CN105728018A - ZSM-5 zeolite catalyst for alkylating benzene and methanol, preparation method and application thereof - Google Patents
ZSM-5 zeolite catalyst for alkylating benzene and methanol, preparation method and application thereof Download PDFInfo
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- CN105728018A CN105728018A CN201410768186.5A CN201410768186A CN105728018A CN 105728018 A CN105728018 A CN 105728018A CN 201410768186 A CN201410768186 A CN 201410768186A CN 105728018 A CN105728018 A CN 105728018A
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 267
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 41
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010457 zeolite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002152 alkylating effect Effects 0.000 title description 3
- 239000002808 molecular sieve Substances 0.000 claims abstract description 112
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 112
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011148 porous material Substances 0.000 claims abstract description 73
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 70
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000029936 alkylation Effects 0.000 claims abstract description 54
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 239000000843 powder Substances 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 34
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 22
- 239000005457 ice water Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000001476 alcoholic effect Effects 0.000 claims description 16
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 15
- 239000011654 magnesium acetate Substances 0.000 claims description 15
- 229940069446 magnesium acetate Drugs 0.000 claims description 15
- 235000011285 magnesium acetate Nutrition 0.000 claims description 15
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000004898 kneading Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000012805 post-processing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 14
- 229960004217 benzyl alcohol Drugs 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 235000019445 benzyl alcohol Nutrition 0.000 description 10
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010412 oxide-supported catalyst Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a ZSM-5 zeolite catalyst for benzene and methanol alkylation, a preparation method and application thereof, wherein the catalyst is gamma-Al2O3Or eta-Al2O3Any one of the molecular sieves and the HZSM-5 molecular sieve of the multilevel pore passage are taken as carriers and are formed by loading MgO; wherein, the total weight of the carrier is 100%, the HZSM-5 molecular sieve with multi-stage pore canals in the carrier accounts for 50-80%, and gamma-Al2O3Or eta-Al2O3Any one of them accounts for 20-50%, and the amount of the loaded MgO is 1-12%. The catalyst of the present invention has high toluene and xylene selectivity and stability.
Description
Technical field
The present invention relates to the catalyst in petrochemical process, particularly to a kind of catalyst for benzene, methanol alkylation.
Background technology
Benzene is mainly derived from the by-product of catalytic reforming, the isomerization of aromatic hydrocarbons and coal tar and ethylene production technique.It is reported, often producing 800,000 tons of ethylene just has the benzene of 150,000 tons to generate, and the increment of China's ethylene will at 2,000,000 more than t/a, and this will cause the excessive of benzene.And methanol is as a kind of excellent reagent cheap and easy to get, it has been obtained for research widely and application in esterification, etherificate etc., but as one of the important products of Coal Chemical Industry, fast development along with Coal Chemical Industry, on market, methanol output will increase rapidly, superfluous situation occur, and dimethylbenzene is as one of most important basic chemical raw materials, its demand presents staggering growth situation.
From 1979, both at home and abroad the research of high concentration xylol is directly synthesized for alkylation of toluene methanol reaction and has carried out substantial amounts of work, carry out modulation by the various methods acidity to ZSM-5 and pore structure.Up to now, in toluene and methanol alkylation react, about how to improve para-selective catalyst and keep a difficult problem for its high activity and high stability to be solved not yet, thus this technique is also not found in industrial applications always.And benzene and methanol alkylation react report seldom, utilize the downstream product such as relatively inexpensive benzene and the toluene of methanol-fueled CLC high added value, dimethylbenzene and ethylbenzene, not only take full advantage of superfluous resource, and to meeting domestic supply and demand present situation and the competitive pressure of domestic chemical enterprise opposing foreign market being had extremely important realistic meaning.Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, phenyl ring is constitutionally stable compound, the diameter of toluene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, it is necessary to consider the problems such as catalyst structure, acidity, pore passage structure.
