalyst of the present invention in accordance with the following steps:
(1) above-mentioned hydrogen zeolite catalyst is carried out to steam treatment.Steam treatment also claims water vapor passivation processing can adopt steam treatment mode (as shown in CN1586721) general in prior art, as carried out in fixed bed reactors, steam treatment can adopt pure water steam, the steam that also can adopt air or nitrogen to carry.In the time carrying out steam treatment, in atmosphere, the appropriate volume percentage of water vapour is 1%～100%, and Balance Air is air or nitrogen; The preference temperature scope of steam treatment is 400～800 DEG C; The optimum range of steam treatment time is 5 minutes～200 hours under these conditions.
The preferred pressure range of steam treatment is normal pressure～5.0MPa.
(2) in the catalyst after steam treatment, add inorganic acid to carry out acid treatment, be then dried, roasting, make finished catalyst.
In acid treatment, the consumption of inorganic acid solution is higher than the saturated water absorption of catalyst, and temperature range is 1 DEG C～80 DEG C.Acid treatment can be carried out in static situation, also can circulate in situation and carry out at acid solution.Under these conditions, acid-treated time range is 0.5～200 hour.Inorganic acid solution of the present invention can be selected the mixed acid solution of hydrochloric acid, nitric acid or sulfuric acid and above inorganic acid thereof, and the hydrogen proton concentration scope in acid solution is preferably 0.001 mol/L～5.0 mol/L, preferably 0.1 mol/L～1.0 mol/L.
After acid treatment finishes, by deionized water by catalyst detergent to neutral, be then dried, roasting, make finished catalyst.The condition of recommending is to be dried at 90～120 DEG C to carry out, and the time is 2～5 hours; Roasting condition is 520～580 DEG C, 2～5 hours.Roasting can be carried out in Muffle furnace, and the temperature-rising method of recommendation is: directly rise to 520～580 DEG C with the heating rate of 1～5 DEG C/min, then constant temperature 2～5 hours.Catalyst is after peracid treatment, and it is large that catalyst pores road index becomes, increased activity.
The present invention also provides a kind of catalyst for carbon four hydroaromatizations being made by said method, it is characterized in that taking catalyst weight as 100wt%, wherein have MFI structure containing Fe zeolite 10～90%, 10～90% aluminium oxide; In catalyst, Fe content is 0.5～2%.If the content of zeolite is too low, can affect activity and the stability of catalyst.Otherwise if the too high levels of zeolite, catalyst granules is easily broken.
In the detection of invention effect of the present invention, catalyst duct patency adopts the method for n-hexane and cyclohexane adsorbance to measure, and the method for the aromatization activity of evaluate catalysts and the adjustment compressive reaction to the just different ratio of butane is measured.The raw material of fixed bed reaction is carbon 4 liquid gas, and wherein C 4 olefin content is no less than 35%, and reaction temperature is at 320 DEG C～480 DEG C, the scope 0.8MPa～4MPa of reaction pressure, charging air speed (WHSV) 0.5～8h of carbon 4 liquid gas
-1.
The present invention combines the roasting Template removal procedure of processing of load iron modification and zeolite powder, not only simplify the processing technology of catalyst, be conducive to reduce the production cost of catalyst, more be conducive to the high-dispersion load of iron species on catalyst, and this load iron method of modifying can make catalyst face in appropriateness under the butylene aromatisation condition of hydrogen and low temperature, there is the ability of obvious conversion iso-butane, this,, by being of value to the just different ratio that improves aromatization residue butane, makes it to be more suitable for the raw material as preparing ethylene by steam cracking.For carbon 4 liquid gas provides possibility by facing hydrogen low temperature aromatization reaction realization comprehensive utilization thoroughly.
