CN1073887C - Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation - Google Patents
Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation Download PDFInfo
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- CN1073887C CN1073887C CN97117321A CN97117321A CN1073887C CN 1073887 C CN1073887 C CN 1073887C CN 97117321 A CN97117321 A CN 97117321A CN 97117321 A CN97117321 A CN 97117321A CN 1073887 C CN1073887 C CN 1073887C
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Abstract
The present invention relates to a novel zeolite catalyst used for preparing ethylenzene by alkylation and alkylation transfer, a method for preparing the zeolite catalyst and a method of alkylation and alkylation transfer on the catalyst.
Description
The present invention relates to a kind of new zeolite catalyzer that is used for alkylation to prepare ethylbenzene, this new zeolite Preparation of catalysts method and the application in alkylation to prepare ethylbenzene thereof also relate to a kind of processing method of novel gas-liquid-solid trichotomy alkylation to prepare ethylbenzene.
As everyone knows, ethylbenzene is the cinnamic precursor of the important industrial chemicals of preparation.Market has promoted the sustainable growth of ethylbenzene output to cinnamic thriving demand and to new ethylbenzene preparation method's further investigation.Ethylbenzene more than 90% is made through alkylated reaction by benzene and ethene in the world at present.Therefore, people also exploring always and development of new and the approach of alkylation to prepare ethene more efficiently.
Up to now, known alkylation to prepare ethylbenzene processing method can reduce two big class, i.e. vapor phase process and liquid phase methods.
Vapor phase process is class methods of early succeeding in developing with industrial application, wherein uses a kind of solid catalyst, and reaction raw materials belongs to the gas-solid phase reaction type with gaseous form contact reacts on catalyzer.To be U.S. Mobil oil company developed since the seventies its representative example, with the ZSM series zeolite be catalyzer, by the processing method of benzene and ethene gas-solid phase method alkylation to prepare ethylbenzene, PefroclemicalProcesses ' 95 parts of " Hydrocarbon Processing "/March 1995 for example, simply reported on the 115th page the third generation ethylbenzene process released with Badger/Mobil with the ZSM-5 zeolite catalyst, make ethylbenzene and rare ethene carry out gas-solid mutually alkylating processing method and indicative flowchart; And for example EP0308099 and EP0308097 disclose respectively with the ZSM-5 zeolites as catalysts and have carried out the method for vapor phase alkylation production ethylbenzene and the method for carrying out the transfering alkylation production ethylbenzene of benzene and diethylbenzene with ZSM-5 and ZSM-11 zeolite as catalyzer.The major advantage of these class methods is, and is not high to the purity requirement of (ethene) raw material, be adapted to the ethylene feed of different sources and different concns, and the throughput of catalyzer is bigger.Vapor phase process also exists than obvious defects, mainly be: need higher temperature of reaction and middle pressure, the alkylation of putting down in writing in for example above-mentioned patent document be 302-485 ℃, normal pressure to 20.79MPa (among the embodiment with 399 ℃, 2.17MPa) condition under carry out, this harsh reaction conditions not only make energy consumption big, to the having relatively high expectations of equipment and operating process, make also that byproduct of reaction is more, ethylbenzene selectivity is not high, the easy coking and deactivation of catalyzer; Another more serious defective is, have in the reaction product relatively large, reach the above xylene content of 1000ppm level, the existence of dimethylbenzene will influence the quality of subsequent product polystyrene, industrial concentration＜the 100ppm that requires dimethylbenzene in the ethylbenzene, as seen xylene content is much higher than this industrial standards in the ethylbenzene of vapor phase process production, so its ethylbenzene product is of low quality.
In addition, Chinese patent application publication number CN1031072A, CN1074392A and USP5233112 etc. also disclose Catalysts and its preparation method follow-on or novel, that be used for the vapor phase process alkylation to prepare ethylbenzene.But no matter what variation or improvement are arranged, and they all keep away the shortcoming of unavoidable above-mentioned vapor phase process.
The another kind of method of alkylation to prepare ethylbenzene is so-called liquid phase method, wherein in the presence of a kind of solid catalyst, make reaction raw materials benzene and ethylene feed be in liquid state by elevated pressures, and on said solid catalyst, make two kinds of liquid material contact reactss, generate ethylbenzene.Liquid phase method alkylation to prepare ethylbenzene technology is large-scale application in industrial production, its major advantage is, temperature of reaction can be reduced to about 200 ℃, catalyst life is long, the selectivity of ethylbenzene is very high, the more important thing is that the content of the impurity dimethylbenzene in the product ethylbenzene is tens ppm only, satisfy the cinnamic industrial requirements of production high purity fully.But liquid phase method also has tangible deficiency, mainly be: though temperature of reaction is lower, but pressure rises to several even tens MPa, this also causes energy consumption increase, equipment and complicated operation, the more important thing is, liquid phase method only is applicable to the situation of using pure ethylene to make reaction raw materials, to rare ethene or contain the ethene source of other composition, because non-ethene composition also must be through high pressure, uneconomical economically, this has limited its scope of application.The catalyzer of liquid phase method alkylation to prepare ethylbenzene and processing method for example have report in following document:
People such as G.Bellussi are at " Journal of Catalysis 157,227-234 publish an article on (1995) " Liquid-Phase Alkylation of Benzene with Light OlefinsCafalysed by β Zeolites ", wherein think, in the liquid phase alkylation reaction of benzene, the β zeolite has higher activity and selectivity than y-type zeolite, think that the activity of β zeolite is subjected to the influence of its composition and particle diameter, and proposed the active mechanism that is subjected to the control of particle internal diffusion.The document is just at the liquid-phase alkylation problem of general benzene, compare the activity and the selectivity of different sorts zeolite.
