CN1605390A - Catalyst for synthesizing para diethyl benzene by ethanol and ethyl benzene combination reaction and its preparation method - Google Patents
Catalyst for synthesizing para diethyl benzene by ethanol and ethyl benzene combination reaction and its preparation method Download PDFInfo
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- CN1605390A CN1605390A CN 200410020397 CN200410020397A CN1605390A CN 1605390 A CN1605390 A CN 1605390A CN 200410020397 CN200410020397 CN 200410020397 CN 200410020397 A CN200410020397 A CN 200410020397A CN 1605390 A CN1605390 A CN 1605390A
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Abstract
The present invention relates to catalyst for alkylating ethanol and ethyl benzene into p-diethylbenzene and its preparation process. The industrial catalyst for efficient synthesis of p-diethylbenzene is prepared with the H-ZSM-5 molecular sieve with Si/Al ratio of 50 as basic matter and through surface acidity and tunnel regulation with B, Mg and Co, and has ideal pore size distribution and in-tunnel acidity distribution and strong coking resisting capacity. The precursor of B is boric acid, that of Mg is magnesium nitrate and that of Co is cobalt nitrate. The mass ratio between B and H-ZSM-5 molecular sieve is 1-3 %, that between Mg and H-ZSM-5 molecular sieve is 0.1-1 % and that between Co and H-ZSM-5 molecular sieve is 1-3 %. Compared with available similar catalyst, the present invention has the features one simple preparation process, low cost, high selectivity and yield of p-diethylbenzene, etc.
Description
Technical field
The present invention relates to the catalyzer of synthetic p-Diethylbenzene, especially for the catalyzer and the preparation method of ethanol and the synthetic p-Diethylbenzene of ethylbenzene alkylation, it has, and the preparation method is simple, low, the p-Diethylbenzene selectivity advantages of higher of Preparation of Catalyst cost.
Background technology
P-Xylol is a kind of important isomer in the dimethylbenzene, for producing the basic material of polyester, and large product of polyester is a fiber, best in quality because of it, in the synthetic fiber industry development, occupy crucial status, as the strippant of p-Xylol adsorptive separation technology process, p-Diethylbenzene is most widely used in three kinds of isomer of present diethylbenzene.Simultaneously, p-Diethylbenzene can also make Vinylstyrene in dehydrogenation, also is important chemical material.The annual amount that consumes p-Diethylbenzene in the whole world is about about 12000 tons at present, and therefore, the study on the synthesis of p-Diethylbenzene has very important social benefit and practical value.
The p-Diethylbenzene industrial production has adsorption method of separation and synthesis method at present.Adsorption method of separation is a kind of technology that Praxair Technology, Inc succeeded in developing in the seventies.This technology by product mixings diethylbenzene (wherein contraposition content is about 20～30%) when producing ethylbenzene be a raw material, and the para-isomeride separation purification with wherein obtains 95% p-Diethylbenzene product.But this method complex technical process, energy consumption is very high.
Synthesis method is to utilize the acid catalysis performance and the distinctive duct shape selectivity matter of ZSM-5 molecular sieve, handle raising contraposition product selectivity by some metal or non-metallic element modification, with ethylbenzene and ethanol (or ethene) directly alkylation obtain selectivity greater than 95% p-Diethylbenzene, perhaps will mix ethylbenzene disproportionation and obtain p-Diethylbenzene, it is successful that it is that China develops voluntarily.The Yanshan Petrochemical Co.'s p-Diethylbenzene device that built up in 1988 is that first cover adopts hundred tonnes of industrial experiment devices selecting the alkylation catalysis technique directly to synthesize p-Diethylbenzene in the world.After this China has successively built up the device that a few cover synthesis methods are produced p-Diethylbenzene again.But the catalyst preparation process complexity that above production process is used, modifying element content higher (as the Mg content that reaches the catalyzer of ideal selectivity is 11wt%), p-Diethylbenzene productive rate lower (5%～10%), the production cost of p-Diethylbenzene is higher.Therefore simplify the Preparation of catalysts process, reduce production costs, improve the yield of p-Diethylbenzene, become the target that people constantly pursue.
