CN1059673A - Composited HZSM-5 zeolite/vermiculite catalyst and uses thereof - Google Patents
Composited HZSM-5 zeolite/vermiculite catalyst and uses thereof Download PDFInfo
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- CN1059673A CN1059673A CN 91107053 CN91107053A CN1059673A CN 1059673 A CN1059673 A CN 1059673A CN 91107053 CN91107053 CN 91107053 CN 91107053 A CN91107053 A CN 91107053A CN 1059673 A CN1059673 A CN 1059673A
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Abstract
Composited HZSM-5 zeolite/vermiculite catalyst (abbreviating HZ-5/V as), be the organically NEW TYPE OF COMPOSITE zeolite catalyst of embedding life on stratiform natural silicate-vermiculite of a kind of zeolite, its preparation method is that vermiculite, NaOH, sodium aluminate, organic amine and water are mixed under vigorous stirring, in 140-180 ° of crystallization, after crystallization finishes after filtration, the washing, the oven dry, the gained powder crystal is after roasting removes amine, exchange with ammonium nitrate solution, more after filtration, washing, oven dry, roasting promptly get composited HZSM-5 zeolite/vermiculite catalyst.
Description
The present invention is a kind of HZSM-5 type zeolite catalyst, is a kind of composited HZSM-5 zeolite/vermiculite catalyst that is applied to reactions such as xylene isomerization, toluene disproportionation, methanol toluene alkylation, propylene aromatisation.
The catalyst of relevant xylene isomerization mainly contains two classes at present.The first kind is the HZSM-5 zeolite catalyst.This kind catalyst does not need noble metal; Can face hydrogen or not face and carry out isomerization under the condition of hydrogen and can transform advantage such as ethylbenzene, but its be active not high enough, and the higher reaction temperature of needs (referring to U.S. Pat 3,856,871; Qin Guanlin, Wu Chuanchang etc., petrochemical industry the 3rd volume, the 223rd page (1978)).
The second class SKI-300,400 type catalyst, it is platinum-modenite-alchlor system, carrying the platinum amount is 0.2～0.3%.It has side reaction few, and therefore yield height, and can transform the advantage of ethylbenzene, but this kind catalyst need consume noble metal, and catalytic reaction needs carry out under hydro condition needs equipment such as the alloy steel products of anti-hydrogen-type corrosion and middle pressure recycle compressor.(referring to U.S. Pat 3,409,686; Japan Patent JP49-41324; Xu Guobin etc., petrochemical industry the 17 is rolled up 513 pages (1988)).
The object of the invention provides and a kind ofly need not consume noble metal, and catalytic activity is than HZSM-5 zeolite catalyst height, can face hydrogen or not face catalyst for reaction such as catalysis xylene isomerization, toluene disproportionation, methanol toluene alkylation, propylene aromatisation under the condition of hydrogen.
Technical solution of the present invention is: vermiculite, NaOH, sodium aluminate, organic amine and water are mixed under the vigorous stirring in reactor, with hydro-thermal method in 140～180 ℃ of crystallization 6～14 days, after crystallization finishes after filtration, the washing (to PH=8～9), (110 °) And is through (550 ℃ of roastings in oven dry, 6 hours) except that behind the amine, get compound ZSM-5 zeolite/vermiculite porous material, abbreviate Z-5/V as.Exchange with ammonium nitrate solution then that (optimum condition is the ammonium nitrate solution with 1 mol, the weight ratio of Z-5/V and ammonium nitrate solution is 1: 10, exchange 6 times down at 95 ℃, each 1 hour), (550 ℃ of washings more after filtration,, oven dry, roasting, 4 hours), promptly obtain composited HZSM-5 zeolite/vermiculite catalyst of the present invention, abbreviate the HZ-5/V catalyst as.
The raw material weight ratio for preparing HZ-5/V catalyst of the present invention has following scope:
20 parts of vermiculites, 1.0～4.0 parts in NaOH, 0.5～2.0 part of sodium aluminate, 6～25 parts of organic amines, 100～300 parts in water.
Wherein the organic amine as the template agent can be TBAB, 4-propyl bromide, 1,6-hexamethylene diamine or n-butylamine etc., and wherein the TBAB effect is best.
HZ-5/V catalyst of the present invention is the organically NEW TYPE OF COMPOSITE zeolite catalyst of embedding life on the vermiculite (V) of stratiform of a kind of zeolite.The SEM figure of HZ-5/V catalyst shows that growth has zeolite " knurl " on the vermiculite of stratiform, through EDS-AN-10000/80 type differential analyzer microcell composition analysis, the results are shown in Table 1, the X diffraction spectrogram of HZ-5/V catalyst shows that the HZ-5/V catalyst has the characteristic peak of HZSM-5 zeolite and vermiculite simultaneously.
