CN1420156A - Alkylation catalyst carried on silica - Google Patents
Alkylation catalyst carried on silica Download PDFInfo
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- CN1420156A CN1420156A CN 01137492 CN01137492A CN1420156A CN 1420156 A CN1420156 A CN 1420156A CN 01137492 CN01137492 CN 01137492 CN 01137492 A CN01137492 A CN 01137492A CN 1420156 A CN1420156 A CN 1420156A
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Abstract
A beta-zeolite catalyst for alkylating benzene-containing raw material is prepared by SiO2 adhesive and has high regeneration coefficient (at least 95%) for at least 3 time regenerations. Its alkylating reaction with C2-C4 alkylating agent includes ethylating benzene with ethylene until the activity of catalyst is lowered to 0.1-1%, and regenarating catalyst under 500 deg.C.
Description
Invention field
The present invention relates to a kind of alkylating aromatic hydrocarbon method, this method relates to aromatic hydrocarbons substrate such as the alkylation of benzene on the aromatic alkylation catalysts of the β zeolite of preparing with silica binder.
Background of invention
The β zeolite is well-known molecular sieve catalyst, is used for the catalytic pyrolysis of hydrocarbon conversion process as dewaxing and high-molecular weight hydrocarbon ils always.Use the β zeolite to be disclosed in United States Patent (USP) 3,308 first in such conversion reaction, 069 (Wadlinger etc.) later at United States Patent (USP) 4,642, disclose so-called modified version among 226 (Calvert etc.).Disclose as the Calvert patent, the useful especially conversion method that uses the β zeolite is dewaxing, hydroisomerizing, cracking, hydrocracking and the aromatization that is converted into aromatic hydrocarbons by light aliphatic hydrocrbon.The β prepare zeolite that is used for such conversion method that the Calvert patent is disclosed can be undertaken by the synthesis method that relates to the digestion of reaction mixture hydro-thermal, and reaction mixture comprises silicon-dioxide, aluminum oxide, various other optional metal oxide or oxyhydroxide and is used to produce the organic formwork agent of the crystalline structure of requirement.In the reaction mixture, silicon-dioxide and alumina amount can change in the 20-250 molar ratio range, the molar ratio range that makes the silica/alumina in the final crystallized product less than in 20 the examples to about 60 to Calvert patents up to 171.
Molecular sieve catalyst such as β zeolite and many other molecular sieves are used in combination usually and as the substrate material of molecular sieve tackiness agent.For example, foregoing Wadlinger patent has disclosed only uses the β zeolite, or as dispersed mixture, is used in combination with the low activity and/or the catalytic active substance of the tackiness agent of forming as zeolite catalysis.Calvert patent noted earlier has disclosed use inorganic substance such as clay, silicon-dioxide or aluminum oxide, or various matrix material such as silica/alumina, silicon-dioxide/magnesium oxide and various other binary and ternary composition.
Comprise during for example dewaxing, hydrocracking or above-mentioned aliphatic aromatic hydrocarbons transform that at hydrocarbon conversion process except that using the β zeolite, many other molecular sieves also are used as catalyzer always in the alkylation of aromatic hydrocarbons substrate.Such alkylation conversion reaction comprises the alkylation of aromatic hydrocarbons substrate such as benzene, produce alkylaromatic hydrocarbon such as ethylbenzene, ethyltoluene, cumene or higher aromatics, and the transalkylation of polyalkylbenzene is a monoalkylated benzenes.Alkylation reactor produces the mixture of monoalkylated benzenes and polyalkylbenzene, and alkylation reactor generally is connected to the transalkylation reactor in downstream by a series of segregation sections.Such alkylated reaction and transalkylation reaction can or carry out under the equal existence condition of liquid and gas in liquid phase, gas phase.
United States Patent (USP) 4,185,040 (Ward) discloses a kind of alkylation that uses the low sodium content molecular sieve catalyst, and allegedly this method especially is suitable for by benzene and ethene and makes ethylbenzene and make isopropyl benzene by benzene and propylene.Sodium oxide content in the zeolite should be less than 0.5 weight %.The example of suitable zeolite comprises X type, Y type, L type, β type, ZSM-5 type and Ω crystal type molecular sieve, better is the Hydrogen Y-zeolite of steam stable.Concrete disclosed is the ammonium type Y-zeolite that contains the steam stable of 0.2% sodium oxide approximately.Various catalyst shape are disclosed in the patent of Ward etc.Although can use the cylindrical catalyzer of extruding, catalyst shape is so-called " three leaves " shape preferably, and its shape is similar to trefoil shape.The ratio of the surface area/volume of this extrudate should be in 85-160 inch-1 scope.Can use upflowing or downflow system to carry out this alkylated reaction, be preferably downflow system, better can there be Partial Liquid Phase in the temperature and pressure condition of reaction at least, and till reaction proceeds to basic all olefin alkylation reagent at least and all be consumed.Catalyzer can rapid deactivation under most of alkylation conditions when not having liquid phase for reports such as Ward.In the Ward method, and in the previously described various ordinary method, zeolite is absorbed on the porous inorganic oxide tackiness agent, reaches the catalyzer such as the trilobal of particle shape.Therefore, Ward has disclosed use alumina gel, cogelled, the various gel of silica/alumina, titanium oxide, and other inorganic oxide and aluminum oxide, all is the better selection that is used in combination with zeolite-Y preferably.