Detailed description of the invention
Raw material sources and specification:
The former powder of sodium type ZSM-5 zeolite: Qi Wangda Science and Technology Ltd. of Dalian University of Technology
HZSM-5 zeolite: Qi Wangda Science and Technology Ltd. of Dalian University of Technology
Sodium type ZSM-8 zeolite powder: Qi Wangda Science and Technology Ltd. of Dalian University of Technology
Embodiment 1:
The former powder of sodium type ZSM-5 zeolite: the former powder (SiO of sodium type ZSM-5 zeolite that not yet removes 20～50 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 26).
(1) de-organic amine template and the exchange of iron ion solid ionic are processed: first make the former powder of nano zeolite of Hydrothermal Synthesis be dried 3 hours at 110 DEG C.The zeolite powder that 3 grams of ferric trichloride crystal are dry with 100 grams mixes, and then in Muffle furnace, carries out temperature-programmed calcination, and temperature-rising method is: rise to 300 DEG C from room temperature with the heating rate of 1 DEG C/min, constant temperature 1 hour at 300 DEG C; Be warming up to 400 DEG C with same heating rate again, constant temperature 1 hour at 400 DEG C; Be warming up to 500 DEG C with same heating rate again, constant temperature 1 hour at 500 DEG C; Be warming up to 550 DEG C with same heating rate again, constant temperature 12 hours at 550 DEG C.(2) moulding: according to the butt weight ratio 4:1 of zeolite and aluminium oxide, get respectively 80 grams of the na-pretreated zeolites (butt) that burnt organic amine template, 20 grams of boehmites (butt), after mixing, make binding agent with rare nitric acid of 10% and carry out kneading, then carry out extruded moulding with a double screw banded extruder, bar footpath size is elected 1 millimeter as.Zeolite granular after extruded moulding is dried 3 hours at 110 DEG C, finally in Muffle furnace, carries out roasting, and temperature-rising method is: directly rise to 550 DEG C from room temperature with the heating rate of 3 DEG C/min, then constant temperature 3 hours.(3) ammonium salt exchange system is for hydrogen type catalyst: the ammonium nitrate solution of 0.6 mol/L for ammonium exchange, and the liquid-solid volume ratio of exchange liquid and zeolite granular solid is 10, exchanges 4 times, and be 1 hour swap time at every turn, and liquid is changed in centre.Zeolite granular after having exchanged, through deionized water washing, is dried processing at 110 DEG C, and be 3 hours drying time.Then, carry out roasting deamination gas in Muffle furnace, temperature-rising method is: directly rise to 550 DEG C from room temperature with the heating rate of 3 DEG C/min, then constant temperature 3 hours.So far, obtain hydrogen type catalyst HZSM-5.(4) water vapor passivation processing: the flat-temperature zone that hydrogen type catalyst is loaded on to fixed bed reactors carries out steam treatment.Steam treatment is carried out in 100% water vapour atmosphere, the temperature of steam treatment is 550 DEG C, the pressure of steam treatment is normal pressure, and the water inlet amount (weight of the water passing through on unit fixed bed reactors cross-sectional area in the unit interval) of reactor is 7.8 grams × hour
-1× square centimeter
-1, the steam treatment time is 3 hours.(5) acid treatment: the HNO of preparation 0.6 mol/L
3the aqueous solution (, the hydrogen proton concentration in acid solution is 0.6 mol/L) carries out acid treatment to above-mentioned steam treatment catalyst.Acid-treated condition is: HNO
3the liquid-solid mass ratio of solution and catalyst is got 5:1, under the condition of 25 DEG C, carries out with static immersion way, and soak time is 24 hours.After acid treatment finishes, by deionized water by catalyst wash to neutral, be then dried, roasting, make finished catalyst.Be dried at 110 DEG C and carry out, be 3 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 550 DEG C from room temperature with the heating rate of 3 DEG C/min, then constant temperature 3 hours.The catalyst of preparing through above-mentioned steps is in iron atom, and the mass content of iron is 0.5%, and note is A.
