CN102247885B - Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst - Google Patents

Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst Download PDF

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CN102247885B
CN102247885B CN 201110132043 CN201110132043A CN102247885B CN 102247885 B CN102247885 B CN 102247885B CN 201110132043 CN201110132043 CN 201110132043 CN 201110132043 A CN201110132043 A CN 201110132043A CN 102247885 B CN102247885 B CN 102247885B
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molecular sieve
zeolite molecular
alcl
zeolite
solid acid
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CN102247885A (en
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王新平
周玉强
徐丹
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Dalian University of Technology
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Abstract

The invention belongs to the technical field of chemical industry, and relates to a method for preparing a AlCl3 loaded zeolite molecular sieve solid acid catalyst. In the method for preparing a AlCl3/zeolite molecular sieve solid acid catalyst, gas phase chloromethane or chloromethane mixed gas reacts with a zeolite molecular sieve, and a corresponding zeolite molecular sieve part is subjected to dealumnization to generate AlCl3, thus AlCl3 is loaded on the surface of the zeolite molecular sieve and a AlCl3/zeolite molecular sieve solid acid is prepared. The invention has the beneficial effects that: no AlCl3 source is required to be additionally added, an -O-AlCl2 group can be loaded on the surface of the zeolite molecular sieve only by virtue of a gas containing chloromethane steam, and mesopores can be arranged on the zeolite molecular sieve by controlling treatment conditions.

Description

A kind of preparation AlCl 3The method of/zeolite molecular sieve solid acid catalyst
Technical field
The invention belongs to chemical technology field, it is immobilized in the preparation method of zeolite molecular sieve solid acid catalyst to relate to alchlor.
Background technology
Alchlor is a kind of superpower L acid, so it is to the alkylation on the phenyl ring, acylated, and the isomerization of alkane, cracking, the polymerization of alkene all show excellent catalytic activity.But, because it during as catalyst and the product separation difficulty, the product postprocessing operation is numerous and diverse and shortcoming such as serious environment pollution, makes it be applied in to a great extent and is restricted.
Patent USP2927087 (1960) proposes, and uses AlCl 3Steam and the surperficial Al that hydroxyl is arranged 2O 3, SiO 2Deng the refractory oxides reaction, thereby with AlCl 3Immobilized method on corresponding refractory oxides.
Patent USP3248343 (1966) proposes, the Al after handling with HCl 2O 3Same again AlCl 3Steam reaction can make active higher catalyst.
(Chem Commun, 1976,342 ~ 343 such as Gates; J Catal. 1977,46,266-274; J Polym Sci, 1977,15,1341-1347) propose, with AlCl 3Steam feeds in the macropore sulfuric acid resin, makes the solid super-strong acid of element than Cl:Al:S=2:1:2.This solid super-strong acid shows very high activity to the isomerization reaction of normal butane.
Patent USP 3880944 (1975), USP 3962133 (1976), USP 3925495 (1975), USP 3992473 (1976) propose, and between the graphite interlayer, are loaded with 5 ~ 55% AlCl 3Corresponding catalyst, C5 ~ C7 linear paraffin is had very high isomerization activity.
Patent USP 4288649 (1981), USP 4306105 (1981), USP 4582818 (1986) propose, under near the temperature 300 ℃, with CCl 4Steam is passed into Al 2O 3In make itself and Al 2O 3React, then Al 2O 3The hydroxyl and the O on surface 2-Replaced by the Cl atom, with AlCl 3Immobilized at Al 2O 3On, thereby preparation AlCl 3/ Al 2O 3The method of solid super-strong acid.
Patent USP4929800 (1990) proposes, with AlCl 3Be dissolved in CCl 4, CH 3Cl, CH 2Cl 2, process AlCl in the benzene, n-hexane equal solvent 3Corresponding solution, at N 2Protection adds Al down 2O 3, SiO 2In carrier, reflux in 50 ~ 80 ℃ of lucifuges, thereby with AlCl 3Immobilized on these carriers.
