CN103028433A

CN103028433A - ZSM-5 catalyst having micro-pore and meso pore, preparing method thereof and method of using the catalyst to conduct catalytic cracking on hydrocarbon to produce light olefins

Info

Publication number: CN103028433A
Application number: CN2012103071673A
Authority: CN
Inventors: 尹敏慧; 金美真; 朴世镐; 宋辅根; 宋仁奎; 李中源
Original assignee: Honam Petrochemical Corp
Current assignee: Honam Petrochemical Corp
Priority date: 2011-09-29
Filing date: 2012-08-24
Publication date: 2013-04-10
Anticipated expiration: 2032-08-24
Also published as: CN103028433B

Abstract

The invention provides a ZSM-5 catalyst having a micro-pore and a meso-pore, a preparing method thereof and a method of using the catalyst to conduct catalytic cracking on hydrocarbon to produce light olefins. Specifically speaking, the method of preparing ZSM-5 catalyst of light olefin including ethylene and propylene by means of C4-C7 hydrocarbonmixture comprises the steps of (a) forming gel by aging mixture solutions including pro-silica and pro-aluminum; (b) adding a template which can possibly form a meso-pore throuh heating into the gel, and stirring and aging the mixture; (c) forming solid products through aged mixture through the step (b); (d) conducting heating on the solid products to remove the template. The ZSM-5 catalyst comprises the micro-pore and the meso-pore, and can have good physica and chemical performance along with good pore performance, and thereby the yield rate of light olefins can be increased.

Description

Have micropore and mesoporous ZSM-5 catalyst, its preparation method and use this catalyst cracking hydrocarbons to produce the method for light olefin

Quoting of related application

The application requires to be filed in the Korean Patent Application No. 10-2011-0098694 of Korea S Department of Intellectual Property and to be filed in the rights and interests of the Korean Patent Application No. 10-2011-0125643 of Korea S Department of Intellectual Property on November 29th, 2011 on September 29th, 2011, and their disclosure by reference integral body is combined in this.

Technical field

The present invention relates to have micropore and mesoporous (mesopore, mesopore) ZSM-5 catalyst, its preparation method and the method by producing light olefin with this catalyst cracking hydrocarbons, and more specifically, relate to by the hydrocarbon mixture that improves 4 to 7 carbon of generation being included in the naphtha cracking by catalytic cracking after and prepare the method that the physical property of the ZSM-5 catalyst of using in the method for the light olefin that comprises ethene and propylene is produced light olefin.

Background technology

Ethene and propylene are the primary raw materials of petroleum chemicals, and for the preparation of polyethylene, polypropylene, acrylonitrile, polyvinyl chloride etc.So far, most of light olefins (such as ethene, propylene etc.) are to prepare by the naphtha of pyrolysis as raw material under at least about 800 ℃ high temperature.Yet about 40% the total energy that consumes in petro chemical industry can be consumed by the conduction of being produced light olefin by the naphtha pyrolysis, and therefore the energy resource consumption by producing light olefin than being very high.In addition, thus having produced a large amount of carbon dioxide has caused environmental pollution.

Therefore, because pyrolysis under at least about 800 ℃ high temperature, the cracking method that uses catalyst has attracted a lot of concerns as a kind of method of energy savings.When comparing with the pyrolytic process of routine, use the catalyst cracking method of catalyst under about 50-200 ℃ lower temperature range, to carry out.Therefore, low-energy consumption can fall, thus and the cycle of operation and the life-span that can suppress the generation extension fixture of coke on the pipeline inner wall.In addition, can reduce the generation of carbon dioxide, and environmental pollution can be down to minimum.Because can control according to demand the component of the alkene that obtains like this, can solve about the unbalanced problem of the Supply and Demand of ethene and propylene.

Typical catalyst system for producing light olefin by catalytic cracking can be divided three classes: acid catalyst, base catalyst and catalyst of transition metal oxide.After having analyzed every kind of catalyst based on the representative instance of every kind of antigravity system, use the cracking process of acid catalyst to be considered to most economical process.Recently, carry out energetically in the research aspect the catalytic cracking process that uses such acid catalyst, and especially, zeolite is widely used as catalyst most.By changing chemical constituent, zeolite is easy to control its acidity, and has shape selective, and therefore has some advantages for the conversion ratio of control reactant and the productive rate of light olefin.The typical zeolite that can be applied to catalytic cracking comprises ZSM-5, USY, REY, beta-zeolite etc.

Different from conventional zeolite, for example have 8 yuan of annular apertures Wessalith CS and erionite, in the hole, have approximately

The faujasite of the supercage of 12 yuan of rings, X zeolite and Y and the modenite with two-dimentional pore structure, because

The size straight channel and The pore structure of the three dimensional intersection in the sinusoidal duct of size, the ZSM-5 catalyst has the medium sized hole of 10 yuan of rings and aperture and the structure of homogeneous.Therefore, when comparing with other zeolite facies, the ZSM-5 catalyst has better shape selective and lower level of deactivation, and has the good heat endurance according to high Si/Al ratio.Therefore, the ZSM-5 catalyst is used for the conversion reaction of methyl alcohol, the alkylated reaction of toluene, the isomerization reaction of dimethylbenzene etc., and typically is used as by catalyst (H.Krannila etc., the J.Catal.vol.135 of catalytic cracking naphtha for the preparation of light olefin, p115,1992).In addition, by using ZSM-5 catalyst cracking n-hexane to be used for producing ethene and propylene, confirmed that reaction rate and response path are subjected to the acidity of catalyst activity position to affect (R.L.V.Mao, Micropor and Mesopor, Mater.vol.28 to a great extent, p9,1999).Especially, can determine according to the character of catalyst and performance the selective and productive rate of final reacting product, and be very important for the strategy of the suitable catalyst of the target product exploitation of hope therefore.As mentioned above, because specific structure and good Acidity, the ZSM-5 catalyst can be used for various reactions, comprises catalytic cracking reaction, isomerization reaction, esterification etc.Yet, when under the condition of high temperature and high humility, reacting, because the dealuminization structure may divide and acidic site may reduce, cause lower catalytic activity.In order to improve the unstable state of catalyst under the reaction condition of high temperature and high humility, the method for having attempted adding various materials.Typically, manganese and phosphorus are joined the heat endurance (people such as T.Blasco, J.Catal.vol.237, p267,2006) that is used for improving catalyst in the zeolite.According to list of references, when by come modified zeolite for example during ZSM-5 with phosphate ion, can pass through phosphate ion (PO ₄ ^3-) come modification conduct in zeolite The Si-OH-Al part that works in the acid position.Then, the P=O group can be stablized unsettled aluminium, and therefore dealuminization can be down to minimum.Even use phosphorus that zeolite is carried out the hydrothermal stability that simple modification can improve catalyst, and can help to suppress for a long time catalysqt deactivation, the increase of light-olefin production amount may be unsuitable.

An important thing is the product distribution that obtains after control is reacted and the heat endurance of making great efforts the raising catalyst.In order to make the output maximization of light olefin, need to suppress the generation of paraffin and aromatic compound, and need to make the output maximization of alkene.People such as (, Appl.Catal A.vol.223, p85,2002) the M.A.den Hollander that needs in the improvement that reduces reaction pressure, improves reaction temperature, reduces the reactant retention time and suitably control the aspects such as ratio of reactant and catalyst.In addition, also need to make great efforts to improve by the development of new catalyst output of light olefin.As the part that this effort is attempted, implemented by transition metal or rare earth metal being joined the method for coming Kaolinite Preparation of Catalyst in ZSM-5 catalyst people such as (, Appl.Catal.A.vol.398, p1,2011) N.Rahimi.According to this list of references, when transition metal (for example iron or chromium) when joining among the ZSM-5, can easily be carried out decomposition reaction by the dehydrogenation of reactant (being hydro carbons), and therefore can produce even more substantial light olefin.When rare earth metal (such as neodymium, cerium, lanthanum etc.) when joining among the ZSM-5, can be increased the selective of light olefin.Yet, on the selective impact that improves of light olefin, various viewpoints have appearred about rare earth metal.When using metal (for example transition metal and rare earth metal), can be positioned at the porch of zeolite pore and can stop up this hole having large-sized metallic atom.In this case, reactivity can reduce.Therefore, the metal-modified existence restriction that has the pure ZSM-5 of micropore character.In order to overcome this restriction, the ZSM-5 that needs preparation to have micropore and mesoporous character.

U.S. Patent number 6,033,555 disclose the method that obtains light olefin from hydrocarbon feed, are included in the first step and produce light olefin by catalytic cracking, produce ethene thereby then at second step continuous gas is carried out pyrolysis.Can improve the productive rate of light olefin according to this method, yet, may stay the economic problems about the cost of setting up an operation multistep process etc.

International Patent Publication No. WO 00/31215 discloses to use and has comprised that ZSM-5 and/or ZSM-11(are as active component) and the catalyst of a considerable amount of inert material (as matrix) for the production of the catalytic cracking process of light olefin.Yet the productive rate of propylene is too low and less than about 20wt%.

Korean patent registration No. 0979580 relates under the stringent condition of high temperature and high humility, by the molded catalyst of naphtha cracking for the preparation of light olefin, and discloses hydrocarbon cracking catalyst for the preparation of light olefin and preparation method thereof.By the MnO of spray-drying by will about 0.01-5.0wt% ₂And the P of about 1-15wt% ₂O ₅Be impregnated into simultaneously in zeolite, clay and the inorganic oxide and then the mixture slurry that obtains is fired, obtain catalyst.Because in this catalyst, come modified zeolite and inorganic oxide with manganese and phosphorus simultaneously, can improve the hydrothermal stability of the spherical mold controlling catalyst that obtains like this, thereby and acidic site that can the passivation zeolite obtain light olefin by catalytic cracking C4 or above hydro carbons (such as naphtha) by higher productive rate.Yet, owing to used the raw material that comprises various hydro carbons, the product wider distribution, and relative reduce selective to ethene and propylene.

U.S. Patent number 5,171,921 disclose the phosphorus that comprises about 1-3wt%, the ZSM-5 catalyst that comprises about 10-25wt% that its Si/Al ratio is about 20-60 and the preparation that comprises the molded catalyst of adhesive (such as kaolin, bentonite etc.), and disclose under about 550-600 ℃ reaction temperature, from the paraffin of C3-C20 and olefin(e) compound, optionally prepared the method for C2-C5 alkene.Yet the ZSM-5 catalyst has the feature of the little micropore that comprises that about 1nm is following.When the reactant with large-size participated in reaction, owing to the hole characteristic molecular diffusion may be restricted, and this may be the primary factor of limiting catalyst reactivity.Therefore, when using above-mentioned catalyst to carry out the catalytic cracking of C3-C20 hydrocarbon mixture, think that then the reactivity of this catalyst is bad.Even when improving the hydrothermal stability of catalyst by interpolation phosphorus, in case in the porch of micropore Formed deposition, then may greatly reduce the activity of catalyst.

U.S. Patent number 6,656,345 disclose the method for preparing light olefin from the hydro carbons that comprises about 10-70wt% alkene and about 5-35wt% paraffin.The aperture of the catalyst that uses in this method is approximately And this catalyst is to have about 200 or the zeolite (MFI, MEL, MTW, TON, MTT, FER, MFS etc.) of larger Si/Al ratio.Because the aperture is very little in this case, the diffusion of reactant may be unsmooth.Owing to do not consider hydrothermal stability, the inactivation of catalyst can be described.

U.S. Patent number 7,304,194 disclose by using the catalyst of introducing phosphorus in the ZSM-5 catalyst to carry out the method for alkylated reaction.In order to improve hydrothermal stability, introduce phosphorus and carry out steam treatment.Yet, unexposed by adding the resulting effect of phosphorus.

U.S. Patent number 6,835,863 disclose the process of using the molded catalyst that comprises about 5-75wt%ZSM-5 and ZSM-11 catalyst, about 25-29wt% silica (silica) or kaolin and about 0.5-10wt% phosphorus in the naphtha cracking process.Yet, the concrete parent material of unexposed phosphorus and the hydrothermal stability of molded catalyst in this patent, and do not use the catalyst with meso pore characteristics.

U.S. Patent Publication No. 20060011513 discloses with a kind of technology of coming modified zeolite (comprising ZSM-5, β, mordenite, ferrierite etc.) among lanthanide series, Sc, Y, La, Fe and the Ca.Yet the particular chemical of unexposed metal phosphate is incomplete for the explanation of its function, and unexposed technology for improving olefins yield.

U.S. Patent number 7,531,706 disclose with having rare earth metal, manganese or zirconium prepare light olefin together with the modified catalyst of the pentasil type zeolite of phosphorus method.The metal of modification it is reported and improved the hydrothermal stability of catalyst and the productive rate of light olefin.Yet, not enough for the explanation of metal concrete function, and a purpose is only pointed to the durability that improves zeolite.

The people such as non-patent literature 1(X.Gao, Solid State Sci.Vol.12, p1278,2010) disclose by preparation and shown that the ZSM-5 catalyst of meso pore characteristics prepares the method for light olefin from butylene.Yet therefore, desilication method for the preparation of mesoporous ZSM-5 catalyst, and is greatly reduced acidic character and ZSM-5 structural stability, and thinks that there is restriction in this catalyst in application.

The people such as non-patent literature 2(Z.Song, Appl.Catal.A, Vol.384, p201,2010) disclose by use and comprised that the ZSM-5 catalyst of phosphorus prepares the method for propylene from ethanol.Come the acidic site of modified catalyst to be used for improving the selective of propylene by introducing phosphorus.Yet, fully openly highly acid position and faintly acid position separate and to the explanation of every kind of acidic site function.In addition, in the situation without steam treatment, greatly reduce the productive rate of alkene, and therefore need other processing.

