CN1045930A - The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation - Google Patents
The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation Download PDFInfo
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- CN1045930A CN1045930A CN 90101436 CN90101436A CN1045930A CN 1045930 A CN1045930 A CN 1045930A CN 90101436 CN90101436 CN 90101436 CN 90101436 A CN90101436 A CN 90101436A CN 1045930 A CN1045930 A CN 1045930A
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- zsm
- ethylbenzene
- diethylbenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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Abstract
Be applicable to the directly synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation, contain the zeolite [molecular sieve of the ZSM-5 of magnesium, aluminium, it is to be raw material through use hydrochloric acid ion-exchange with the Na-ZSM-5 zeolite, and usefulness aluminium, magnesium salts modification are dried roasting again and made.It is used for ethylbenzene-ethanol is the directly alkylated reaction of synthetic p-diethylbenzene of raw material, and the transformation efficiency of ethylbenzene reaches 5-10%, and the selectivity of p-diethylbenzene reaches 95-98%, and the catalyzer one way reaches more than 1200 hours work-ing life, and good regenerability is arranged.
Description
The invention belongs to the ZSM-5 zeolite [molecular sieve that contains magnesium, aluminium.
Important source material p-Xylol in the synthesizing polyester industry is to get by the sorbent material separation from the mixture of three kinds of isomerss.Need in this course p-Xylol to be separated the sucking-off fork-like farm tool used in ancient China from sorbent material with strippant.This strippant is that purity is at the p-diethylbenzene more than 95%.The high purity p-diethylbenzene was the C from reformate in the past
10Make by adsorption method of separation in the diethylbenzene of by product-three kind of the isomers of aromatic hydrocarbons and production ethylbenzene.But because the content of p-diethylbenzene is low in the raw material, add the neighbour,, to the boiling point of three kinds of diethylbenzenes near [1], therefore very high to the requirement of sorbent material, the preparation difficulty.
United States Patent (USP) 4365104,4465886 and the article [2] of Jong-Hokim and Tatusuaki Yashima in been reported to cross with ethylbenzene-ethene be that raw material is being a main component with the ZSM-5 zeolite, method with synthetic p-diethylbenzene under the catalyst action of P, Mg modification, but just be in conceptual phase, industrial production device is not arranged as yet.Its subject matter is poor catalyst stability, and majority can only be with about 100 hours.
The objective of the invention is to the Na-ZSM-5 zeolite is main ingredient, make H-ZSM-5 by ion-exchange, mix with aluminum nitrate solution then and use ammonia precipitation process, after flooding modification (or directly H-ZSM-5 being flooded modification with magnesium nitrate solution) with magnesium nitrate solution again, the drying roasting is made a kind ofly to be had high selectivity and better stability is arranged, and is applicable to the catalyzer of ethylbenzene-ethanol alkylation direct synthesis of high purity p-diethylbenzene.
The present invention is to contain SiO
2/ Al
2O
3Than being raw material for the Na-ZSM-5 zeolite of 38-55, be that the hydrochloric acid of 0.1-0.4 carries out ion-exchange 1 hour with concentration under 50-95 ℃, exchange 2-4 time altogether, the oven dry roasting is made H-ZSM-5, its Na
2O is 0.05-0.5%, with proportion be that the aluminum nitrate solution of 1.09 grams per milliliters mixes and is heated to 50-80 ℃ and adds 1: 1 concentration ammonia precipitation process subsequently, transfer to PH=7-8, the Lu goes out precipitation and oven dry, again with a certain amount of magnesium nitrate solution dipping (or directly with a certain amount of magnesium nitrate solution flood H-ZSM-5), 80-100 ℃ down after the oven dry in 550-700 ℃ of following roasting 2-6 hour, thereby make aluminium, magnesium ZSM-5 zeolite [molecular sieve-8912 catalyzer that MgO content is 6-10%.