Up to now, about benzene, methanol alkylation reaction research report and patent documentation all fewer at home and abroad.Chinese patent 201210025588.7 describes the technical scheme adopting the molecular sieve carried alkaline earth of HMCM-22, thulium, and after using it for benzyl alcohol alkylation, the selectivity of dimethylbenzene increases.Chinese patent 200910242740.5 describes with HMCM-56 molecular sieve for carrier, carried metal Mo or Ni, and its mass content is respectively with MoO3Or NiO meter, load quality is 3～15%, after benzyl alcohol alkylation, and conversion per pass >=45% of benzene, selectivity >=89% of toluene and dimethylbenzene.Chinese patent 200910075173.9 essentially describes the impact on benzene, methanol alkylation reaction of technological design and process conditions thereof.Catalyst respectively HMCM-22, the HMCM-56 used in above-mentioned the first two patent, although selectivity all increases, but the stability of catalyst is but not as, thus limit its industrial applications, the patent of Shanxi Hengyang Science & Technology Co., Ltd.'s application is only made the change of technological design and process conditions, and its industrial applications is worth and is also extremely limited.
The deficiency that prior art exists is, current catalyst exists easy in inactivation when being used for the alkylated reaction of benzene and methanol, the problem of low conversion rate, selectivity of product difference.How to provide a kind of catalyst for benzene Yu the alkylated reaction of methanol so that it is there is higher toluene, dimethylbenzene selective and stability, namely become those skilled in the art's problem demanding prompt solution.
Summary of the invention
It is an object of the invention to provide a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its method for making and application, make this catalyst have higher toluene, dimethylbenzene selective and stability.
For achieving the above object, the present invention provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Or η-Al2O3In any one and multistage pore canal HZSM-5 molecular sieve be carrier, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3Or η-Al2O3In any one account for 20～50%, the amount of load MgO is 1～12%.
Wherein, described carrier is multistage pore canal HZSM-5 molecular sieve and γ-Al2O3。
Wherein, in described carrier, weight ratio shared by multistage pore canal HZSM-5 molecular sieve is preferably 60～75%.
Wherein, γ-Al in described carrier2O3Shared weight ratio is preferably 25～40%.
Wherein, in described carrier, weight ratio shared by load MgO is preferably 5～10%.
Wherein, described multistage pore canal HZSM-5 molecular sieve is: adopt the micropore HZSM-5 molecular sieve of silica alumina ratio 180-300, in the basic conditions, modifiy with sodium aluminate solution, adopt tetraethyl orthosilicate alcoholic solution to carry out the multistage pore canal HZSM-5 molecular sieve that secondary pore-forming prepares with acid modulation simultaneously.
Wherein, described multistage pore canal HZSM-5 molecular sieve recipe step is as follows:
1) when pH value 13-13.5, adding the sodium aluminate solution of 0.005～0.05mol/L in the micropore HZSM-5 molecular sieve of silica alumina ratio 180-300 according to solid-to-liquid ratio 1:10-20, stirring 40～60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction 3～6h, and roasting 5-6h in 500～550 DEG C of Muffle furnaces, obtain white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 90～140min in 65～90 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:5-20 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve.
Through modified, the duct of the molecular sieve of formation is contained a certain amount of mesoporous, increases the specific surface area of catalyst.Giving pore-size distribution and the XRD figure of HZSM-5 molecular sieve after before modified in accompanying drawing of the present invention, the life-span of catalyst is greatly improved as seen from the figure.
The present invention also provides for a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) silica alumina ratio micropore HZSM-5 molecular sieve between 180-300 is taken, when pH value 13-13.5, add the sodium aluminate solution of 0.005～0.05mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:10-20, stirring 40～60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction roasting, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 90～140min in 65～90 DEG C of tetraethyl orthosilicate alcoholic solution；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction, roasting, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In any one mixing, add the dilute nitric acid solution that mass fraction is 1～5% and carry out kneading, extrusion, dry, roasting, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated, after dry, roasting, obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation.
Wherein, in step 2) in, by filtration cakes torrefaction 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces, obtain white (or having slight yellowish) powder.
Wherein, in step 3) in, tetraethyl orthosilicate alcoholic solution is tetraethyl orthosilicate and the ethanol 1:5-20 in molar ratio solution mixed.
Wherein, in step 4) in, by filter cake dry 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces at 120 DEG C, obtain white powder multistage pore canal HZSM-5 molecular sieve.
Wherein, in step 5) in, described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In the mixed proportion of any one mixing be that, with total weight of carrier for 100%, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3 or any one in η-Al2O3 account for 20～50%.
Wherein, in step 5) in, described drying and roasting is roasting 4～12h at 450～600 DEG C.
Wherein, in step 6) in, the time of described dipping is 8～48h (being preferably 18～36h)；Described roasting is in atmosphere with 450～600 DEG C of roasting 4～12h；Magnesium acetate solution is analytical pure.