The people such as non-patent literature 3(T.F.Degnan, Micropor.and Mesopor.Mater.Vol.35-36, p245,2000) disclose by improving the technology of hydrothermal stability in the catalytic cracking reaction that phosphorus is joined the ZSM-5 catalyst.The function of phosphorus is described as be in and prevents dealuminzation from the framework of ZSM-5 catalyst under the high reaction temperature.Yet, unexposed impact on acidity of catalyst.

The people such as non-patent literature 4(G.Zhao, J.Catal, vol.248, p29,2007) be for improving hydrothermal stability among the HZSM-5 by phosphorus is incorporated into.In fact, improved hydrothermal stability by introducing phosphorus.Yet the phosphorus of introducing has stopped up the entrance of micropore, and greatly reduces its surface area and pore volume.As can be known from the results, there is restriction in phosphorus aspect the raising light-olefin production amount.

The people such as non-patent literature 5(J.Lu, Catal.Commun.vol.7, p199,2006) be for the research that the catalytic cracking reaction by iso-butane is prepared the light olefin method.Based on ZSM-5 zeolite, and be produced and be used for reaction with the catalyst of iron modification.The iron modification of catalyst it is reported and the acidity that has improved catalyst causes the increase of light-olefin production amount.Yet along with the increase of iron amount, activity reduces rapidly.This is because the reunion of the iron atom that causes because of the micropore character of ZSM-5.In addition, do not show any explanation to the catalyst hydrothermal stability.

The people such as non-patent literature 6(W.Xiaoning, J.Rare Earths, vol.25, p321,2007) be from the standby light olefin of butane for the ZSM-5 catalyst that comprises rare earth metal for use, for the impact of rare earth metal on acidity of catalyst, and for the change of the acidity of catalyst research on the reactivity impact.Yet, do not consider rare earth metal to the impact of alkaline matter, and the acid-alkaline of unexposed catalyst is on the impact of cracking reaction mechanism.

Because the ZSM-5 catalyst has the following little micropore of about 1nm, when large-sized reactant participated in reaction, molecular diffusion may be restricted, and this restriction may become a primary factor that limits this catalytic reaction activity.Therefore, make great efforts to prepare mesoporous zeolite and be used for slowing down the catalysqt deactivation that causes owing to the molecular diffusion effect.Start from the MCM-41/FAU composite manufacture (people such as K.R.Kloetstra for the research of making mesoporous zeolite, Micropor.Mater.vol.6, p287,1996), and comprise with epoxy resin and prepare the mesoporous ZSM-5 catalyst (people such as M.Fujiwara, Micropor.and Mesopor.Mater.vol.142, p381,2011).International Patent Publication No. WO 97/04871 discloses with acid solution processes zeolite catalyst, and then will this acid-treated zeolite catalyst be used for the method for cracking reaction.According to disclosed method, because removed impurity and enlarged the hole, improved the selective of butylene.Yet, so far, there is no the report of method that preparation has the ZSM-5 catalyst of the selective and simple manufacture method of gratifying light olefin.

Recently, because oil price rise and the trend of using heavy crude, set up in addition and be used for from obtain the natural gas cracking unit of ethene than the relative more cheap natural gas of naphtha.In this case, the natural gas cracking unit can optionally be produced ethene, and may cause that the Supply and Demand of propylene is uneven.Different from the western countries that have a large amount of natural gases, most of crude oil import countries (comprising Korea S) rely on the naphtha pyrolysis and are being disadvantageous aspect the minimizing greenhouse gas emission.In Korea S, the ethene of being produced by the naphtha cracking process can be up to about 5,000,000 ton/year, and can be up to 700,000 ton/years as the C 5 fraction of byproduct emission.Yet this accessory substance is not effectively utilized.Therefore, highly need exploitation to be used for the technology of control ethylene/propene demand and supply, need the technology of light olefin restructuring procedure, and highly need to use C 5 fraction to carry out light olefin reconstruct as raw material.

Summary of the invention

The invention provides the hydrocarbon mixture with carbon number 4-7 that after the naphtha cracking, obtains by catalytic cracking, preparation method for the preparation of the ZSM-5 catalyst of the light olefin that comprises ethene and propylene, wherein this ZSM-5 catalyst has the physics and chemistry character of conventional catalyst, thereby and shows even productive rate that better porous has improved light olefin.

The present invention also provides the preparation method of the ZSM-5 catalyst with the maximized optimum condition of productive rate that makes ethene and propylene, by the catalyst of the method preparation, and uses this catalyst preparation to comprise the method for the light olefin of ethene and propylene.

According to an aspect of the present invention, provide preparation to have the method for micropore and mesoporous ZSM-5 catalyst.This catalyst prepares the light olefin that comprises ethene and propylene for the hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking.This hydrocarbon mixture produces after the naphtha cracking process.Described method comprises that (a) comprises that by aging the mixture solution of silica (silica) precursor and aluminum precursor forms gel; (b) will may form mesoporous template by heat treatment and join in the described gel, stirring and then aging; (c) by crystalline mixture aging in the step (b) is formed solid product; Thereby and (d) described solid product is heat-treated remove template.

In the exemplary embodiment, can come the mixture solution in the preparation process (a) by comprising following every method: (a-1) monovalent metal hydroxide and tetrapropyl ammonium halide are dissolved in the distilled water; (a-2) thus adding silica precursor forms uniform mixture; And (a-3) aluminum precursor of liquid phase is added drop-wise in the described uniform mixture.

In the exemplary embodiment, described silica precursor can be cataloid (Ludox), and described aluminum precursor can be to be selected from by sodium aluminate (NaAlO ₂), aluminum nitrate (Al (NO ₃) ₃), the group that forms of aluminium secondary butylate, tert-butyl alcohol aluminium, three aluminium secondary butylates, three tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide at least a.

In the exemplary embodiment, described template can be carbon dust or nanometer polymerization composition granule.

In the exemplary embodiment, carbon dust or nanometer polymerization composition granule can have the sphere with about 2-50nm diameter, square, rectangle and cylindrical at least a shape.

In the exemplary embodiment, described nanometer polymer can be selected from the group that is comprised of Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(expoxy propane), polyactide and polymethyl methacrylate at least a.

In the exemplary embodiment, based on 100 parts of silica precursors by weight, the amount of template can be by weight about 5-80 part.

In the exemplary embodiment, the Si/Al atomic ratio that has micropore and a mesoporous ZSM-5 catalyst can be about 5-300.

In the exemplary embodiment, the heat treatment in the step (d) can be carried out under about 300-750 ℃ temperature, continues about 3-10 hour.

In the exemplary embodiment, described method may further include at completing steps (d) afterwards, (d-1) cation of the described heat treated solid product of displacement; And (d-2) solid product of described cation replacement is heat-treated.

In the exemplary embodiment, can comprise by use and being selected from by ammonium nitrate (NH ₄NO ₃), ammonium chloride (NH ₄Cl), ammonium carbonate ((NH ₄) ₂CO ₃) and ammonium fluoride (NH ₄At least a solution of the group that F) forms carries out cationic displacement.

In the exemplary embodiment, the heat treatment in the step (d-2) can be carried out under about 400-700 ℃ temperature, continues about 3-10 hour.

According to a second aspect of the present invention, described method may further include (e) and by dipping method or ion-exchange process the phosphorus precursor is incorporated in the described heat treated solid product.

In the exemplary embodiment, the dipping method of phosphorus precursor can comprise (e-1) thus water obtains hydration solution with described phosphorus precursor hydration; (e-2) with step (d) thus in heat treated solid product join in this hydration solution with this hydration solution dipping; And the solid product that (e-3) will flood is dry and heat-treat.

In the exemplary embodiment, described phosphorus precursor can be to be selected from by phosphoric acid (H ₃PO ₄), mono phosphoric acid ester ammonium ((NH ₄) H ₂PO ₄), Diammonium phosphate (DAP) ((NH ₄) ₂HPO ₄) and ammonium phosphate ((NH ₄) ₃PO ₄) group that forms at least a.

In the exemplary embodiment, based on by weight 100 parts have micropore and mesoporous ZSM-5 catalyst, the amount of phosphorus precursor can be by weight about 0.01-10 part.

In the exemplary embodiment, based on by weight 100 parts have micropore and mesoporous ZSM-5 catalyst, the amount of phosphorus precursor can be by weight about 0.1-1.5 part.

In the exemplary embodiment, the heat treatment in the step (e-3) can be carried out under about 500-750 ℃ temperature, continues about 1-10 hour.

According to a third aspect of the present invention, described method may further include, and (f) by dipping method or ion-exchange process, rare earth metal precursor or alkali metal precursor is incorporated in the heat treated solid product that comprises described phosphorus precursor.

In the exemplary embodiment, the dipping method of step (f) middle rare earth metal precursor or alkali metal precursor can comprise: (f-1) in water with described rare earth metal precursor or alkali metal precursor hydration; (f-2) will comprise that the solid product of phosphorus in the step (e) joins in the solution of the rare earth metal precursor that comprises described hydration or alkali metal precursor in order to use this solution impregnation; And the solid product that (f-3) will flood is dry and heat-treat.

In the exemplary embodiment, described rare earth metal can be selected from the group that is comprised of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu) at least a.

In the exemplary embodiment, alkali metal can be selected from the group that is comprised of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs) at least a.

In the exemplary embodiment, based on the atomic ratio with respect to phosphorus, rare earth metal or alkali-metal amount can be about below 2.

In the exemplary embodiment, the heat treatment in the step (f-3) can be carried out under about 500-750 ℃ temperature, continues about 1-10 hour.

In the exemplary embodiment, described hydrocarbon mixture can comprise C 5 fraction.

According to another aspect of the present invention, provide and had micropore and mesoporous ZSM-5 catalyst.This catalyst prepares the light olefin that comprises ethene and propylene for the hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking.Described hydrocarbon mixture produces after the naphtha cracking process, and by coming Kaolinite Preparation of Catalyst with carbon dust or nanometer polymerization composition granule as template.

In the exemplary embodiment, can come Kaolinite Preparation of Catalyst by comprising step (a) to the method for (d), and this catalyst can have about 360-410m ²The specific area of/g, about 0.1-0.2cm ³Volume, about 0.05-0.3cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with about 2nm or larger diameter of/g and according to the about 130-145 μ of the temperature programmed desorption of ammonia mol-NH ₃The acidity of/g-catalyst.

In the exemplary embodiment, based on by weight 100 parts have micropore and mesoporous ZMS-5 catalyst, described catalyst may further include by weight about 0.01-10 part phosphorus precursor.

In the exemplary embodiment, can come Kaolinite Preparation of Catalyst by comprising step (a) to the method for (e), and this catalyst can have about 340-400m ²The specific area of/g, about 0.05-0.2cm ³Volume, about 0.05-0.2cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with about 2nm or larger diameter of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 80-95 μ mol-NH ₃The acidity of/g-catalyst and at highly acid position about 15-50 μ mol-NH ₃The acidity of/g-catalyst and the carbon deposition of analyzing about 2-7wt% according to the CHNS after catalyst reaction 40 hours.

In the exemplary embodiment, based on the atomic ratio with respect to phosphorus, described catalyst may further include rare earth metal or the alkali metal of about amount below 2.

In the exemplary embodiment, based on the atomic ratio with respect to phosphorus, described catalyst may further include rare earth metal or the alkali metal of the amount of about 0.1-1.5.

In the exemplary embodiment, can come Kaolinite Preparation of Catalyst by comprising step (a) to the method for (f), and described catalyst can have about 300-400m ²The specific area of/g, about 0.05-0.2cm ³Volume, about 0.05-0.15cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with about 2nm or larger diameter of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 70-90 μ mol-NH ₃The acidity of/g-catalyst, at highly acid position about 20-45 μ mol-NH ₃The acidity of/g-catalyst and about 2-30 μ mol-CO ₂The basicity of/g-catalyst.

According to again another aspect of the present invention, provide the hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking to prepare the method for the light olefin that comprises ethene and propylene.Described hydrocarbon mixture produces after the naphtha cracking process, and described hydrocarbon mixture is at about 1-20h ^-1Weight hourly space velocity (WHSV) under, under about 300-700 ℃ temperature range, react having under micropore and the mesoporous ZMS-5 catalyst.