8912 catalyzer that aforesaid method is made are used for to be the directly alkylated reaction of synthetic p-diethylbenzene of raw material, to be 360-390 ℃ in temperature of reaction that ethylbenzene and alcoholic acid mol ratio are 6-8 with ethylbenzene-ethanol, and weight space velocity is 6-9 hour
-1Condition under, conversion of ethylbenzene reaches 5-10%, the selectivity of p-diethylbenzene reaches 95-98%, the catalyzer one way reaches more than 1200 hours work-ing life, and satisfactory stability is arranged.Performance can return to the level of live catalyst behind this catalyst regeneration.This catalyzer uses on the industrial installation of producing the p-diethylbenzene more than 300 tons per year.
Example 1
Using " direct method " [3] synthetic SiO
2/ Al
2O
3Than being respectively 38,45,55 Na-ZSM-5 zeolite powder with 0.1 and the hydrochloric acid soln of 0.4N 95 ℃ of exchanges 4 times down, each 1 hour (every gram Na-ZSM-5 adds the 5ml hydrochloric acid soln during exchange), be washed till no Cl after the exchange, in 110 ℃ of oven dry, through 550 ℃ of roastings 2 hours, compression molding is ground into 20-30 purpose particle again, analyzes Na
2O content is 0.05%.Take by weighing 10 these samples of gram,, after 80-100 ℃ of oven dry,, make MgO content and be 7.5% catalyzer in 600 ℃ of roastings 4 hours with 8-10ml magnesium nitrate (5 restrain magnesium nitrates is dissolved in the 8-10ml water) solution impregnation.Taking by weighing this catalyzer 1 gram bore of packing into is atmospheric fixed bed reactor inner evaluation ethylbenzene-ethanol alkylation reactivity worth of 6mm.Reaction conditions is 360 ℃ of temperature of reaction, ethylbenzene/ethanol=6, weight space velocity 6 hours
-1, evaluation result sees Table 1.
Example 2
Using " direct method " synthetic SiO
2/ Al
2O
3Be 38 Na-ZSM-5 zeolite powder with the hydrochloric acid soln of 0.3N 95 ℃ of exchanges 3 times down, each 1 hour (every gram Na-ZSM-5 adding 5ml hydrochloric acid soln during exchange) is washed till no Cl after the exchange
-, in 110 ℃ of oven dry after 550 ℃ of roastings after 2 hours compression molding be ground into 20-30 purpose particle, its Na again
2O content is 0.1%.Take by weighing three parts in this sample respectively, every part 10 gram (is respectively 4 with different concns, 5,6 gram magnesium nitrates are dissolved in the 9-10ml water) magnesium nitrate solution dipping, in 80-100 ℃ of oven dry, then in 600 ℃ of following roastings 5 hours, make MgO content and be respectively three kinds of catalyzer of 6.8%, 7.5% and 9.2%.Take by weighing above-mentioned catalyzer respectively and respectively 1 restrain in the atmospheric fixed bed reactor of packing into, estimate ethylbenzene-ethanol alkylation reactivity worth.Reaction conditions is: 360 ℃ of temperature of reaction, ethylbenzene/ethanol=6, weight space velocity 7 hours
-1Evaluation result sees Table 2
Example 3
Using " direct method " synthetic SiO
2/ Al
2O
3Being 55 Na-ZSM-5 zeolite powder is washed till no Cl with the 0.4N hydrochloric acid soln after 50 ℃ exchange exchanges 2 times each 1 hour (every gram Na-ZSM-5 adds the 5ml hydrochloric acid soln during exchange) down
-, after 700 ℃ of following roastings 4 hours, compression molding again, and then be ground into 20-30 purpose particle is analyzed its Na in 110 ℃ of oven dry
2O content is 0.5%.Take by weighing this sample 10 grams, with magnesium nitrate solution (6.5 gram magnesium nitrates are dissolved in the 8-10ml water) dipping, in 80-100 ℃ of oven dry down, be divided into two parts then, dry by the fire down at 550 ℃ and 700 ℃ respectively and burnt 6 hours, make that to contain MgO be 10% catalyzer, respectively take by weighing 1 gram, put into the performance that atmospheric fixed bed reactor is estimated the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation respectively.Reaction conditions is: 380 ℃ of temperature of reaction, ethylbenzene/ethanol=8, weight space velocity 9 hours
-1Evaluation result sees Table 3.