Wherein, in step 6) in, concrete operation step is: measure respective carrier weight by final required catalyst, and calculate required load MgO weight (with total weight of carrier for 100%, the amount of load MgO is 1～12%), the magnesium acetate solution of suitable concentration is selected with required load MgO, weigh carrier and magnesium acetate, at ambient temperature, magnesium acetate is poured in deionized water and is completely dissolved, finally adopt equi-volume impregnating to carry out described dip operation.
For achieving the above object, the present invention also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 400 DEG C～500 DEG C, reaction pressure 0.1～1MPa, weight space velocity 1～8h-1, benzene and methanol molar ratio 0.8～1.2.
The present invention is analytical pure for the purity of alkylating raw material (benzene, methanol), catalyst performance has the conversion ratio X (B) of benzene with active primary evaluation index, toluene, dimethylbenzene overall selectivity S (TX) and total recovery Y (TX), and the selectivity S (X) of the selectivity S (T) of toluene, dimethylbenzene.Their computational methods are as follows respectively:
S (X)=Q/N × 100% (3-5)
M in formula: the molal quantity of benzene in feedstock；
N: the molal quantity of benzene homologues in product；
P: the molal quantity of toluene in product；
Q: the molal quantity of dimethylbenzene in product.
Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, phenyl ring is constitutionally stable compound, the diameter of toluene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, to consider the problem such as acidity, pore passage structure in the structural design of catalyst.The diffusion that suitable acid amount and pore passage structure are conducive to benzyl alcohol alkylated reaction to generate product, it is prevented that carbon distribution is too fast, is conducive to the stability of catalyst.
Carbon is easily tied based on the catalyst existed in above-mentioned theory and prior art, when catalyst is for benzene, methanol alkylation reaction, catalysis activity is low, the problem of selectivity of product difference, the present invention provides a kind of and uses metal oxide supported catalyst, and it has the following technical effect that
1) present invention is by adopting post processing HZSM-5 zeolite as catalyst activity main body, metal oxide-loaded modified, at 400 DEG C～500 DEG C, 0.1～1MPa, weight space velocity 1～10h-1, benzene/methanol (mol ratio) 0.6～1.2 operating condition under, the conversion ratio of benzene is 49.39%, and the selectivity of toluene and dimethylbenzene is 87.91%, and yield is 43.41%.When the catalyst of the present invention is for benzene, methanol alkylation reaction, having not easily coking, activity is high, the advantage that selectivity of product is high.
2) catalyst of the present invention has higher toluene, dimethylbenzene selective and stability, it is possible to comprehensive utilization benzene and methanol resource produce the chemical products that various value are higher effectively, alleviate and environment is impacted.
3) relative to prior art, catalyst of the present invention has high activity and hydrothermal stability and longer service life.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 is the BET phenogram of the embodiment of the present invention 1 and embodiment 2 Middle molecule sieve；
Fig. 2 is the multistage pore canal HZSM-5 molecular sieve bore diameter scattergram of the embodiment of the present invention 2；
Fig. 3 is the XRD spectra of the embodiment of the present invention 1 and embodiment 2 gained catalyst；
Fig. 4 is the preparation method flow chart of steps of catalyst of the present invention.
Wherein, accompanying drawing labelling:
1,1 ': embodiment 1 curve
2,2 ': embodiment 2 curve
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail, and what listed illustrative embodiments was only used as to illustrate, it is not intended as the restriction of the present invention.
Refer to Fig. 4, it is the preparation method flow chart of steps of catalyst of the present invention.For making catalyst have higher toluene, dimethylbenzene selective and stability, the present invention provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Or η-Al2O3In any one and multistage pore canal HZSM-5 molecular sieve be carrier, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3Or η-Al2O3In any one account for 20～50%, the amount of load MgO is 1～12%.
Wherein, described carrier is multistage pore canal HZSM-5 molecular sieve and γ-Al2O3。
Wherein, in described carrier, weight ratio shared by multistage pore canal HZSM-5 molecular sieve is preferably 60～75%.
Wherein, γ-Al in described carrier2O3Shared weight ratio is preferably 25～40%.
Wherein, in described carrier, weight ratio shared by load MgO is preferably 5～10%.