Simply introduced on the 114th page of PetroclemicalProcesses ' 95 part of " Hydrocarbon Processing "/March 1995 and used Lummus/Unocal/UOP fixed bed zeolite catalyst to carry out the technology and the indicative flowchart of liquid-phase alkylation system ethylbenzene, but wherein do not related to concrete catalyzer and operational condition.
The USP5 of Dow chemical company, 145,817 have narrated a kind of bimetal overstable gamma zeolite that is used for benzene alkylation/transfering alkylation system ethylbenzene under liquid-phase condition, and wherein the reactor back pressure is 35 engineering pressures (500psig), and temperature of reaction is 223-301 ℃;
The USP5 of Chevron research and technology company, 081,323 chat and a kind of in the presence of the catalyzer that contains the β zeolite, make aromatic hydrocarbons and C
2-C
4Olefin alkylation/transfering alkylation prepares the method for alkylated aromatic hydrocarbons, in the embodiment of embodiment 6-by benzene alkylation with ethylene system ethylbenzene, has used about 160 ℃ (325) and 31.5 engineering pressures (450psig);
The USP5 of Fina technology company, 030,786 chat and the method for a kind of alkylating aromatic hydrocarbon/transfering alkylation system ethylbenzene, wherein the aromatic feed after dehydration enters the reaction zone that contains molecular sieve catalyst, contact with being selected from Y zeolite, omega zeolite and the catalyzer of β zeolite, be reflected under the liquid-phase condition of 225 ℃, 24.5 engineering pressures (350psig) and carry out.
Chinese patent application publication number CN1096470A chat and a kind of beta-zeolite-gamma-alumina catalyst that is used for the benzene liquid phase alkylation reaction, the fluorine or chlorine that has wherein added 0.5-10% (weight), preferred 1-5% (weight) is used for stimulating and improves activity of such catalysts.In embodiment 4,200 ℃, the evaluating catalyst condition of 2.94Mpa have been used.
The shortcoming that the method for the liquid-phase alkylation system ethylbenzene of above-mentioned bibliographical information and suitable catalyzer thereof are all kept away unavoidable above-mentioned liquid phase method.
From above-mentioned prior art as seen, all the time exist a kind of needs, promptly develop a kind of processing method that has the novel alkylation to prepare ethylbenzene of vapor phase process and liquid phase method advantage concurrently, and develop be applicable to this processing method, have high reactivity, highly selective, reaction conditions gentleness, a high performance catalyst that by product is few.
Therefore, an object of the present invention is, a kind of new modified zeolite catalyst that is used for alkylation to prepare ethylbenzene is provided, it comprises activeconstituents and a kind of inorganic oxide binder of a kind of β zeolite that is selected from modification, Y type stone, ultrastable Y.
Another object of the present invention is, a kind of method for preparing new modified zeolite catalyst is provided, comprising zeolite or catalyzer base substrate are exchanged, roasting, exchange again, a plurality of modification treatment steps such as roasting, and the forming step of zeolite and inorganic oxide binder again.
Another object of the present invention is the application of said new modified zeolite catalyst in producing phenylethane from alkylation of benzene.
Another purpose more of the present invention is, a kind of processing method of novel gas-liquid-solid three-phase alkylation to prepare ethylbenzene is provided, it is included in above-mentioned new modified zeolite catalyst and exists down, reaction raw materials benzene and ethene are contacted in the enterprising promoting the circulation of qi of said catalyzer-liquid-solid three, generation contains the reaction mixture of purpose product ethylbenzene, separate reacted mixture obtains highly purified ethylbenzene then.
Another purpose more of the present invention is, provides a kind of and prepares the method for ethylbenzene by benzene and diethylbenzene, comprising benzene is contacted on above-mentioned new modified zeolite catalyst with diethylbenzene, carries out the transfering alkylation reaction.
Fig. 1 wherein uses pure ethylene as ethylene feed for the schema by a preferred embodiment of alkylation to prepare ethylbenzene method of the present invention.
Fig. 2 wherein uses rare ethene as ethylene feed for the schema by another preferred embodiment of alkylation to prepare ethylbenzene method of the present invention.
Catalyst of the present invention comprises active component and inorganic oxide binding.
Active component is selected from the Si-Al zeolite through the inventive method modification, is preferably H β zeolite, HY zeolite, super steady type HY zeolite or its mixture. Said several zeolite both can be commercial, also can process through reaming, and its aperture is in the 6-9 scope.
The inorganic oxide binder that is suitable in the catalyst of the present invention is this area inorganic oxide binder commonly used, but the example that its example is enumerated has Al2O
3Or SiO2。
The weight ratio of active component and inorganic oxide binder is 95: 5 to 70: 30 in the catalyst finished product, preferred 90: 10 to 85: 15.
As everyone knows, acid site on the zeolite (comprising B acid site and L acid site) is alkylation between catalysis benzene and the ethene and the effective active center of the transfering alkylation between benzene and the many ethylbenzene, and its total acid content has material impact to the alkylation of ethene and benzene and the transfering alkylation reactivity worth of benzene and many ethylbenzene. The inventor finds, the quantity in B acid site and intensity distributions, B/L value also have material impact to the performance of catalyst, alkylation and transfering alkylation reaction mainly occur on the B acid site of medium above intensity, and there is mating reaction in the L acid site to the catalytic process of reaction. So except must guaranteeing enough total acid contents, also must make the ratio in B acid site quantity and its acid strength, B acid site and the L acid site guarantee catalyst that meets some requirements have excellent performance.