Description of drawings

By explaining with reference to the accompanying drawings its illustrative embodiments, above-mentioned and other feature and advantage of the present invention will become clearer, wherein:

Fig. 1 is the flow chart for preparing micropore and mesoporous ZSM-5 catalyst method for first embodiment of explanation design according to the present invention;

Fig. 2 conceives preparation at the flow chart of the process of the mixture solution of preparation method's step (a) of micropore and mesoporous ZSM-5 catalyst for explanation according to the present invention;

Fig. 3 conceives in the method for preparing micropore and mesoporous ZSM-5 catalyst according to the present invention for explanation, uses the flow chart of the process of the heat treated solid product of cation replacement;

Fig. 4 is the flow chart for preparing the method for micropore and mesoporous ZSM-5 catalyst for second embodiment of explanation design according to the present invention;

Fig. 5 conceives the flow chart that floods the process of phosphorus precursor in the method for preparing micropore and mesoporous ZSM-5 catalyst for explanation according to the present invention;

Fig. 6 is the flow chart for preparing the method for micropore and mesoporous ZSM-5 catalyst for the 3rd embodiment of explanation design according to the present invention;

Fig. 7 conceives the flow chart that floods the process of rare earth metal precursor or alkali metal precursor in the method for preparing micropore and mesoporous ZSM-5 catalyst for explanation according to the present invention;

Fig. 8 is a curve map, and the x-ray analysis result according to embodiment 1 to 5 and comparing embodiment ZSM-5 catalyst has been described;

Fig. 9 is a curve map, and the x-ray analysis result according to embodiment 3 and 6 to 9, ZSM-5 catalyst has been described;

Figure 10 is a curve map, and the x-ray analysis result according to

embodiment

7 and 11 to 14, ZSM-5 catalyst has been described;

Figure 11 is a curve map, and the x-ray analysis result according to embodiment 15 to 17, ZSM-5 catalyst has been described;

Figure 12 A and 12B are curve maps, have illustrated according to the nitrogen adsorption and desorption curve map (12A) of embodiment 1 to 5 and comparing embodiment ZSM-5 catalyst and the result of graph of pore diameter distribution (12B);

Figure 13 A to 13F is according to embodiment 3,5 and the photo figure of the ZSM-5 catalyst crystal structure that obtains by high-resolution transmission electron microscope of comparing embodiment;

Figure 14 is a curve map, and the experimental result according to the nitrogen adsorption and desorption of

embodiment

7 and 11 to 14, ZSM-5 catalyst has been described;

Figure 15 is a curve map, has illustrated according to embodiment 1 to 5 and comparing embodiment, the experimental result of the temperature programmed desorption of ammonia of ZSM-5 catalyst;

Figure 16 is a curve map, and the experimental result according to the temperature programmed desorption of ammonia of embodiment 1 and 6 to 10, ZSM-5 catalyst has been described;

Figure 17 is a curve map, and the experimental result according to the temperature programmed desorption of ammonia of

embodiment

7 and 11 to 14, ZSM-5 catalyst has been described;

Figure 18 is a curve map, and the experimental result according to the temperature programmed desorption of ammonia of embodiment 15 to 17, ZSM-5 catalyst has been described;

Figure 19 is a curve map, and the experimental result according to the temperature programmed desorption of ammonia of

embodiment

7 and 11 to 14, ZSM-5 catalyst has been described;

Figure 20 is a curve map, has illustrated according to the hydrogen transfer activity of the measurement of

embodiment

7 and 11 to 14, ZSM-5 catalyst and the relation of alkalescence;

Figure 21 is a curve map, has illustrated according to embodiment 1 to 5 and comparing embodiment to pass through to use the conversion ratio of ZSM-5 catalyst C 5 fraction and the productive rate of light olefin (ethene+propylene);

Figure 22 A and 22B are curve maps, illustrated according to embodiment 3 and 6 to 10, and comparing embodiment, according to the time of ZSM-5 catalyst, the process of the selective and productive rate variation of the conversion ratio of C 5 fraction, light olefin;

Figure 23 A and 23B are curve maps, have illustrated according to embodiment 3 and 6 to 10, according to the acidity of the highly acid position of ZSM-5 catalyst, the conversion ratio of C 5 fraction and the productive rate of light olefin;

Figure 24 A to 24F is according to embodiment 3,7 and 9, the photo figure of the crystal structure of the ZSM-5 catalyst that obtains by use high-resolution transmission electron microscope after reacting lasting 40 hours;

Figure 25 A and 25B are curve maps, have illustrated according to the impact on reactivity of the Acidity of Aikalinity of

embodiment

7 and 11 to 14, ZSM-5 catalyst; And

Figure 26 is a curve map, and the relation between lanthanum on the ZSM-5 catalyst/phosphorus atoms ratio and light olefin productive rate has been described according to

embodiment

7 and 11 to 14.

The specific embodiment

With reference now to accompanying drawing, the present invention will be described more fully, wherein show embodiment of giving an example of the present invention.Term only is the target for the embodiment that concrete example is described as used herein, is not intended to limit the present invention.Unless otherwise defined, otherwise as used herein all terms (comprising technology and scientific terminology) have with the present invention under in the field those of ordinary skill the identical meanings usually understood.Should further be understood that these terms, those that for example in dictionary commonly used, define, should be interpreted as having the implication consistent with their implication in the context of this specification and association area, and should not make an explanation with Utopian or too formal implication, unless in this clearly like this definition.With various embodiments of giving an example are described more fully, wherein shown the embodiment that some are given an example.Yet the present invention can embody with multiple different form, and should not be construed as the embodiment of giving an example that is limited in this proposition.More properly, provide these embodiments of giving an example so that specification of the present invention becomes thorough and complete, and can fully scope of the present invention have been conveyed to those skilled in the art.

In this manual, " micropore " expression has the character in the following aperture of about 1nm (diameter), consider to have the common ZSM-5 catalyst of the following micropore of about 1nm, and " mesoporous (mesopore) " expression has more than about 1nm the character in the preferred above aperture of 2nm (diameter).Yet the numerical value in aperture can not have restrictive sense, but can represent the relative value according to the preparation condition of catalyst etc.Hereinafter, " mesoporous " in this specification only represents to have the hole in the above aperture of about 2nm (diameter).

The first embodiment

Fig. 1 is the flow chart for preparing the method for micropore and mesoporous ZSM-5 catalyst for first embodiment of explanation design according to the present invention, Fig. 2 is for the flow chart of explanation in the mixture solution process of conceiving the method preparation process (a) for preparing micropore and mesoporous ZSM-5 catalyst according to the present invention, and Fig. 3 is for the flow chart of explanation in the process of conceiving the heat treated solid product of method usefulness cation replacement for preparing micropore and mesoporous ZSM-5 catalyst according to the present invention.

Referring to Fig. 1, according to the method for preparing in the first embodiment micropore and mesoporous ZSM-5 catalyst, the method for preparing micropore and mesoporous ZSM-5 catalyst comprises that (a) forms gel (step S 100) by the mixture solution of aging silica precursor and aluminum precursor; (b) will may form mesoporous template by heat treatment and join in the described gel, and stir and then wear out (step S200); (c) by crystalline mixture aging in the step (b) is formed solid product (step S300); Thereby and (d) described solid product is heat-treated remove template (step S400).

Having the hydro carbons with C4 to C7 that micropore and mesoporous ZSM-5 catalyst can be used for producing after carrying out the naphtha cracking process by catalytic cracking and prepare the light olefin that comprises ethene and propylene by the first embodiment preparation.Preferably, this catalyst can prepare the light olefin that comprises ethene and propylene for the C 5 fraction that obtains by catalytic cracking after carrying out the naphtha cracking process.

Normally, can be by using organic cation as template, hydro-thermal ground synthesizes the ZSM-5 catalyst in alkaline alumino-silicate reaction mother liquor.According to conceive the method for preparing the ZSM-5 catalyst according to the present invention, comprise that by aging the mixture solution of silica precursor and aluminum precursor forms gel, and then can form mesoporous template adding such as step (a) with in the gel (b) by heat treatment.The template of adding can be removed by the heat treatment operation of firing that carries out subsequently, and mesoporous and micropore can be formed.To provide detailed description hereinafter.

Produce uniform crystalline solid product in order to be easy to be stirred in the gel mixture that forms among the step S100 of (a) with the template that adds subsequently, may be for the preparation of the method for optimizing of the mixture solution that is used to form gel.Referring to Fig. 2, can come mixture solution in the preparation process (a) by the method that comprises the following: (a-1) monovalent metal hydroxide and tetrapropyl ammonium halide are dissolved in (step S110) in the distilled water; (a-2) add silica precursor in order to form homogeneous mixture (step S120); And (a-3) aluminum precursor of liquid phase is added drop-wise in the described uniform mixture (step S130).

Monovalent metal hydroxide can comprise NaOH (NaOH), potassium hydroxide (KOH) etc., and tetrapropyl ammonium halide can comprise 4-propyl bromide, 4-propyl ammonium chloride etc.

To explain the preparation process of mixture solution in the step (a).At first, monovalent metal hydroxide and tetrapropyl ammonium halide can be dissolved in (step S110) in the distilled water fully, thereby and then can add silica precursor and form mixture (step S120).In this case, need mixture to have even attitude.Silica precursor can comprise cataloid, and can be particularly be selected from by

HS-40, AS-40 and At least a in the group that HS-30 forms.After this, aluminum precursor is joined (step S130) in the homogeneous mixture.In this case, wish aluminum precursor is joined in the homogeneous mixture lentamente.Particularly, can dropwise aluminum precursor be joined in the homogeneous mixture.Aluminum precursor can be to be selected from by sodium aluminate (NaAlO ₂), aluminum nitrate (Al (NO ₃) ₃), at least a in the group that forms of aluminium secondary butylate, tert-butyl alcohol aluminium, three aluminium secondary butylates, three tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide.

The mixture solution that obtains is so suitably stirred, thus and the mixture (step S100) of the formation gel state that then wears out.Can be by at room temperature with mixture solution stir about 1-3 hour, and the aging mixture that obtained gel state in about 2-10 hour at room temperature then.

Then, such as explanation in step (b), template is joined in the mixture of gel state (step S200).After adding, when heat treatment catalyst, template can form mesoporous.As forming mesoporous template, soft template (for example surfactant) and hard template (for example carbon, polymeric material) can be described.Yet hard template may be favourable, because can easily remove hard template by thermal decomposition, and the morphology Control of hard template can be favourable.In addition, when comparing with soft template, hard template provides larger hole and less expensive.

In the exemplary embodiment, hard template can comprise carbon dust or nanometer polymerization composition granule.Hard template can suitably be selected and make up in consideration availability, structure control aspect etc.Particularly, for carbon dust, the product with various shapes and granularity is commercially available, and is easy to obtain.In addition, carbon dust is easy to store and process.For the nanometer polymerization composition granule, heat decomposition temperature is lower than carbon dust, and its surface treatment is easier to.Therefore, when considering the structure control aspect, the nanometer polymerization composition granule is preferred.

Can have as the carbon dust of template or nanometer polymerization composition granule and to be used to form mesoporous any shape, and without limits, comprise sphere, square, rectangle, cylindrical etc.When considering adsorption and desorption favourable on the catalyst activity position of catalytic cracking production (hydro carbons of C4 to C7), the size of template (diameter) can be about 2-50nm.

Only may form during the catalyst that comprises the nanometer polymerization composition granule is heat-treated when mesoporous, the nanometer polymerization composition granule can comprise any material and without limits.Particularly, the nanometer polymerization composition granule can comprise Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(propane oxide), polyactide, polymethyl methacrylate etc.Preferably, can use Merlon or the polystyrene that keeps a small amount of residue during by heat treatment removal process.

In addition, can control the amount of template, so that mesoporous can the development well pro rata with the template addition.Based on 100 parts of silica precursors by weight, the amount of template can be by weight about 5-80 part.When the amount of template less than by weight 5 parts the time, the mesoporous volume that forms like this may be not satisfied, and when quantity above by weight 80 parts the time, the catalyst activity position may be reduced, and catalytic activity may some reduction.Can be by adding a large amount of templates and it being removed improve subsequently mesoporous character.Yet, the mitigation that the molecular diffusion that causes according to the space size owing to the adsorption and desorption that is used for C4 to C7 hydrocarbon mixture, product etc. limits, the raising of catalyst reaction activity may be always not proportional with mesoporous character.In note adding template during the amount of carbon dust (KetjenBlack Co.), based on 100 parts of silica precursors by weight, the reactivity of catalyst can be increased to 80 parts by weight.Yet, when the carbon dust amount surpasses by weight 80 parts, do not find the improvement degree of catalyst reaction activity.

In advance under about 100-150 ℃ with dry about 1-5 hour of template, and at room temperature with mixture stir about 1-5 hour, and then at room temperature aging about 1-5 hour so that the preparation crystallisation step.

Can add template in the formation step of gel phase mixture.Yet in this case, the template addition may increase relatively, and may need very meticulous Chemical Control to realize selective crystallization of zeolites.Therefore, this process is undesired.Verified by template being joined quantitatively in the mixture of gel phase, stir and aging simple procedure, can be had even the better preparation of the ZSM-5 catalyst of reactivity.

By adding the having among micropore and the mesoporous ZSM-5 catalyst of template preparation, can select preferably to have micropore and mesoporous ZSM-5 catalyst, so that the atomic ratio of its Si/Al (molar ratio) is about 5-300.When the Si/Al atomic ratio less than 5 the time, the catalyst activation changes and may greatly do not affected.Yet, along with catalyst acidity increases, may cause inactivation by coking etc.When the Si/Al atomic ratio surpassed 300, the acidity of catalyst may be not satisfied, and the conversion ratio of catalytic cracking C4 to C7 hydrocarbon mixture may reduce.

Then will be by template be joined in the gel, thus stir and the crystalline mixture of aging preparation forms solid product (step S300).Can be by carrying out crystallization with the method for usually using,, dry glue established law synthetic such as Hydrothermal Synthesis, microwave etc.By crystallization, zeolite can center on template, carbon dust or nanometer polymerization composition granule, thereby grows into larger monocrystalline.

After this, thus template is heat-treated and removed to solid product forms mesoporous (step S400).In this case, the solid product that will obtain by the crystallization process as preprocessing process filters, with distilled water washing several, and lower dry about 5-15 hour at about 100-120 ℃.With the solid product crushing of drying, and under about 300-750 ℃, heat-treat by firing about 3-10 hour.The preferred firing condition that is used for firing fully template is lower lasting about 4-6 hour at about 500-600 ℃.By heat treatment, the zeolite mono-crystalline structures can become comprise by carbon form mesoporous.

Have the method for mesoporous ZSM-5 catalyst according to preparation, can further implement as shown in Figure 3 the step (step S410) with the heat treated solid product of cation replacement.Normally, implement with cation replacement so that with proton (H ⁺) exchange sodium ion (Na ⁺) displacement zeolite.When comparing with other cations, increase with the acid strength of the zeolite catalyst of proton displacement, and catalyst is effectively applied to cracking process.Particularly, can replace cation by under about 70-90 ℃, solid product being put into solution, and then under same temperature conditions, carry out cation replacement in stir about 2-4 hour.The aqueous solution of cation replacement is filtered and washing, and the cation replacement process can be repeated 1-3 time.As the solution that is used for cation replacement, at least a can being selected from by ammonium nitrate (NH ₄NO ₃), ammonium chloride (NH ₄Cl), ammonium carbonate ((NH ₄) ₂CO ₃) and ammonium fluoride (NH ₄F) group that forms.