To using the situation of zeolite in conversion method or the alkylation process, the process that relates to the β zeolite that is used for alkylation process or transalkylation is carried out using aluminum oxide to provide as tackiness agent under the matrix of zeolite catalyst usually.Therefore, United States Patent (USP) 4,891,458 (people such as Ennes) disclose a kind of use beta-zeolite catalyst, make the method for aromatic hydrocarbons liquid-phase alkylation or transalkylation.Be disclosed in the β zeolite of people's patents such as Ennes, the atomic ratio of its silicon and aluminium is greater than 5: 1, and less than 100: 1, preferably greater than 5: 1, less than 50: 1.The disclosed alkylation conditions of Ennes is that the mol ratio of aromatic hydrocarbons and alkene is at least 4-1, poisons rapidly to prevent catalyzer.Range of reaction temperature is about 100-600 °F, and reaction pressure is about 50-100psig usually, and fully guarantees Partial Liquid Phase at least.The zeolite of β preferably that uses in the Ennes method is mainly hydrogen form, and by the ammonium exchange of synthetic product, calcining subsequently reaches this form.Innes discloses pure zeolite and can use together with inorganic oxide adhesive, as aluminum oxide, silicon-dioxide, silica/alumina or natural clay.Innes thinks that still tackiness agent is an aluminum oxide preferably.
At United States Patent (USP) 4, disclosed another kind of alkylation among 798,816 (Raticliffe etc.), this method relates to the use molecular sieve allcylation catalyst, especially in hydrocinnamyl production cumene, this catalyzer is handled monoalkylation selectivity mode according to improving.At first deposit carbon material on catalyzer makes the carbon-contained catalyst particle burning that makes then, makes selectivity improve 1 percentage point at least.Concrete zeolite crystal molecular sieve comprises those that are selected from Y zeolite, fluorizated Y zeolite, β zeolite, L zeolite and omega zeolite.Y-type zeolite reaches silicon-dioxide and compares greater than 6 with aluminum oxide through dealuminzation preferably.In former various documents, refractory inorganic oxide preferably as tackiness agent is an aluminum oxide, especially catapal is although also disclose other tackiness agent such as aluminum oxide, gallium oxide, thallium oxide, titanium oxide, zirconium white, beryllium oxide, silicon-dioxide, silica/alumina and various other material.
The EPA of Butler applies for that openly 467,007 disclose the alkylation reaction zone that has separately and the another kind of method of transalkylation reaction zone, and it uses various molecular sieve catalysts and the output of transalkylation reactor is circulated to the intermediate section abscission zone.In this application, the benzene disengaging zone has the prefractionation district, reclaims ethylbenzene/many ethylbenzene cut from bottom, benzene disengaging zone, and the benzene cut at top is circulated in the alkylation reactor.Described prefractionation district produces top benzene cut (this cut is circulated to alkylation reactor with the top benzene cut of benzene separator column) and contains the bottom fraction of benzene, ethylbenzene and many ethylbenzene.Two later separation districts are arranged between benzene disengaging zone and transalkylation reactor, be used to reclaim processed products ethylbenzene and heavy constituent residual fraction.The many ethylbenzene cut that obtains from last disengaging zone is admitted to transalkylation reactor, and the output of transalkylation reactor is directly sent into the second benzene separator column or letter and connected separator and send into the second benzene separator column.Butler has reported that alkylation reactor can use catalyzer (as beta-zeolite, Y-zeolite or Ω-zeolite) to operate, and perhaps uses catalyzer (as silicon zeolite or ZSM-5) to operate in gas phase in liquid phase.
Relate to the alkylating another kind of method of aromatic hydrocarbons substrate liquid phase and be disclosed in EPA507,761 (Shamshoum etc.).This method relates to use based on the β zeolite, but adds the molecular sieve catalyst of lanthanum modification.Shamshoum has disclosed the β zeolite of lanthanum modification, and is different with the β zeolite that uses hydrogen form, under medium liquid-phase alkylation condition seldom or do not have dimethylbenzene to generate.In people's such as Shamshoum method, the silica/alumina ratio of initial β zeolite is preferably 20-50, begins through ion-exchange step, subsequently in about 570 ℃ of calcinings 2 hours or longer time.After ion-exchange and calcining subsequently,, in the zeolite system, add lanthanum, subsequent drying by carrying out ion-exchange with the lanthanum salts solution.Disclosed lanthanum β such as Shamshoum zeolite mixes with tackiness agent, as alumina gel, gamma-alumina or other refractory oxide, makes the Zeolite bound agent composition, then granulation.