Example 4
Using " direct method " synthetic SiO
2/ Al
2O
3Be 38 and 55 Na-ZSM-5 zeolite powder, 70 ℃ of exchanges 3-4 time down, each 1 hour, the Lu was washed till Cl except that mother liquor with distilled water with the 0.3N hydrochloric acid soln
-,, analyze its Na in 110 ℃ of oven dry down
2O content is 0.1%.Take by weighing H-ZSM-5 80 grams after the oven dry, put into the beaker of 1000ml.110 gram Al(NO
3)
3, 9H
2O is soluble in water to make the solution that proportion is 1.09 grams per milliliters.This solution is poured in the beaker of the above-mentioned H-ZSM-5 of filling, be heated to 50-80 ℃ while stirring,, stop to add ammoniacal liquor when treating PH=7-8, restir 10 minutes with the ammonia precipitation process of 1: 1 concentration.Cross the Lu and go out precipitation, and with distillation washing PH=7, dry down in 90-100 ℃, compression molding was ground into 20-30 purpose particle again, in 600 ℃ of following roasting 3-4 hours.Take by weighing the good sample of roasting 10 grams, with 8-10ml magnesium nitrate solution (6 gram magnesium nitrate solutions are in 8-10ml water) dipping, 80-100 ℃ of oven dry down, then at 550-700 ℃ of following roasting 4-6 hour, the catalyzer that makes contains MgO9.2%.Take by weighing this catalyzer 1 gram and put into the performance of the synthetic p-diethylbenzene of normal pressure reactor inner evaluation ethylbenzene-ethanol alkylation.Evaluation result sees Table 4
The catalyzer of this example preparation is at 370 ℃, ethylbenzene/ethanol=6, air speed 6 hours
-1Under the condition, primary first-order equation 1200 hours, functional.Its performance can return to the level of live catalyst behind the catalyst regeneration.
Example 5
Using " direct method " synthetic SiO
2/ Al
2O
3Be 38 zeolite powder, make H-ZSM-5, take by weighing the beaker that 80 grams are put into 1000ml according to the condition and the step of example 4.The Al(NO of 140 grams
3)
3, 9H
2O is dissolved in and makes proportion in the water is that the solution of 1.09 grams per milliliters is poured the above-mentioned H-ZSM-5 of filling into and had in the beaker, be heated to 70 ℃ while stirring, ammonia precipitation process with 1: 1 concentration, stop to add ammoniacal liquor when treating PH=7-8, restir 10 minutes, cross the Lu and go out precipitation and be washed till PH=7 with distilled water, in 90-100 ℃ of oven dry, compression molding is ground into 20-30 purpose particle again in 700 ℃ of following roasting 3-4 hours.Sample 10 grams that take by weighing roasting one-tenth flood with 8-10ml magnesium nitrate solution (6 gram magnesium nitrates are dissolved in the 8-10ml water), dry the back down in 550 ℃ of following roastings 6 hours at 80-100 ℃, make the performance that catalyzer 1 gram that contains MgO9.2% is put into the synthetic p-diethylbenzene of atmospheric fixed bed reactor inner evaluation ethylbenzene-ethanol alkylation.Evaluation result sees Table 5.