In addition, can carry out to the solid product of cation replacement further heat treatment process (step S420).Can heat-treat in about 3-10 hour by under about 400-700 ℃, solid product being fired.When heat treatment temperature is lower than 400 ℃, the ammonium salt of at first replacing zeolite catalyst can not be removed fully, and can be reduced the acid strength of zeolite.When heat treatment temperature surpasses 700 ℃, catalyst can be pulverized, and

Acidic site may disappear.When heat treatment time during less than 3 hours, may be difficult to remove salt, and when heat treatment time surpasses 10 hours, may cause power loss.Preferably, can after the about 5-15 of drying hour, heat-treat the solid product of cation replacement under about 100-120 ℃.

The mesoporous ZSM-5 catalyst of the first embodiment of design preparation can comprise micropore and mesoporous character simultaneously according to the present invention.These catalyst properties can improve the diffusion of reactant and intermediate, thereby raising is from the productive rate of the light olefin that comprises ethene and propylene of the hydrocarbon mixture production of C4 to C7.Particularly, having micropore and mesoporous ZSM-5 catalyst can be by preparing as template with carbon, and can have about 360-410m ²The specific area of/g, about 0.1-0.2cm ²Volume, about 0.05-0.3cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with the above diameter of about 2nm of/g and according to the about 130-145 μ of the temperature programmed desorption of ammonia mol-NH ₃The acidity of/g-catalyst.

The having micropore and mesoporous ZSM-5 catalyst can be used for the C4 to C7 that produces by catalytic cracking after the naphtha cracking process hydrocarbon mixture and prepare the light olefin that comprises ethene and propylene of the first embodiment preparation by the present invention design.In this case, can be by under about 300-700 ℃ reaction temperature, have in the presence of micropore and the mesoporous ZSM-5 catalyst, at about 1-20h ^-1The condition of weight hourly space velocity (WHSV) under make hydrocarbon mixture react to prepare light olefin.When weight hourly space velocity less than 1h ^-1The time, can increase conversion ratio, yet owing to side reaction selectively may reduce.When weight hourly space velocity surpasses 20h ^-1The time, conversion ratio can be reduced and catalyst life can be reduced.

The second embodiment

Fig. 4 is the flow chart for preparing micropore and mesoporous ZSM-5 catalyst method for second embodiment of explanation design according to the present invention, and Fig. 5 is at the flow chart of conceiving the method dipping phosphorus precursor process for preparing micropore and mesoporous ZSM-5 catalyst according to the present invention for explanation.

Referring to Fig. 4, the method that has micropore and mesoporous ZSM-5 catalyst according to the second embodiment preparation comprises that (a) comprises that by aging the mixture solution of silica precursor and aluminum precursor forms gel (step S100); (b) template is joined in the gel, stir and then wear out (step S200); (c) form solid product (step S300) by mixture aging in the crystallisation step (b); (d) thus described solid product heat-treated removes template (step S400); (e) by dipping method or ion-exchange process the phosphorus precursor is incorporated into (step S500) in the heat treated solid product.

Be similar to and have micropore and a mesoporous ZSM-5 catalyst, having C4 to the C7 hydrocarbon mixture that micropore and mesoporous ZSM-5 catalyst can be used for producing after carrying out the naphtha cracking by catalytic cracking and prepare the light olefin that comprises ethene and propylene according to the preparation of the second embodiment according to the first embodiment preparation.Preferably, having the C 5 fraction that micropore and mesoporous ZSM-5 catalyst can be used for producing after the naphtha cracking by catalytic cracking and prepare the light olefin that comprises ethene and propylene according to the second embodiment preparation.Because considered can be used for the second embodiment such as the integral body formation of described in the first embodiment step (a) to (d), explanation will concentrate on step (e) upward to avoid repeat specification hereinafter.

The second embodiment of design according to the present invention, can be by the phosphorus precursor being incorporated in the heat treated solid product in the step (d) in order to come modified ZSM-5 catalyst to obtain preparing to have the method for micropore and mesoporous ZSM-5 catalyst with phosphorus.

Can carry out by dipping method or ion-exchange process the introducing of phosphorus precursor.When considering the control acidic site, particularly during the highly acid position, preferred dipping method.

Referring to Fig. 5, for example, can the phosphorus precursor be impregnated in the ZSM-5 catalyst by following method.Can in water, make phosphorus precursor hydration (step S510), and the heat treated solid product of step (d) can be joined in the hydration solution in order to flood (step S520), and then dry and heat-treat (step S530).

Especially, the phosphorus precursor can be dissolved in the water (distilled water) (step S510) for the capacity of the phosphorus precursor that dissolves entire quantity, and at about 70-90 ℃ of lower stir about 5-15 minute.Can under 70-90 ℃, add heat treated solid product, and stir in order to fully flood (step S520).After with whole water evaporates, about 90-110 ℃ lower dry about 10-15 hour, and can under about 500-750 ℃, fire lasting about 1-10 hour (step S530) thus obtain catalyst.When comparing with dipping at room temperature, under about 70-90 ℃, flood the framework that has increased the ZSM-5 catalyst and be combined with phosphorus component.When firing temperature during less than 500 ℃, the organic substance and the inorganic substances that comprise in the phosphorus precursor fully can not be removed, and when firing temperature surpassed 750 ℃, specific consumption was bad, and the removal capacity possible deviation of the organic substance that comprises in the phosphorus precursor and inorganic substances.

Considered acidity and the carbon deposition of the ZSM-5 catalyst of final preparation according to catalyst reaction, introducing amount that can the phosphorus precursor is set to optimum range.Based on 100 parts of ZSM-5 catalyst with micropore and mesoporous final generation in the quantitative range of template by weight, the introducing amount of phosphorus precursor can be by weight about 0.01-10 part, preferably can be by weight about 0.05-3 part, more preferably can be by weight about 0.1-1.5 part, and most preferably can be by weight about 0.1-1 part.

The phosphorus precursor can comprise phosphoric acid (H ₃PO ₄), mono phosphoric acid ester ammonium ((NH ₄) _H2PO ₄), Diammonium phosphate (DAP) ((NH ₄) ₂HPO ₄) and ammonium phosphate ((NH ₄) ₃PO ₄).

The method that the second embodiment preparation of design has micropore and a mesoporous ZSM-5 catalyst according to the present invention may further include before introducing the phosphorus precursor, the cation replacement step (step S410) of the heat treated solid product of step (d) and the solid product of cation replacement heat-treated (step S420).Concrete method can be with described in the first embodiment identical.

The second embodiment preparation by the present invention design have micropore and mesoporous ZSM-5 catalyst can have micropore and mesoporous character simultaneously.These catalyst properties can improve the diffusion of reactant and intermediate, thereby have improved from the productive rate of the light olefin that comprises ethene and propylene of the hydrocarbon mixture production of C4 to C7.In addition, thus the having micropore and mesoporous ZSM-5 catalyst and can introduce the ZSM-5 catalyst that phosphorus production of optimised quantity has optimum acidity of the second embodiment preparation by the present invention design.When being used for preparing the light olefin that comprises ethene and propylene from the hydrocarbon mixture of C4 to C7 with the ZSM-5 catalyst, having micropore and mesoporous ZSM-5 catalyst and can stablize for a long time and can have good activity.Particularly, based on by weight 100 parts have micropore and mesoporous ZSM-5 catalyst, have micropore and mesoporous ZSM-5 catalyst and may further include by weight about 0.1-10 part phosphorus precursor, and can have about 340-400m ²The specific area of/g, about 0.05-0.2cm ³The volume of the micropore with the following diameter of 1nm of/g, about 0.05-0.2cm ³The mesoporous volume with the above diameter of about 2nm of/g, according to the about 80-95 μ of the temperature programmed desorption of ammonia mol-NH ₃The acidity of the faintly acid position of/g-catalyst and about 15-50 μ mol-NH ₃The acidity of the highly acid position of/g-catalyst and the carbon deposition of analyzing about 2-7wt% according to CHNS after catalyst reaction 40 hours.

The having micropore and mesoporous ZSM-5 catalyst can be used for the C4 to C7 that produces by catalytic cracking after carrying out the naphtha cracking process hydrocarbon mixture and prepare the light olefin that comprises ethene and propylene of the second embodiment preparation by the present invention design.Concrete reaction condition can be with described in the first embodiment identical.

The 3rd embodiment

Fig. 6 is that the 3rd embodiment for explanation design according to the present invention prepares the flow chart of micropore and mesoporous ZSM-5 catalyst method, and Fig. 7 floods the flow chart of rare earth metal precursor or alkali metal precursor process for explanation conceiving the method that prepare micropore and mesoporous ZSM-5 catalyst according to the present invention.

Referring to Fig. 6, the method that has micropore and mesoporous ZSM-5 catalyst according to the 3rd embodiment preparation comprises that (a) comprises that by aging the mixture solution of silica precursor and aluminum precursor forms gel (step S100); (b) template is added in the gel, stir and then wear out (step S200); (c) by crystalline mixture aging in the step (b) is formed solid product (step S300); (d) thus described solid product heat-treated removes template (step S400); (e) by dipping method or ion-exchange process the phosphorus precursor is incorporated in the described heat treated solid product (step S500); And (f) by dipping method or ion-exchange process rare earth metal precursor or alkali metal precursor are incorporated into (step S600) in the solid product that comprises the phosphorus precursor.

Be similar to and have micropore and a mesoporous ZSM-5 catalyst, having C4 to the C7 hydrocarbon mixture that micropore and mesoporous ZSM-5 catalyst can be used for producing after the naphtha cracking by catalytic cracking and prepare the light olefin that comprises ethene and propylene according to the preparation of the 3rd embodiment according to the preparation of first and the second embodiment.Preferably, having the C 5 fraction that micropore and mesoporous ZSM-5 catalyst can be used for producing after the naphtha cracking by catalytic cracking and prepare the light olefin that comprises ethene and propylene according to the second embodiment preparation.Because considered can be used for the 3rd embodiment such as described in the first embodiment step (a) to (d) and such as the integral body formation in the step (e) described in the second embodiment, explanation will concentrate on step (f) in order to avoid repeat specification hereinafter.

The 3rd embodiment of design according to the present invention, can be by rare earth metal precursor or alkali metal precursor being incorporated in the solid product that comprises the phosphorus precursor in the step (e) so that control catalyst acid and alkaline, obtain preparing the method with micropore and mesoporous ZSM-5 catalyst.Can respectively or side by side carry out the introducing of rare earth metal precursor and alkali metal precursor, so that explanation can obtain catalyst property by introducing simultaneously every kind of metal.

In order to introduce rare earth metal precursor or alkali metal precursor, can use dipping method or ion-exchange process.Yet, can help to control dipping method acid and alkalescence and make us wishing.

Referring to Fig. 7, can carry out by the similar procedure of introducing the phosphorus precursor rare earth metal precursor or alkali metal precursor are impregnated into method in the ZSM-5 catalyst.Particularly, in water with rare earth metal precursor or alkali metal precursor hydration (step S610), the solid product of introducing phosphorus in the step (e) is joined in the hydration solution in order to carry out dipping process (step S620), and the product that then will obtain like this is dry and heat-treat (step S630).

Especially, the phosphorus precursor can be dissolved in for the water of the capacity of dissolving rare earth metal precursor or alkali metal precursor fully (distilled water) (step S610), and can be under about 70-90 ℃ with solution stir about 5-15 minute.Then, can under about 70-90 ℃, add heat treated solid product and stirring in order to fully flood.After with whole water evaporates, under about 90-110 ℃ in baking oven dry about 10-15 hour, and can under about 500-750 ℃, fire lasting about 1-10 hour (step S630).

In this case, according to the catalyst reaction of the ZSM-5 catalyst of final production, consider acidity, basicity and carbon deposition, can determine the introducing amount of rare earth metal precursor or alkali metal precursor.Therefore, with respect to the phosphorus in the template addition scope, rare earth metal precursor or preferably introducing amount of alkali metal precursor can be the atomic ratios below 2.Preferred amount can be the atomic ratio of 0.1-1.5, and most preferred amount can be the atomic ratio of 0.5-0.9.

The rare earth metal that comprises in the rare earth metal precursor can be to be selected from by lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), the group that terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu) form at least a.Preferably, can select lanthanum.The alkali metal that comprises in alkali metal precursor can be selected from the group that is comprised of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs) at least a.Preferably, alkali metal can be a kind of in potassium, rubidium and the caesium, and more preferably, alkali metal can be caesium.Especially, in order to select lanthanum as rare earth metal, can introduce lanthanum nitrate (La (NO ₃) ₃6H ₂O) as the rare earth metal precursor, and in order to select lithium as alkali metal, can introduce lithium nitrate (LiNO ₃) as alkali metal precursor.

The method that the 3rd embodiment preparation of design has micropore and a mesoporous ZSM-5 catalyst according to the present invention may further include before introducing the phosphorus precursor, the cation replacement step (step S410) of the heat treated solid product of step (d) and the solid product of cation replacement heat-treated (step S420).Concrete method can be with described in the first embodiment identical.