People such as Clark (Chem. Comm., 1995,2037-2040) propose, with AlCl 3Be dissolved in and process AlCl in the benzene 3Benzole soln, handle Al with mesopore with circumfluence method 2O 3, SiO 2, acid-treated imvite and K-10 (carrier) with part mesopore, make AlCl respectively 3Immobilized at Al 2O 3, SiO 2, in the acid-treated imvite and the solid acid in the K-10 hole.
Stephan Jaenicke (J. Catal., 2000,195:412-41) with C. Song etc. (J. Mol. Catal., 2003,191:67-74) with AlCl 3Be dissolved in and process AlCl in the benzene 3Benzole soln, handle the MCM-41 molecular sieve with circumfluence method, make AlCl 3Immobilized solid acid on the MCM-41 molecular sieve.
U. people (Chemical Engineering Journal 83,2001:185 – 189) such as Sridevi is with AlCl 3Process AlCl in being dissolved in the absolute ethyl alcohol 3Ethanol solution, handle the 13X molecular sieve with circumfluence method, obtained AlCl 3Loading is the AlCl of 15wt. % 3/ 13X solid acid.
People such as Wu Wei (modern chemical industry, 2004,24 (12): 30-32) with AlCl 3Be dissolved in and process AlCl in the absolute ethyl alcohol 3Ethanol solution, handle the HY molecular sieve with circumfluence method, obtained AlCl 3Immobilized solid acid on the HY molecular sieve.
People such as Xu (Applied Catalysis A:General, 217,2001:1 – 9; Journal of Catalysis, 195,2000:412 – 415) and people (Journal of Molecular Catalysis A:Chemical 191,2003:67 – 74) research such as Zhao reported MCM-41 at AlCl 3With reflow treatment in the benzene, thus preparation AlCl 3The method of/MCM-41 solid acid.
Dube ' waits people (Microporous and Mesoporous Materials 79,2005:137 – 144) research to report that multiple mesoporous molecular sieve is at AlCl 3With reflow treatment in the benzene, thus preparation AlCl 3Be grafted on the method for these mesoporous molecular sieve surface gained solid acids.
AlCl has been reported in people (J Porous Mater (2009) 16:631 – 634) such as Woong Yoon research 3With the oligomerisation reaction that is used for isobutene after ultra-steady Y molecular sieve (USY zeolite) mechanical mixture.
People such as Tang Hua (the catalysis journal, 2010,31 (7): 725 ~ 728) reported and used Al by research 2O 3With CCl 4Steam reacts down at 500 ℃ and generates AlCl 3, again by N 2Carrier band is to the Al-MCM-41 mesoporous molecular sieve, thus preparation AlCl 3The method of/Al-MCM-41 solid acid.
People such as Qi Lili (the catalysis journal, 2010,31 (4): 383 ~ 385) reported and used Al by research 2O 3With CCl 4Steam reacts down at 500 ℃ and generates AlCl 3, again by N 2Carrier band is to the MCM-41 mesoporous molecular sieve, thus preparation AlCl 3The method of/MCM-41 solid acid.
(J. Phys. Chem. B 106,2002:12140-12143) AlCl has been reported in research to people such as Mingcan 3Steam contacts with MCM-41 under the condition of finding time, with AlCl 3Immobilized on MCM-41, thus preparation AlCl 3The method of/MCM-41 solid acid.
Patent CN 1324690A (2001) and CN 1939590A (2007) propose, and use high-purity Al 2O 3With CCl 4Steam reacts down at 400-650 ℃ and generates AlCl 3, by N 2, H 2Carrier band is to the Al with double-pore structure 2O 3In, with AlCl 3Immobilized at this Al 2O 3On, thereby preparation AlCl 3/ Al 2O 3The method of solid acid.
Patent CN101638455A (2010) proposes, with sublimed method, infusion process or CCl 4Two-stage method is with AlCl 3Immobilized aluminium oxide, alumina silicate or silica, and Y zeolite, X zeolite, MFI, MEL, NaX, NaY, faujasite or modenite on, prepare the method for corresponding solid acid.Described sublimed method is about to the AlCl that distils 3Steam and the Al that has surface hydroxyl 2O 3, SiO 2Deng carrier reaction generation-O-AlCl 2The surface-active center; Described infusion process is promptly used CCl 4, CH 3Cl or CH 2Cl 2Be solvent, dissolving AlCl 3After with AlCl 3Be carried on the method on these carriers; Described CCl 4Two-stage method is promptly used high-purity Al 2O 3With CCl 4Steam reacts down at 400-650 ℃ and generates AlCl 3, again by N 2The method of carrier band to these carriers.
