CN103831126A - C4 liquefied gas hydrogenation aromatization catalyst and preparation method thereof - Google Patents
C4 liquefied gas hydrogenation aromatization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a C4 liquefied gas hydrogenation aromatization catalyst and a preparation method thereof. A matrix of the catalyst is zeolite with an MFI structure and the grain size less than 500nm; and zeolite-containing particles are subjected to ammonium salt exchange and steam treatment and then are treated with an inorganic acid solution containing iron ions. The catalyst is good in carbon deposit resistance and high in butane conversion rate in a low-temperature mixed C4 hydrogenation aromatization reaction, and is remarkable in iso-butane conversion capability and easy to prepare.
Description
Technical field
The invention belongs to petrochemical catalyst preparation field, relate to a kind of carbon 4 liquid gas hydroaromatization Catalysts and its preparation method.
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 that US4150062 (1979) discloses 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).
The aromatization of low carbon hydrocarbon catalyst that CN1057476 (1992) discloses is containing zinc ZSM zeolite catalyst, describes a kind of Zn-Ti (SO in embodiment 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) has disclosed 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 that CN1232071 (1999) discloses 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 that CN1321728 (calendar year 2001) discloses 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 at 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 that CN1340601 (2002) discloses, 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%.
A kind of aromatized catalyst that CN 1341699 (2002) discloses is 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.The present invention is the alkene reducing in catalytically cracked 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.
The key of development aromatized catalyst is to improve its anti-carbon deactivation.In CN1586721, invent a kind of method of preparing aromatization of low carbon hydrocarbon catalyst.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.
In prior art, people are in the time of development liquefied gas through aromatization catalyst, major concern be the selective and productive rate of the anti-carbon deactivation of catalyst and 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.
The industrial comprehensive utilization that realizes liquefied gas, will ensure that the alkene in liquefied gas raw material transforms as far as possible completely in aromatization, on the one hand 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.Key is, 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) has 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) has 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 M0
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) has disclosed a kind of method of the synthetic ZSM-5 zeolite containing 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) has 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, 4-propyl bromide template, and product has microballoon pattern.
CN1586721 relates to a kind of Catalysts and its preparation method that is applicable to carbon four liquefied petroleum gas aromatisation in fixed bed reactors.Its technical characterictic is, the parent of catalyst is that grain size is the silica-rich zeolite of 10～500 nanometers, and zeolite parent, with being prepared into hydrogen type catalyst by conventional method after aluminium oxide moulding, then carries out modification to hydrogen type catalyst.The effect of this invention and benefit be the catalyst of preparation during for catalyzed carbon four liquefied petroleum gas aromatisation reaction temperature low, olefin conversion is high, anti-carbon deposition ability is strong.But catalyst prepared by the method is not high to the aromatization activity of iso-butane.
CN101121526A (2006) has disclosed a kind of method of the synthetic Fe-ZSM-5 zeolite containing 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, 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, solid ionic exchange to realize; but the program complexity that these methods have, have need inert gas shielding, what also have needs to use the special material that is unfavorable for environment and equipment.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, the preparation method who is not directed to the iron content ZSM-5 zeolite that passes through aromatization selective conversion butylene and iso-butane under normal butane reports.
Summary of the invention
The invention provides a kind of ZSM-5 type aromatized catalyst and preparation method of iron modification.The aromatized catalyst of preparing with the present invention is 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 the liquefied gas (as 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:
The former powder of the na-pretreated zeolite with MFI structure that grain size is less than to 500 nanometers carries out temperature-programmed calcination and removes organic formwork agent, and sintering temperature scope is 300～600 DEG C, and calcination atmosphere is air atmosphere, and roasting time is 3～24 hours; To take off that organic formwork agent na-pretreated zeolite powder art is mixed with aluminium oxide, be dried and roasting after moulding, roasting condition is 500～600 DEG C, 3～8 hours; By moulding, roasting containing zeolite granular after ammonium salt exchange, at 400～800 DEG C of temperature, use steam treatment 5 minutes～200 hours, at 1 DEG C～80 DEG C, add the inorganic acid solution that contains molysite to process 0.5～200 hour, through washing, dry, roasting, make catalyst again.