Table 1 HZ-5/V microcell composition analysis (in oxide Wt%)
Form
Sample Na
2O MgO Al
2O
3SiO
2K
2O Fe
2O
3
Zeolite part (knurl) 1.31 0.093 3.86 94.49/0.25
Vermiculite part (layer) 1.60 1.65 19.94 68.82 5.89 2.10
The characteristics of HZ-5/V catalyst of the present invention are: need not use noble metal; Its activity is compared with the HZSM-5 catalyst and is significantly increased.For xylene isomerization reaction, the HZ-5/V activity of such catalysts is four times of HZSM-5 catalyst, and also can transform ethylbenzene, and for reactions such as propylene aromatisation, toluene disproportionation and methanol toluene alkylations, its activity also exceeds 1～2 times than HZSM-5 catalyst.HZ-5/V catalyst of the present invention can face hydrogen or not carry out catalytic reaction under the hydro condition.
Description of drawings: Fig. 1 is miniature catalyst reaction activity test schematic representation of apparatus.
1, nitrogen steel cylinder; 2, pressure-reducing valve; 3, needle-valve; 4, spinner flowmeter; 5, hydrogen gas cylinder; 6, micro syringe; 7, miniature syncmotor; 8, thermocouple; 9, temperature-controlling system; 10, (φ 4 * 320mm) for U type reactor; 11, catalyst bed; 12, heating furnace; 13, six-way valve; 14, quantity tube; 15, chromatographic column; 16, conductance cell; 17, measuring system.
Embodiment:
1, HZ-5/V Preparation of catalysts:
With vermiculite 20 grams, NaOH (C.P) 2.1 grams, sodium aluminate (C.P) 1.25 grams, TBAB (C.P) 25 grams, water 150 grams place in the reactor, under vigorous stirring, mix, with hydro-thermal method in 160 ℃ of crystallization 10 days, after the crystallization, cooling, filter, wash to PH=8～9, after oven dry under 110 ℃, 550 ℃ of following roastings 6 hours, after the cooling, with the ammonium nitrate solution of 1 mol 95 ℃ of exchanges 6 times down, each 1 hour, the each consumption of ammonium nitrate solution is 10 times of Z-5/V, filter then, washing, oven dry, 550 ℃ of following roastings 4 hours, (HZ-5/V urged promptly to obtain composited HZSM-5 zeolite/vermiculite catalyst again
Change agent) have the structure of HZSM-5 and vermiculite through the identification of phases of X-ray thing.
Preparation HZ-5/V catalyst is listed in table 2 and the table 3 under conditions of similarity.
2, catalyst activity test
The catalyst activity test is all carried out in miniature catalyst reaction activity test device as shown in Figure 1.Its operating procedure is:
(A) catalyst sample through compressing tablet be shaped, broken, sieve, getting granularity is the catalyst bed (11) that 20～40 purpose catalyst sample 70mg fill in U type reactor, the quartz sand filling of two ends through inertization.
(B) at 450 ℃, under the nitrogen stream (40ml/min), activating catalyst 2 hours, reduce to reaction temperature then, after treating temperature constant, promote micro syringe (6) by miniature syncmotor (7) and be injected into reactant, rotate six-way valve (13) at regular intervals, make the interior gas of quantity tube (14) enter chromatograph and carry out composition analysis with constant speed.