Wherein, described multistage pore canal HZSM-5 molecular sieve is: adopt the micropore HZSM-5 molecular sieve of silica alumina ratio 180-300, in the basic conditions, modifiy with sodium aluminate solution, adopt tetraethyl orthosilicate alcoholic solution to carry out the multistage pore canal HZSM-5 molecular sieve that secondary pore-forming prepares with acid modulation simultaneously.
Wherein, described multistage pore canal HZSM-5 molecular sieve recipe step is as follows:
1) when pH value 13-13.5, adding the sodium aluminate solution of 0.005～0.05mol/L in the micropore HZSM-5 molecular sieve of silica alumina ratio 180-300 according to solid-to-liquid ratio 1:10-20, stirring 40～60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction 3～6h, and roasting 5-6h in 500～550 DEG C of Muffle furnaces, obtain white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 90～140min in 65～90 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:5-20 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve.
Through modified, the duct of the molecular sieve of formation is contained a certain amount of mesoporous, increases the specific surface area of catalyst.Giving pore-size distribution and the XRD figure of HZSM-5 molecular sieve after before modified in accompanying drawing of the present invention, the life-span of catalyst is greatly improved as seen from the figure.
The present invention also provides for a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) silica alumina ratio micropore HZSM-5 molecular sieve between 180-300 is taken, when pH value 13-13.5, add the sodium aluminate solution of 0.005～0.05mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:10-20, stirring 40～60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction roasting, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 90～140min in 65～90 DEG C of tetraethyl orthosilicate alcoholic solution；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction, roasting, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In any one mixing, add the dilute nitric acid solution that mass fraction is 1～5% and carry out kneading, extrusion, dry, roasting, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated, after dry, roasting, obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation.
Wherein, in step 2) in, by filtration cakes torrefaction 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces, obtain white (or having slight yellowish) powder.
Wherein, in step 3) in, tetraethyl orthosilicate alcoholic solution is tetraethyl orthosilicate and the ethanol 1:5-20 in molar ratio solution mixed.
Wherein, in step 4) in, by filter cake dry 3～6h, roasting 5-6h in 500～550 DEG C of Muffle furnaces at 120 DEG C, obtain white powder multistage pore canal HZSM-5 molecular sieve.
Wherein, in step 5) in, described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In the mixed proportion of any one mixing be that, with total weight of carrier for 100%, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3 or any one in η-Al2O3 account for 20～50%.
Wherein, in step 5) in, described drying and roasting is roasting 4～12h at 450～600 DEG C.
Wherein, in step 6) in, the time of described dipping is 8～48h (being preferably 18～36h)；Described roasting is in atmosphere with 450～600 DEG C of roasting 4～12h；Magnesium acetate solution is analytical pure.
Wherein, in step 6) in, concrete operation step is: measure respective carrier weight by final required catalyst, and calculate required load MgO weight (with total weight of carrier for 100%, the amount of load MgO is 1～12%), the magnesium acetate solution of suitable concentration is selected with required load MgO, weigh carrier and magnesium acetate, at ambient temperature, magnesium acetate is poured in deionized water and is completely dissolved, finally adopt equi-volume impregnating to carry out described dip operation.
The present invention also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 400 DEG C～500 DEG C, reaction pressure 0.1～1MPa, weight space velocity 1～8h-1, benzene and methanol molar ratio 0.8～1.2.
Embodiment a
The present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) taking the micropore HZSM-5 molecular sieve that silica alumina ratio is 180, under pH value 13 condition, add the sodium aluminate solution of 0.005mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:10, stirring 40min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by dry at filter cake 120 DEG C 3h, roasting 5h in 500 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 90min in 65 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:5 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 3h, roasting 5h in 500 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3(mixed proportion is for total weight of carrier for 100% in mixing, multistage pore canal HZSM-5 molecular sieve accounts for 50%, γ-Al2O3 accounts for 20%), add the dilute nitric acid solution that mass fraction is 1% carry out kneading, extrusion, dry, at 450 DEG C roasting 4h, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated 8h, it is ensured that final load MgO weight is vehicle weight 1%, dry, in atmosphere to obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation after 450 DEG C of roasting 4h.
The present embodiment provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Being carrier with multistage pore canal HZSM-5 molecular sieve, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 50%, γ-Al2O3Accounting for 20%, the amount of load MgO is 1%.
The present embodiment also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 400 DEG C, reaction pressure 0.1MPa, weight space velocity 1h-1, benzene and methanol molar ratio 0.8.