The 3rd embodiment preparation by the present invention design have micropore and mesoporous ZSM-5 catalyst can have micropore and mesoporous character simultaneously.These catalyst properties can improve the diffusion of reactant and intermediate, thereby improve from the productive rate of the light olefin that comprises ethene and propylene of C4 to C7 hydrocarbon mixture generation.In addition, the 3rd embodiment preparation by the present invention design have phosphorus that micropore and mesoporous ZSM-5 catalyst can introduce optimised quantity together with rare earth metal or alkali metal, be used for producing the ZSM-5 catalyst with optimum acidity and basicity.When coming to prepare the light olefin that comprises ethene and propylene from the hydrocarbon of C4 to C7 with the ZSM-5 catalyst, have micropore and mesoporous ZSM-5 catalyst and can stablize for a long time and can have good activity.Particularly, based on by weight 100 parts have micropore and mesoporous ZSM-5 catalyst, have micropore and mesoporous ZSM-5 catalyst and may further include rare earth metal or alkali metal with respect to the about 2 following atomic ratios of phosphorus, and can have about 300-400m ²The specific area of/g, about 0.05-0.2cm ³Volume, about 0.05-0.15cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with the above diameter of about 2nm of/g, according to the about 70-90 μ of the temperature programmed desorption of ammonia mol-NH ₃The acidity of the faintly acid position of/g-catalyst, about 20-45 μ mol-NH ₃The acidity of the highly acid position of/g-catalyst and about 2-30 μ mol-CO ₂The basicity of/g-catalyst.

The having C4 to the C7 hydrocarbon mixture that micropore and mesoporous ZSM-5 catalyst can be used for producing after the naphtha cracking process by catalytic cracking and prepare the light olefin that comprises ethene and propylene of the 3rd embodiment preparation by the present invention design.Specific reaction condition can be with described in the first embodiment identical.

Embodiment 1

Add 1.6g NaOH (Samchun Chem) and be dissolved in the 150ml distilled water.Then, the structure induced material of 2.28g 4-propyl bromide (TPABr, sigma-Aldrich) as ZSM-5 joined in this aqueous solution, then stir until TPABr dissolves fully.At room temperature in the aqueous solution that comprises NaOH and TPABr, slowly drip cataloid (Ludox HS-40, Sigma-Aldrich) and stirring, until form homogeneous mixture.With 0.78g sodium aluminate (NaAlO ₂, Junsei) be dissolved in another 30ml distilled water, and stirred 1 hour.The solution that obtains is like this joined in the solution that comprises silica precursor (cataloid) lentamente and dropwise, thereby and at room temperature stir and formed gel in 1 hour.Based on 100 parts of silica precursors by weight, take by weighing by weight 15 parts under 110 ℃ in baking oven predrying 3 hours carbon dust (EC600JD, KetjenBlack), join in the gel as template, and then stirred 3 hours.The solution that stirs is put into autoclave, and then continue 72 hours at 160 ℃ of lower Hydrothermal Synthesiss.After Hydrothermal Synthesis, the product of producing is like this filtered and washs for several times with distilled water.Then, under 110 ℃ with dry 10 hours of the solid sample of washing.After drying, with the solid product crushing that obtains like this, and then under 650 ℃, fired 10 hours in order to remove template (carbon).For the solid product after the drying is carried out cation replacement, prepare the ammonium nitrate (Junsei) of 100ml 1mol concentration and remain on 80 ℃.The 4g solid product is joined in the ammonium nitrate, and 80 ℃ of lower stirrings 3 hours.The aqueous solution of cation replacement is filtered and washing, and then the cation replacement process is carried out twice again.Dry 10 hours of the solid product under 110 ℃, cation replacement finished, thus and then under 650 ℃, fire to produce in 5 hours and have micropore and mesoporous ZSM-5 catalyst.

Embodiment 2

Carry out with embodiment 1 in identical step, except the carbon addition is set to 30 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 3

Carry out with embodiment 1 in identical step, except the carbon addition is set to 45 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 4

Carry out with embodiment 1 in identical step, except the carbon addition is set to 60 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 5

Carry out with embodiment 1 in identical step, except the carbon addition is set to 75 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 6

The phosphorus precursor is weighed and be impregnated in the ZSM-5 catalyst that in embodiment 3, obtains, comprise that 0.17 part of phosphorus precursor has micropore and mesoporous ZSM-5 catalyst by weight based on 100 parts of final ZSM-5 catalyst that form by weight thereby produce.With phosphoric acid (85%, Sigma-Aldrich) weigh, and be dissolved in the 10ml distilled water.Stirred 10 minutes at 60 ℃ of lower solution that will obtain like this, and then add the ZSM-5 catalyst that 1g obtains in embodiment 3.Fully flood in order to realize 60 ℃ of lower maintenance continuous stirring.With after the distilled water evaporation, under 100 ℃ in baking oven dry 12 hours, thus and under 650 ℃, carry out sintering procedure and continue to produce in 3 hours and have micropore and mesoporous ZSM-5 catalyst.

Embodiment 7

Carry out with embodiment 6 in identical step, except the pickup of phosphorus precursor is set to 0.3 part by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 8

Carry out with embodiment 6 in identical step, except the pickup of phosphorus precursor is set to 0.7 part by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 9

Carry out with embodiment 6 in identical step, except the pickup of phosphorus precursor is set to 1.4 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 10

Carry out with embodiment 6 in identical step, except the pickup of phosphorus precursor is set to 2.7 parts by weight, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 11

In rare earth metal, select lanthanum (La), weigh in order to have 0.3 lanthanum/phosphorus atoms ratio, and then be incorporated in the ZSM-5 catalyst that in embodiment 7, obtains by dipping method.With lanthanum nitrate (La (NO ₃) ₃-6H ₂O, Sigma-Aldrich) weigh and be dissolved in the 10ml distilled water, and 60 ℃ of lower stirrings 10 minutes.Add the catalyst that 1g produces in

embodiment

1, and 60 ℃ of lower continuous stirring to realize abundant dipping.With after the distilled water evaporation, under 100 ℃ in baking oven dry 12 hours, thus and under 650 ℃, carry out sintering procedure and continue to produce in 3 hours and have micropore and mesoporous ZSM-5 catalyst.

Embodiment 12

Carry out the step identical with embodiment 11, except the pickup of lanthanum precursor is set to 0.7 lanthanum/phosphorus atoms ratio, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 13

Carry out with embodiment 11 in identical step, except the pickup of lanthanum precursor is set to 0.9 lanthanum/phosphorus atoms ratio, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 14

Carry out with embodiment 11 in identical step, except the pickup of lanthanum precursor is set to 1.2 lanthanum/phosphorus atoms ratio, thereby production has micropore and mesoporous ZSM-5 catalyst.

Embodiment 15

In alkali metal, select lithium (Li), and the lithium precursor is weighed, in order to have 0.7 lithium/phosphorus atoms ratio, then be incorporated in the ZSM-5 catalyst that in embodiment 7, obtains by dipping method.With lithium nitrate (LiNO ₃, Sigma-Aldrich) weigh, and be dissolved in the 10ml distilled water, and 60 ℃ of lower stirrings 10 minutes.Add the catalyst that 1g produces in

embodiment

1, and 60 ℃ of lower continuous stirring to realize abundant dipping.After with the evaporation of whole distilled water, under 100 ℃ in baking oven dry 12 hours, thus and under 650 ℃, carry out sintering procedure and continue to produce in 3 hours and have micropore and mesoporous ZSM-5 catalyst.

Embodiment 16

In alkali metal, select potassium (K), and the potassium precursor weighed in order to have 0.7 potassium/phosphorus atoms ratio, then be incorporated in the ZSM-5 catalyst that in embodiment 7, obtains by dipping method.With potassium nitrate (KNO ₃, Sigma-Aldrich) weigh and be dissolved in the 10ml distilled water, and 60 ℃ of lower stirrings 10 minutes.Add the catalyst that 1g produces in

embodiment

Embodiment 17

In alkali metal, select caesium (Cs), the caesium precursor is weighed in order to have 0.7 caesium/phosphorus atoms ratio, then be incorporated in the ZSM-5 catalyst that in embodiment 7, obtains by dipping method.With cesium nitrate (CsNO ₃, Sigma-Aldrich) weigh and be dissolved in the 10ml distilled water, and 60 ℃ of lower stirrings 10 minutes.Add the catalyst that 1g produces in

embodiment

Comparing embodiment

Carry out with embodiment 1 in identical step, except not producing pure ZSM-5 catalyst with carbon as template.

Experiment 1: to having the assessment of micropore and mesoporous ZSM-5 catalyst property

1. the assessment that the ZSM-5 catalyst crystal structure is affected

(1) carbon is on the impact of ZSM-5 catalyst crystal structure

In order to assess carbon to the impact according to the ZSM-5 catalyst crystal structure of the first embodiment, the ZSM-5 catalyst of producing by embodiment 1 to 5 and comparing embodiment is carried out X-ray diffraction analysis (D-MAX2500-PC, Rigaku).The results are shown among Fig. 8.

Referring to Fig. 8, at the catalyst that uses carbon to produce in as the embodiment 1 to 5 of template and do not comprising the catalyst of producing in the comparing embodiment of carbon as template, developed well characteristic peak.Can confirm that from these results carbon is not to suppress to produce the factor of ZSM-5 catalyst crystal structure as template.

(2) phosphorus is on the impact of ZSM-5 catalyst crystal structure

In order to assess phosphorus to the impact according to the ZSM-5 catalyst crystal structure of the second embodiment, the ZSM-5 catalyst of producing by embodiment 6 to 10 is carried out X-ray diffraction analysis (D-MAX2500-PC, Rigaku).The results are shown among Fig. 9.The result who obtains for the ZSM-5 catalyst of producing in embodiment 3 shows together, is used for relatively.

Referring to Fig. 9, the catalyst for the catalyst of producing in the embodiment 6 to 10 that introduces phosphorus and production in the embodiment 3 that does not comprise phosphorus has developed characteristic peak well.Simultaneously, along with phosphorus introducing amount increases, the relative sensitivity of observing ZSM-5 catalyst characteristics peak reduces.Because by making a part of framework distortion by the-ZSM-5 that Si-O-Al-consists of owing to introduce dealuminization that phosphorus causes.Therefore, along with phosphorus introducing amount increases, the amount of dealuminization also increases and the relative sensitivity reduction at ZSM-5 catalyst characteristics peak.

(3) rare earth metal and alkali metal are on the impact of ZSM-5 catalyst crystal structure

In order to assess rare earth metal and alkali metal to the impact according to the crystal structure of the ZSM-5 catalyst of the 3rd embodiment, the ZSM-5 catalyst of producing by embodiment 11 to 17 is carried out X-ray diffraction analysis (D-MAX2500-PC, Rigaku).The results are shown in Figure 10 and 11.The result who obtains for the ZSM-5 catalyst of producing in embodiment 7 shows together, is used for relatively.

Referring to Figure 10, for the catalyst of in the embodiment 11 to 14 that introduces phosphorus and lanthanum, producing and comprising the catalyst of producing among the embodiment 7 of phosphorus, developed well characteristic peak.Simultaneously, along with lanthanum introducing amount increases, the relative sensitivity of observing ZSM-5 catalyst characteristics peak reduces, as shown in figure 10.Report that according to the chemical species that exists, the intensity at ZSM-5 catalyst characteristics peak can greatly change (people such as L.Zhang, Catal, Lett.vol.130, p355,2009) under low angle in passage in the XRD of ZSM-5 pattern.Therefore, the relative sensitivity reduction of introducing the catalyst of lanthanum under low angle can be thought to exist the lanthanum chemical species to cause in the passage of the ZSM-5 catalyst of producing.Owing to do not observe the characteristic peak of lanthanum and lanthana in the X-ray diffraction analysis, thereby thinking that its size is very little can not be detected by the X-ray diffraction analytical equipment.

Referring to Figure 11, as in embodiment 15 to 17, introduce alkali-metal catalyst for all, find that the characteristic peak of ZSM-5 forms well.Therefore, introduce the structural change that alkali metal is not considered to affect ZSM-5.In addition, owing to do not observe other peak except the characteristic peak of ZSM-5, can think that the size of the alkali metal particles introduced is very little, thereby can not be detected by the X-ray diffraction analytical equipment.

2. the assessment that has micropore and mesoporous ZSM-5 catalyst for formation

(1) carbon is on the impact of micropore and mesoporous formation

In order to confirm to form micropore and mesoporous by the ZSM-5 catalyst that the first embodiment of the design according to the present invention is produced, specific area and pore volume, nitrogen adsorption and desorption curve and pore-size distribution to the ZSM-5 catalyst produced by embodiment 1 to 5 and comparing embodiment are assessed, and every photo figure on the observation crystal structure.

At first, measured specific area and the pore volume of the ZSM-5 catalyst of in embodiment 1 to 5 and comparing embodiment, producing, and be shown in Table 1.

＜table 1 〉

Referring to table 1, do not compare as the catalyst of template with do not comprise carbon according to comparing embodiment, use carbon to have larger mesoporous volume as the catalyst of template according to embodiment 1 to 5.In addition, along with the carbon amount increases, increase significantly according to the mesoporous volume of the catalyst of embodiment 1 to 5.Yet, comprise carbon does not affect catalyst significantly as template specific area.From found that, when using carbon as template, can greatly affect the porous of ZSM-5 catalyst, and the carbon amount can affect mesoporous volume as central factor.

Figure 12 A and 12B are curve maps, illustrated by using BET(ASAP-2010, Micrometrics Instrument) according to the nitrogen adsorption and desorption curve map (12A) of the ZSM-5 catalyst of embodiment 1 to 5 and comparing embodiment and the result of graph of pore diameter distribution (12B).

Referring to Figure 12 A, the nitrogen adsorption and desorption curve map of the catalyst of producing by comparing embodiment has shown typical I type curve.That is, at (P/P ₀Adsorbed relatively large nitrogen near the relative pressure of)=0, and along with relative pressure increases, the increase of adsorption and desorption amount is less.Yet the nitrogen adsorption and desorption curve map of the catalyst of producing by embodiment 1 to 5 has shown IV type curve, and wherein along with relative pressure increases, the amount of adsorption and desorption little by little increases.In addition, found in the thermoisopleth of measuring between adsorption cycle and the inconsistent hysteresis of thermoisopleth of during desorption, measuring.Step and the ZSM-5 catalyst that uses carbon to produce as template have and satisfy the mesoporous of the application's purpose according to the present invention in discovery.