Summary of the invention
The invention provides a kind of catalyzer and preparation method who is used for ethanol and the synthetic p-Diethylbenzene of ethylbenzene alkylation.It is simple that this catalyzer has the preparation method, and cost is low, selectivity height, advantage such as by product is few.
The present invention is to be basic thing with Si/Al than the H-ZSM-5 molecular sieve that is 50, and by B and Co element, perhaps B, Mg and Co are element modified makes.
The mass ratio of described modifying element B and H-ZSM-5 molecular sieve is 1%～3%, and the mass ratio of Mg and H-ZSM-5 molecular sieve is 0.1%～1%, and the mass ratio of Co and H-ZSM-5 molecular sieve is 1%～3%.
The presoma of described modifying element B, Mg and Co is respectively boric acid, magnesium nitrate and Xiao Suangu.
Described Preparation of catalysts method comprises the steps:
1) it is soluble in water to take by weighing first modifying element precursor by metering, adds the H-ZSM-5 zeolite molecular sieve of metering;
2) mixed solution that the obtains rotating speed with 500～800r/min was stirred 10 hours, mixed solution is 80～120 ℃ of oven dry down;
3) the gained powder is water-soluble again, adds second modifying element precursor, repeats 2); Perhaps add the 3rd modifying element precursor again, repeat above-mentioned stirring, baking step;
4) the gained powder was in 450～550 ℃ of roastings 4 hours;
5) the gained powder is crossed 400～800 tm screen behind compressing tablet, obtains catalyzer.
The using method that described catalyzer is used for the p-Diethylbenzene preparation comprises the steps: under experiment condition, 370 ℃ of temperature of reaction, and catalyst levels 0.6g, ethylbenzene/alcoholic acid mole is 2: 1, carrier gas N
2Flow velocity 10ml/min is with synthetic p-Diethylbenzene under ethylbenzene and the ethanol normal pressure.The selectivity of p-Diethylbenzene reaches 100%, and yield is higher than 14%.
The present invention is to be basic thing with Si/Al than the H-ZSM-5 molecular sieve that is 50, by B, Mg and Co the surface acidity and the duct of catalyzer are regulated, had desirable pore size distribution and duct inner acidic and distribute and the strong efficient p-Diethylbenzene compound probability catalyzer of anti-coking performance.Compare with present similar catalyst, have mild condition, conversion of ethylbenzene height and p-Diethylbenzene good selective.Preparation process of the present invention is simple, and is with low cost, is easy to realize, is a kind of ethylbenzene and synthetic p-Diethylbenzene catalyzer of ethanol alkylation with high p-Diethylbenzene selectivity and high yield, has a extensive future.
Description of drawings
Fig. 1 is B (1%)-Co (2%)-ZSM-5-01 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.
Fig. 2 is B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.
Fig. 3 is B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.
Embodiment
Synthesizing of example 1 B (1%)-Co (2%)-ZSM-5-01 catalyzer
Take by weighing the 0.5g Xiao Suangu and 5g H-ZSM-5 molecular sieve is dissolved in the 40ml distilled water, stir fast in the baking oven that (800r/min) after 10 hours change mixed solution over to 80 ℃ and dry, then the gained powder is dissolved in the 40ml distilled water again, add the precursor of 0.305g boric acid as B, repeat the step of above-mentioned stirring, oven dry, at last the gained powder is put into 550 ℃ retort furnace roasting 4 hours, the catalyzer that sifts out 400～800 microns behind compressing tablet is standby.
Synthesizing of example 2 B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 catalyzer
Take by weighing the 0.25g Xiao Suangu and 5g H-ZSM-5 molecular sieve is dissolved in the 40ml distilled water, stir fast in the baking oven that (800r/min) after 10 hours change mixed solution over to 80 ℃ and dry, then the gained powder is dissolved in the 40ml distilled water again, add the 0.27g magnesium nitrate, repeat above-mentioned stirring, the step of oven dry, the gained powder is dissolved in the 40ml distilled water again, add the precursor of 0.305g boric acid as B, repeat above-mentioned stirring again, the step of oven dry, at last the gained powder is put into 550 ℃ retort furnace roasting 4 hours, the catalyzer that sifts out 400～800 microns behind compressing tablet is standby.