To sum up Cha Xin is visible, is used to prepare AlCl at present 3The method of/zeolite molecular sieve solid acid catalyst all is by existing AlCl 3, or prepare AlCl earlier through an additional reaction in advance 3, and then with the AlCl that generates 3React through physics or chemical method and molecular sieve and to make, corresponding processing step is complicated, and the reaction time is long, the cost of material height.
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, a kind of preparation AlCl is provided 3The method of/zeolite molecular sieve solid acid catalyst, the characteristics of this method are that method is simple, do not need to add in addition AlCl 3Source and addition reaction only can be with zeolite molecular sieve surface-O-AlCl with the gas that contains chloromethanes steam 2Change, the control treatment conditions can also be left mesopore on zeolite molecular sieve.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is: a kind of preparation AlCl 3The method of/zeolite molecular sieve solid acid catalyst, gas phase chloromethanes or chloromethanes mist and zeolite molecular sieve effect make corresponding zeolite molecules screen sections dealuminzation generate AlCl 3Thereby, with AlCl 3Immobilized on the zeolite molecular sieve surface, to make AlCl 3/ zeolite molecular sieve solid acid.
Said method comprises the dehydration preliminary treatment and two steps of part dealuminzation chlorination of zeolite molecular sieve:
(1) dehydration preliminary treatment: under 100 ~ 600 ℃, feed dry N to zeolite molecular sieve bed as carrier 2, air, O 2, one or more mists are removed the free moisture in the zeolite molecular sieve to described zeolite molecular sieve preliminary treatment 0.5 ~ 5 h among the Ar, He;
(2) part dealuminzation chlorination: under 80 ~ 500 ℃, be passed into chloromethanes steam or the mist that contains chloromethanes steam in this zeolite molecular sieve bed, contain AlCl to detecting in the gas that from bed, discharges 3In time, finish.
Said part dealuminzation chlorination length in time; Whether foundation will leave the stability of new mesopore and said zeolite molecular sieve on said zeolite molecular sieve; The concentration of chloromethanes in the air speed of treatment temperature, chloride steam methane gas and this gas and deciding, the needed processing time of dealuminzation is 1 minute ~ 12 hours.
The height of said part dealuminzation chlorination temperature, when will on zeolite molecular sieve, leaving new mesopore, and the stability of said zeolite molecular sieve is when strong, and the dealuminzation chlorination temperature is selected in 300 ~ 500 ℃, handles the concentration 1 ~ 10% of chloromethanes steam in the mist; To contain aluminium less when zeolite molecular sieve, or during the less stable of said zeolite molecular sieve, the dealuminzation chlorination temperature is handled concentration 10 ~ 1000 ppm of chloromethanes steam in the mist at 80 ~ 250 ℃, and described chloromethanes is CCl 4, HCCl 3, H 2CCl 2, H 3Plant the mixture of pressing arbitrary proportion among the CCl arbitrarily.
Described gas phase chloromethanes is the steam of chloromethanes, or contains the mist of chloromethanes steam, i.e. chloromethanes and dry air, N 2, Ar, CO 2, He, O 2In the mist that mixes of one or more gases; The volume total concentration of chloromethanes in mist (is CCl 4, HCCl 3, H 2CCl 2, H 3The summation of CCl concentration) at 10 ppm ~ 100%.
Saidly be used for immobilized AlCl 3Zeolite molecular sieve be traditional micro-pore zeolite molecular sieve; Like Y type, MFI type, MOR type, X type, Beta (β) type, FER type, SAPO-34 molecular sieve; Or mesoporous molecular sieve; Like Al-MCM-41, Al-MCM-48 molecular sieve; Or existing micropore, again the middle micro porous molecular sieve of mesopore arranged, or be called as acid imvite, Acidic Bentonite, the Emathlite of two-dimentional molecular sieve and mass percent that pillared inorganic material (pillared montmorillonite) zeolite molecular sieve that these stratified materials are obtained through chemical modifications accounts for gross weight greater than 50%.