Known in the art, available absorption method is measured in the acid of zeolite or temperature programmed desorption(TPD) method (TPD) is measured.Strength of acid distribution available programs desorption by heating method is measured, and the intensity of the high more then expression of desorption temperature acid is strong more, and the acid amount of the big more expression respective strengths of desorption peaks area is many more.
Because pyridine can be adsorbed in the B acid, can be adsorbed on again in the L acid, therefore available pyridine adsorption method is measured the zeolite total acid content.Because 2, the 6-lutidine only is adsorbed in the B acid, and is therefore available 2, and 6-lutidine adsorptive capacity calculates B acid amount.The difference of total acid content and B acid amount is a L acid amount (referring to Benesi, H.A.J.Catal.28,176 (1973)).
By pyridine or 2,6-lutidine temperature programmed desorption(TPD) method also can correspondingly be measured total acid content or B acid amount.
The present invention measures total acid content with the pyridine adsorption method down at 200 ℃, measures the total acid intensity distribution with pyridine temperature programmed desorption(TPD) method.With 200 ℃ down 2,6-lutidine determination of adsorption method B acid amount, with 2,6-lutidine temperature programmed desorption(TPD) method is measured the B strength of acid and is distributed, and with 400 ℃ down 2, the strong B of 6-lutidine determination of adsorption method is sour to be measured.
Describe these measuring methods below in detail.
30 milligrams of zeolites of 60-80 purpose are packed in (quartz) pipe, handled 1 hour, be cooled to 200 ℃ then with 550 ℃ helium, extremely saturated with Pulse Chromatographic method absorption pyridine well known in the art, use nitrogen purging half hour again.Under carrier gas (He) flow velocity of 30 ml/min, be warming up to 700 ℃ with 20 ℃/minute temperature rise rates, with the temperature variant TPD curve of gas chromatograph record pyridine desorption rate.By the corresponding desorption peaks under certain desorption temperature of this curve representation, strength of acid distributes as can be seen, and promptly desorption temperature is high more, and then acidity is strong more, and peak area is big more, and then corresponding acid amount is many more.Can calculate total acid content by whole peak areas.This value with can verify mutually with pyridine adsorption method observed value.Calculation formula is as follows:
B acid amount and intensity distribution measuring method thereof are the same, just change pyridine into 2, and the 6-lutidine gets final product.Calculate B acid amount by being similar to above-mentioned formula, by 2, the TPD curve of 6-lutidine B strength of acid as can be seen distributes.
Above-mentioned 2, two desorption peaks under mainly existing in 300-400 ℃ and the 500-650 ℃ of scope on the TPD curve of 6-lutidine, they are corresponding to the acid site and the strong acid center of medium tenacity.Therefore, available 2, the 6-lutidine is similar to the saturated extent of adsorption of aforesaid method under 400 ℃ and calculates strong B acid amount.Can relatively and mutually verify with above-mentioned TPD curve calculation value by this determination of adsorption method value.
According to the said determination method, to satisfy following performance requriements according to modified zeolite catalyst of the present invention:
(ⅰ) at 200 ℃ of total acid content 〉=0.6 mmole/gram catalyzer of measuring with the pyridine adsorption method down;
(ⅱ) descend with 2 the B of 6-lutidine determination of adsorption method acid amount 〉=0.5 mmole/gram catalyzer at 200 ℃:
(ⅲ) B acid is 2.5-12 with the ratio (B/L) of L acid site number, preferred 5-7;
(ⅳ) descend with 2 strong B acid amount=0.1-0.3 mmole/gram catalyzer of 6-lutidine determination of adsorption method at 400 ℃;
In order to make modified zeolite catalyst of the present invention have above-mentioned performance, can prepare as follows, comprise one, the performance evaluation of raw material zeolite
Because available different types of zeolite, the zeolite properties of the same race of different product batch numbers also has certain difference, so have stable performance by the catalyzer that makes after the inventive method modification in order to guarantee, need be its initial performance of sampling analysis behind commercial raw material zeolite, and carry out different modifications at raw material zeolite and handle with different performance.Following table 1 is listed the initial performance evaluation result of several typical raw material zeolites, and its evaluation method is identical with above-mentioned evaluation method to catalyzer of the present invention.
The initial performance evaluation result of table 1 different material zeolite
Two, moulding
| Sequence number | Zeolite type | The zeolite source | Na 2O(％) | Total acid (mmole/gram) | B acid (mmole/gram) | L acid (mmole/gram) |
| 1 2 3 4 | The super steady Y of H β Na β Y | Catalyst plant Fushun, Fushun catalyst plant Petroleum Chemical Engineering Institute Wenzhou catalyst plant | 0.06 2.1 11 0.14 | 0.76 0.52 0.24 0.74 | 0.48 0.21 0.12 0.51 | 0.28 0.31 0.12 0.23 |
The moulding of catalyzer or its base substrate comprises and mud, refining, extruding, oven dry and five steps of roasting, and in the art, they all can be undertaken by known method in itself.For example, 180-200 purpose raw material zeolite or modified zeolite powder, SB powder and sesbania powder is fully mixed, and it is agglomerating to add an amount of 10% aqueous nitric acid and mud, and regulates walk soft or hard degree with deionized water.Neither too hard, nor too soft walk is put into soil kneader, extrude 2-4 time repeatedly, make the acid content and the moisture content homogeneous of walk.The walk that refining is good is put into banded extruder and is extruded into uniform slice, and size is in accordance with regulations cut off, and in 60-80 ℃ of baking down.When the moisture content in the slice is about 30%, be molded into the catalyzer base substrate particle of predetermined shape through former.At last with the base substrate particle modification, put in order, sieve and sabot.