Embodiment b
The present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) taking the micropore HZSM-5 molecular sieve that silica alumina ratio is 300, under pH value 13.5 condition, add the sodium aluminate solution of 0.05mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:20, stirring 60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by dry at filter cake 120 DEG C 6h, roasting 6h in 550 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 140min in 90 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:20 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 6h, roasting 6h in 550 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3(mixed proportion is for total weight of carrier for 100% in mixing, multistage pore canal HZSM-5 molecular sieve accounts for 80%, γ-Al2O3 accounts for 50%), add the dilute nitric acid solution that mass fraction is 5% carry out kneading, extrusion, dry, at 600 DEG C roasting 12h, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated 48h, it is ensured that final load MgO weight is vehicle weight 12%, dry, in atmosphere to obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation after 600 DEG C of roasting 12h.
The present embodiment provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Being carrier with multistage pore canal HZSM-5 molecular sieve, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 80%, γ-Al2O3Accounting for 50%, the amount of load MgO is 12%.
The present embodiment also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 500 DEG C, reaction pressure 1MPa, weight space velocity 8h-1, benzene and methanol molar ratio 1.2.
Embodiment c
The present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) taking the micropore HZSM-5 molecular sieve that silica alumina ratio is 200, under pH value 13.2 condition, add the sodium aluminate solution of 0.01mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:15, stirring 50min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by dry at filter cake 120 DEG C 4h, roasting 5.2h in 520 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 100min in 70 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:10 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 4h, roasting 5.2h in 520 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3(mixed proportion is for total weight of carrier for 100% in mixing, multistage pore canal HZSM-5 molecular sieve accounts for 60%, γ-Al2O3 accounts for 25%), add the dilute nitric acid solution that mass fraction is 2% carry out kneading, extrusion, dry, at 500 DEG C roasting 8h, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated 18h, it is ensured that final load MgO weight is vehicle weight 5%, dry, in atmosphere to obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation after 500 DEG C of roasting 8h.
The present embodiment provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Being carrier with multistage pore canal HZSM-5 molecular sieve, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 60%, γ-Al2O3Accounting for 25%, the amount of load MgO is 5%.
The present embodiment also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 450 DEG C, reaction pressure 0.5MPa, weight space velocity 3h-1, benzene and methanol molar ratio 0.9.
Embodiment d
The present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, comprises the following steps:
1) taking the micropore HZSM-5 molecular sieve that silica alumina ratio is 250, under pH value 13.4 condition, add the sodium aluminate solution of 0.03mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:17, stirring 55min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by dry at filter cake 120 DEG C 5h, roasting 5.4h in 540 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；
3) gained white (or having slight yellowish) powder is sufficiently stirred for reaction 120min in 80 DEG C of tetraethyl orthosilicate alcoholic solution (tetraethyl orthosilicate and the ethanol 1:15 in molar ratio solution mixed)；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 5h, roasting 5.4h in 540 DEG C of Muffle furnaces at 120 DEG C, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3(mixed proportion is for total weight of carrier for 100% in mixing, multistage pore canal HZSM-5 molecular sieve accounts for 75%, γ-Al2O3 accounts for 40%), add the dilute nitric acid solution that mass fraction is 4% carry out kneading, extrusion, dry, at 550 DEG C roasting 10h, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated 36h, it is ensured that final load MgO weight is vehicle weight 10%, dry, in atmosphere to obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation after 550 DEG C of roasting 10h.
The present embodiment provides a kind of ZSM-5 zeolite catalyst for benzene, methanol alkylation, and described catalyst is with γ-Al2O3Being carrier with multistage pore canal HZSM-5 molecular sieve, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 75%, γ-Al2O3Accounting for 40%, the amount of load MgO is 10%.
The present embodiment also provides for a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation: above-mentioned catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 470 DEG C, reaction pressure 0.7MPa, weight space velocity 5h-1, benzene and methanol molar ratio 1.0.
The present invention is analytical pure for the purity of alkylating raw material (benzene, methanol), catalyst performance has the conversion ratio X (B) of benzene with active primary evaluation index, toluene, dimethylbenzene overall selectivity S (TX) and total recovery Y (TX), and the selectivity S (X) of the selectivity S (T) of toluene, dimethylbenzene.Their computational methods are as follows respectively:
S (X)=Q/N × 100% (3-5)
M in formula: the molal quantity of benzene in feedstock；
N: the molal quantity of benzene homologues in product；
P: the molal quantity of toluene in product；
Q: the molal quantity of dimethylbenzene in product.
Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, phenyl ring is constitutionally stable compound, the diameter of toluene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, to consider the problem such as acidity, pore passage structure in the structural design of catalyst.The diffusion that suitable acid amount and pore passage structure are conducive to benzyl alcohol alkylated reaction to generate product, it is prevented that carbon distribution is too fast, is conducive to the stability of catalyst.
Carbon is easily tied based on the catalyst existed in above-mentioned theory and prior art, when catalyst is for benzene, methanol alkylation reaction, catalysis activity is low, the problem of selectivity of product difference, the present invention provides a kind of and uses metal oxide supported catalyst, and it has the following technical effect that
1) present invention is by adopting post processing HZSM-5 zeolite as catalyst activity main body, metal oxide-loaded modified, at 400 DEG C～500 DEG C, 0.1～1MPa, weight space velocity 1～10h-1, benzene/methanol (mol ratio) 0.6～1.2 operating condition under, the conversion ratio of benzene is 49.39%, and the selectivity of toluene and dimethylbenzene is 87.91%, and yield is 43.41%.When the catalyst of the present invention is for benzene, methanol alkylation reaction, having not easily coking, activity is high, the advantage that selectivity of product is high.
2) catalyst of the present invention has higher toluene, dimethylbenzene selective and stability, it is possible to comprehensive utilization benzene and methanol resource produce the chemical products that various value are higher effectively, alleviate and environment is impacted.
3) relative to prior art, catalyst of the present invention has high activity and hydrothermal stability and longer service life.
Below by the embodiment under different technology conditions and experimental data thereof, the invention will be further described, to clearly show that its technique effect.
Embodiment 1
Weigh the micropore HZSM-5 molecular sieve 7g bought from south catalyst plant, add γ-Al2O33g, after mix homogeneously, adds 4% dust technology and carries out kneading, extruded moulding, puts into thermostatic drying chamber in 120 DEG C when after dry 12h, and roasting strip break-up of catalyst are to the granule of 20～40 orders, finally then through obtaining catalyst A after roasting.
Embodiment 2
Weigh a certain amount of micropore HZSM-5 molecular sieve (southization catalyst plant), under pH value 13.3 (can regulate with sodium hydroxide) condition, with the sodium aluminate solution of 0.005mol/L, HZSM-5 molecular sieve is modified, solid-to-liquid ratio 1:10, stirring 40min, and wash to filtrate neutral, by filtration cakes torrefaction 6h, roasting 6h in 500～550 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；Gained powder is sufficiently stirred in 90 DEG C of tetraethyl orthosilicate alcoholic solution reaction 100min, reactor is carried out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 6h at 120 DEG C, roasting 6h in 500～550 DEG C of Muffle furnaces, sucking filtration obtains multistage pore canal HZSM-5 molecular sieve；Weigh the multistage pore canal HZSM-5 molecular sieve 7g after this process, add γ-Al2O33g, after mix homogeneously, adds 4% dust technology and carries out kneading, extruded moulding, puts into thermostatic drying chamber in 120 DEG C when after dry 12h, and roasting strip break-up of catalyst are to the granule of 20～40 orders, finally then through obtaining catalyst B after roasting.
Embodiment 3
Weigh a certain amount of micropore HZSM-5 molecular sieve (southization catalyst plant), under pH value 13.5 (can regulate with sodium hydroxide) condition, with the sodium aluminate solution of 0.05mol/L, HZSM-5 molecular sieve is modified, solid-to-liquid ratio 1:20, stirring 60min, and wash to filtrate neutral, by filtration cakes torrefaction 6h, roasting 6h in 500～550 DEG C of Muffle furnaces, obtains white (or having slight yellowish) powder；Gained powder is sufficiently stirred in 75 DEG C of tetraethyl orthosilicate alcoholic solution reaction 120min, reactor is carried out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filter cake dry 6h at 120 DEG C, roasting 6h in 500～550 DEG C of Muffle furnaces, sucking filtration obtains multistage pore canal HZSM-5 molecular sieve；Weigh the multistage pore canal HZSM-5 molecular sieve 7g after this process, add γ-Al2O33g, after mix homogeneously, adds 4% dust technology and carries out kneading, extruded moulding, puts into thermostatic drying chamber in 120 DEG C when after dry 12h, and roasting strip break-up of catalyst are to the granule of 20～40 orders, finally then through obtaining catalyst C after roasting.