Said zeolite molecular sieve is single skeleton structure zeolite molecular sieve, and perhaps multiple skeleton structure zeolite molecular sieve mixes, perhaps zeolite molecular sieve and Al 2O 3, SiO 2, natural clay mixes coexistence, zeolite molecular sieve accounts for the mass percent of gross weight greater than 50%.
Principle involved in the present invention is, when the mist that will contain chloromethanes steam is passed in the zeolite molecular sieve bed under 80 ~ 500 ℃, chloromethanes promptly with the aluminium atom effect on zeolite molecular sieve surface
Because AlCl 3Has volatility (normal boiling point is 178 ℃), the AlCl of generation 3Molecule can be spread to other position, zeolite molecular sieve surface and surface hydroxyl effect and forms-O-AlCl 2The acid site.
Like this, by the surface portion dealuminzation that zeolite molecular sieve and chloromethanes effect cause, can realize the zeolite molecular sieve surface-O-AlCl 2Grafting makes AlCl 3Immobilized solid acid on zeolite molecular sieve.
Prepare AlCl with the inventive method 3During immobilized solid acid on zeolite molecular sieve, the reaction condition of control zeolite molecular sieve and chloromethanes effect can realize making zeolite molecular sieve surface-O-AlCl simultaneously 2Grafting and on zeolite molecular sieve, leave the effect of mesopore.
The inventive method is applicable to various molecular sieves: be used for immobilized AlCl 3Zeolite molecular sieve; It can be traditional micro-pore zeolite molecular sieve; Like Y type, MFI type, MOR type, X type, Beta (β) type, FER type, SAPO-34 molecular sieve (seeing instance 1,2,3 and 4); Can be mesoporous molecular sieve (seeing instance 9); Like Al-MCM-41, Al-MCM-48 molecular sieve, can be existing micropore, again the middle micro porous molecular sieve of mesopore arranged, can also be acid imvite, Acidic Bentonite, Emathlite that is called as two-dimentional molecular sieve and the pillared inorganic material (pillared montmorillonite) (seeing instance 8) that these stratified materials are obtained through chemical modifications; The aluminium zeolite molecular sieve that contains involved in the present invention; Its pore structure or layer structure can be natural formation (like modenite, imvite) (seeing instance 3 and 8), also can manual work synthesize and (like the ZSM-5 molecular sieve) (seeing instance 1,2,3,4,5 and 6) of formation; Invent the related aluminium zeolite molecular sieve that contains, when carrying out chloridized with the inventive method, residing form can be Hydrogen (like HY, HZSM-5, HMOR, H β), also can be that the ammonium type is (like NH 4Y, NH 4ZSM-5, NH 4MOR, NH 4β) (see instance 1 and 3).When the zeolite molecular sieve as carrier was the ammonium type, the pretreatment stage before reacting with chloromethanes got final product big portion or all becomes Hydrogen.And in its duct remaining NH 4 +, also can chloridized stage of molecular sieve with NH 4The form of Cl is discharged from bed.
The inventive method is applicable to that multiple skeleton structure zeolite molecular sieve mixes the situation of coexistence.In this case, from containing the AlCl that Al zeolite molecular sieve top dealuminzation forms 3, can be spread to the surface that does not contain the Al molecular sieve and form-O-AlCl with its surface hydroxyl effect 2The acid site.
The inventive method is applicable to zeolite molecular sieve and Al 2O 3, SiO 2, the natural clay situation (seeing instance 5 and 7) of mixing coexistence.For moulding that helps zeolite molecular sieve and the mechanical strength that improves shaped granule, in molecular sieve, sneak into a certain proportion of boehmite, natural clay, SiO usually 2Deng inorganic binder.With this moulded zeolite molecular screen material is carrier, does not only influence AlCl on the zeolite molecular sieve 3Immobilized, on the contrary can be with being suitable for the immobilized AlCl of the inventive method 3Molecular sieve further expand to the zeolite molecular sieve that does not contain Al from containing the Al molecular sieve.Because by the inorganic binder that contains Al (like Al 2O 3, clay) AlCl that generates of part dealuminzation 3Also can be diffused into the zeolite molecular sieve surface that does not contain Al, form-O-AlCl with its surface hydroxyl effect 2Acid site (seeing instance 9).