Drying is about 4 hours under 120 ℃.Then in 450-650 ℃, preferred 500-600 ℃ the about 4-6 of following roasting hour, accumulation is cooled to room temperature under envrionment conditions at last.
Catalyzer base substrate particle shape can be the honeycombed in sphere, cylindricality, sheet shape, cloverleaf pattern, Raschig ring shape or 3-9 hole.Three, acid modulation
After moulding, need that also catalyzer base substrate particle is carried out the acidity modulation and handle to do modification, promptly according to performance evaluation result, take the different treatment step that it is carried out the acidity modulation, so that it reaches the catalyst performance index of stipulating previously to the raw material zeolite.Can handle catalyzer base substrate particle after the moulding by one or more various combination of following three kinds of acid modulation processing methods: (I) type treatment process: with necessarily concentrate, in the ammonium salt aqueous solution and/or hydrochloric acid of preferred 0.5N-5N, preferred its pH value is 2-3, to the boiling temperature of solution, handled zeolite 1-6 hour in room temperature, filter the back and be washed till no acid ion with deionized water, in 120 ℃ of dryings, then at 400-600 ℃ of following roasting 2-6 hour.This process can repeat 2-5 time.Wherein said ammonium salt can be ammonium chloride or ammonium nitrate.(II) type treatment process: the inorganic salt solution with finite concentration, preferred 0.5-4N was handled zeolite 1-6 hour under boiling, filter the back and be washed till no acid ion with deionized water, dry under 120 ℃, then at 400-600 ℃ of following roasting 2-6 hour, this process can repeat 2-5 time.
Above-mentioned inorganic acid salt comprises muriate, nitrate or vitriol etc.Metal ion comprises magnesium, zinc, copper, calcium or metal ions such as rare earth such as strontium in the inorganic salt.(III) type treatment process: to the boiling temperature of solution, handled zeolite 1-6 hour in room temperature with the phosphoric acid of 0.1～1% (weight) and magnesium nitrate or the magnesium chloride brine of 5-15% (weight), filter the back in 120 dryings.Under 400-600 roasting 3-6 hour then.This process can repeat 2-5 time.
For non-H type zeolite, generally carry out the I type earlier and handle, carry out II type and/or III type then and handle; And to H type zeolite, also can directly carry out II type and/or III type and handle.In a word, by using one or more the combination in kind of the treatment process, make B acid amount, B/L value and the strong B acid of catalyzer measure and be in the scope of defined value.
According to the preparation method of modified zeolite catalyst of the present invention, also can carry out above-mentioned acidity modulation to the raw material zeolite earlier, and then moulding.Promptly get commercial raw material zeolite, carry out in above-mentioned treatment step (I)-(III) the acid modulation treatment of a step or the combination of a few step as required earlier, and then carry out above-mentioned molding procedure with inorganic oxide binder and other processing aid in case of necessity, make have predetermined particle shape, meet above-mentioned performance requriements by modified zeolite catalyst of the present invention.
After the above-mentioned moulding of process and three kinds of treatment processs were carried out the acidity modulation, modified zeolite catalyst of the present invention had following physicochemical property: alkylation activity X
B〉=16.0% alkylation selectivity S
E1〉=95.0% transfering alkylation active X
D〉=40.0% transfering alkylation selectivity S
E2〉=93.0% total acid content 〉=0.6 mM/amount=0.1-0.3 mM/gram of 〉=0.5 mM/gram of the gram catalyst B acid amount catalyst strong B acid of≤0.1 mM/gram catalyst of the L acid amount catalyst strength 〉=10N/ grain granularity 2.5mm grain density≤about 0.56 grams per milliliter specific surface of 0.99 grams per milliliter bulk density 〉=400 meters squared per gram catalyst pore volumes 〉=0.28 cubic centimetre/restrain catalyst aperture 6-9 Na2O%≤0.2%
Wherein, active X
BWith selectivity S
E1Evaluation method as follows.1. alkylation activity and selective evaluation
Adopt the fixedly alkylation activity of bubbling bed reactor evaluate catalysts, this reactor is a stainless steel chuck tubular type isothermal reaction pipe, internal diameter 25mm, and chuck external diameter 45mm, chuck is interior to melt salt constant temperature.Φ 2.7mm spherical catalyst 50 grams are at 500 ℃ of following roastings 4 hours, the reaction tubes of packing into after the cooling.Benzene and ethene are added by reaction tubes bottom and stream, and outlet liquid is formed the transformation efficiency X that calculates benzene when measuring stable state
BSelectivity S with ethylbenzene
E1Reaction pressure: 1.0MPa; Temperature of reaction: 160 ℃; Benzene/alkene mol ratio: 6/1; Benzene weight space velocity: 4h
-1Transformation efficiency and selectivity are calculated by following formula:
Transformation efficiency X
B=(1-B) * 100% selectivity
Wherein, B and EB are respectively the mole fraction of benzene and ethylbenzene in the product, X
BBe the transformation efficiency of benzene, S
ESelectivity for ethylbenzene.2. transalkylation reaction activity and selective evaluation
Adopt the transalkylation reaction activity of fixed bed isothermal reactor evaluate catalysts, reaction tubes is the stainless steel tube of internal diameter 25mm, chuck external diameter 45mm, and chuck is interior to melt salt constant temperature.2.7mm spherical catalyst consumption 40 grams, benzene and diethylbenzene are added by reactor lower end and stream, and outlet liquid is formed the transformation efficiency X that calculates diethylbenzene when measuring stable state
DSelectivity S with ethylbenzene
E2Temperature of reaction: 240 ℃, reaction pressure: 2.6MPa, benzene/diethylbenzene mol ratio: 8/1, gross weight air speed: 6h
-1
Transformation efficiency and selectivity are calculated by following formula: transformation efficiency
Selectivity
Wherein, EB
0And EB
1Be the mole fraction of ethylbenzene in raw material and the product, DEB
0And DEB
1Be the mole fraction of diethylbenzene in raw material and the product, X
DBe the transformation efficiency of diethylbenzene, S
E2Selectivity for ethylbenzene.