Our research work shows, face in appropriateness under the condition of hydrogen, carry out modification and have the zeolite molecular sieve aromatized catalyst (as ZSM-5) of MFI structure with a small amount of ferro element specific process, 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.
In order to utilize the short intrinsic anti-carbon inactivation advantage in small crystal grain molecular sieve duct, the ZSM-5 zeolite that the preferred grain size of the present invention is less than 500 nanometers is catalyst Precursors.ZSM-5, ZSM-11, ZSM-8 belong to MFI structure, have similar catalytic performance.In common Hydrothermal Synthesis, ZSM-5 zeolite and ZSM-11 zeolite inseparable mixed crystal often.Therefore, the present invention is applicable to ZSM-11 or the ZSM-8 zeolite that grain size is less than 500 nanometers completely, or any mixed crystal of ZSM-5, ZSM-11, ZSM-8.
In the present invention, said inorganic acid solution 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 recommended range in acid solution is 0.001 mol/L～5.0 mol/L, preferably 0.1 mol/L～1.0 mol/L.
In the present invention, said soluble ferric iron salt refers to ferrous iron or ferric any soluble salt, as nitrate, sulfate and hydrochloride, and preferably nitrate and hydrochloride.By the load capacity of iron on catalyst, (saturated water absorption in Fe atom and catalyst determines the concentration of iron ion in acid solution.
Ammonium salt give-and-take conditions of the present invention are general conditions of the prior art, as can be the ammonium ion solution of 0.1～1.0 mol/L by concentration, liquid-solid volume ratio exchange according to 1～100 1～15 time, with dry after deionized water washing, roasting, 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 ammonium salt exchange of the present invention is by ammonium nitrate, and the ammonium salts such as ammonium chloride, ammonium acetate or ammonium carbonate provide.
The concrete technical step of the present invention is as follows:
Adopt hydrothermal synthesis method to prepare the ZSM-5 zeolite parent that grain size is less than 500 nanometers, or other have zeolite and the mixed crystal thereof of MFI structure.
Prepare with hydrothermal synthesis method the method that grain size is less than the above-mentioned silica-rich zeolite of 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, DanishPatent PR 173, 486, GB1334243A, Chem.Mater 5 (1993) 452, Zeolites 14 (1994) 557, Zeolites 14 (1994) 643, T.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 less than 500 nanometers, adopt respectively X-ray polycrystal powder art diffraction approach and scanning (transmission) electron microscope method to confirm zeolite structured and zeolite grain size.
In the present invention, the former powder of na-pretreated zeolite carries out temperature-programmed calcination and removes the method for organic formwork agent, recommends following process:
By dry former above-mentioned na-pretreated zeolite dried bean noodles, intensification roasting.Drying condition: 100～120 DEG C of temperature, air atmosphere, 3～12 hours.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.The object of roasting is to remove the organic formwork agent occupying in zeolite cavity.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.
Described temperature-programmed calcination carries out in Muffle furnace, and temperature-rising method is: rise to 300～350 DEG C from 20 DEG C～30 DEG C heating rates with 1～5 DEG C/min, 300 DEG C～350 times constant temperature 1～3 hour; Be warming up to 400～450 DEG C with same heating rate again, constant temperature 1～3 hour at 400～450 DEG C; Be warming up to 490～520 DEG C with same heating rate again, constant temperature 0.5～3 hour at 490～520 DEG C; Be warming up to 550～600 DEG C with same heating rate again, constant temperature 0.5～15 hour at 550～600 DEG C.