Comparative example A 1
Repeat embodiment 1 catalyst preparation step, the zinc that change ferric trichloride is same quality.The catalyst note of preparing through above-mentioned steps is a1.
Comparative example A 2
Repeat embodiment 1 catalyst preparation step, except not carrying out (5) acid treatment.The catalyst note of preparing through above-mentioned steps is a2.
Comparative example A 3
Adopt commercially available HZSM-5 zeolite to replace the zeolite powder in step (1), do not carry out step (3) ammonia exchange system for hydrogen type molecular sieve in catalyst preparation process, other step is with embodiment 1.The catalyst note of preparing through above-mentioned steps is a3.
Embodiment 2
Select sodium type ZSM-8 zeolite powder: the sodium type ZSM-8 zeolite powder (SiO that not yet removes 400～500 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 10).
Repeating embodiment 1 catalyst preparation step, is ZSM-8 but change na-pretreated zeolite type in step (1), and the ratio of ferric trichloride and dry na-pretreated zeolite is 4 grams/100 grams.The butt weight ratio that changes the middle iron-containing zeolite of step (2) and aluminium oxide is 3:1, the ammonium nitrate solution that changes ammonia exchange 1.0 mol/L in step (3) exchanges 5 times, each exchange 5 hours, liquid-solid volume ratio is 1, then directly rises to 520 DEG C with the heating rate of 4 DEG C/min, constant temperature 5h, the concentration that changes steam in step (4) is 70%, and other 30% is nitrogen, 800 DEG C of steam treatment temperature, pressure 0.5MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2, the processing time is 5 minutes, changing acid solution in step (5) is the hydrochloric acid solution of 0.1 mol/L, and 50,50 DEG C of liquid-solid volume ratios, circulation flushing 36 hours, dry under 90 DEG C of conditions, constant temperature 5h, roasting is raised to 520 DEG C with 5 DEG C/min, constant temperature 4h.The catalyst of preparing through above-mentioned steps is in iron atom, and iron-holder is 1%, and note is B.
Comparative example B1
Select sodium type ZSM-8 zeolite powder: the sodium type ZSM-8 zeolite powder (SiO of 600～800 nanometers
2/ Al
2o
3mol ratio 10).Other step is with embodiment 2, and the catalyst note of preparing through above-mentioned steps is b1.
Comparative example B2
Select sodium type ZSM-8 zeolite powder: the sodium type ZSM-8 zeolite powder (SiO of 5～8 nanometers
2/ Al
2o
3mol ratio 10).Other step is with embodiment 2, and the catalyst note of preparing through above-mentioned steps is b2.
Contrast row B3
Use the preparation method of catalyst in embodiment 2, changing ferric trichloride in step (1) is ferrous chloride, the ratio of adding ferrous chloride and dry na-pretreated zeolite is 3.1 grams/100 grams, and other condition is constant, and the catalyst note of preparing through above step is b3.
Embodiment 3:
Select sodium type ZSM-11 zeolite powder: the sodium type ZSM-11 zeolite powder (SiO of 50～400 nanometers
2/ Al
2o
3mol ratio 41).
Adopting method for preparing catalyst in embodiment 1, is ZSM-11 but change na-pretreated zeolite type in step (1), and the ratio of ferric trichloride and dry molecular sieves na-pretreated zeolite is 5.4 grams/100 grams, is then warming up to 600 DEG C with 3 DEG C/min, constant temperature 3 hours.The butt weight ratio that changes the middle iron-containing zeolite of step (2) and aluminium oxide is 5:1, and the dilute sulfuric acid with 8% carries out kneading, rises to 510 DEG C with the speed of 4 DEG C/min, constant temperature 6 hours.The sal volatile that changes ammonia exchange 0.1 mol/L in step (3) exchanges 3 times, each exchange 3 hours, then directly rise to 500 DEG C with the heating rate of 5 DEG C/min, constant temperature 6h, the percentage by volume that changes steam in step (4) is 60%, other 40% is air, steam treatment temperature is 750 DEG C, pressure 4MPa, and changing acid solution in step (5) is the sulfuric acid solution of 0.2 mol/L, 20 DEG C, soak 100 hours, dry under 120 DEG C of conditions, constant temperature 3h, roasting is raised to 580 DEG C with 5 DEG C/min, constant temperature 2h.The catalyst of preparing through above-mentioned steps is in iron atom, and iron-holder is that 1.5 notes are C.