The zeolite catalyst that makes by the inventive method has many-sided advantage during as alkylation and transfering alkylation preparation, mainly show as active high, selectivity is good
When for example being used for the alkylation of ethene and benzene, temperature of reaction is 140-185 ℃, and reaction pressure is 0.8-1.2MPa. benzene weight space velocity＞4.0h
-1, benzene/ethylene molar ratio is 6/1～8/1, the ethene utilization ratio can reach 100%, benzene transformation efficiency X
B=15.5-12.5%, the selectivity S of ethylbenzene
E1=92.5-95.5%; When being used for the alkylation of rare ethene and benzene, temperature of reaction is 150-180 ℃, and reaction pressure is 0.8-1.3MPa, and benzene/ethylene molar ratio is 6/1～8/1, and the ethene utilization ratio can reach 95%, X
B=14.8-11.9%, S
E1=93.0-95.5%.Reaction can be to carry out under the gas-liquid-solid three-phase condition under the relatively mild condition
Under above-mentioned 150-180 ℃, 0.8～1.3MPa operation condition, ethene is gaseous state, benzene is in a liquid state, two kinds of reagent are at the enterprising promoting the circulation of qi of solid zeolite catalyst-liquid-solid phase reaction, avoid the higher reaction temperatures of vapor phase process, avoided the higher working pressure of liquid phase method again, saved energy consumption, lowered the requirement to equipment material and manufacturing process, operating process is also easy to be many.Stronger to adaptability to raw material
Both can use the pure ethylene charging, also can use the dilute concentration ethylene feed, and make system good turndown ratio be arranged, all can obtain very high conversion of ethylene raw material.Quality product height, by product are few
Particularly temperature is not high owing to the reaction conditions gentleness, adds obviously not help polyalkylated active centre on the zeolite catalyst that makes by the present invention, so by-products content is low in the product, especially can reflect the xylene content＜50ppm of product quality.Meet in the world requirement fully to high-quality ethylbenzene.The catalyzer operation lifetime is long
Under normal reaction conditions, as being 178 ℃ in temperature of reaction, pressure is 1.3MPa, and benzene/ethylene molar ratio is 7.1/1, benzene weight space velocity 1h
-1The time, through 1026 hours longevity tests, activity of such catalysts and selectivity no change.In case behind the catalyst deactivation, also carry out manipulation of regeneration easily, as by under 450-550 ℃, making charcoal, just catalyst activity is recovered substantially by oxygen-containing gas.
In order to adapt to the premium properties of zeolite catalyst of the present invention, the present invention also provides a kind of method that is prepared ethylbenzene by ethene and benzene alkylation, raw material ethene is contacted in the presence of by catalyzer of the present invention with benzene, carry out gas-liquid-solid three-phase alkylated reaction, from reaction mixture, isolate product ethylbenzene again.This preparation process comprises that raw material charging, reaction and product separate three master operations, and the raw material charging separates with product by known in fact mode to be undertaken, and reaction process is the key component of whole processing method.
In reaction process, adopt the fixed bed bubbling reactor, to pack in the reactor by catalyst segments of the present invention, benzene feedstock enters the beds bottom after the feeding process preheating, axially move to the beds top along reactor; The raw material ethylene feed can be divided into several strands, and from each section beds bottom and benzene forward feeding, the mol ratio of benzene and ethene is 6-10 in the charging respectively, and the WHSV of benzene is 1-5 hour
-1Beds remains on 100～200 ℃, 0.3-1.5MPa, and preferred 140-160 ℃, 0.8-1.2MPa makes ethene and benzene that gas-liquid-solid phase reaction take place on catalyzer.A benefit of this method is, ethene can be directly with the gaseous form charging, and benzene is then with liquid feed, and this has removed the compression of gas feed from, has both saved energy, is convenient to operation again.
In a preferred embodiment of alkylation to prepare ethylbenzene method of the present invention, by the temperature and pressure in the control catalyst bed, so that benzene is in solution-air phase transformation criticality in bed, take the heat release of alkylated reaction away by the evaporation of benzene, substantially do not need to take away the refrigerating unit of reaction heat, make reaction conditions be easy to control and held stationary.