Refer to Fig. 1 to Fig. 3, which show the catalyst performance parameter of the embodiment of the present invention 1 to embodiment 3.
Fig. 1 is the molecular sieve BET phenogram of embodiment 1, embodiment 2, and abscissa is relative pressure (Relativepressure), and vertical coordinate is adsorbance (Quantityabsorbed).Fig. 1 comprises four curves altogether, the adsorption curve of two, the top curve 2 multistage pore canal HZSM-5 molecular sieve obtained by embodiment 2 and desorption curve, two, bottom curve 1 is adsorption curve and the desorption curve (two curve is to overlap) of the common HZSM-5 molecular sieve of embodiment 1.It addition, aperture (Poresize) scattergram that Fig. 2 is multistage pore canal HZSM-5 molecular sieve in embodiment 2.
Adopting N2 physical absorption that molecular sieve is characterized, obtaining the performances such as the pore volume of molecular sieve, pore-size distribution and specific surface area, thus judging the pore passage structure of synthesis of molecular sieve.By Fig. 1, carrying 2 it can be seen that classification according to IUPAC (IUPAC), multistage pore canal HZSM-5 molecular sieve is at relative pressure P/P0Having obviously hysteresis loop (belonging to H2 type hysteretic loop) between=0.6～1.0, this hysteresis loop, owing to occurring capillary condensation phenomenon to be formed in meso-hole structure, illustrates that the HZSM-5 molecular sieve synthesized exists a certain amount of mesoporous.
Fig. 3 is the XRD spectra of embodiment 1 and embodiment 2 gained catalyst.Curve 1 ' is embodiment 1, and curve 2 ' is embodiment 2.As seen from the figure, compared with common HZSM-5 molecular sieve, the width that multistage pore canal HZSM-5 molecular sieve locates characteristic diffraction peak in 2 θ=22～25 ° increases to some extent, and this shows that sample has nano-scale.
It addition, catalyst A, B, C of preparation are loaded in tubular reactor respectively in Example 1～3, and carry out the alkylation catalytic performance of its benzene, methanol investigating evaluation on fixed window reaction evaluating equipment.The loadings of catalyst is 2.5g, and at benzene/methanol=1mol/1mol, mass space velocity is 2.0h-1, N2When flow is 50ml/min, having investigated the impact on benzene, methanol alkylation reaction of three kinds of different catalysts, reaction result is listed in table 1.
Table 1
Data by table 1, after post-treated for the HZSM-5 molecular sieve bought by south catalyst plant, the catalytic performance of its benzene-methanol alkylation reaction obtains and is greatly improved, the conversion ratio of its benzene improves nearly 9 percentage points, toluene, dimethylbenzene overall selectivity also improve 2 percentage points, wherein, it is worth mentioning that most that the selectivity of dimethylbenzene improves nearly 8 percentage points, further increase economic benefit and the social benefit of benzene-methanol alkylation reaction, there is reasonable industrial applications prospect.
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (10)
1. the ZSM-5 zeolite catalyst for benzene, methanol alkylation, it is characterised in that described catalyst is with γ-Al2O3Or η-Al2O3In any one and multistage pore canal HZSM-5 molecular sieve be carrier, load MgO is constituted；Wherein, with total weight of carrier for 100%, in carrier, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3Or η-Al2O3In any one account for 20～50%, the amount of load MgO is 1～12%.
2. the ZSM-5 zeolite catalyst for benzene, methanol alkylation according to claim 1, it is characterised in that described carrier is multistage pore canal HZSM-5 molecular sieve and γ-Al2O3。
3. the ZSM-5 zeolite catalyst for benzene, methanol alkylation according to claim 1, it is characterised in that in described carrier, weight ratio shared by multistage pore canal HZSM-5 molecular sieve is 60～75%.
4. the ZSM-5 zeolite catalyst for benzene, methanol alkylation according to claim 1, it is characterised in that γ-Al in described carrier2O3Shared weight ratio is 25～40%.
5. the ZSM-5 zeolite catalyst for benzene, methanol alkylation according to claim 1, it is characterised in that in described carrier, weight ratio shared by load MgO is 5～10%.
