CN103272632B - Porous silica/ZSM-5 molecule sieve catalyst preparation method - Google Patents
Porous silica/ZSM-5 molecule sieve catalyst preparation method Download PDFInfo
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- CN103272632B CN103272632B CN201310226158.6A CN201310226158A CN103272632B CN 103272632 B CN103272632 B CN 103272632B CN 201310226158 A CN201310226158 A CN 201310226158A CN 103272632 B CN103272632 B CN 103272632B
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- molecule sieve
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229960000892 attapulgite Drugs 0.000 claims abstract description 45
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011630 iodine Substances 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 68
- 239000002808 molecular sieve Substances 0.000 claims description 67
- 230000001413 cellular effect Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000004575 stone Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 42
- 238000006317 isomerization reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000005804 alkylation reaction Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 8
- 235000013675 iodine Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 3
- -1 ZSM-5 or MCM-22 Chemical compound 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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)
- Catalysts (AREA)
Abstract
The present invention relates to a porous silica/ZSM-5 molecule sieve catalyst preparation method, and belongs to the technical field of shape selecting catalysis. The preparation method comprises: dispersing a ZSM-5 molecule sieve in ethanol, adding purified nanometer attapulgite to a hydrophilic organic solvent, slowly adding the obtained mixed solution to the ZSM-5 molecule sieve ethanol dispersion to prepare an attapulgite/ZSM-5 molecule sieve, and placing the prepared attapulgite/ZSM-5 molecule sieve in iodine vapor to prepare the porous silica/ZSM-5 molecule sieve catalyst. According to the present invention, the attapulgite/ZSM-5 molecule sieve is placed in the iodine vapor so as to provide a doping effect, such that the attapulgite can be converted into porous silica, the number of acid active sites on the outer surface of the ZSM-5 molecule sieve is reduced, isomerization reactions of p-xylene on the outer surface of the molecule sieve is effectively reduced, and selectivity on p-xylene is further increased.
Description
Technical field
The present invention relates to the preparation method of a kind of cellular silica/ZSM-5 molecular sieve catalyst, belong to shape selective catalysis technical field.
Background technology
Paraxylene is the important source material of synthetic polyester fibers, agricultural chemicals, medicine and dyestuff.At present, industrial main employing mixed xylenes isomerization, toluene and C
9the method such as aromatic disproportion and selective disproportionation of toluene produces paraxylene.The paraxylene that first two method obtains is only thermodynamical equilibrium concentration, about 24% in dimethylbenzene three kinds of isomers, and the condition that later separation goes out paraxylene is quite harsh, and power consumption is large; And in toluene selective disproportionation reaction, needing the toluene with two moles could generate the paraxylene of a mole, toluene utilization rate is lower.
It is the focus studied that toluene and methanol alkylation react the paraxylene technique of directly synthesizing high concentration always.It is the focus studied that toluene and methanol alkylation react the paraxylene technique of directly synthesizing high concentration always.Catalyst conventional in alkylation of toluene methanol process is the micro porous molecular sieves such as ZSM-5 or MCM-22, alkylated reaction can obtain simultaneously neighbour, isomers to three kinds of dialkyl benzenes, this mainly generates ortho-xylene and meta-xylene because the paraxylene generated in course of reaction is easy to the outer surface generation isomerization reaction at catalyst.Therefore, want to improve the selective of paraxylene in alkylation process, namely improve the Shape-selective of catalyst, just must carry out modification to molecular sieve.The object of modification mainly contains 2 points: one is the acidic site quantity reducing catalyst external surface, reduces the isomerization reaction of product paraxylene at molecular sieve outer surface; Two is modulation molecular sieve port sizes, increases the diffusional resistance of ortho-xylene and meta-xylene.
The modification to ZSM-5 molecular sieve structure is proposed in US Patent No. 3965210 and US4145315, namely silanes or polysiloxanes compounds is selected, under high temperature action, thermal decomposition becomes siliceous deposits, reduce molecular sieve port size and shielding outer surface acidity active sites, thus improve the para-selectivity of dimethylbenzene.The operation that employing metal oxide modified covers molecular sieve outer surface acidity position is very simple, and the successful of para-selectivity, but the method also can cause the reduction of molecular sieve pore passage inner acidic while reducing outer surface acidity, causes toluene conversion to reduce.
Concave-convex clay rod is a kind of natural, unique and rare silicate mineral, and have threadiness or rhabdolith structure, its single crystal diameter about 20 nanometer, length can reach micron order, is a kind of monodimension nanometer material with high length-diameter ratio.China's Concave-convex clay rod aboundresources, has obvious price advantage.Attapulgite is prepared cellular silica/ZSM-5 molecular sieve composite catalyst by interfacial reaction by the present invention, synthesizes paraxylene for shape selective catalysis toluene and methanol alkylation.