The major advantage of the processing method of the gas-liquid-solid three-phase alkylation to prepare ethylbenzene of the present invention is, the operational condition gentleness, and product purity height, by product are few; Require not harsh, easy and simple to handle, stable to equipment material and complete processing; Energy consumption is lower; The ethylene feed that adapts to different concns and source, or the like.
In a preferred embodiment of the processing method of the gas-liquid-solid three-phase alkylation to prepare ethylbenzene of the present invention, adopt pure ethylene as ethylene feed, its reaction process is as shown in Figure 1.Catalyst segments is contained in the multi-stage type fixed bed bubbling reactor, liquid phenenyl enters reactor from the bottom, pure ethylene gas is divided into some stocks and does not enter reactor from reactor bottom and each catalyst bed interval bottom, and reaction product is extracted out from reactor head, send separation circuit.
In another embodiment preferred of alkylation to prepare ethylbenzene processing method of the present invention, (ethylene concentration 20% (volume), all the other are N to adopt rare ethene
2) charging, its reaction process is as shown in Figure 2.Catalyzer is contained in several discrete reactor bed unit, liquid phase benzene is passed through each beds unit successively with series system, collect the product liquid mixture from last top, unit and send down the step separation circuit, and rare ethene enters from the unitary bottom of each bed respectively, discharges vaporization benzene and non-reacted N from this top, unit
2With other rare gas element and make it to separate.
It is a kind of by benzene and the diethylbenzene processing method through transfering alkylation system ethylbenzene that the present invention also provides, wherein making benzene and diethylbenzene is that 230-280 ℃, pressure are under the 2.3-4.3MPa, contact in the presence of catalyzer of the present invention in temperature, wherein the mol ratio of benzene and diethylbenzene is 8-12, and the WHSV of benzene and diethylbenzene charging is 6-10 hour
-1
Below further explain the present invention with non-limiting example.Preparation of catalysts embodiment
In the following example, used zeolite is all commercially available to be got, and wherein the performance that has of each raw material zeolite sees the following form
Beta zeolite/Y zeolite overstable gamma zeolite Na
2O (%)≤2.0≤11 0.2SiO
2/ Al
2O
315-30 〉=5.0 10-70 degree of crystallinity 〉=70% 〉=90% 〉=90 intracrystalline aperture (A) 5.9-6 8-9 8-9 specific surface area (BET method) 〉=400m
2/ g 〉=400m
2/ g 〉=400m
2/ g embodiment 1 (Comparative Examples 1)
500 grams sequence number in table 1 be 2 commercial Na β raw material zeolite through with the binding agent moulding after, pass through following processing: (1) was 550 ℃ of following roastings 3 hours; (2) measure acid matter, alkylated reaction and the transalkylation reaction activity of zeolite as stated above.The results are shown in Table 2.
Embodiment 2 (Comparative Examples 2)
500 grams sequence number in table 1 be 1 commercial H β raw material zeolite through with the binding agent moulding after, through as processing of (1) and (2) step and evaluation in embodiment 1.The results are shown in Table 2.
Embodiment 3
The Na β zeolite (with embodiment 1) of 500 gram moulding, the following processing of process: (1) was 550 ℃ of following roastings 3 hours; (2) under agitation add 1000ml 1N aqueous ammonium chloride solution, keep boiling 6 hours; (3) cooled and filtered is removed mother liquor, with deionized water wash to there not being Cl
-(4) 120 ℃ of oven dry down; (5) repeating step (1)～(4) is three times; (6) 550 ℃ of following roastings 3 hours; (7) stirred 6 hours under boiling state with 1000ml 0.5% (wt.) phosphoric acid and 10% (wt.) magnesium chloride brine; (8) 120 ℃ of oven dry down; (9) 550 ℃ of following roastings 3 hours; (10) measure acid matter, alkylated reaction and the transalkylation reaction activity of zeolite as stated above.The results are shown in Table 2.
Embodiment 4
The H β zeolite of 100 gram moulding, the following processing of process: (1) handled zeolite 6 hours with 1000ml 1N solder(ing)acid under stirring and boiling condition; (2) cooled and filtered is removed mother liquor, with deionized water wash to there not being Cl
-1(3) 120 ℃ of oven dry down; (4) 550 ℃ of following roastings 3 hours; (5) repeating step (1)～(4) is three times; (6) with embodiment 3 steps (7)～(10).
Embodiment 5 (1) transfers to the 1N aqueous ammonium chloride solution of PH=2～3 in the following exchange of boiling stirring 6 hours with hydrochloric acid with 500ml more with the zeolite 50g of embodiment 4; (2) 120 ℃ of oven dry down; (3) 550 ℃ of following roastings 3 hours; (4) repeating step (1)～(3); (5) measure acid matter, alkylated reaction and the transalkylation reaction activity of zeolite as stated above.The results are shown in Table 2.
Embodiment 6
The Na β zeolite of 100 gram moulding, through following processing: (1) 550 ℃ of following roasting 3 hours: (2) are stirred and are added 1000ml has transferred to pH=2～3 with hydrochloric acid 1N aqueous ammonium chloride solution down, keep boiling 6 hours; (3) 120 ℃ of oven dry down; (4) 550 ℃ of following roastings 3 hours; (5) repeating step (2)～(4) is three times; (6) with embodiment 3 steps (7)～(10).