Description of drawings
Fig. 1 is the XRD figure before and after the HZSM-5 molecular sieve chloridized of the present invention.
Fig. 2 is the XRD figure before and after the Hydrogen SAPO-34 molecular sieve chloridized of the present invention.
Fig. 3 is the XRD figure before and after the ammonium type natural mordenite zeolite chloridized of the present invention, (1) ammonium type natural mordenite zeolite among the figure, (2) AlCl 3/ Hydrogen natural mordenite zeolite.
Fig. 4 is the XRD figure of HY molecular sieve of the present invention before and after 12 min chloridized, (1) parent HY molecular sieve among the figure, (2) AlCl 3/ HY.
Fig. 5 is the graph of pore diameter distribution before and after the HY molecular sieve chloridized of the present invention.
Fig. 6 is the XRD figure of HY molecular sieve of the present invention before and after 4 min chloridized, (1) parent HY molecular sieve among the figure; (2) AlCl 3/ HY.
The specific embodiment
Specify AlCl below in conjunction with instantiation 3The preparation of/zeolite molecular sieve solid acid catalyst, but the present invention is not limited to specific embodiment.
Instance 1:AlCl 3 The preparation of/HZSM-5 solid acid
With 1 g (the compressing tablet screening is 20 ~ 40 orders) Hydrogen ZSM-5 (HZSM-5, SiO 2/ Al 2O 3=50) molecular sieve places quartz fixed bed reactor, feeds pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min, to remove moisture wherein.Bed temperature is reduced to 300 ℃, under this temperature with CCl 4Concentration be 5% CCl 4/ N 2Mist is passed in the reactor with the flow velocity of 300 ml/min this molecular sieve is carried out chloridized 20 min.Gained AlCl 3The XRD figure spectrum of/HZSM-5 and former parent Hydrogen ZSM-5 molecular sieve is as shown in Figure 1.
Instance 2:AlCl 3 The preparation of/HSAPO-34 solid acid
With 1 g (the compressing tablet screening is 20 ~ 40 orders) Hydrogen SAPO-34 (SiO 2/ Al 2O 3=0.9) molecular sieve places quartz fixed bed reactor, feeds pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min, to remove moisture wherein.Bed temperature is reduced to 250 ℃, under this temperature with CCl 4Concentration be 5% CCl 4/ N 2Mist is passed in the reactor with the flow velocity of 300 ml/min this Hydrogen SAPO-34 molecular sieve is carried out chloridized 10 min.Gained AlCl 3The XRD figure spectrum of/HSAPO-34 and former parent Hydrogen SAPO-34 is as shown in Figure 2.
Instance 3:AlCl 3 The preparation of/Hydrogen natural mordenite zeolite solid acid
Get 1 g through three NH 4NO 3Solution-treated is carried out the natural mordenite zeolite (20 ~ 40 order) of ammonium exchange, and promptly ammonium type modenite feeds pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min.Bed temperature is reduced to 300 ℃, under this temperature with CCl 4Concentration be 5% CCl 4/ N 2Mist is passed in the reactor with the flow velocity of 300 ml/min this ammonium type zeolite molecular sieve is carried out chloridized 10 min.Ammonium type zeolite molecular sieve has become corresponding h-type zeolite molecular sieve after preliminary treatment and chloridized.Gained AlCl 3The XRD figure spectrum of/Hydrogen natural mordenite zeolite and former parent ammonium type natural mordenite zeolite is as shown in Figure 3.
Instance 4:AlCl 3 The preparation of/HY solid acid
With 1 g (the compressing tablet screening is 20 ~ 40 orders) HY (SiO 2/ Al 2O 3=5) molecular sieve places quartz fixed bed reactor, feeds pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min, to remove moisture wherein.Bed temperature is reduced to 250 ℃, under this temperature with CCl 4Concentration be 5% CCl 4/ N 2Mist is passed in the reactor this HY chloridized 12 min with the flow velocity of 300 ml/min.Gained AlCl 3The XRD figure spectrum of/HY and former parent HY molecular sieve is as shown in Figure 4.Can infer that by this figure HY molecular sieve its part skeleton after chloridized has collapsed and collapsed.Use N 2The pore-size distribution of the HY that absorption method records before and after chloridized is as shown in Figure 5, and this figure shows.HY has produced the mesopore of about 2 nm of diameter after chloridized.