Reference
[1]Weast，R.C.，“CRC Handbook of Chemistry and Physics”P.C-158，58 th Edition，1977-1978
[2]Jong-Ho Kim and Tatusuaki Yashima，Bull.Chem.Soe.Jpn，61，1051（1988）
[3] Li He is noisy etc., SCI, 2(4) 517(1981)-
Claims (5)
1, a kind of ethylbenzene-ethanol alkylation directly synthetic p-diethylbenzene of being applicable to, ZSM-5 zeolite [molecular sieve with magnesium, aluminium modification, it is characterized in that it is is raw material with Na-ZSM-5, through carry out ion-exchange with hydrochloric acid soln is 11-ZSM-5, mix with aluminum nitrate solution then and use ammonia precipitation process, flood modification (or directly H-ZSM-5 being flooded modification with magnesium nitrate solution) with magnesium nitrate solution again after, the drying roasting is made, the content of MgO was 6-10% during it was formed, SiO
2/ Al
2O
3Be 30-60, Na
2O content is the ZSM-5 zeolite catalyst of 0.05-0.5%.
2, a kind of ethylbenzene-ethanol alkylation directly synthetic p-diethylbenzene of being applicable to, preparation method with the ZSM-5 zeolite [molecular sieve of magnalium modification, it is characterized in that it is is that the hydrochloric acid soln of 0.1-0.4N carries out ion-exchange to the Na-ZSM-5 zeolite and becomes H-ZSM-5 under 50-95 ℃ with concentration, mixes (H-ZSM-5: Al then with aluminum nitrate solution
2O
3=90-75: 10-25), use a certain amount of magnesium nitrate solution [(H-ZSM-5+Al more also with the ammonia precipitation process (PH=7-8) of 1: 1 concentration
2O
3): MgO=(95-90): (5-10)] dipping modification (or directly H-ZSM-5 being flooded with magnesium nitrate solution), obtain above-mentioned catalyzer after the drying roasting.
3, by the manufacture method of the said catalyzer of claim 2, it is characterized in that be 1 hour with hydrochloric acid to the time that Na-ZSM-5 carries out ion-exchange, the exchange number of times is 2-4 time.
4, by the manufacture method of the said catalyzer of claim 2, it is characterized in that maturing temperature is 550-700 ℃, roasting time is 2-6 hour.
5, can be used for the directly synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation according to claim 1,2 said catalyzer, it is characterized in that carrying out above-mentioned when synthetic, temperature of reaction is 360-390 ℃, and ethylbenzene and alcoholic acid mol ratio are 6-8, and weight space velocity is 6-9 hour
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90101436 CN1045930A (en) | 1990-03-15 | 1990-03-15 | The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation |
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|---|---|---|---|
| CN 90101436 CN1045930A (en) | 1990-03-15 | 1990-03-15 | The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053388C (en) * | 1995-11-27 | 2000-06-14 | 南开大学 | Catalyst for preparation of high purity para-diethylbenzene by using ethylbenzene disproportionation and its technology |
| CN1060099C (en) * | 1994-04-18 | 2001-01-03 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
| CN103894222A (en) * | 2012-12-29 | 2014-07-02 | 新煤化工设计院（上海）有限公司 | Modified zeolite catalyst for preparing propylene through methanol dehydration and preparation method of modified zeolite catalyst |
-
1990
- 1990-03-15 CN CN 90101436 patent/CN1045930A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060099C (en) * | 1994-04-18 | 2001-01-03 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
| CN1053388C (en) * | 1995-11-27 | 2000-06-14 | 南开大学 | Catalyst for preparation of high purity para-diethylbenzene by using ethylbenzene disproportionation and its technology |
| CN103894222A (en) * | 2012-12-29 | 2014-07-02 | 新煤化工设计院（上海）有限公司 | Modified zeolite catalyst for preparing propylene through methanol dehydration and preparation method of modified zeolite catalyst |
| CN103894222B (en) * | 2012-12-29 | 2016-03-30 | 新煤化工设计院（上海）有限公司 | For the modified zeolite catalyst and preparation method thereof of methanol dewatered propylene |
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