In the present invention, will take off that organic formwork agent na-pretreated zeolite powder art is mixed with aluminium oxide, be dried and roasting after moulding, recommend following process:
Take off that organic formwork agent na-pretreated zeolite powder art carries out mixing with aluminium oxide according to a conventional method, moulding, as the na-pretreated zeolite powder art of taking off organic formwork agent is mixed with aluminium oxide, and with inorganic acid as 8～12% rare nitric acid (percentage by weight) and even, then carry out according to a conventional method compressing tablet or extrusion or shoot out or roller forming.The butt weight ratio of na-pretreated zeolite and aluminium oxide is preferably 1: 9～and 9: 1.This ratio is determined according to process conditions, and under general situation, the content of zeolite is too low, the activity of catalyst and poor stability.Otherwise if the too high levels of zeolite, catalyst granules is easily broken.After moulding, be dried and roasting containing zeolite granular granular.Drying condition: 100～120 DEG C of temperature, air atmosphere, 3～12 hours.Roasting can be used general conditions, and optimum condition is: air atmosphere, 500～600 DEG C, 3～8 hours.Heating rate is preferably 2～4 DEG C/min.The object of roasting is herein the mechanical strength that strengthens particle.
Described zeolite moulding can be carried out on a double screw banded extruder, and bar footpath size is elected 1～3 millimeter as.
In the present invention, by moulding, roasting containing the particle of zeolite after ammonium salt exchange, dry, roasting.Process, all available prior aries of condition of ammonium salt exchange, the present invention is not limited, generally at 20 DEG C～30 DEG C, carry out, the ammonium concentration optimum scope of exchange liquid used is 0.1～1.0 mol/L, the liquid-solid volume ratio of exchange liquid and zeolite granular solid is generally 1～100, exchange times is generally 1～5 time, and be generally 0.5～10 hour each swap time.After each exchange, outwell raffinate, add fresh exchange liquid.Ammonium ion in exchange liquid is generally by ammonium nitrate, and the ammonium salts such as ammonium chloride, ammonium acetate or ammonium carbonate provide.After all ammonium exchange work completes, outwell raffinate, wash and contain best 1～5 time of zeolite granular by deionized water.Dry, roasting condition available condition of the prior art as mentioned above.The optimum condition of roasting is: air atmosphere, 500～600 DEG C, 3～8 hours, heating rate was preferably 2～4 DEG C/min.The object of roasting is herein to discharge ammonia, zeolite is obtained acid.
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.While carrying out steam treatment in the present invention, the preference temperature scope of steam treatment is 400～800 DEG C.The preferable range of steam treatment time is 5 minutes～200 hours.In atmosphere, the preferred volume percentage of water vapour is 1%～100%, and Balance Air is preferably air or nitrogen; The preferred pressure range of steam treatment is normal pressure～5.0MPa.
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 optimum range in inorganic acid solution is 0.001 mol/L～5.0 mol/L, preferably 0.1 mol/L～1.0 mol/L.Said molysite is generally soluble ferric iron salt, is often referred to ferrous iron or ferric any soluble salt, as nitrate, hydrochloride, sulfate, and preferably nitrate and hydrochloride.The concentration of iron ion in inorganic acid solution is calculated by the load capacity (in Fe atom) of iron on catalyst and the saturated water absorption of catalyst.
Both can carry out under normal pressure in the inorganic acid solution processing procedure that contains molysite, the consumption of the inorganic acid solution that contains molysite is higher than the saturated water absorption of catalyst, and preferred temperature range is 1 DEG C～80 DEG C.Can in static situation, carry out, also can circulate in situation and carry out at acid solution.Under these conditions, preferably time range is 0.5～200 hour.After this process finishes, by deionized water by catalyst wash to neutral, be then dried, roasting, make finished catalyst.The condition of recommending is to be dried at 100～120 DEG C to carry out, and be 2～5 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 500～600 DEG C from room temperature with the heating rate of 1～3 DEG C/min, then constant temperature 3～5 hours.
The present invention also provides a kind of catalyst for carbon 4 liquid gas hydroaromatization being made by said method, it is characterized in that taking catalyst weight as 100wt%, wherein has the zeolite 8～90% of MFI structure, aluminium oxide 8～90%; Fe 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, 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 invention has the beneficial effects as follows that load iron modification 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.Load iron modification and sour reaming processing are combined, not only simplify the processing technology of catalyst, be conducive to reduce the production cost of catalyst, and the strong acid solution of low pH value can also prevent iron ion in the aqueous solution, be hydrolyzed generate colloidal substance, thereby be conducive to the high-dispersion load of iron species on catalyst.