Summary of the invention
For the problem that existing for alkylation synthesis paraxylene, para-selectivity is low on ZSM-5 molecular sieve of the methylbenzene methanol in background technology, provide the preparation method of a kind of cellular silica/ZSM-5 molecular sieve catalyst.Cellular silica/ZSM-5 molecular sieve catalyst prepared by the method is used for alkylation of toluene methanol reaction, has higher catalytic activity and para-selectivity.
Technical scheme of the present invention is: be first scattered in ethanol by ZSM-5 molecular sieve, nano-attapulgite stone after purifying is joined in hydrophilic organic solvent, then it is slowly joined in the alcohol dispersion liquid of ZSM-5 molecular sieve, prepare attapulgite/ZSM-5 molecular sieve, finally prepared attapulgite/ZSM-5 molecular sieve is placed in iodine vapor, obtained cellular silica/ZSM-5 molecular sieve catalyst.
Characterization step of the present invention is as follows:
1. the preparation of attapulgite/ZSM-5 molecular sieve:
Be scattered in by ZSM-5 molecular sieve in ethanol, join in hydrophilic organic solvent by the nano-attapulgite stone after purifying, wherein attapulgite and hydrophilic organic solvent mass ratio are 0.1 ~ 0.3:1, and attapulgite and ZSM-5 molecular sieve mass ratio are 1 ~ 4:1; Then under 0-25 DEG C of water bath condition, the dispersion liquid of attapulgite is slowly poured in ZSM-5 molecular sieve dispersion liquid, continue to stir, insulation reaction 2 ~ 6 hours, filter, washing, dry, i.e. obtained attapulgite/ZSM-5 molecular sieve;
2. the preparation of cellular silica/ZSM-5 molecular sieve catalyst:
Attapulgite/ZSM-5 molecular sieve obtained by step 1 and iodine are placed in airtight container, wherein iodine and attapulgite/ZSM-5 molecular sieve mass ratio are 0.2 ~ 0.6:1, under temperature is 90 ~ 120 DEG C of conditions, is incubated 2 ~ 4 hours, is cooled to room temperature i.e. obtained cellular silica/ZSM-5 molecular sieve catalyst.
Hydrophily organic reagent described in step 1 is the one in oxolane, acetone or alcohol.
The invention has the beneficial effects as follows:
1. the present invention carries out surface modification by selecting attapulgite to ZSM-5 molecular sieve, covers the acid active sites on ZSM-5 molecular sieve surface, improves the selective of paraxylene in product.
2. attapulgite/ZSM-5 molecular sieve is placed in iodine vapor by the present invention, play chanza, attapulgite can be made to be transformed into cellular silica, reduce the quantity of ZSM-5 molecular sieve outer surface acidity active sites, effective reduction paraxylene, in the isomerization reaction of molecular sieve outer surface, further increases the selective of paraxylene in product.
3. the nano-attapulgite stone that the present invention selects has special one dimension fibre structure and more superior mechanical mechanics property, further increases the combination property of catalyst, has expanded its range of application, and attapulgite is cheap simultaneously, reduces production cost.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but invention which is intended to be protected is not limited to the scope involved by embodiment:
Embodiment 1
1. the ZSM-5 molecular sieve of 1.5 grams is joined in 10.0 grams of ethanol, the nano-attapulgite stone of 6.0 grams of purifying is scattered in 20.0 grams of acetone, under temperature is 25 DEG C of conditions, nano-attapulgite stone dispersion liquid is slowly added in the dispersion liquid of ZSM-5 molecular sieve, after continue stir, insulation reaction 2 hours, filter, washing, dry, i.e. obtained attapulgite/ZSM-5 molecular sieve;
2. attapulgite/the ZSM-5 molecular sieve got obtained by 5.0 grams of steps 1 is placed in airtight container, adds 3.0 grams of elemental iodines, is incubated 2 hours, is cooled to room temperature under temperature is 120 DEG C of conditions, i.e. obtained cellular silica/ZSM-5 molecular sieve catalyst.
Embodiment 2
1. the ZSM-5 molecular sieve of 3.0 grams is joined in 10.0 grams of ethanol, the nano-attapulgite stone of 3.0 grams of purifying is scattered in 30.0 grams of oxolanes, under temperature is 0 DEG C of condition, nano-attapulgite stone dispersion liquid is slowly added in the dispersion liquid of ZSM-5 molecular sieve, after continue stir, insulation reaction 2 hours, filter, washing, dry, i.e. obtained attapulgite/ZSM-5 molecular sieve;
2. attapulgite/the ZSM-5 molecular sieve got obtained by 5.0 grams of steps 1 is placed in airtight container, adds 1.0 grams of elemental iodines, is incubated 6 hours, is cooled to room temperature under temperature is 110 DEG C of conditions, i.e. obtained porous, shape silica/ZSM-5 molecular sieve catalyst.