Comparative example C1
Select the sodium type MCM-22 zeolite powder (SiO of 200～300 nanometers
2/ Al
2o
3mol ratio 41).
All the other steps are with embodiment 3, and the catalyst note of preparing through above-mentioned steps is c1.
Comparative example C2
Select the former powder (SiO of sodium y-type zeolite of 100～200 nanometers
2/ Al
2o
3mol ratio 41).
All the other steps are with embodiment 3, and the catalyst note of preparing through above-mentioned steps is c2.
Embodiment 4
Select the former powder of sodium type ZSM-5 zeolite: the former powder (SiO of sodium type ZSM-5 zeolite of 300～400 nanometers
2/ Al
2o
3mol ratio 55).
Repeat catalyst Preparation Example 3, the ratio that changes the middle ferric trichloride crystal of step (1) and dry na-pretreated zeolite is 17 grams/100 grams, and the catalyst note of preparing through above-mentioned steps is D.
Embodiment 5
Select the former powder of sodium type ZSM-5 zeolite: the former powder (SiO of sodium type ZSM-5 zeolite of 300～400 nanometers
2/ Al
2o
3mol ratio 64).
Repeat catalyst Preparation Example 3, the ratio that changes the middle ferric trichloride crystal of step (1) and dry na-pretreated zeolite is 1 gram/100 grams, and the catalyst note of preparing through above-mentioned steps is E.
Embodiment 6
Select sodium type ZSM-5, ZSM-8, ZSM-11 zeolite powder to mix with the weight ratio of 1:2:3: sodium type ZSM-5, the ZSM-8, the ZSM-11 zeolite powder (SiO that not yet remove 100～200 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 30).
Repeating catalyst Preparation Example 1, is that ZSM-5, ZSM-8, ZSM-11 mix with the part by weight of 1:2:3 but change na-pretreated zeolite type in step (1), and the ratio of ferric trichloride and dry na-pretreated zeolite is 7.1 grams/100 grams.Temperature-rising method is: rise to 270 DEG C from room temperature with the heating rate of 0.8 DEG C/min, constant temperature 25 hours at 270 DEG C; Be warming up to 380 DEG C with same heating rate again, constant temperature 20 hours at 380 DEG C; Be warming up to 480 DEG C with same heating rate again, constant temperature 10 hours at 480 DEG C; Be warming up to 600 DEG C with same heating rate again, constant temperature 1 hour at 600 DEG C.The butt weight ratio that changes the middle iron-containing zeolite of step (2) and aluminium oxide is 9:1, the ammonium chloride solution that changes ammonia exchange 0.4 mol/L in step (3) exchanges 1 time, exchange 8 hours, liquid-solid volume ratio is 100, then directly rises to 500 DEG C with the heating rate of 1 DEG C/min, constant temperature 7h, the concentration that changes steam in step (4) is 10%, and other 90% is air, 400 DEG C of steam temperatures, pressure 1MPa, the inlet amount of aqueous vapor is 100 grams × hour
-1× cm
-2processing time is 50 hours, changing acid solution in step (5) is the hydrochloric acid of 1 mol/L and the mixed solution of nitric acid, and wherein the mol ratio of hydrochloric acid and nitric acid is 1:1, liquid-solid ratio 4,80 DEG C, soak 0.5 hour, dry under 110 DEG C of conditions, constant temperature 3h, roasting is raised to 580 DEG C with 2 DEG C/min, constant temperature 3h.The catalyst of preparing through above-mentioned steps is in iron atom, and iron-holder is 2%, and note is F.