Other method that relates to the benzene liquid-phase alkylation is disclosed in United States Patent (USP) 5,030,786 (Shamshoum etc.) and 5,073,653 (Bulter).Shamshoum's ' 786 patent discloses uses the molecular sieve of empty footpath greater than 6.5 dusts, and especially empty footpath is at the Y zeolite and the β zeolite of 7-7.5 dust scope.The patent of Bulter discloses, and in the benzene liquid-phase alkylation, the catalyzer of use comprises zeolite such as omega zeolite, β zeolite and Y zeolite.Bulter is disclosed in the gentle relatively liquid-phase condition alkylation reactor of operation down, can use low relatively benzene-ethylene molar ratio, and about 5: 1 or littler is 4: 1 or little of about 2: 1 preferably.Higher ratio up to 15: 1 is also disclosed.Bulter specifically discloses a kind of catalyzer that contains 80% (weight) crystallization omega zeolite and 20% (weight) alumina adhesive.
Summary of the invention
The invention provides and contain benzene raw materials alkylating alkylating aromatic hydrocarbon method on the β zeolite alkylated catalyst.Prepare the β zeolite alkylated catalyst with silica binder, and at least 3 regenerated gain factors are at least 95%.In liquid phase or C is arranged
2-C
4The supercritical region of alkylating agent carries out alkylated reaction.In the embodiment, alkylating agent is an ethylating agent, especially ethene preferably in the present invention.Benzene/ethylene molar ratio value was less than 10 o'clock, and benzene is with after the ethylene ethylization, and the gain factor of catalyzer is at least 95%.
The present invention will contain benzene raw materials and supply with the reaction zone that comprises molecular sieve catalyst on the other hand, and described catalyzer comprises the β zeolite alkylated catalyst with the silica binder preparation.With ethene supply response district, in that being under the temperature and pressure condition of liquid phase or supercritical phase, operates benzene.The ethylization of benzene is carried out under the initial original activity of setting.Reaction zone operation lasts till that the styroyl activity of such catalysts is by the original activity of initial setting at least 0.1% of this value that descends.This drop-out value must not be above 1% of the original value of setting.The alkylated reaction operation stops, the beginning regenerative process.In the regenerative process, catalyzer is regenerated not being higher than under 500 ℃ the medial temperature in well-oxygenated environment.When regenerative process finished, reaction zone began alkylation operation again, and the temperature and pressure condition should make benzene liquid phase ethylation under liquid phase or supercritical phase.The initial activity of the catalyzer of subordinate phase should be at least 95% the secondary activity that initial activity can be provided.Alkylation reaction zone operation lasts till that the initial secondary of catalyst activity reduction is active at least 0.1%, and alkylation reaction zone operation stops once more, and catalyzer is by top described regeneration.When regenerative process finished, benzene and ethene were supplied with alkylation reaction zone once more.Reaction zone is operated, three activity that are at least active 95% the styroylization of secondary is provided in that benzene is under the temperature and pressure condition of liquid phase or supercritical phase.
The accompanying drawing summary
The curve representation of Fig. 1 under the liquid-phase alkylation condition of the beta-zeolite catalyst that uses the alumina adhesive preparation, the percent by volume of catalyst bed under the top temperature.
The curve representation of Fig. 2 uses the regeneration beta-zeolite catalyst of silica binder preparation, gradually under liquid-phase condition, and the percent by volume of catalyst bed under the maximum alkylation temperature under the benzene/ethylene molar ratio value that reduces gradually.
Fig. 3 is a synoptic diagram of implementing segmentation reactor system of the present invention.
Detailed description of the Invention
The present invention relates to the aromatic hydrocarbons substrate and comprise that benzene is comprising the beta-zeolite catalyst reaction zone, the alkylation under relative demulcent liquid-phase alkylation condition.The present invention especially can be applicable to the ethylization of benzene under the mitigation liquid-phase condition that seldom produces or do not produce dimethylbenzene, with reference to production specific descriptions the present invention of ethylbenzene.Yet, can be applicable to other alkylated reaction and implement the present invention.For example, the present invention can be applicable to propylene and cumene is produced in the benzene reaction.Usually, can also use the olefin alkylation agent, other alkylating agent such as alkynes, haloalkane, alcohol, ether and ester are as United States Patent (USP) 3,551, described in 510 (Pollitzer etc.) patent.