Synthesizing of example 3 B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 catalyzer
Take by weighing the 0.25g Xiao Suangu and 5g H-ZSM-5 molecular sieve is dissolved in the 40ml distilled water, stir fast in the baking oven that (600r/min) after 10 hours change mixed solution over to 80 ℃ and dry, then the gained powder is dissolved in the 40ml distilled water again, add the 0.27g magnesium nitrate, repeat above-mentioned stirring, the step of oven dry, the gained powder is dissolved in the 40ml distilled water again, add the precursor of 0.455g boric acid as B, repeat above-mentioned stirring again, the step of oven dry, at last the gained powder is put into 550 ℃ retort furnace roasting 4 hours, the catalyzer that sifts out 400～800 microns behind compressing tablet is standby.
The performance evaluation of the synthetic p-Diethylbenzene of example 4 B (1%)-Co (2%)-ZSM-5-01 ethylbenzene and ethanol alkylation
Carry out performance test with example 1 prepared catalyzer.The activity rating of catalyst device is the stainless steel fixed-bed reactor of 7mm for length for 40cm, internal diameter.Catalyzer is placed on the middle part of reactor, supports with glass wool below.The loadings of each catalysts is 0.6g, is reflected under the normal pressure and carries out.After catalyst loading finishes, feed the carrier gas of certain flow rate, be heated to assigned temperature and stablized 15 minutes.Use liquid sampling pump sample introduction to reactor head then, and pass through beds after carrier gas mixes.Product is collected with condenser condenses after reactor bottom flows out, and every two hours gets sample one time, and analyzes with the SP-502 gas chromatograph.Reaction conditions is: 370 ℃ of temperature; Catalyst levels 0.6g; 10 hours reaction times; Mass space velocity 6h
-1Ethylbenzene/ethanol (mol) 2: 1; Carrier gas (N
2) flow velocity 10ml/min.Experimental result sees Table 1 and Fig. 1.Table 1 is that B (1%)-Co (2%)-ZSM-5-01 catalyzer is shown over time to the transformation efficiency of ethylbenzene, the selectivity and the yield of p-Diethylbenzene; Fig. 1 is B (1%)-Co (2%)-ZSM-5-01 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.The calculation formula of the transformation efficiency of ethylbenzene and the selectivity of p-Diethylbenzene and yield is as follows:
Ethylbenzene amount of substance in conversion of ethylbenzene (%)=(in the reactant in ethylbenzene amount of substance-product ethylbenzene amount of substance)/reactant;
The amount of substance of the diethylbenzene in the p-Diethylbenzene amount of substance/product in p-Diethylbenzene selectivity (%)=product;
Ethylbenzene amount of substance in p-Diethylbenzene amount of substance/reactant in p-Diethylbenzene yield (%)=product.
Table 1B (1%)-Co (2%)-ZSM-5-01 is to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield change list in time
The performance evaluation of the synthetic p-Diethylbenzene of example 5 B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 ethylbenzene and ethanol alkylation
Carry out performance test with example 2 prepared catalyzer.Activity rating of catalyst carries out on the stainless steel fixed-bed reactor.Reaction conditions is: 370 ℃ of temperature; Catalyst levels 0.6g; 10 hours time; Mass space velocity 6h
-1Ethylbenzene/ethanol (mol) 2: 1; Carrier gas (N
2) flow velocity 10ml/min.Experimental result sees Table 2 and Fig. 2.Table 2 is that B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 catalyzer is shown over time to the transformation efficiency of ethylbenzene, the selectivity and the yield of p-Diethylbenzene; Fig. 2 is B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.
Table 2 B (1%)-Mg (0.5%)-Co (1%)-ZSM-5-02 is to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield change list in time
The performance evaluation of the synthetic p-Diethylbenzene of example 6 B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 ethylbenzene and ethanol alkylation
Carry out performance test with example 3 prepared catalyzer.Activity rating of catalyst carries out on the stainless steel fixed-bed reactor.Reaction conditions is: 370 ℃ of temperature; Catalyst levels 0.6g; 10 hours time; Mass space velocity 4.5h
-1Ethylbenzene/ethanol (mol) 2: 1; Carrier gas (N
2) flow velocity 10ml/min.Experimental result sees Table 3 and Fig. 3.Table 3 is that B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 catalyzer is shown over time to the transformation efficiency of ethylbenzene, the selectivity and the yield of p-Diethylbenzene; Fig. 3 is B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 catalyzer to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield graphic representation over time.