Comparative example F1 repeats catalyst Preparation Example 6, change ferric trichloride and from step (1), do not add, but in step (2), mix with aluminium oxide, zeolite, moulding, roasting.The catalyst note of preparing through above-mentioned steps is done f2 note and is f1.
Comparative example F2 repeats catalyst Preparation Example 6, change ferric trichloride does not add from step (1), but in step (2), step (3) is before afterwards, carry out ion-exchange with the liquor ferri trichloridi of 1 mol/L, solid-to-liquid ratio is 10, exchanges 5 times, and be 3 hours each swap time, liquid is changed in centre, then drying and roasting.The catalyst note of preparing through above-mentioned steps is f2.
Comparative example F3 repeats catalyst Preparation Example 6, change ferric trichloride does not add from step (1), but in step (3), step (4) is before afterwards, carry out ion-exchange with the liquor ferri trichloridi of 0.5 mol/L, solid-to-liquid ratio is 10, exchanges 7 times, and be 5 hours each swap time, liquid is changed in centre, then drying and roasting.The catalyst note of preparing through above-mentioned steps is f3.
Comparative example F4 uses the preparation method of embodiment 6, change ferric trichloride does not add from step (1), but in Hydrothermal Synthesis preparation has the zeolite parent process of MFI structure, add, be about to the ferric trichloride of 8 grams join in template, fully stir after crystallization, dry, roasting.The catalyst note of preparing through above-mentioned steps is f4.
Embodiment 7
Select sodium type ZSM-8, ZSM-11 zeolite powder to mix with the weight ratio of 5:3: the sodium type ZSM-8, the ZSM-11 zeolite powder (SiO that not yet remove 100～150 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 20).
Repeating catalyst Preparation Example 1, is that ZSM-8, ZSM-11 mix with the part by weight of 5:3 but change na-pretreated zeolite type in step (1), and the ratio of ferric trichloride and dry na-pretreated zeolite is 6 grams/100 grams.Temperature-rising method is: rise to 330 DEG C from room temperature with the heating rate of 4 DEG C/min, constant temperature 0.5 hour at 330 DEG C; Be warming up to 390 DEG C with same heating rate again, constant temperature 10 hours at 390 DEG C; Be warming up to 530 DEG C with same heating rate again, constant temperature 10 hours at 530 DEG C; Be warming up to 580 DEG C with same heating rate again, constant temperature 4 hours at 580 DEG C.Changing the butt weight ratio of iron-containing zeolite and aluminium oxide in step (2) is 1:9, in air atmosphere 500 DEG C, and roasting 6 hours.The ammonium chloride solution that changes ammonia exchange 0.8 mol/L in step (3) exchanges 2 times, each exchange 8 hours, liquid-solid volume ratio is 30, then directly rise to 550 DEG C with the heating rate of 2 DEG C/min, constant temperature 3h, the concentration that changes steam in step (4) is 1%, other 99% is nitrogen, 650 DEG C of steam temperatures, pressure 0.05MPa, the inlet amount of aqueous vapor is 600 grams × hour
-1× cm
-2processing time is 200 hours, changing acid solution in step (5) is the mixed solution of hydrochloric acid, nitric acid and the sulfuric acid of 4 mol/L, and wherein the mol ratio of hydrochloric acid, nitric acid and sulfuric acid is 1:1:2, liquid-solid ratio 2,1 DEG C, soak 200 hours, dry under 120 DEG C of conditions, constant temperature 2h, roasting is raised to 520 DEG C with 5 DEG C/min, constant temperature 5h.The catalyst of preparing through above-mentioned steps is in iron atom, and iron-holder is 0.75%, and note is G.