Referring to Figure 12 B, the catalyst demonstration of producing by comparing embodiment does not comprise mesoporous pore-size distribution less than about 2nm diameter.Yet the catalyst of producing by embodiment 1 to 5 has shown the mesoporous distribution with about 4nm diameter.

Catalyst according to embodiment 1 to 5 has shown along with the carbon amount increases the trend (referring to Figure 12 A) that the absorption of per unit weight nitrogen increases and mesoporous clear observation (referring to Figure 12 B).Therefore, when using carbon as template, can prepare and have mesoporous ZSM-5 catalyst.Especially, can change the multiple physical property that comprises catalyst pores character by control carbon amount.

Figure 13 A to 13F is according to embodiment 3,5 and the crystal structure photo figure of the ZSM-5 catalyst that obtains by high-resolution transmission electron microscope (JEM-3010, Jeol) of comparing embodiment.Figure 13 A and 13B be corresponding to the photo figure of the catalyst of producing by comparing embodiment, and Figure 13 C and 13D be corresponding to the photo figure of the catalyst of producing by embodiment 3, and Figure 13 E and 13F are corresponding to the photo figure of the catalyst that produces by embodiment 5.

Referring to Figure 13 A to 13F, the catalyst of producing by comparing embodiment has shown the crystal structure of high density and atresia, has shown by sintering procedure by embodiment 3 and 5 catalyst of producing to consist of the hole that this structure produces together with the carbon of ZSM-5 crystal by removing.Simultaneously, the porous of the catalyst produced is found in position rather than centre with larger thickness in embodiment 3 and 5 around the crystal with less thickness.

(2) phosphorus is on the impact of micropore and mesoporous formation

For the ZSM-5 catalyst that confirms to produce by the second embodiment of the design according to the present invention forms micropore and mesoporous, specific area and the pore volume of the ZSM-5 catalyst produced by embodiment 6 to 10 are measured.The results are shown in the table 2.The result of the catalyst of producing by comparing embodiment and embodiment 3 shows together, is used for relatively.

＜table 2 〉

Referring to table 2, compare with not comprising the ZSM-5 catalyst that carbon is produced by comparing embodiment as template, use carbon to have larger mesoporous volume as template by embodiment 3 and 6 to the 10 ZSM-5 catalyst of producing.As can be known from the results, using carbon is to comprise the mesoporous catalyst that satisfies the application's purpose as the ZSM-5 catalyst of template.

Simultaneously, along with the phosphorus amount increases, the not very large change of the physical property of catalyst, and near specific area slight reduction according to the amount of embodiment 10.When phosphorus was excessive, the phosphorus component of introducing may not be to be completed into individual layer on the surface of catalyst, thereby thereby but generating unit divide to assemble and enlarge its size and stop up these holes.For the ZSM-5 catalyst with micropore, because the phosphorus plugging hole that is introduced into, the acidic site in the micropore may not work as active sites.Yet for having mesoporous ZSM-5 catalyst, thereby the phosphorus that can suppress to be introduced into stops up the reduction that catalytic activity is reduced in larger hole.Design when the mesoporous character of needs, can be incorporated into phosphorus in the ZSM-5 catalyst according to the present invention.By confirming this point, can propose to consider acidity and the carbon deposition of ZSM-5 catalyst, preparation comprises its best forms and quantity has the method for micropore and mesoporous ZSM-5 catalyst.

(3) rare earth metal is on the impact of micropore and mesoporous formation

In order to confirm to form micropore and mesoporous by the ZSM-5 catalyst that the 3rd embodiment of the design according to the present invention is produced, the ZSM-5 catalyst of producing by embodiment 11 to 14 is carried out the adsorption and desorption experiment, and measure specific area and the pore volume of catalyst.Figure 14 is a curve map, has illustrated by using BET(ASAP-2010, Micrometrics Instrument) experimental result of the ZSM-5 catalyst nitrogen adsorption and desorption that obtains.Use the specific area of ZSM-5 catalyst and the results are shown in the table 3 of pore volume of this measurement device.The result of the catalyst of producing by embodiment 7 shows together, is used for relatively.

＜table 3 〉

Referring to Figure 14, shown IV type curve by using carbon as the nitrogen adsorption and desorption curve map of all catalyst of template production, wherein along with relative pressure (P/P ₀) increase, the adsorption and desorption amount little by little increases.In addition, found in the thermoisopleth of measuring between adsorption cycle and the inconsistent hysteresis of thermoisopleth during desorption, measured.Discovery is step and have by the ZSM-5 catalyst that uses carbon to produce as template and to satisfy the mesoporous of the application's purpose according to the present invention.

Referring to table 3, when with the ZSM-5 catalyst of only introducing phosphorus (embodiment 7) when comparing, have less specific area and micro pore volume and mesoporous volume by introducing the ZSM-5 catalyst (embodiment 11 to 14) that phosphorus and lanthanum produce.Along with lanthanum introducing amount increases, cause the micropore hole plug owing to introduce lanthanum, micro pore volume reduces greatly.Yet along with the lanthanum amount increases, mesoporous volume is without remarkable reduction.From these results, can think when comparing with the ZSM-5 catalyst that only has micropore character, can suppress hole plug by giving the mesoporous character of ZSM-5 catalyst.

3. to the assessment of the acidity of ZSM-5 catalyst and alkalescence

(1) carbon is on the impact of acidity

The acidity with micropore and mesoporous ZSM-5 catalyst for the first embodiment production of finding according to the present invention design, and in order to confirm that carbon is on the impact of ZSM-5 acidity of catalyst, the ZSM-5 catalyst of producing by embodiment 1 to 5 and comparing embodiment is carried out temperature programmed desorption experiment, and calculate such preparation catalyst acidity and compare.

Carry out temperature programmed desorption experiment (BELCAT-B, BEL Japan) for the ZSM-5 catalyst of producing by embodiment 1 to 5 and comparing embodiment, and the results are shown among Figure 15 of obtaining like this.Peak area from Figure 15 calculates the acidity of every kind of catalyst and is shown in Table 4.

＜table 4 〉

Classification	Acidity (μ mol-NH ₃/ g-catalyst)
		Embodiment 1	139
Embodiment 2	138
		Embodiment 3	139.5
Embodiment 4	135
		Embodiment 5	133
Comparing embodiment	141

Referring to Figure 15, according to the method for the Kaolinite Preparation of Catalyst of embodiment 1 to 5 and comparing embodiment, do not observe the difference of acid strength.In addition, referring to table 4, observe similar acidity for the catalyst of producing by embodiment 1 to 5 and comparing embodiment.From this result, confirmed when preparation ZSM-5 catalyst, be used as the carbon of template to not impact of acidity.

(2) phosphorus is on the impact of acidity

The acidity with micropore and mesoporous ZSM-5 catalyst for the second embodiment production of finding according to the present invention design, and in order to confirm that phosphorus is on the impact of ZSM-5 acidity of catalyst, the ZSM-5 catalyst of producing by embodiment 6 to 10 is carried out temperature programmed desorption experiment (BELCAT-B, and the results are shown among Figure 16 of obtaining like this BEL Japan).Peak area from Figure 16 calculates the acidity of every kind of catalyst, and is shown in Table 5.The result of the catalyst of producing by embodiment 3 shows together, is used for relatively.Referring to Figure 16, for all catalyst, locate and locate to have found main desorption peaks at about 370-420 ℃ at about 100-150 ℃.The peak of locating to show at 100-150 ℃ can be defined as the faintly acid position, and the peak of locating to show at 370-420 ℃ can be defined as the highly acid position.

＜table 5 〉

Referring to table 5, along with phosphorus introducing amount increases, the faintly acid position is without larger variation, yet, highly acid position slight reduction.And acidic site as if the phosphorus of introducing be combined with highly acid position rather than faintly acid position people such as (, J.Catal.Vol.248, p29,2007) G. Zhao particularly.Therefore, along with phosphorus introducing amount increases, the acidity of highly acid position reduces.

(3) rare earth metal and alkali metal are on the impact of acidity

In order to confirm that rare earth metal and alkali metal are on the impact of the acidity with micropore and mesoporous ZSM-5 catalyst of the 3rd embodiment production of the design according to the present invention, the ZSM-5 catalyst of producing by embodiment 11 to 17 is carried out temperature programmed desorption experiment (BELCAT-B, and the results are shown in Figure 17 and 18 of obtaining like this BEL Japan).Peak area from Figure 17 and 18 calculates the acidity of every kind of catalyst, and is shown in table 6 and 7.The result of the catalyst of producing by embodiment 7 is shown in Figure 17 and the table 6 together, be used for relatively, and the result of the catalyst of producing by embodiment 12 is shown in Figure 18 and the table 7 together, is used for relatively.Referring to Figure 17 and 18, for all catalyst at about 100-150 ℃ and locate to have found main desorption peaks at about 370-420 ℃.The peak of locating to show at 100-150 ℃ can be defined as the faintly acid position, and the peak of locating to show at 370-420 ℃ can be defined as the highly acid position.

＜table 6 〉

＜table 7 〉

Referring to table 6, the change of not observing acid strength is consistent with the increase of lanthanum introducing amount.Yet along with lanthanum introducing amount increases, both reduce faintly acid position and highly acid position.As if the lanthanum of introducing be combined people such as (, Catal, Lett.vol.130, p355,2009) L.Zhang with a part of acidic site.Therefore, find that acidity reduces along with lanthanum introducing amount increases.

Referring to table 7, based on the same amount of introducing metal, with the order of lanthanum, caesium, potassium and lithium, the acidity of catalyst reduces.For all catalyst, the acidity of faintly acid position does not show significant difference, yet the acidity of highly acid position greatly reduces.The alkali metal of introducing and the acidic site of catalyst are considered to different from the combination degree of highly acid position particularly.

(4) rare earth metal is on the impact of alkalescence

In order to confirm that rare earth metal is on the impact with micropore and mesoporous ZSM-5 catalyst alkalescence of the 3rd embodiment production of the design according to the present invention, the ZSM-5 catalyst of producing by embodiment 11 to 14 is carried out carbon dioxide temperature programmed desorption experiment (BELCAT-B, and the results are shown among Figure 19 of obtaining like this BEL Japan).Peak area from Figure 19 calculates the basicity of every kind of catalyst and is shown in Table 8.The result of the catalyst of producing by embodiment 7 shows together, is used for relatively.As shown in Figure 19, locate to observe a characteristic peak for all catalyst at about 100-200 ℃.

＜table 8 〉

	Basicity (μ mol-CO ₂/ g-catalyst)
		Embodiment 7	4.3
Embodiment 11	7.3
		Embodiment 12	11.7
Embodiment 13	14.7
		Embodiment 14	24.5

Referring to table 8, along with the lanthanum amount increases, basicity increases.Owing to introduce lanthanum, as if generated basic sites people such as (, Appl.Catal.A, vol.333, p202,2007) Y.Zhang on the surface of ZSM-5.

The cracking reaction of hydro carbons is usually known finishes people such as (, J.Catal.vol.135, p115,1992) H.Krannila by unimolecule cracking and two kinds of mechanism of bimolecular cracking.For the unimolecule cracking, thereby can easily decompose hydro carbons production multi-products, for example alkene by the β-cracking of acidity of catalyst position or by high reaction temperature.For the bimolecular cracking, can and be adsorbed on the acidic site by paraffin that hydride shifts to form larger carbonium ion between the carbonium ion, and then can pass through β-cracking generation cracking reaction, can form aromatic compound by cyclization, maybe can form the isomers (people such as D.Mier by isomerization reaction, Ind.Eng.Che m.Res.vol.49, p8415,2010).Therefore, for the output maximization with light olefin, the mechanism that needs inhibition to be carried out by the bimolecular cracking, but need activation by the mechanism of unimolecule cracking execution.Hydrogen transfer activity is for the index of determining the key reaction path in these two kinds of mechanism.Can determine hydrogen transfer activity by the paraffin/olefin ratio of particular hydrocarbon in the product that produces in the reaction starting stage.When hydrogen transfer activity was higher, namely when hydride ion capacity (capacity) was higher, bimolecular cracking mechanism was main, and can produce a large amount of aromatic compounds and paraffin.When hydrogen transfer activity was low, namely when the hydride ion capacity hangs down, the unimolecule cracking by direct β-cracking carbonium ion was main, and can generate a large amount of light olefins.

For the impact on above-mentioned hydride transfer activity of the alkalescence of determining the ZSM-5 catalyst, measured the hydride transfer activity of the ZSM-5 catalyst of producing according to embodiment 11 to 14, and the relation of itself and catalyst alkalescence is shown among Figure 20.Ratio by (iso-butane+normal butane)/butylene has shown hydrogen transfer activity.The result of the catalyst of producing by embodiment 7 shows together, is used for relatively.

Referring to Figure 20, along with catalyst basicity increases, namely along with lanthanum introducing amount increases, the hydride transfer activity reduces.From this result as can be known, can be incorporated into by the metal that will show alkalescence and control the hydride transfer activity in the ZSM-5 catalyst, and by effectively preparing light olefin with this character.

Experiment 2: for the assessment that has the light olefin productive rate that micropore and mesoporous ZSM-5 catalyst crackene mixture produce by use and the analysis of catalytic activity.