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
Molysite, inorganic acid, ammonium salt all use analysis pure.
Aluminium oxide: Qi Wangda Science and Technology Ltd. of Dalian University of Technology
Embodiment 1:
The former powder of sodium type ZSM-5 zeolite: with the former powder (SiO of sodium type ZSM-5 zeolite of 20～50 nanometers
2/ Al
2o
3mol ratio 26).
(1) de-organic amine template processing: be dried 3 hours at 110 DEG C, then carry out temperature-programmed calcination in Muffle furnace, 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 of zeolite and aluminium oxide 8: 2, 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 exchange: the ammonium nitrate solution of 0.6 mol/L for ammonium exchange, exchange liquid is 10 with the liquid-solid volume ratio containing zeolite granular, exchanges 4 times, and be 1 hour each swap time, and liquid is changed in centre.Washing through deionized water containing zeolite granular after having exchanged 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) steam treatment: 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) load iron and acid treatment: the catalyst saturated water absorption that carries iron amount and 0.6 ml/g according to 1 % by weight, preparing iron concentration with the pure ferric nitrate of analysis and red fuming nitric acid (RFNA) is 0.3 mM/l, hydrogen proton concentration is the salpeter solution of 0.6 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 5: 1, processes under the condition of normal pressure and 25 DEG C and carries out with static immersion way, and soak time is 24 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, 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 note of preparing through above-mentioned steps is A.
Comparative example 1: do not add soluble ferric iron salt, the other the same as in Example 1 in the 5th step.
The former powder of sodium type ZSM-5 zeolite: with the former powder (SiO of sodium type ZSM-5 zeolite of 20～50 nanometers
2/ Al
2o
3mol ratio 26).
(1) de-organic amine template processing: be dried 3 hours at 110 DEG C, then carry out temperature-programmed calcination in Muffle furnace, 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 of zeolite and aluminium oxide 8: 2, get respectively 80 grams of the na-pretreated zeolites (butt) that burnt organic amine template, 20 grams of boehmites (butt), after hand mix is even, 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 exchange: the ammonium nitrate solution of 0.6 mol/L for ammonium exchange, the liquid-solid volume ratio of exchange liquid and zeolite granular solid is 10, exchanges 4 times, and be 1 hour each swap time, 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) steam treatment: 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, and acid treatment is carried out with static immersion way under the condition of normal pressure and 25 DEG C, and soak time is 24 hours.After acid 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 note of preparing through above-mentioned steps is a1.
Comparative example 2
Select sodium type ZSM-8 zeolite powder: the sodium type ZSM-8 zeolite powder (SiO of 600～800 nanometers
2/ Al
2o
3mol ratio 26).
Repeat catalyst Preparation Example 1, the catalyst note of preparing through above-mentioned steps is a2.
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.
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is ZSM-8, the butt weight ratio that changes step (2) mesolite 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 rise 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%, 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
-2processing time is 5 minutes, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.7 ml/g according to 2 % by weight, preparing iron concentration with analytical pure sulfuric acid iron and the concentrated sulfuric acid is 0.4 mM/l, hydrogen proton concentration is the solution of 0.6 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 4:1, processes under the condition of normal pressure and 25 DEG C and carries out with static immersion way, and soak time is 36 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 120 DEG C and carry out, be 5 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 580 DEG C from room temperature with the heating rate of 4 DEG C/min, then constant temperature 4 hours.The catalyst note of preparing through above-mentioned steps is done note and is B.
Embodiment 3
Select sodium type ZSM-11 zeolite powder: the sodium type ZSM-11 zeolite powder (SiO that not yet removes 10～50 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 30).