Embodiment 8
Repeat catalyst Preparation Example 1, but the sodium type ZSM-5 zeolite that not yet removes 20～50 nanometers of organic formwork agent in change step (1) is the sodium type ZSM-5, the ZSM-11 zeolite that not yet remove 100～150 nanometers of organic formwork agent to be mixed with the part by weight of 1:2, and the ratio of ferric trichloride and dry na-pretreated zeolite is 10 grams/100 grams.Temperature-rising method is: rise to 320 DEG C from room temperature with the heating rate of 2 DEG C/min, constant temperature 1 hour at 320 DEG C; Be warming up to 380 DEG C with same heating rate again, constant temperature 12 hours at 380 DEG C; Be warming up to 530 DEG C with same heating rate again, constant temperature 10 hours at 530 DEG C; Be warming up to 590 DEG C with same heating rate again, constant temperature 5 hours at 590 DEG C.Changing the butt weight ratio of iron-containing zeolite and aluminium oxide in step (2) is 4:1, in air atmosphere 520 DEG C, and roasting 6 hours.The ammonium chloride solution that changes ammonia exchange 1 mol/L in step (3) exchanges 2 times, each exchange 10 hours, liquid-solid volume ratio is 20, then directly rise to 550 DEG C with the heating rate of 3 DEG C/min, constant temperature 4h, the concentration that changes steam in step (4) is 10%, other 90% is nitrogen, 640 DEG C of steam temperatures, pressure 0.1MPa, the inlet amount of aqueous vapor is 550 grams × hour
-1× cm
-2processing time is 150 hours, changing acid solution in step (5) is the nitric acid of 3.5 mol/L and the mixed solution of sulfuric acid, and wherein the mol ratio of nitric acid and sulfuric acid is 1:2, liquid-solid ratio 4,1 DEG C, soak 150 hours, dry under 110 DEG C of conditions, constant temperature 4h, roasting is raised to 540 DEG C with 4 DEG C/min, constant temperature 7h.
The catalyst note of preparing through above-mentioned steps is H.
Embodiment 9
Repeat catalyst Preparation Example 1, the sodium type ZSM-5 zeolite that still changes 20～50 nanometers that not yet remove organic formwork agent in step (1) is sodium type ZSM-5, ZSM-8, the ZSM-11 zeolite powder (SiO that not yet removes 200～300 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 40), ZSM-5, ZSM-8, ZSM-11 zeolite powder are with the weight ratio mixed zeolite of 4:1:11, and the ratio of iron chloride and dry na-pretreated zeolite is 7 grams/100 grams.Temperature-rising method is: rise to 320 DEG C from room temperature with the heating rate of 1 DEG C/min, constant temperature 2 hours at 320 DEG C; Be warming up to 400 DEG C with same heating rate again, constant temperature 10 hours at 400 DEG C; Be warming up to 520 DEG C with same heating rate again, constant temperature 12 hours at 520 DEG C; Be warming up to 580 DEG C with same heating rate again, constant temperature 6 hours at 580 DEG C.Changing the butt weight ratio of iron-containing zeolite and aluminium oxide in step (2) is 2:3, in air atmosphere 530 DEG C, and roasting 5 hours.The ammonium chloride solution that changes ammonia exchange 1.7 mol/L in step (3) exchanges 3 times, each exchange 9 hours, liquid-solid volume ratio is 15, then directly rise to 580 DEG C with the heating rate of 4 DEG C/min, constant temperature 6h, the concentration that changes steam in step (4) is 80%, other 20% is nitrogen, 630 DEG C of steam temperatures, pressure 0.5MPa, the inlet amount of aqueous vapor is 600 grams × hour
-1× cm
-2processing time is 200 hours, changing acid solution in step (5) is the nitric acid of 2.0 mol/L and the mixed solution of sulfuric acid, and wherein the mol ratio of hydrochloric acid and sulfuric acid is 3:2, liquid-solid ratio 6,10 DEG C, soak 120 hours, dry under 120 DEG C of conditions, constant temperature 3h, roasting is raised to 550 DEG C with 3 DEG C/min, constant temperature 6h.