Embodiment 3
1. the ZSM-5 molecular sieve of 2.0 grams is joined in 10.0 grams of ethanol, the nano-attapulgite stone of 4.0 grams of purifying is scattered in 20 grams of ethanol, under temperature is 5 DEG C of conditions, nano-attapulgite stone dispersion liquid is slowly added in the dispersion liquid of ZSM-5 molecular sieve, after continue stir, insulation reaction 4 hours, filter, washing, dry, i.e. obtained attapulgite/ZSM-5 molecular sieve;
2. attapulgite/the ZSM-5 molecular sieve got obtained by 5.0 grams of steps 1 is placed in airtight container, adds 2.0 grams of elemental iodines, is incubated 4 hours, is cooled to room temperature under temperature is 100 DEG C of conditions, i.e. obtained cellular silica/ZSM-5 molecular sieve catalyst.
Cellular silica/ZSM-5 molecular sieve catalyst performance evaluation
Below by the experiment of toluene and methanol alkylation being synthesized paraxylene, cellular silica/ZSM-5 molecular sieve catalyst is evaluated, reaction condition is: the mol ratio n(toluene of toluene and methyl alcohol): n(methyl alcohol)=4:1, reaction temperature 400 DEG C, mass space velocity 1 h
-1, result of the test is as shown in table 1.From table 1, cellular silica/ZSM-5 molecular sieve catalyst prepared by the present invention synthesizes during paraxylene tests at toluene and methanol alkylation, with unmodified ZSM-5 molecular sieve as compared with catalyst, when the conversion ratio of toluene remains unchanged substantially, the selective of paraxylene significantly improves, and has preferably catalytic effect.
Table 1 cellular silica/ZSM-5 molecular sieve catalyst performance evaluation
| Catalyst | Toluene conversion, % | Selectivity for paraxylene, % |
| Unmodified ZSM-5 | 41.3 | 24.1 |
| Embodiment 1 | 39.4 | 64.5 |
| Embodiment 2 | 37.8 | 59.1 |
| Embodiment 3 | 38.4 | 62.2 |
Claims (3)
1. the preparation method of cellular silica/ZSM-5 molecular sieve catalyst, it is characterized in that: first ZSM-5 molecular sieve is scattered in ethanol, nano-attapulgite stone after purifying is joined in hydrophilic organic solvent, then it is slowly joined in the alcohol dispersion liquid of ZSM-5 molecular sieve, prepare attapulgite/ZSM-5 molecular sieve, finally prepared attapulgite/ZSM-5 molecular sieve is placed in iodine vapor, obtained cellular silica/ZSM-5 molecular sieve catalyst.
2. preparation method according to claim 1, is characterized in that: the concrete steps of described preparation method are as follows:
1) preparation of attapulgite/ZSM-5 molecular sieve:
Be scattered in by ZSM-5 molecular sieve in ethanol, join in hydrophilic organic solvent by the nano-attapulgite stone after purifying, wherein attapulgite and hydrophilic organic solvent mass ratio are 0.1 ~ 0.3:1, and attapulgite and ZSM-5 molecular sieve mass ratio are 1 ~ 4:1; Then under 0-25 DEG C of water bath condition, the dispersion liquid of attapulgite is slowly poured in ZSM-5 molecular sieve dispersion liquid, continue to stir, insulation reaction 2 ~ 6 hours, filter, washing, dry, i.e. obtained attapulgite/ZSM-5 molecular sieve;
2) preparation of cellular silica/ZSM-5 molecular sieve catalyst:
Attapulgite/ZSM-5 molecular sieve obtained by step 1 and iodine are placed in airtight container, wherein iodine and attapulgite/ZSM-5 molecular sieve mass ratio are 0.2 ~ 0.6:1,2 ~ 4 hours are incubated under temperature is 90 ~ 120 DEG C of conditions, be cooled to room temperature, i.e. obtained cellular silica/ZSM-5 molecular sieve catalyst.
3. preparation method according to claim 1 and 2, is characterized in that: described hydrophilic organic solvent is the one in oxolane, acetone or alcohol.
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Denomination of invention: Preparation of a Porous Silica/ZSM-5 Zeolite Catalyst Effective date of registration: 20190122 Granted publication date: 20150128 Pledgee: China Co truction Bank Corp Guangzhou economic and Technological Development Zone sub branch Pledgor: Guangzhou Guangyi Chemical Technology Development Co., Ltd. Registration number: 2019440000038 |