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is ZSM-11, the butt weight ratio that changes step (2) mesolite and aluminium oxide is 1: 5, using 8% dilute sulfuric acid instead mediates, the ammonium nitrate solution that changes ammonia exchange 0.8 mol/L in step (3) exchanges 4 times, each exchange 7 hours, liquid-solid volume ratio is 2, then directly rise to 580 DEG C with the heating rate of 3 DEG C/min, constant temperature 5h, the concentration that changes steam in step (4) is 50%, other 50% is air, 800 DEG C of steam treatment temperature, pressure 0.5MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2processing time is 5 minutes, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.7 ml/g according to 4 % by weight, preparing iron concentration with the pure iron chloride of analysis and concentrated hydrochloric acid is 0.4 mM/l, hydrogen proton concentration is the solution of 0.6 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 4: 1, processes under the condition of normal pressure and 25 DEG C and carries out with static immersion way, and soak time is 36 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 120 DEG C and carry out, be 5 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 580 DEG C from room temperature with the heating rate of 4 DEG C/min, then constant temperature 4 hours.The catalyst note of preparing through above-mentioned steps is done note and is C.
Embodiment 4
Select sodium type ZSM-8 to mix with ZSM-11 zeolite powder: the sodium type ZSM-8 and the ZSM-11 zeolite powder (SiO that not yet remove 100～300 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 25) mix with the ratio of 1:3.
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is that ZSM-8 mixes with the ratio of 1: 3 with the zeolite powder of ZSM-11, the butt weight ratio that changes step (2) mesolite and aluminium oxide is 1: 2, using rare nitric acid of 12% instead mediates, the ammonium nitrate solution that changes ammonia exchange 0.1 mol/L in step (3) exchanges 5 times, each exchange 8 hours, liquid-solid volume ratio is 8, then directly rise to 560 DEG C with the heating rate of 3 DEG C/min, constant temperature 8h, the concentration that changes steam in step (4) is 1%, other 99% is air, 800 DEG C of steam treatment temperature, pressure 2MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2processing time is 50 hours, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.4 ml/g according to 5 % by weight, preparing iron concentration with analytical pure sulfuric acid iron and the concentrated sulfuric acid is 1 mM/l, hydrogen proton concentration is the solution of 2 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 100: 1, processes under the condition of normal pressure and 25 DEG C and carries out with static immersion way, and soak time is 36 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 120 DEG C and carry out, be 5 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 580 DEG C from room temperature with the heating rate of 4 DEG C/min, then constant temperature 4 hours.The catalyst note of preparing through above-mentioned steps is done note and is D.
Embodiment 5
Select sodium type ZSM-5 to mix with ZSM-11 zeolite powder: the sodium type ZSM-5 and the ZSM-11 zeolite powder (SiO that not yet remove 100～300 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 25) mix with the ratio of 1: 1.
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is that ZSM-5 mixes with the ratio of 1: 1 with the zeolite powder of ZSM-11, the butt weight ratio that changes step (2) mesolite and aluminium oxide is 1: 9, using 9% acid solution (the mixing quality ratio of sulfuric acid and nitric acid is 1: 4) instead mediates, the ammonium nitrate solution that changes ammonia exchange 0.5 mol/L in step (3) exchanges 4 times, each exchange 4 hours, liquid-solid volume ratio is 2, then directly rise to 500 DEG C with the heating rate of 4 DEG C/min, constant temperature 5h, the concentration that changes steam in step (4) is 30%, other 70% is air, 800 DEG C of steam treatment temperature, pressure 5MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2processing time is 4 hours, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.5 ml/g according to 0.1 % by weight, preparing iron concentration with analytical pure sulfuric acid iron and the concentrated sulfuric acid is 10 mM/ls, hydrogen proton concentration is the solution of 5 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 5:1, processes under the condition of normal pressure and 15 DEG C and carries out with static immersion way, and soak time is 200 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 100 DEG C and carry out, be 5 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 2 DEG C/min, then constant temperature 5 hours.The catalyst note of preparing through above-mentioned steps is done note and is E.
Embodiment 6
Select sodium type ZSM-5, ZSM-8 to mix with ZSM-11 zeolite powder: sodium type ZSM-5, the ZSM-8 and the ZSM-11 zeolite powder (SiO that not yet remove 100～300 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 20) mix with the ratio of 1: 3: 5.