The catalyst note of preparing through above-mentioned steps is I.
Aromatization is evaluated:
In conventional fixed bed pressurized reactor, carry out the experiment of low-temperature hydro aromatization.Reaction raw materials is the carbon 4 liquid gas of catalytic cracking unit by-product, specifically consists of: iso-butane: 26.24%, and normal butane: 11.53%, positive isobutene: 29.54%, trans-butene-2: 18.60%, cis-butene-2: 13.86%, carbon five (C
5): 0.23%.Normal butane/iso-butane ratio in above-mentioned raw materials is about 0.44.Hydrogen (gas volume)/liquefied gas (liquid volume)=50/1, loaded catalyst is 2 grams, and reaction temperature is 380 DEG C, and reaction pressure is 3MPa, and the charging air speed (WHSV) of carbon 4 liquid gas is 0.8h
-1.Sample analysis in the time of successive reaction 72 hours, and calculate C 4 olefin conversion ratio, the above liquid of carbon five is received, normal butane/iso-butane ratio in Aromatic Hydrocarbon in Gasoline content, residue liquefied gas.Reaction result sees the following form 1.
The definition of the method that the present invention provides according to CN200410050202.3 patent and duct restricted index is carried out duct restricted index mensuration to the catalyst in embodiment and comparative example, the results are shown in Table 1.
Table 1 embodiment and contrast test and measurement result
| Catalyst | C 4 olefin conversion ratio | The above liquid of carbon five is received | Aromatic Hydrocarbon in Gasoline content | Normal butane/iso-butane | Duct restricted index |
| A | 99.7％ | 54.4％ | 52.7％ | 0.63 | 1.13 |
| a1 | 99.6％ | 54.2％ | 52.5％ | 0.43 | 1.13 |
| a2 | 91.3％ | 46.1％ | 46.2％ | 0.47 | 1.26 |
| a3 | 99.6％ | 54.2％ | 52.7％ | 0.44 | 1.13 |
| B | 99.6％ | 54.2％ | 48.3％ | 0.67 | 1.12 |
| b1 | 87.2％ | 48.1％ | 8.4％ | 0.46 | 1.10 |
| b2 | 86.8％ | 47.6％ | 11.3％ | 0.45 | 1.15 |
| b3 | 99.6％ | 54.2％ | 50.6％ | 0.43 | 1.12 |
| C | 99.6％ | 54.2％ | 59.6％ | 0.61 | 1.15 |
| c1 | 78.2％ | 37.1％ | 12.1％ | 0.43 | 1.13 |
| c2 | 99.6％ | 54.4％ | 59.7％ | 0.43 | 1.12 |
| D | 99.6％ | 54.3％ | 59.5％ | 0.61 | 1.12 |
| E | 99.4％ | 54.4％ | 58.9％ | 47 | 1.12 |
| F | 99.9％ | 54.2％ | 61.2％ | 0.54 | 1.18 |
| f1 | 99.8％ | 53.9％ | 61.1％ | 0.43 | 1.18 |
| f2 | 99.9％ | 54.1％ | 61.2％ | 0.43 | 1.17 |
| f3 | 99.9％ | 54.3％ | 61.0％ | 0.43 | 1.18 |
| f4 | 99.9％ | 54.3％ | 59.8％ | 0.43 | 1.18 |
| G | 99.6％ | 54.2％ | 50.8％ | 0.64 | 1.10 |
| H | 99.7％ | 54.3％ | 52.8％ | 0.63 | 1.11 |
| I | 99.7％ | 54.3％ | 52.7％ | 0.63 | 1.12 |
Claims (12)
1. the preparation method of carbon four hydroaromatization catalyst, it is characterized in that preparation process at least comprises: by dry, not yet remove organic formwork agent, grain size is that the former powder of the na-pretreated zeolite with MFI structure of 10～500 nanometers mixes with ferric trichloride or ferric trichloride crystal, carry out temperature-programmed calcination and remove organic formwork agent, sintering temperature scope is 300～600 DEG C, calcination atmosphere is air atmosphere, and roasting time is 3～24 hours; By take off organic formwork agent and load has that the na-pretreated zeolite powder of iron mixes with aluminium oxide, be dried and roasting after moulding, roasting condition is 500～600 DEG C, 3～8 hours, then exchange through ammonium salt, makes hydrogen type catalyst; Then at 400～800 DEG C of temperature, with the above-mentioned hydrogen type catalyst of steam treatment 5 minutes～200 hours, at 1 DEG C～80 DEG C, with inorganic acid solution, the catalyst after to above-mentioned steam treatment carries out the acid treatment of 0.5～200 hour, then through washing, dry, roasting, makes finished catalyst.