Embodiment 7
The NaY type zeolite of 50 gram moulding is through following processing: (1) 550 ℃ of following roasting 3 hours; (2) under the boiling condition under agitation, handled zeolite 6 hours with the 1N aqueous ammonium chloride solution that hydrochloric acid transfers to pH=2～3 with 500ml; (3) cooled and filtered is removed mother liquor, with deionized water wash to there not being Cl
-1(4) 120 ℃ of oven dry down; (5) 550 ℃ of following roastings 3 hours; (6) repeating step (2)～(5) is three times; (7) measure acid matter, alkylated reaction and the transalkylation reaction activity of zeolite as stated above.The results are shown in Table 2.
Embodiment 8
50g forming U SY zeolite is through following processing: (1) 550 ℃ of following roasting 3 hours; (2) under stirring and boiling condition, handled 6 hours with 500ml 1N lanthanum nitrate aqueous solution; (3) with embodiment 7 steps (3)～(7).
Embodiment 9
Be used for this routine catalyzer and be handling zeolite according to the method identical with embodiment 6, reaction unit as mentioned above, 50g Φ 2.7mm spherical catalyst, raw material ethene are that 20% (all the other are N
2) rare ethene, temperature of reaction: 178 ℃, benzene/alkene mol ratio: 7.1/1, benzene weight space velocity: 1h
-1, after carrying out reaction in 1062 hours, conversion of ethylene 〉=95%, the transformation efficiency of benzene 〉=15.0%, ethylbenzene selectivity 〉=95%.
Embodiment 10
Be used for this routine catalyzer and be handling zeolite according to the method identical with embodiment 4, reaction unit as mentioned above, catalyzer is the Φ 2.7mm spheroidal particle of 40 grams, benzene and diethylbenzene are by the reactor lower end and flow into adding, temperature of reaction: 245 ℃, reaction pressure: 3.0MPa, gross weight air speed: 1.5h
-1, benzene/diethylbenzene mol ratio: 8/1, after carrying out reaction in 1200 hours, the transformation efficiency of diethylbenzene 〉=55%, ethylbenzene selectivity 〉=95.0%.
The acid matter and the reactive behavior of table 2. catalyzer
| Embodiment | The raw material zeolite | The catalyst acid amount | B/L | Alkylated reaction | The transfering alkylation reaction | Life-span (hour) | |||||||
| B acid amount mmol/g | Strong B acid amount mmol/g | 10% ethene | 20% ethene | ～100% ethene | X D ％ | S E2 ％ | |||||||
| X B,％ | S E1,％ | X B,％ | S E1,％ | X B,％ | S E1,％ | ||||||||
| 1 2 3 4 5 6 7 8 | Naβ Hβ Naβ Hβ Hβ Naβ NaY USY | 0.18 0.48 0.52 0.54 0.54 0.52 0.54 0.56 | 0.02 0.12 0.15 0.14 0.25 0.24 0.20 0.23 | 0.3 1.7 9.0 2.9 5.4 7.0 8.9 4.8 | --- 6.8 11.9 12.1 14.9 14.7 14.6 14.4- | --- ～100 95.2 96.0 95.2 95.1 95.2 95.6 | 4.9 --- 12.6 12.7 15.7 15.9 15.8 15.5 | ～100 --- 95.4 94.9 95.2 95.3 95.4 95.8 | 5.4 8.9 13.3 13.4 16.0 16.1 16.0 15.7 | ～100 98.6 95.7 94.7 95.8 96.0 95.7 93.7 | 3.2 11.4 45.5 42.3 45.2 46.4 --- --- | ～100 99.1 94.9 95.3 94.6 94.1 --- --- | ＞1200 **＞1062 * |
Annotate:
*The alkylated reaction life-span
*The transalkylation reaction life-span
Claims (17)
1. modified zeolite catalyst that can be used for synthesizing ethyl benzene, it comprises: (A) a kind of as the modified zeolite of activeconstituents and (B) optional a kind of inorganic oxide binder,
This modified zeolite catalyst has following performance:
(ⅰ) at 200 ℃ of total acid content 〉=0.6 mmole/gram catalyzer of measuring with the pyridine adsorption method down;
(ⅱ) descend with 2 the B of 6-lutidine determination of adsorption method acid amount 〉=0.5 mmole/gram catalyzer at 200 ℃;
(ⅲ) B acid is 2.5-12 with the ratio (B/L) of L acid site number;
(ⅳ) descend with 2 strong B acid amount=0.1-0.3 mmole/gram catalyzer of 6-lutidine determination of adsorption method at 400 ℃.
2. according to the catalyzer of claim 1, it is characterized in that described zeolite is y-type zeolite, overstable gamma zeolite or β zeolite.
3. according to the catalyzer of claim 1, it is characterized in that the weight ratio of modified zeolite and inorganic oxide binder is 95: 5 to 70: 30.
4. according to the catalyzer of claim 3, it is characterized in that said weight ratio is 90: 10 to 85: 15.
5. according to the catalyzer of claim 1, it is characterized in that the aperture of described zeolite is 6-9 .