(1) carbon is on the productive rate of light olefin and the impact of catalytic activity

Have micropore and mesoporous ZSM-5 catalyst by the light olefin of catalytic cracking hydrocarbon mixture production for what analyze the first embodiment production by using the design according to the present invention, particularly ethene and propylene, productive rate, be prepared reaction according to preparation feedback embodiment 1.Hydrocarbon mixture as reactant is C 5 fraction, and the component ratio is shown in Table 9.

＜table 9 〉

Chemical name	Component ratio (mol%)
		Pentane	33.4
Isopentane	25.0
		Amylene	8.3
Iso-amylene	25.0
		Pentamethylene	8.3

[preparation feedback embodiment 1]

In order to carry out the catalytic cracking of C 5 fraction, will put into respectively reactor according to the ZSM-5 catalyst of embodiment 1 to 5 and comparing embodiment production, and before reacting, at 500 ℃ of lower nitrogen (40ml) that pass through catalyst be activated 1 hour.After the catalyst activation, reactant is reacted by the catalyst layer in the reactor continuously.The weight hourly space velocity of reactant (WHSV) remains on 3.5h ^-1, and the catalytic cracking temperature of C 5 fraction is 500 ℃.By gas chromatography the product that obtains after the reaction is analyzed.The productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) is shown among table 10 and Figure 21.At this, calculate the productive rate of selective and light olefin (ethene+propylene) of conversion ratio, the light olefin of C 5 fraction by equation 1 to 4.

＜equation 1 〉

＜equation 2 〉

＜equation 3 〉

＜equation 4 〉

The productive rate of ethene and propylene (%)

The conversion ratio of=C 5 fraction * (ethene selective+propylene selective)/100

＜table 10 〉

Referring to table 10, by the catalytic cracking C 5 fraction, also produced methane, ethane, propane and butane and their isomers, and light olefin, for example ethene and propylene.And, machine-processed by the catalytic cracking of C 5 fraction except being undertaken the cracking by β-cracking, can produce the hydrocarbon chain longer than C5 hydro carbons by the polymerisation between the carbonium ion.

When in the preparation ZSM-5 catalyst according to as the carbon amount of template relatively during the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene), when when not comprising that according to comparing embodiment carbon is compared as the catalyst of template, when using when using carbon as the catalyst of template according to embodiment, the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) increases.When comparing with the pure ZSM-5 catalyst of producing according to comparing embodiment, because comprise the mesoporous of good development according to these embodiment by the catalyst that uses carbon to produce as template, the reactivity of catalyst produces difference.Comprise according to the good mesoporous catalyst of the development of these embodiment productions can relax in the catalytic cracking of C 5 fraction when using the pure ZSM-5 catalyst that only comprises the following micropore of 1nm the diffusion-restricted of issuable reactant, product and intermediate.Therefore, when use comprises mesoporous catalyst, can obtain even better reactivity.Along with the carbon amount increases, namely use even further comprise the mesoporous catalyst of good development, the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) can increase.

Simultaneously, when during preparation ZSM-5 catalyst, being up to by weight (referring to embodiment 1 to 3) 45 parts the time as the carbon amount of template, the productive rate of the conversion ratio of C 5 fraction and light olefin (ethene+propylene) increases, yet, when the carbon amount increase to surpass by weight 45 parts (referring to embodiment 4 and 5), the conversion ratio of C 5 fraction and the productive rate of light olefin no longer increase.Join according to the amount in the ZSM-5 catalyst of embodiment 3 productions by carbon, the mesoporous character of catalyst provides sufficient space for adsorption and desorption C 5 fraction, product and intermediate.Even the ZSM-5 catalyst comprises the larger mesoporous volume (the carbon addition surpasses 45 parts by weight in the preparation process of catalyst) of ZSM-5 catalyst that beguine is produced according to embodiment 3, also no longer show because the activity of the catalyst reaction that the mitigation diffusion-restricted causes improves.In addition, as described in Figure 15 and the table 4, according to the preparation method of catalyst, the acidity of catalyst differs from one another, and therefore, can ignore the acidity of catalyst to the impact of reactivity difference.Show the physical property that is better than pure ZSM-5 catalyst according to the first embodiment by the mesoporous ZSM-5 catalyst that has that uses carbon to produce as template.From this result as can be known, by preparing light olefin and be considered to very effective with having mesoporous ZSM-5 catalyst cracking C 5 fraction.In addition, can propose to consider that the best of productive rate adds the carbon amount, in order to obtain the most effective ZSM-5 catalyst for the preparation of light olefin.

(2) phosphorus is on the productive rate of light olefin and the impact of catalytic activity

Have micropore and mesoporous ZSM-5 catalyst by catalytic cracking hydrocarbon mixture generation light olefin for what analyze the second embodiment production by using the design according to the present invention, particularly ethene and propylene, productive rate, be prepared reaction according to preparation feedback embodiment 2.Hydrocarbon mixture as reactant is the C 5 fraction that has such as the composition ratio that shows in the top table 9.

[preparation feedback embodiment 2]

In order to carry out the catalytic cracking of C 5 fraction, will put into respectively reactor according to embodiment 3,6 to the 10 ZSM-5 catalyst of producing, and before reacting, at 650 ℃ of lower nitrogen (40ml) that pass through catalyst be activated 1 hour.After the catalyst activation, reactant is reacted by the catalyst layer in the reactor continuously.The weight hourly space velocity of reactant (WHSV) remains on 3.5h ^-1, and the catalytic cracking Temperature Setting of C 5 fraction is 600 ℃.By gas chromatography the product that obtains after the reaction is analyzed.The conversion ratio of C 5 fraction and the selective and productive rate of light olefin (ethene+propylene) in Figure 22 A and 22B, have been shown.At this, calculate the productive rate of selective and light olefin (ethene+propylene) of conversion ratio, the light olefin of C 5 fraction by equation 1 to 4.

Referring to Figure 22 A and 22B, use carbon to show than pure catalyst (comparing embodiment) even better active as the activity (embodiment 3) of the ZSM-5 catalyst of template.When comparing with the pure ZSM-5 catalyst of producing according to comparing embodiment, because comprise the mesoporous of good development according to these embodiment by the catalyst that uses carbon to produce as template, the reactivity of catalyst has produced difference.Comprise that mesoporous catalyst according to the good development of these embodiment productions can relax in the catalytic cracking C 5 fraction diffusion-restricted of issuable reactant, product and intermediate by using the pure ZSM-5 catalyst that only comprises the following micropore of 1nm.Therefore, when use comprises mesoporous catalyst, can obtain even better reactivity.

In addition, pure ZSM-5 catalyst shows fast catalysqt deactivation during about 40 hours reaction time.This inactivation is caused by carbon deposition between the stage of reaction.The immediate cause of carbon deposition is the polymerisation between the carbonium ion that produces as accessory substance during the catalytic cracking C 5 fraction.When producing the carbon deposition owing to the polymerisation between the carbonium ion in the micropore porch of pure ZSM-5 catalyst, the avtive spot that the inner avtive spot that exists of micropore may not be re-used as the cracking C 5 fraction works.Therefore, along with the carbon deposition increases, catalytic activity can fast reducing.

On the contrary, in by the ZSM-5 catalyst of use carbon as the template preparation, inactivation trend shows consistent with the reaction time slightly, yet this inactivation trend is lower than pure ZSM-5 catalyst.Because by using carbon as the mesoporous character of the ZSM-5 catalyst of template preparation, can obtain this character.In this case, even form the carbon deposition in the porch in hole, stop up fully mesoporous before C 5 fraction can infiltrate fully in the inside in hole, and can react.Yet along with the reaction time prolongs, the carbon deposition can little by little increase, and finally may stop up these holes, and may reduce reactivity.Therefore, may need to show mesoporous characteristic and minimum ZSM-5 catalyst is down in the catalysqt deactivation effect, and will introduce phosphorus as the ZSM-5 catalyst of template preparation by using carbon.

For by phosphorus being incorporated into the ZSM-5 catalyst (embodiment 6 to 10) for preparing in the ZSM-5 catalyst of carbon as the template preparation by using, during 40 hours reaction time, show metastable activity.Only when the amount of introducing phosphorus is low a little (embodiment 6), according to the passage in reaction time, observe the trend of inactivation.Yet when the amount of introducing phosphorus increases (embodiment 7 to 10), the ZSM-5 catalyst shows stable reactivity during 40 hours reaction time.

In order to study the acidity of ZSM-5 catalyst, particularly for the impact on reactivity of the acidity of the highly acid position of studying ZSM-5 catalyst as shown in table 5, in Figure 23 A and 23B, arrange and illustrated the relation between the productive rate of the conversion ratio of acidity, C 5 fraction of the highly acid position of ZSM-5 catalyst and light olefin (ethene+propylene).

Referring to Figure 23 A and 23B, with respect to the acidity of highly acid position, react the conversion ratio of C 5 fraction after 40 hours and the productive rate of light olefin and show that the volcano type distributes.At this, as shown in Figure 22 A and 22B, initial activity is good, yet, for the ZSM-5 catalyst that has larger acidity in the highly acid position according to embodiment 3 to 6, active slight reduction after reacting 40 hours.For the ZSM-5 catalyst according to embodiment 8 to 10, when the amount of the phosphorus of introducing is larger, can show stable reactivity, yet the acidity of highly acid position has reduced a bit and the reactivity slight reduction.Therefore, for according to the ZSM-5 catalyst of embodiment 7 by introducing the phosphorus of appropriate amount, by the acidity of control highly acid position, the deactivation of ZSM-5 catalyst can be down to minimum, and can be with the productive rate maximization of light olefin (ethene+propylene).

Simultaneously, for assess be incorporated into by use carbon as the amount of phosphorus in the ZSM-5 catalyst of template preparation on the impact according to the deposition of the reaction time carbon of catalyst, to analyzing according to embodiment 3 and 6 to the 10 ZSM-5 catalyst that after reacting 40 hours, produce, carry out CHNS(CHNS 932, Leco) analyze, and the results are shown in the table 11 the carbon deposition.

＜table 11 〉

Classification	Carbon deposition (wt%)
		Embodiment 3	9.4
Embodiment 6	6.8
		Embodiment 7	3.5
Embodiment 8	3.3
		Embodiment 9	3.4
Embodiment 10	2.5

Referring to table 11, do not comprise that the carbon deposition of the ZSM-5 catalyst (embodiment 3) of phosphorus is higher than the ZSM-5 catalyst (embodiment 6 to 10) that comprises phosphorus significantly.In addition, for the ZSM-5 catalyst that comprises phosphorus, along with the phosphorus amount increases, the carbon deposition reduces.As can be known from the results, can greatly be suppressed in the ZSM-5 catalyst of carbon as the template preparation in the catalytic cracking C 5 fraction because the catalysqt deactivation that the carbon of catalyst deposition causes by phosphorus being incorporated into by using.The acidity of highly acid position is considered to reduce along with the introducing of phosphorus.As shown in Figure 22 A and 22B, for the ZSM-5 catalyst of the highly acid position with high acidity (for the ZSM-5 catalyst that does not comprise phosphorus or comprise the ZSM-5 catalyst of very a small amount of phosphorus), react 40 hours reactivity slight reductions afterwards, yet, ZSM-5 catalyst (for the ZSM-5 catalyst that comprises appropriate amount phosphorus) for the highly acid position with low acidity has shown stable reactivity.Therefore, the carbon deposition can be easily produced by highly acid position rather than faintly acid position, and when controlling the acidity of highly acid position by introducing phosphorus, the catalyst that has carbon deposition tolerance can be prepared.Only when introducing excessive phosphorus, the activity of catalyst can slight reduction, and therefore expectation adds the phosphorus of appropriate amount.

Figure 24 A to 24F is the photo figure of ZSM-5 catalyst crystal structure after reaction 40 hours that obtains by high-resolution transmission electron microscope (JEM-3010, Jeol) according to embodiment 3,7 and 9.In Figure 24 A to 24F, C-ZSM5,0.3P/C-ZSM5 and 1.4P/C-ZSM5 are respectively corresponding to embodiment 3, embodiment 7 and embodiment 9.

Referring to Figure 24 A to 24F, around the crystal structure that does not comprise the ZSM-5 catalyst of phosphorus (embodiment 3), formed the strip that is different from the catalyst crystal lattice structure.This band is considered to be formed by the carbon deposition.Do not observe this banded structure for the ZSM-5 catalyst that comprises phosphorus (embodiment 7 to 9).This result is consistent with the CHNS analysis result in the table 11, and from this result as can be known, for comprising the ZSM-5 catalyst for preparing in the ZSM-5 catalyst of carbon as template by phosphorus is included in, confirms to have suppressed the carbon deposition.

(3) rare earth metal is on the productive rate of light olefin and the impact of catalytic activity

Have micropore and a mesoporous ZSM-5 catalyst in order to analyze by what the 3rd embodiment that uses the design according to the present invention produced, light olefin by the generation of catalytic cracking hydrocarbon mixture, particularly ethene and propylene, productive rate, be prepared reaction according to preparation feedback embodiment 3.The C 5 fraction that has such as the component ratio that shows in the table 9 in the above as the hydrocarbon mixture of reactant.

[preparation feedback embodiment 3]

In order to carry out the catalytic cracking of C 5 fraction, will put into respectively reactor according to

embodiment

7 and 11 to the 14 ZSM-5 catalyst of producing, and before reacting, at 600 ℃ of lower nitrogen (40ml) that pass through catalyst be activated 1 hour.After catalyst activation, with reactant continuously by the catalyst layer in the reactor in order to react.The weight hourly space velocity of reactant (WHSV) remains on 3.5h ^-1, and the catalytic cracking temperature of C 5 fraction is 600 ℃.Come the product that obtains after the reaction is analyzed by gas chromatography.Calculate the conversion ratio of C 5 fraction and the selective and productive rate of light olefin (ethene+propylene), and acidity and the alkaline impact on reactivity of catalyst have been described in Figure 25 A and 25B.At this, in Figure 26, shown the relation between lanthanum/phosphorus atoms ratio and the light olefin productive rate.At this, calculate the productive rate of selective and light olefin (ethene+propylene) of conversion ratio, the light olefin of C 5 fraction by equation 1 to 4.Reaction result among Figure 25 A and the 25B is based on the result that reaction obtained afterwards in 20 hours.