2. preparation method according to claim 1, the zeolite powder that it is characterized in that having MFI structure is one or more zeolite powders in ZSM-5 zeolite, ZSM-8 zeolite, ZSM-11 zeolite.
3. preparation method according to claim 1, is characterized in that inorganic acid solution is the mixed acid solution of hydrochloric acid, nitric acid, sulfuric acid solution or above inorganic acid.
4. preparation method according to claim 1, is characterized in that the hydrogen proton concentration scope in inorganic acid solution is 0.001 mol/L～5.0 mol/L.
5. preparation method according to claim 4, is characterized in that in inorganic acid solution, hydrogen proton concentration scope is 0.1 mol/L～1.0 mol/L.
6. preparation method according to claim 1, it is characterized in that making hydrogen type catalyst process through ammonium salt exchange is: be the ammonium ion solution of 0.1～1.0 mol/L by concentration, exchange according to 1～100 liquid-solid volume ratio with the particle of the na-pretreated zeolite that has iron containing load, with dry after deionized water washing, roasting, obtain hydrogen type catalyst, sintering temperature is 500～600 DEG C, and the time is 3～8 hours.
7. preparation method according to claim 1, it is characterized in that making hydrogen type catalyst process through ammonium salt exchange is: at 20 DEG C～30 DEG C with ammonium ion solution and the load that contains have the particle of the na-pretreated zeolite of iron to exchange, exchange times is 1～5 time, and be 0.5～10 hour each swap time; After all ammonium exchange work completes, outwell raffinate, with dry after deionized water washing, roasting.
8. according to the preparation method described in claim 6 or 7, it is characterized in that ammonium ion in ammonium ion solution is by ammonium nitrate, ammonium chloride, ammonium acetate or ammonium carbonate provide.
9. preparation method according to claim 1, is characterized in that the temperature-rising method that temperature-programmed calcination removes organic formwork agent is: rise to 270～330 DEG C from 20 DEG C～30 DEG C heating rates with 0.8～4 DEG C/min, constant temperature 0.5～30 hour; Be warming up to 380～400 DEG C with same heating rate again, constant temperature 0.5～30 hour; Be warming up to 470～530 DEG C with same heating rate again, constant temperature 0.5～30 hour; Be warming up to 540～600 DEG C with same heating rate again, constant temperature 8～40 hours.
10. preparation method according to claim 1, while it is characterized in that steam treatment, in atmosphere, the percentage by volume of water vapour is 1%～100%, Balance Air is air or nitrogen.
11. preparation methods according to claim 1, after it is characterized in that acid treatment finishes, by deionized water, catalyst detergent is extremely neutral, then it is dried to 2～5 hours at 90～120 DEG C, under 520～580 DEG C of conditions, roasting 2～5 hours, makes finished catalyst.
12. 1 kinds of catalyst that obtain by claim 1～7,9～11 arbitrary described preparation methods, is characterized in that taking catalyst weight as 100%, wherein have MFI structure containing Fe zeolite 10～90%, 10～90% aluminium oxide; In catalyst, Fe content is 0.5～2%.
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