(C) chromatographic operating condition
H
2Flow velocity 40ml/min bridge stream 180mA
110 ℃ of 150 ℃ of sensing chamber's temperature of temperature of vaporization chamber
Column temperature: 95 ℃ of column length: 2m
Fixer: DNP
(1) o-xylene isomerization catalyst activity test
Reaction temperature: the liquid hourly space velocity (LHSV) of 300 ℃ of ortho-xylenes: 1.6/hr
It the results are shown in Table 4
(2) contain the Mixed XYLENE isomerization catalyst activity test of ethylbenzene
Reaction temperature: 300 ℃ of Mixed XYLENE liquid hourly space velocity (LHSV) 1.6/hr
It the results are shown in Table 5
As can be seen from Table 5, at normal pressure, under the reaction condition of non-hydrogen:
PX/∑X：HZSM-5＜HZ-5/V＝23%
EB conversion ratio: HZSM-5＜HZ-5/V=22%
C
8Yield: HZSM-5=HZ-5/V＞99%
(3) toluene disproportionation catalyst activity test
Reaction temperature: 430 ℃ of toluene liquid hourly space velocity (LHSV): 1.6/hr
It the results are shown in Table 6
(4) methanol toluene alkylation catalyst activity test
Reaction temperature: 280 ℃ of reactants: methyl alcohol: toluene=1: the 1(mole)
Reactant mixture liquid hourly space velocity (LHSV): 1.6/hr
It the results are shown in Table 7
(5) propylene aromatized catalyst activity test
Fill out Porapak Q.S. in the chromatographic column during test of propylene virtue materialization catalyst activity,
Other condition is: H
2Flow velocity: 30ml/min bridge stream: 150mA
Temperature of vaporization chamber: 150 ℃ of sensing chamber's temperature: 180 ℃
Column length: 2m
Column temperature: 70～210 ℃ (temperature programming, speed: 8 ℃/min)
Propylene virtue physical reaction temperature is 500 ℃, catalyst amount 100mg
Propylene hourly space velocity 4.5/hr, carrier gas: N
2, flow velocity: 40ml/min
It the results are shown in Table 8
Claims (5)
1, composited HZSM-5 zeolite/vermiculite catalyst, it is characterized in that vermiculite, NaOH, sodium aluminate, organic amine and water are mixed under vigorous stirring, in 140-180 ° of crystallization, after crystallization finishes after filtration, the washing, the oven dry, the gained powder crystal exchanges with ammonium nitrate solution after roasting removes amine, more after filtration, washing, oven dry, roasting make.
2, catalyst according to claim 1 is characterized in that the raw material weight ratio has following scope:
20 parts of vermiculites, 1.0～4.0 parts in NaOH, 0.5～2.0 part of sodium aluminate, 6～25 parts of organic amines, 100～300 parts in water.
3, catalyst organic amine according to claim 1 can be TBAB, tetrapropyl bromination bromine, 1,6-hexamethylene diamine or n-butylamine, and wherein the TBAB effect is best.
4, catalyst according to claim 1, the concentration that it is characterized in that ammonium nitrate solution is 1 mol, the weight ratio of powder crystal and solution is 1: 10, exchanges 6 times each 1 hour best results down at 95 ℃.
5, catalyst according to claim 1 can be applicable to the isomerization of dimethylbenzene, the isomerization that contains the mixed xylenes of ethylbenzene, toluene disproportionation, methanol toluene alkylation and propylene aromatization.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91107053.2A CN1022544C (en) | 1991-05-21 | 1991-05-21 | Composited HZSM-5 zeolite/vermiculite catalyst and its usage |
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| CN91107053.2A CN1022544C (en) | 1991-05-21 | 1991-05-21 | Composited HZSM-5 zeolite/vermiculite catalyst and its usage |
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| CN1059673A true CN1059673A (en) | 1992-03-25 |
| CN1022544C CN1022544C (en) | 1993-10-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058643C (en) * | 1996-07-22 | 2000-11-22 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN1069848C (en) * | 1996-06-05 | 2001-08-22 | 中国石油化工总公司 | Mordenite/metal or ceramic catalyzing composite material and preparation thereof |
| CN1114561C (en) * | 1998-11-07 | 2003-07-16 | 中国科学院山西煤炭化学研究所 | Preparation of small-grain FeZSMS zeolite molecular sieve |
| CN115228385A (en) * | 2021-04-23 | 2022-10-25 | 国家能源集团宁夏煤业有限责任公司 | Fixed bed catalyst filling method and corresponding reaction testing method |
-
1991
- 1991-05-21 CN CN91107053.2A patent/CN1022544C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069848C (en) * | 1996-06-05 | 2001-08-22 | 中国石油化工总公司 | Mordenite/metal or ceramic catalyzing composite material and preparation thereof |
| CN1058643C (en) * | 1996-07-22 | 2000-11-22 | 中国石油化工总公司 | Catalytic ZSM-5/metal or ceramic compounded material and its preparation |
| CN1114561C (en) * | 1998-11-07 | 2003-07-16 | 中国科学院山西煤炭化学研究所 | Preparation of small-grain FeZSMS zeolite molecular sieve |
| CN115228385A (en) * | 2021-04-23 | 2022-10-25 | 国家能源集团宁夏煤业有限责任公司 | Fixed bed catalyst filling method and corresponding reaction testing method |
| CN115228385B (en) * | 2021-04-23 | 2023-11-10 | 国家能源集团宁夏煤业有限责任公司 | Fixed bed catalyst filling method and corresponding reaction test method |
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| Publication number | Publication date |
|---|---|
| CN1022544C (en) | 1993-10-27 |
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