Instance 5:AlCl 3 The preparation of/HY solid acid
Repeat instance 4, but the Hydrogen Y molecular sieve chloridized time is shortened to 4 min by 12 min.The XRD figure spectrum of molecular sieve after the gained chlorination and former parent Hydrogen Y molecular sieve is as shown in Figure 6.
Instance 6:AlCl 3 The preparation of/HY solid acid
Repeat instance 4, but the mist that will be used for Hydrogen Y molecular sieve dealumination treatment is by CCl 4Concentration be 5% CCl 4/ N 2Change and be CHCl 3Concentration be the CHCl of 300 ppm 3/ N 2, simultaneously, the flow velocity of mist is changed into 600 ml/min, the dealumination treatment time is extended to 1 h by 12 min.The AlCl of gained after above-mentioned chloridized 3/ HY is similar with the XRD figure spectrum of former parent Hydrogen Y molecular sieve.
Instance 7:AlCl 3 The preparation of/HY solid acid
With 2.7 g Hydrogen Y molecular sieve (SiO 2/ Al 2O 3=5) mix with 0.3 g kaolin, add small amount of deionized water furnishing mud shape, the extruding slivering, the crushing screening of dry back is 20 ~ 40 orders.Take by weighing wherein that 1 g places quartz fixed bed reactor, feed pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min, to remove moisture wherein.Bed temperature is reduced to 200 ℃, and under this temperature, feeding flow velocity is the CCl of 600 ml/min 4/ N 2(CCl wherein 4Concentration is 300 ppm) 1 h.After above-mentioned chloridized the gained sample with handle before the XRD figure of biased sample compose similar.
Instance 8:AlCl 3 / Al 2 O 3 The preparation of pillared montmorillonite solid acid
With 1 g (the compressing tablet screening is 20 ~ 40 orders) Al 2O 3Pillared montmorillonite places quartz fixed bed reactor, feeds pure N down at 500 ℃ 2To this zeolite preliminary treatment 40 min, to remove moisture wherein.Bed temperature is reduced to 200 ℃, and under this temperature, feeding flow velocity is the CCl of 600 ml/min 4/ N 2(CCl wherein 4Concentration is 300 ppm) 1 h.After above-mentioned chloridized the gained sample with handle before the XRD figure of biased sample compose similar.
Instance 9:AlCl 3 / Al 2 O 3 The preparation of-MCM-41 solid acid
In 2 g total silicon MCM-41 mesoporous molecular sieves, add 0.5 gram boehmite and fully mix, add small amount of deionized water furnishing mud shape again, the extruding slivering.The crushing screening of dry back is 20 ~ 40 orders.Take by weighing wherein that 1 g places quartz fixed bed reactor, feed pure N down at 500 ℃ 2To this zeolite preliminary treatment 60 min, to remove moisture wherein.Bed temperature is reduced to 250 ℃, and under this temperature, feeding flow velocity is the CCl of 600 ml/min 4/ N 2(CCl wherein 4Concentration is 300 ppm) 1 h.After above-mentioned chloridized the gained sample with handle before the XRD figure of biased sample compose similar.
Two, AlCl 3 / zeolite molecular sieve solid acid catalyst acid strength is measured
Get 0.04 gram 2,4-dinitrotoluene (DNT) (p K a=-13.75), it is dissolved in 50 mL in the benzene of 5A molecular sieve drying processed, obtains indicator solution in advance as the Hammett indicator.
In glove box, take a morsel (~ 0.1 gram) respectively by instance 1 ~ 8 gained AlCl 3/ zeolite molecular sieve solid acid sample is put in the small test tube of dry clear, colorless, adds benzene after drying and dehydrating is handled immediately with the sample submergence, adds several above-mentioned Hammett indicator solutions again, shakes, and observes each sample surface color.Find that instance 1 ~ 9 gained sample surfaces color becomes yellow (the acid type look of indicator) by white, can judge by instance 1 ~ 9 gained AlCl thus 3/ zeolite molecular sieve sample all has H 0≤-13.75 solid super-strong acid character.