At first, do not show that for reaction time of 20 hours reactivity reduces.From this experimental result, find that the phosphorus component of introducing has prevented dealuminization and suitably realized inhibit feature aspect catalysqt deactivation.

Referring to Figure 25 A, the alkalescence of catalyst has greatly affected the product that obtains and has distributed after reaction.Along with the basicity increase of catalyst, the selectively greatly increase of light olefin.Yet, the selectively reduction of aromatic compound (benzene,toluene,xylene etc.).These trend are to be increased by the alkalescence along with catalyst, and hydrogen transfer activity reduces (referring to the Figure 20) that causes.When the hydrogen transfer activity of catalyst reduces, can suppress the bimolecular cracking, yet, can promote the unimolecule cracking, and therefore, can be preferably directly β-cracking be used for cyclisation carbonium ion and isomerization.Therefore, the selective of light olefin can be improved, and the generation of aromatic compound can be suppressed.

Referring to Figure 25 B, introduce lanthanum and be not considered to playing positive acting aspect the conversion ratio that improves C 5 fraction.As mentioned above, the introducing of lanthanum can reduce the acidity (referring to Figure 17) of catalyst, and the acidity of reduction catalyst may cause the reduction of cracking activity, thereby has reduced reactivity.That is, the lanthanum of introducing can be combined to reduce with a part of acidic site of catalyst the acidity of catalyst, and can reduce cracking activity.Therefore, along with lanthanum introducing amount increases, can reduce the conversion ratio of C 5 fraction.

Referring to Figure 26, for the atomic ratio of lanthanum/phosphorus, the productive rate of light olefin shows that the volcano type distributes.The increase of lanthanum can reduce the acidity of catalyst and reduce the conversion ratio of C 5 fraction, yet, increased the selective of light olefin thereby can increase the basicity of catalyst and weaken hydrogen transfer activity.Therefore, the catalyst that has suitable lanthanum/phosphorus atoms ratio by preparation is controlled such as the optical states in acidity and the alkalescence of the catalyst described in the embodiment 12, the inactivation of catalyst can be down to minimum and can be with the productive rate maximization of light olefin.

(4) alkali metal is on the productive rate of light olefin and the impact of catalytic activity

For the 3rd embodiment of analyzing by using the design according to the present invention has micropore and mesoporous, and comprise phosphorus and alkali-metal ZSM-5 catalyst, light olefin by the generation of catalytic cracking hydrocarbon mixture, especially ethene and propylene, productive rate, be prepared reaction for the ZSM-5 catalyst of being produced by embodiment 15 to 17 according to preparation feedback embodiment 3.The results are shown in the table 12.Use shows together according to the result of the ZSM-5 catalyst of

embodiment

7 and 12 preparations, is used for relatively.

＜table 12 〉

Referring to table 12, compare with the catalyst (embodiment 12) of the catalyst (embodiment 7) of introducing phosphorus or introducing phosphorus and lanthanum, introduce lithium or potassium and show lower a little reactivity as alkali-metal catalyst (embodiment 15 and 16).Yet catalyst (embodiment 17) demonstration of introducing caesium has improved the selective of light olefin, even show the conversion ratio of low a little C 5 fraction, thereby shows high yield.In addition, compare with the catalyst of introducing phosphorus or rare earth metal, introduce alkali-metal all catalyst and shown the selective of lower aromatic compound.As can be known from the results, introduce the reaction mechanism that alkali metal has been considered to suppress the bimolecular cracking, activated simultaneously the reaction mechanism of unimolecule cracking.When specific alkali metal optionally being incorporated in the ZSM-5 catalyst that comprises phosphorus, when comparing with the ZSM-5 catalyst of introducing rare earth metal together with phosphorus, prepare more effective that light olefin can carry out by the catalytic cracking C 5 fraction.

As mentioned above, design can prepare and comprises as the carbon of template and the ZSM-5 catalyst that has simultaneously micropore character and mesoporous character according to the present invention.This catalyst property can improve the diffusion of reactant and intermediate, and can increase from the productive rate of the light olefin that comprises ethene and propylene of the hydrocarbon mixture of C4 to C7.

In addition, can optimize phosphorus introducing amount, thereby provide the catalyst of the ZSM-5 with optimum acidity so that control has the acidity of the highly acid position of micropore and mesoporous ZSM-5 catalyst.When with having micropore and mesoporous ZSM-5 catalyst when coming to comprise the light olefin of ethene and propylene from the hydrocarbon mixture preparation of C4 to C7, can show for a long time stable and good activity.

In addition, by phosphorus and rare earth metal or alkali metal are incorporated in the ZSM-5 catalyst with micropore and mesoporous character, can form the catalyst that best atomic ratio could easily be controlled and have to its bronsted lowry acids and bases bronsted lowry.When with having micropore and mesoporous ZSM-5 catalyst when coming to comprise the light olefin of ethene and propylene from the hydrocarbon mixture preparation of C4 to C7, can improve the output of light olefin, and can keep for a long time stable and good activity.

Although the present invention has been carried out showing particularly and illustrating with reference to its illustrative embodiments, those of ordinary skills should be understood that the change that wherein can make on various ways and the details, and do not depart from the spirit and scope of the present invention that limit as by following claims.

Claims

1. one kind prepares the method with micropore and mesoporous ZSM-5 catalyst, described catalyst prepares the light olefin that comprises ethene and propylene for the hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking, described hydrocarbon mixture produces after the naphtha cracking process, and described method comprises:

(a) comprise that by aging the mixture solution of silica precursor and aluminum precursor forms gel;

(b) will may form mesoporous template by heat treatment and join in the described gel, stir then aging;

(c) by crystalline mixture aging in the step (b) is formed solid product; And

(d) thus described solid product heat-treated removes described template.

2. method according to claim 1, wherein by comprising that following every method comes the mixture solution in the preparation process (a):

(a-1) monovalent metal hydroxide and tetrapropyl ammonium halide are dissolved in the distilled water;

(a-2) thus adding described silica precursor forms homogeneous mixture; And

(a-3) the described aluminum precursor with liquid phase is added drop-wise in the described homogeneous mixture.

3. method according to claim 2, wherein said silica precursor is cataloid, and described aluminum precursor is to be selected from by sodium aluminate (NaAlO ₂), aluminum nitrate (Al (NO ₃) ₃), at least a in the group that forms of aluminium secondary butylate, tert-butyl alcohol aluminium, three aluminium secondary butylates, three tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide.

4. method according to claim 1, wherein said template is carbon dust or nanometer polymerization composition granule.

5. method according to claim 4, wherein said carbon dust or nanometer polymerization composition granule have sphere for about 2-50nm diameter, square, rectangle and cylindrical at least a shape.

6. method according to claim 4, wherein said nanometer polymer are to be selected from least a in the group that is comprised of Merlon, polystyrene, polyethylene, polypropylene, poly-(oxirane), poly-(expoxy propane), polyactide and polymethyl methacrylate.

7. method according to claim 1, wherein based on 100 parts of described silica precursors by weight, the amount of template is by weight about 5-80 part.

8. method according to claim 1, the Si/Al atomic ratio that wherein has micropore and mesoporous ZSM-5 catalyst is about 5-300.

9. method according to claim 1, wherein the heat treatment in the step (d) is to carry out under about 300-750 ℃ temperature, continues about 3-10 hour.

10. method according to claim 1 further is included in completing steps (d) afterwards:

(d-1) cation of the heat treated described solid product of displacement; And

(d-2) the described solid product of cation replacement is processed.

11. method according to claim 10, wherein said cationic displacement are to comprise by use being selected from by ammonium nitrate (NH ₄NO ₃), ammonium chloride (NH ₄Cl), ammonium carbonate ((NH ₄) ₂CO ₃) and ammonium fluoride (NH ₄F) at least a solution in the group that forms is realized.

12. method according to claim 10, wherein the heat treatment in the step (d-2) is to carry out under about 400-700 ℃ temperature, continues about 3-10 hour.

13. method according to claim 1 further comprises:

(e) by dipping method or ion-exchange process the phosphorus precursor is incorporated in the heat treated described solid product.

14. method according to claim 13, the dipping method of wherein said phosphorus precursor comprises:

(e-1) thus make water that described phosphorus precursor hydration is obtained hydration solution;

(e-2) heat treated described solid product in the step (d) is joined in the described hydration solution in order to flood with described hydration solution; And

(e-3) the described solid product of dipping carried out drying and heat treatment.

15. method according to claim 14, wherein said phosphorus precursor is to be selected from by phosphoric acid (H ₃PO ₄), mono phosphoric acid ester ammonium ((NH ₄) H ₂PO ₄), Diammonium phosphate (DAP) ((NH ₄) ₂HPO ₄) and ammonium phosphate ((NH ₄) ₃PO ₄) at least a in the group that forms.

16. method according to claim 14, wherein based on by weight 100 parts have micropore and mesoporous described ZSM-5 catalyst, the amount of described phosphorus precursor is by weight about 0.01-10 part.

17. method according to claim 14, wherein based on by weight 100 parts have micropore and mesoporous described ZSM-5 catalyst, the amount of described phosphorus precursor is by weight about 0.1-1.5 part.

18. method according to claim 14, wherein the heat treatment in the step (e-3) is to carry out under about 500-750 ℃ temperature, continues about 1-10 hour.

19. method according to claim 13 further comprises:

(f) by dipping method or ion-exchange process, rare earth metal precursor or alkali metal precursor are incorporated in the heat treated described solid product that comprises described phosphorus precursor.

20. method according to claim 19, wherein the dipping method of rare earth metal precursor or alkali metal precursor comprises described in the step (f):

(f-1) in water, make described rare earth metal precursor or alkali metal precursor hydration;

The solid product that (f-2) will comprise phosphorus described in the step (e) joins in the solution of the rare earth metal precursor of the hydration that includes stand-by described solution impregnation or alkali metal precursor; And

(f-3) the described solid product of dipping carried out drying and heat treatment.

21. method according to claim 20, wherein said rare earth metal are to be selected from least a in the group that is comprised of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu).

22. method according to claim 20, wherein said alkali metal are to be selected from least a in the group that is comprised of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and caesium (Cs).

23. method according to claim 20, wherein based on the atomic ratio with respect to described phosphorus, described rare earth metal or alkali-metal amount are about below 2.

24. method according to claim 20, wherein based on the atomic ratio with respect to described phosphorus, described rare earth metal or alkali-metal amount are about 0.1-1.5.

25. method according to claim 20, wherein the heat treatment in the step (f-3) is to carry out under about 500-750 ℃ temperature, continues about 1-10 hour.

26. method according to claim 1, wherein said hydrocarbon mixture comprises C 5 fraction.

27. one kind has micropore and mesoporous ZSM-5 catalyst, described catalyst prepares the light olefin that comprises ethene and propylene for the hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking, described hydrocarbon mixture produces after the naphtha cracking process, and described catalyst is by preparing as template with carbon dust or nanometer polymerization composition granule.

28. catalyst according to claim 27, wherein said catalyst prepares by method claimed in claim 1, and described catalyst has about 360-410m ²The specific area of/g, about 0.1-0.2cm ³Volume, about 0.05-0.3cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with the above diameter of about 2nm of/g and according to the about 130-145 μ of the temperature programmed desorption of ammonia mol-NH ₃The acidity of/g-catalyst.

29. catalyst according to claim 27, wherein based on by weight 100 parts have micropore and mesoporous described ZMS-5 catalyst, further comprise by weight about 0.01-10 part phosphorus precursor.

30. catalyst according to claim 29, wherein said catalyst is by the described method preparation of claim 11, and described catalyst has about 340-400m ²The specific area of/g, about 0.05-0.2cm ³Volume, about 0.05-0.2cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with the above diameter of about 2nm of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 80-95 μ mol-NH ₃The acidity of/g-catalyst and at highly acid position about 15-50 μ mol-NH ₃The acidity of/g-catalyst and the carbon deposition of analyzing about 2-7wt% according to the CHNS after catalyst reaction 40 hours.

31. catalyst according to claim 29 based on the atomic ratio with respect to described phosphorus, further comprises about 2 or more in a small amount rare earth metal or alkali metal.

32. catalyst according to claim 31, wherein said catalyst is by the described method preparation of claim 17, and described catalyst has about 300-400m ²The specific area of/g, about 0.05-0.2cm ³Volume, about 0.05-0.15cm of the micropore with the following diameter of about 1nm of/g ³The mesoporous volume with the above diameter of about 2nm of/g, according to the temperature programmed desorption of ammonia at faintly acid position about 70-90 μ mol-NH ₃The acidity of/g-catalyst, at highly acid position about 20-45 μ mol-NH ₃The acidity of/g-catalyst and about 2-30 μ mol-CO ₂The basicity of/g-catalyst.

33. catalyst according to claim 27, wherein said hydrocarbon mixture comprises C 5 fraction.

34. a hydrocarbon mixture that has 4 to 7 carbon by catalytic cracking prepares the method for the light olefin that comprises ethene and propylene, described hydrocarbon mixture produces after the naphtha cracking process, and described hydrocarbon mixture is at about 1-20h ^-1Weight hourly space velocity (WHSV) under, under about 300-700 ℃ temperature range, according to claim 27 have under micropore and the mesoporous ZMS-5 catalyst react.

35. method according to claim 34, wherein said hydrocarbon mixture comprises C 5 fraction.