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is ZSM-5, ZSM-8 mixes with the ratio of 1: 3: 5 with the zeolite powder of ZSM-11, the butt weight ratio that changes step (2) mesolite and aluminium oxide is 9: 1, using 8% acid solution (the mixing quality ratio of hydrochloric acid and nitric acid is 1: 4) instead mediates, the ammonium nitrate solution that changes ammonia exchange 0.7 mol/L in step (3) exchanges 5 times, each exchange 0.5 hour, liquid-solid volume ratio is 4, then directly rise to 600 DEG C with the heating rate of 3 DEG C/min, constant temperature 2h, the concentration that changes steam in step (4) is 70%, other 30% is air, 600 DEG C of steam treatment temperature, pressure 2MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2processing time is 30 hours, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.5 ml/g according to 0.05 % by weight, preparing iron concentration with analytical pure sulfuric acid iron and the concentrated sulfuric acid is 1 mM/l, hydrogen proton concentration is the solution of 5 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 3: 1, processes under the condition of normal pressure and 15 DEG C and carries out with static immersion way, and soak time is 100 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 120 DEG C and carry out, be 1 hour drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 570 DEG C from room temperature with the heating rate of 4 DEG C/min, then constant temperature 4 hours.The catalyst note of preparing through above-mentioned steps is done note and is F.
Embodiment 7
Select sodium type ZSM-5, ZSM-8 to mix with ZSM-11 zeolite powder: sodium type ZSM-5, the ZSM-8 and the ZSM-11 zeolite powder (SiO that not yet remove 100～300 nanometers of organic formwork agent
2/ Al
2o
3mol ratio 20) mix with the ratios of 5: 3: 4.
Repeat catalyst Preparation Example 1, but changing na-pretreated zeolite type in step (1) is ZSM-5, ZSM-8 mixes with the ratio of 5: 3: 4 with the zeolite powder of ZSM-11, the butt weight ratio that changes step (2) mesolite and aluminium oxide is 4.5: 3, use 11% acid solution (hydrochloric acid instead, the mixing quality ratio of sulfuric acid and nitric acid is 1: 2: 4) mediate, the ammonium nitrate solution that changes 0.: 1 mol/L of ammonia exchange in step (3) exchanges 5 times, each exchange 8 hours, liquid-solid volume ratio is 7, then directly rise to 600 DEG C with the heating rate of 1 DEG C/min, constant temperature 5h, the concentration that changes steam in step (4) is 40%, other 60% is nitrogen, 400 DEG C of steam treatment temperature, pressure 3MPa, the inlet amount of aqueous vapor is 1000 grams × hour
-1× cm
-2processing time is 100 hours, change step (5) and carry the catalyst saturated water absorption of iron amount and 0.6 ml/g according to 3.5 % by weight, preparing iron concentration with analytical pure sulfuric acid iron and the concentrated sulfuric acid is 8 mM/ls, hydrogen proton concentration is the solution of 4 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 9: 1, processes under the condition of normal pressure and 20 DEG C and carries out with static immersion way, and soak time is 120 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, be dried at 120 DEG C and carry out, be 5 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 590 DEG C from room temperature with the heating rate of 4 DEG C/min, then constant temperature 5 hours.The catalyst note of preparing through above-mentioned steps is done note and is G.
Comparative example 3 changes and in the 4th step, does not carry out steam treatment, the other the same as in Example 1.
The former powder of sodium type ZSM-5 zeolite: with the former powder (SiO of sodium type ZSM-5 zeolite of 20～50 nanometers
2/ Al
2o
3mol ratio 26).
(1) de-organic amine template processing: be dried 3 hours at 110 DEG C, then carry out temperature-programmed calcination in Muffle furnace, 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 of zeolite and aluminium oxide 8: 2, get respectively 80 grams of the na-pretreated zeolites (butt) that burnt organic amine template, 20 grams of boehmites (butt), after hand mix is even, 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 exchange: the ammonium nitrate solution of 0.6 mol/L for ammonium exchange, the liquid-solid volume ratio of exchange liquid and zeolite granular solid is 10, exchanges 4 times, and be 1 hour each swap time, 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) load iron and acid treatment: the catalyst saturated water absorption that carries iron amount and 0.6 ml/g according to 1 % by weight, preparing iron concentration with the pure ferric nitrate of analysis and red fuming nitric acid (RFNA) is 0.3 mM/l, hydrogen proton concentration is the salpeter solution of 0.6 mol/L, and above-mentioned steam treatment catalyst is processed.The liquid-solid mass ratio of solution and catalyst is got 5: 1, processes under the condition of normal pressure and 25 DEG C and carries out with static immersion way, and soak time is 24 hours.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, 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 note of preparing through above-mentioned steps is a3.