Three, use that isobutene is oligomeric to be that probe reaction measures AlCl 3 The instance that/zeolite molecular sieve solid acid catalysis is active
Instance 10:AlCl 3 The determination of activity of/zeolite molecular sieve solid acid catalyst
The AlCl that under nitrogen protection, will obtain by instance 4 3/ HY molecular sieve solid acid catalyst 0.5 restrains the stainless steel reaction pipe middle part of packing into, and all the other volumes are filled with quartz sand in the reaction tube.With the pressure in the YT-4 control piper at 3.0 MPa; With plunger displacement pump reaction mixture (mol ratio of normal butane, isobutene is 1:2) is injected reaction tube with the flow velocity of 4 ml/h; The temperature of keeping reaction system with water-bath is at 30 ℃, and obtaining conversion for isobutene is 80%.When HY molecular sieve 0.5 gram was reacted under same condition as catalyst, conversion for isobutene was merely 9%.This result shows with the inventive method gained AlCl 3It is active that/zeolite molecular sieve solid acid catalyst has stronger acid catalysis.

Claims (3)

1. one kind prepares AlCl 3The method of/zeolite molecular sieve solid acid catalyst is characterized in that: chloromethanes steam perhaps contains the mist and the zeolite molecular sieve effect of chloromethanes steam, makes corresponding zeolite molecules screen sections dealuminzation generate AlCl 3Thereby, with AlCl 3Immobilized on the zeolite molecular sieve surface, to make AlCl 3/ zeolite molecular sieve solid acid; Wherein said chloromethanes is CCl 4, HCCl 3, H 2CCl 2, H 3Plant the mixture of pressing arbitrary proportion among the CCl arbitrarily; Said mist is chloromethanes and dry air, N 2, Ar, CO 2, He, O 2In the mist that mixes of one or more gases; Be specially the dehydration preliminary treatment and two steps of part dealuminzation chlorination of zeolite molecular sieve:
(1) dehydration preliminary treatment: under 100 ~ 600 ℃, feed dry N to zeolite molecular sieve bed as carrier 2, air, O 2, one or more mists among the Ar, He are to said zeolite molecular sieve preliminary treatment 0.5 ~ 5 h, the free moisture in the zeolite molecular sieve is removed;
(2) part dealuminzation chlorination: be passed into chloromethanes steam or the mist that contains chloromethanes steam in this zeolite molecular sieve bed, contain AlCl to detecting in the gas that from bed, discharges 3In time, finish; When will on zeolite molecular sieve, leaving new mesopore, and the stability of said zeolite molecular sieve is when strong, and the dealuminzation chlorination temperature is 300 ~ 500 ℃, the concentration 1 ~ 10% of chloromethanes steam in the mist; To contain aluminium less when zeolite molecular sieve, and during the less stable of said zeolite molecular sieve, the dealuminzation chlorination temperature is at 80 ~ 250 ℃, and the volume total concentration of chloromethanes steam is at 10 ~ 1000 ppm in the mist.
2. a kind of preparation AlCl according to claim 1 3The method of/zeolite molecular sieve solid acid catalyst is characterized in that: the needed processing time of said part dealuminzation chlorination is 1 minute ~ 12 hours.
3. a kind of preparation AlCl according to claim 1 and 2 3The method of/zeolite molecular sieve solid acid catalyst is characterized in that: be used for immobilized AlCl 3Zeolite molecular sieve be traditional micro-pore zeolite molecular sieve, or mesoporous molecular sieve, or existing micropore has the middle micro porous molecular sieve of mesopore again.
4 .A kind of preparation AlCl according to claim 1 and 2 3The method of/zeolite molecular sieve solid acid catalyst is characterized in that: said zeolite molecular sieve adopts Y type, MFI type, MOR type, X type, Beta type, FER type, SAPO-34 molecular sieve, Al-MCM-41 or Al-MCM-48 molecular sieve.
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