6. the preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation described in a claim 1, it is characterised in that comprise the following steps:
1) silica alumina ratio micropore HZSM-5 molecular sieve between 180-300 is taken, when pH value 13-13.5, add the sodium aluminate solution of 0.005～0.05mol/L in described micropore HZSM-5 molecular sieve according to solid-to-liquid ratio 1:10-20, stirring 40～60min makes molecular sieve all dissolve；
2) reactor is carried out ice-water bath chilling operation after terminating by reaction, makes reaction all standing, and sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction roasting, obtains white powder；
3) gained white powder is sufficiently stirred in 65～90 DEG C of tetraethyl orthosilicate alcoholic solution reaction 90～140min；
4) reactor carrying out ice-water bath chilling operation, make reaction all standing, sucking filtration also washs to filtrate neutral, by filtration cakes torrefaction, roasting, obtains white powder multistage pore canal HZSM-5 molecular sieve；
5) by described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In any one mixing, add the dilute nitric acid solution that mass fraction is 1～5% and carry out kneading, extrusion, dry, roasting, obtain a carrier；
6) described carrier magnesium acetate solution is impregnated, after dry, roasting, obtain the described post processing ZSM-5 zeolite catalyst for benzene, methanol alkylation.
7. the preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation according to claim 6, it is characterised in that in step 3) in, tetraethyl orthosilicate alcoholic solution is tetraethyl orthosilicate and the ethanol 1:5-20 in molar ratio solution mixed.
8. the preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation according to claim 6, it is characterised in that in step 5) in, described multistage pore canal HZSM-5 molecular sieve and γ-Al2O3Or η-Al2O3In the mixed proportion of any one mixing be that, with total weight of carrier for 100%, multistage pore canal HZSM-5 molecular sieve accounts for 50～80%, γ-Al2O3 or any one in η-Al2O3 account for 20～50%.
9. the preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation according to claim 6, it is characterised in that in step 6) in, the time of described dipping is 8～48h；Described roasting is in atmosphere with 450～600 DEG C of roasting 4～12h.
10. the application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation described in a claim 1, it is characterized in that, by stating described in claim 1, catalyst is used for benzene, methanol alkylation reaction is produced in toluene, dimethylbenzene, reaction temperature 400 DEG C～500 DEG C, reaction pressure 0.1～1MPa, weight space velocity 1～8h-1, benzene and methanol molar ratio 0.8～1.2.
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| MARIA MILINA等: ""Interdependence between porosity, acidity, and catalytic performance in hierarchical ZSM-5 zeolites prepared by post-synthetic modification"", 《JOURNAL OF CATALYSIS》 * |
| 陆璐: ""ZSM-5分子筛催化苯、甲醇烷基化反应的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN106669791B (en) * | 2017-01-20 | 2019-08-27 | 河北玺尧新能源科技有限公司 | A kind of ZSM-5 Type Zeolites agent and its preparation method and application |
| CN107777700B (en) * | 2017-10-16 | 2019-07-09 | 中国石油天然气股份有限公司 | Stepped hole HZSM-5 molecular sieve and preparation method thereof |
| CN107777700A (en) * | 2017-10-16 | 2018-03-09 | 中国石油天然气股份有限公司 | Stepped hole HZSM-5 molecular sieve and preparation method thereof |
| CN108187728A (en) * | 2018-01-11 | 2018-06-22 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications for being molded ZSM-5 molecular sieve catalyst |
| CN108187728B (en) * | 2018-01-11 | 2019-12-03 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications forming ZSM-5 molecular sieve catalyst |
| CN108970636A (en) * | 2018-06-27 | 2018-12-11 | 大连理工大学 | A kind of preparation method of benzene alkylation catalyst |
| CN108970636B (en) * | 2018-06-27 | 2021-01-05 | 大连理工大学 | Preparation method of benzene alkylation catalyst |
| CN109847794A (en) * | 2018-12-17 | 2019-06-07 | 兰州理工大学 | The catalyst and its preparation method and application of toluene is prepared for benzene and methanol |
| CN109603903A (en) * | 2018-12-17 | 2019-04-12 | 兰州理工大学 | The catalyst and its preparation method and application that benzene is reacted with methanol alkylation |
| CN109603903B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for benzene and methanol alkylation reaction and preparation method and application thereof |
| CN109847794B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for preparing toluene from benzene and methanol, and preparation method and application thereof |
| CN111518584A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for producing high-octane aromatic gasoline by alkylating benzene and methanol |
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