The step Kaolinite Preparation of Catalyst that comparative example 4 provides according to embodiment in CN02146191.0 4.Its concrete steps were as follows: (1) moulding: according to the butt weight ratio of zeolite and aluminium oxide 8: 2, get respectively 80 grams of the na-pretreated zeolites (butt) that burnt organic amine template, 20 grams of boehmites (butt), after hand mix is even, 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.(2) load iron: the catalyst of preparation in step (1) is put into the 0.5 mol/L FeCl preparing with 1: 5 ratio of solid-liquid volume ratio
3in solution, flood, each 3 hours, totally 4 times.After immersion finishes, in air, drain catalyst, then by deionized water by catalyst wash to neutral, and then be dried, roasting, make finished catalyst.Wherein, 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.In the catalyst preparing, the Fe content of active component is 1 % by weight.The catalyst note of preparing through above-mentioned steps is a4.
The step Kaolinite Preparation of Catalyst that comparative example 5 provides according to embodiment in CN200810034930.3 6.Its concrete steps are as follows: (1) iron load: by the roasting 12 hours at 400 DEG C of the HZSM-5 molecular sieve of silica alumina ratio 65, then put into 1: 5 ratio of solid-liquid volume ratio the 0.5 mol/L FeCl preparing
3in solution, flood, each 3 hours, totally 4 times.Be dried at 120 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.In the catalyst preparing, the Fe content of active component is 1%.(2) moulding: take 8 grams of good molecular sieves of modification and add 2 grams of γ-Al
2o
3, add rare nitric acid kneading of 5wt% even, extruded moulding, dries 3 hours 550 DEG C of roastings 3 hours for 110 DEG C.The catalyst note of preparing through above-mentioned steps is a5.
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 (A, %), the above liquid of carbon five is received (B, % by weight), normal butane/iso-butane ratio (D) in Aromatic Hydrocarbon in Gasoline content (C, % by weight) and residue liquefied gas
Table 1 embodiment and comparative example measuring result
| Project | A，％ | B, % by weight | C, % by weight | D |
| A | ≥99 | 39.2 | 57.8 | 0.52 |
| a1 | ≥99 | 36.2 | 53.9 | 0.44 |
| a2 | 82.2 | 28.8 | 35.7 | 0.43 |
| B | ≥99 | 37.5 | 55.6 | 0.54 |
| C | ≥99 | 40.0 | 52.7 | 0.58 |
| D | ≥99 | 40.5 | 56.3 | 0.61 |
| E | ≥99 | 38.7 | 58.8 | 0.55 |
| F | ≥99 | 43.3 | 60.4 | 0.57 |
| G | ≥99 | 41.4 | 56.7 | 0.53 |
| a3 | 94.3 | 27.4 | 50.1 | 0.48 |
| a4 | 87.5 | 34.6 | 43.5 | 0.43 |
| a5 | 85.9 | 35.9 | 42.3 | 0.44 |
Claims (12)
1. a preparation method for carbon 4 liquid gas hydroaromatization catalyst, is characterized in that preparation process at least comprises:
The former powder of the na-pretreated zeolite with MFI structure that grain size is less than to 500 nanometers carries out temperature-programmed calcination and removes organic formwork agent, and sintering temperature scope is 300～600 DEG C, and calcination atmosphere is air atmosphere, and roasting time is 3～24 hours; To take off that organic formwork agent na-pretreated zeolite powder art is mixed with aluminium oxide, be dried and roasting after moulding, roasting condition is 500～600 DEG C, 3～8 hours; By moulding, roasting containing zeolite granular after ammonium salt exchange, at 400～800 DEG C of temperature, use steam treatment 5 minutes～200 hours, at 1 DEG C～80 DEG C, add the inorganic acid solution that contains molysite to process 0.5～200 hour, through washing, dry, roasting, make catalyst again.