Table 3 B (1.5%)-Mg (0.5%)-Co (1%)-ZSM-5-03 is to the selectivity of the transformation efficiency of ethylbenzene, p-Diethylbenzene and yield change list in time
Claims (5)
1, a kind of catalyzer that is used for the synthetic p-Diethylbenzene of ethanol and ethylbenzene alkylation is characterized in that it is is basic thing with Si/Al than the H-ZSM-5 molecular sieve that is 50, and by B and Co element, perhaps B, Mg and Co are element modified makes.
2, catalyzer according to claim 1, the mass ratio that it is characterized in that described modifying element B and H-ZSM-5 molecular sieve is 1%～3%, the mass ratio of Mg and H-ZSM-5 molecular sieve is 0.1%～1%, and the mass ratio of Co and H-ZSM-5 molecular sieve is 1%～3%.
3, catalyzer according to claim 2 is characterized in that the presoma of described modifying element B, Mg and Co is respectively boric acid, magnesium nitrate and Xiao Suangu.
4, the described Preparation of catalysts method of claim 1 is characterized in that it comprises the steps:
1) it is soluble in water to take by weighing first modifying element precursor by metering, adds the H-ZSM-5 zeolite molecular sieve of metering;
2) mixed solution that the obtains rotating speed with 500～800r/min was stirred 10 hours, mixed solution is 80～120 ℃ of oven dry down;
3) the gained powder is water-soluble again, adds second modifying element precursor, repeats 2); Perhaps add the 3rd modifying element precursor again, repeat above-mentioned stirring, baking step;
4) the gained powder was in 450～550 ℃ of roastings 4 hours;
5) the gained powder is crossed 400～800 tm screen behind compressing tablet, obtains catalyzer.
5, the described catalyzer of claim 1 is used for the using method of p-Diethylbenzene preparation, it is characterized in that it comprises the steps: under experiment condition, 370 ℃ of temperature of reaction, and catalyst levels 0.6g, ethylbenzene/alcoholic acid mole is 2: 1, carrier gas N
2Flow velocity 10ml/min is with synthetic p-Diethylbenzene under ethylbenzene and the ethanol normal pressure.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618335B (en) * | 2009-08-06 | 2011-08-03 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
| CN102746095A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether |
| CN104084233A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of boron oxide-modified microporous molecular sieve shape-selective catalyst |
| CN108786907A (en) * | 2018-05-22 | 2018-11-13 | 河南师范大学 | A kind of B modification H-ZSM-5 molecular sieves and its preparation method and application |
| CN114073978A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Metal modified ZSM-5 molecular sieve and preparation method and application thereof |
-
2004
- 2004-09-03 CN CN 200410020397 patent/CN1268428C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618335B (en) * | 2009-08-06 | 2011-08-03 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
| CN102746095A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether |
| CN102746095B (en) * | 2011-04-20 | 2015-04-08 | 中国石油化工股份有限公司 | Method for preparing petroleum-level toluene from benzene and methanol or dimethyl ether |
| CN104084233A (en) * | 2014-07-17 | 2014-10-08 | 常州大学 | Preparation method of boron oxide-modified microporous molecular sieve shape-selective catalyst |
| CN108786907A (en) * | 2018-05-22 | 2018-11-13 | 河南师范大学 | A kind of B modification H-ZSM-5 molecular sieves and its preparation method and application |
| CN114073978A (en) * | 2020-08-10 | 2022-02-22 | 中国科学院大连化学物理研究所 | Metal modified ZSM-5 molecular sieve and preparation method and application thereof |
| CN114073978B (en) * | 2020-08-10 | 2023-06-30 | 中国科学院大连化学物理研究所 | Metal modified ZSM-5 molecular sieve and preparation method and application thereof |
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