6. Preparation of catalysts method by claim 1, comprise, at first with the raw material zeolite 450-550 ℃ of following roasting 3 hours, handle the raw material zeolite in order to the combination of next or a plurality of steps again, then with the inorganic oxide binder moulding, or earlier with raw material zeolite and inorganic oxide binder moulding, again with forming composition 450-550 ℃ of following roasting 3 hours, handle forming composition after roasting in order to the combination of the next one or a plurality of steps then:
(I) filtered the back and is washed till no acid ion with deionized water in the ammonium salt aqueous solution and/or hydrochloric acid of 0.5-5N, handled zeolite 1-6 hour in room temperature to the boiling temperature of solution, and dry back was at 400-600 ℃ of following roasting 2-6 hour, and this process can repeat 2-5 time;
(II) handled zeolite 1-6 hour with the inorganic salt solution of 0.5-4N under boiling, filter the back and be washed till no acid ion with deionized water, and dry back was at 400-600 ℃ of following roasting 2-6 hour, and this process can repeat 2-5 time;
(III) handled zeolite 1-6 hour in room temperature with the phosphoric acid of 0.1～1% (weight) and magnesium nitrate or the magnesium chloride brine of 5-15% (weight) to the boiling temperature of solution, filter after drying, at 400-600 ℃ of following roasting 3-6 hour, this process can repeat 2-5 time then.
7. according to the preparation method of claim 6, it is characterized in that the pH value in treatment step (I) is 2-3.
8. according to the preparation method of claim 6, it is characterized in that the ammonium salt in treatment step (I) is ammonium chloride or ammonium nitrate.
9. according to the preparation method of claim 6, it is characterized in that the inorganic salt in treatment step (II) are muriate, nitrate or the vitriol of magnesium, zinc, copper, calcium or rare earth metal.
10. by the Application of Catalyst of claim 1-5, be used for preparing the alkylation and the transfering alkylation reaction of ethylbenzene by ethene and benzene.
11. the method with ethene and benzene synthesizing ethyl benzene comprises making ethylene feed and benzene charging under temperature 100-200 ℃, pressure 0.3-1.5MPa, contact in the presence of the catalyzer according to claim 1, carries out the air-liquid-solid phase reaction.
12. the method according to claim 11 is characterized in that, temperature wherein is that 140-160 ℃, pressure are 0.8-1.2MPa.
13. the method according to claim 11 is characterized in that, the conditioned reaction temperature and pressure makes the Liquid-Vapor Phase Transition critical state that the is reflected at benzene operation down of ethene and benzene.
14. according to each method among the claim 11-13, it is characterized in that wherein the mol ratio of benzene and ethene is 6-10, the WHSV of benzene is 1-5 hour
-1
15. the method according to claim 14 is characterized in that, said ethene is with gaseous feed, and benzene is with liquid feed.
16. the method by the transfering alkylation prepared in reaction ethylbenzene of benzene and diethylbenzene comprises, making benzene and diethylbenzene is that 230～280 ℃, pressure are under 2.3～4.3MPa, contact in the presence of the catalyzer according to claim 1 in temperature.
17. the method according to claim 16 is characterized in that, wherein the mol ratio of benzene and diethylbenzene is 8～12, and the WHSV of benzene and diethylbenzene charging is 6～10 hours
-1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97117321A CN1073887C (en) | 1997-08-08 | 1997-08-08 | Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation |
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|---|---|---|---|
| CN97117321A CN1073887C (en) | 1997-08-08 | 1997-08-08 | Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1150142C (en) | 1999-12-10 | 2004-05-19 | 北京服装学院 | Benzene and oil refinery dry gas catalyzed alkylation distillation process and equipment of preparing ethylbenzene |
| KR101354235B1 (en) * | 2010-04-14 | 2014-02-13 | 에스케이이노베이션 주식회사 | Catalyst for hydrodewaxing process and a method of preparing the same |
| CN102909059B (en) * | 2011-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | BETA zeolite-containing alkylation catalyst for ethylene and benzene, a preparation method and applications thereof |
| CN103801389B (en) * | 2012-11-14 | 2016-04-13 | 洛阳市科创石化科技开发有限公司 | A kind of Catalysts and its preparation method for ethene and benzene preparing ethylbenzene by reaction and application |
| CN103611564B (en) * | 2013-11-21 | 2015-10-28 | 中国科学院山西煤炭化学研究所 | A kind of catalyst of transforming for durol and method for making and application |
| CN106669776A (en) * | 2017-01-05 | 2017-05-17 | 兰州理工大学 | Preparation method of toluene alkylation catalyst prepared from benzene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| US5116794A (en) * | 1988-03-30 | 1992-05-26 | Uop | Method for enhancing the activity of zeolite beta |
| US5145816A (en) * | 1990-12-10 | 1992-09-08 | Mobil Oil Corporation | Method for functionalizing synthetic mesoporous crystalline material |
| CN1096025A (en) * | 1993-12-16 | 1994-12-07 | 美孚石油有限公司 | The production of ethylbenzene |
| CN1096470A (en) * | 1993-06-15 | 1994-12-21 | 中国石油化工总公司 | Beta-zeolite-gamma-alumina catalyst and preparation thereof |
-
1997
- 1997-08-08 CN CN97117321A patent/CN1073887C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| US5116794A (en) * | 1988-03-30 | 1992-05-26 | Uop | Method for enhancing the activity of zeolite beta |
| US5145816A (en) * | 1990-12-10 | 1992-09-08 | Mobil Oil Corporation | Method for functionalizing synthetic mesoporous crystalline material |
| CN1096470A (en) * | 1993-06-15 | 1994-12-21 | 中国石油化工总公司 | Beta-zeolite-gamma-alumina catalyst and preparation thereof |
| CN1096025A (en) * | 1993-12-16 | 1994-12-07 | 美孚石油有限公司 | The production of ethylbenzene |
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