2. preparation method according to claim 1, the former powder of na-pretreated zeolite that it is characterized in that having MFI structure refers to that sodium type has grain size to be less than ZSM-5 zeolite, ZSM-8 zeolite or ZSM-11 zeolite and or any mixture of above zeolite thereof of 500 nanometers.
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. according to the preparation method described in claim 1 or 3, it is characterized in that the hydrogen proton concentration scope in inorganic acid solution is 0.001 mol/L～5.0 mol/L, be preferably 0.1 mol/L～1.0 mol/L.
5. preparation method according to claim 1, the process and the condition that it is characterized in that ammonium salt exchange are: be the ammonium ion solution of 0.1～1.0 mol/L by concentration, with be 1～100 containing the liquid-solid volume ratio of zeolite granular, according to 1～100 liquid-solid volume ratio exchange, with dry after deionized water washing, roasting, sintering temperature is 500～600 DEG C, the time is 3～8 hours.
6. preparation method according to claim 5, is characterized in that ammonium salt exchange process is: at 20 DEG C～30 DEG C, exchange with containing zeolite granular with ammonium ion solution, 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.
7. according to the preparation method described in claim 5 or 6, it is characterized in that ammonium ion in ammonium ion solution is by ammonium nitrate, ammonium chloride, ammonium acetate or ammonium carbonate provide.
8. preparation method according to claim 1, is characterized in that molysite is soluble ferric iron salt, is preferably divalence or ferric nitrate, sulfate or hydrochloride, preferably nitrate and hydrochloride.
9. 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.
10. preparation method according to claim 1, it is characterized in that the temperature-rising method that temperature-programmed calcination removes organic formwork agent is: be warming up to 300～350 DEG C from 20 DEG C～30 DEG C heating rates with 1～5 DEG C/min, 300 DEG C～350 times constant temperature 1～3 hour; Be warming up to 400～450 DEG C with same heating rate again, constant temperature 1～3 hour at 400～450 DEG C; Be warming up to 490～520 DEG C with same heating rate again, constant temperature 0.5～3 hour at 490～520 DEG C; Be warming up to 550～600 DEG C with same heating rate again, constant temperature 0.5～14 hour at 550～600 DEG C.
11. preparation methods according to claim 1, it is characterized in that adding at 1 DEG C～80 DEG C the inorganic acid solution that contains molysite to process after 0.5～200 hour, by deionized water by catalyst detergent to neutral, be then dried, roasting, make finished catalyst; Be dried at 100～120 DEG C and carry out, the time is 2～5 hours; Roasting condition is 500～600 DEG C, 3～5 hours.
12. 1 kinds of catalyst that obtain by the arbitrary described preparation method of claim 1～11, is characterized in that taking catalyst weight as 100% wherein having the zeolite 8～90% of MFI structure, aluminium oxide 8～90%; Fe0.5～2%.
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| CN105772070A (en) * | 2016-02-23 | 2016-07-20 | 新疆恒晟能源科技有限公司 | Catalyst for non-hydrogenation upgrading of gasoline and preparation method of catalyst |
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| CN1353087A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing ZSM-5 molecular sieve |
| CN1557707A (en) * | 2004-01-19 | 2004-12-29 | 复旦大学 | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material |
| CN1586721A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | Catalyst for C4 liquefied petroleum gas aromatization and its preparing method |
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| CN1353087A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing ZSM-5 molecular sieve |
| CN1557707A (en) * | 2004-01-19 | 2004-12-29 | 复旦大学 | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material |
| CN1586721A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | Catalyst for C4 liquefied petroleum gas aromatization and its preparing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105772070A (en) * | 2016-02-23 | 2016-07-20 | 新疆恒晟能源科技有限公司 | Catalyst for non-hydrogenation upgrading of gasoline and preparation method of catalyst |
| CN105772070B (en) * | 2016-02-23 | 2019-07-16 | 新疆恒晟能源科技股份有限公司 | A kind of catalyst and preparation method thereof for the modification of gasoline non-hydrogen |
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