Point out that as top alkylation reactor should be operated, and promptly is being lower than the critical temperature of benzene under benzene is in the relative mitigation pressure and temperature condition of liquid phase, and guarantees that fully benzene is in the pressure operation down of liquid phase.But, can be at benzene and carry out alkylated reaction under the supercritical phase condition, promptly carry out being higher than under the temperature and pressure condition of critical temperature and pressure.Unless particularly point out in this article, term " liquid phase " or " liquid phase reaction " all can be understood the operation that refers in supercritical range and liquid phase zone at this.
The β zeolite that the present invention uses can be common β zeolite, or any through the β of modification zeolite, will describe these types in detail below.Do not consider the person's character of β zeolite, the present invention carries out according to the mode that is different from ordinary method, common and alumina adhesive such as gamma-alumina or catapal alumina lap of β zeolite in the ordinary method.Therefore, as described in detail later, the β zeolite that the present invention uses is prepared with silica binder, makes the β zeolite that is used for liquid-phase alkylation, and its inactivation and reproducing characteristic are significantly better than the β zeolite with conventional alumina adhesive preparation.β zeolite with silica binder preparation has reproducing characteristic described below, promptly after at least 3 regeneration the gain factor of this catalyzer be to use at least alumina adhesive (consumption of alumina adhesive is identical with silica binder) beta-zeolite catalyst 105%.
The β zeolite that the present invention uses is the β zeolite of high silicon dioxide/alumina ratio of describing in detail below, the β zeolite or the ZSM-12 modified beta zeolite of lanthanum modification.Certainly, can also more or less be conventional β zeolite, described in for example described in front United States Patent (USP) 3,308,609 (Wadlinger etc.) and 4,642,226 (Calvert etc.).Do not consider the person's character of β zeolite, its available silica binder preparation provides the more stable β zeolite of preparing with alumina adhesive than according to traditional way of β zeolite.In addition, β zeolite-silicon-dioxide of the present invention-bonded catalyzer is stable under being starkly lower than with the benzene/ethylene ratio under the corresponding β zeolite situation of alumina adhesive preparation.
As noted, the β zeolite is a molecular sieve catalyst well-known in the art, and the basic skills of its preparation is also known in the art.The method for preparing crystallization β zeolite is disclosed in foregoing United States Patent (USP) 3,308,069 (Wadlinger etc.) and 4,642,226 (Calvert etc.) and European patent 159,846 (Reuben), and these documents are in full with reference to being incorporated into this.Can prepare low sodium content and (promptly be less than 0.2% (weight), with Na
2O represents) the β zeolite, sodium content can also further be reduced to about 0.02% (weight) by ion-exchange.
United States Patent (USP) (Wadlinger etc. with Calvert etc.) is disclosed as previously referenced, can be by comprising the hydro-thermal digestion preparation β zeolite of silicon-dioxide, aluminum oxide, sodium or other alkyl metal oxide, for example and organic formwork agent composition.Typical digestion condition comprises temperature range (boiling point that is lower than water under the environmental stress is to about 170 ℃), and pressure is to be equal to or greater than the vapour pressure that relates under the temperature.The mitigation stirred reaction mixture reached the required crystallization degree of formation β zeolite to the several months in about 1 day.The characteristics of the β zeolite that makes are that the molar ratio of silicon-dioxide and aluminum oxide (is pressed SiO
2/ Al
2O
3Expression) is about 20-50.
Then, do not controlling under the pH, β zeolite and ammonium ion carry out ion-exchange.Should use inorganic ammonium salt such as aqueous ammonium nitrate solution medium as ion-exchange.Ammonium ion exchange filters out the β zeolite after handling, and cleans and drying, afterwards calcining 2 hours or longer time under about 530-580 ℃.
The feature of β zeolite can be described with the symmetry and the X-ray diffracting spectrum of its crystalline structure.The β zeolite is the molecular sieve of intermediate pore size, and about 5-6 dust comprises the channel system that 12-encircles.The β zeolite is that square is symmetric, P4
122, a=12.7, c=26.4 (W.M.Meier and D.H.Olson Butterworth, Atlas of ZeoliteStructure Types, Heinemann, 1992, p.58); The characteristics of ZSM-12 are oblique crystal symmetry.The hole of β zeolite is generally along 001 planar circle, and diameter is about 5.5 dusts, is oval along 100 planes, and diameter is about 6.5 and 7.6 dusts.People such as Higgins are at " The framework topology of zeolite beta " Zeolites, and 1988, Vol.8, November has further described the β zeolite among the pp.446-452, and the document is in full with reference to being incorporated into this.
The β zeolite prescription of implementing the present invention's use can be based on the β zeolite (as described in people's such as front Calvert patent) of routine or the β zeolite (as described in people's such as front Shamshoum EPA communique) of lanthanum modification, or the modified beta zeolite by ZSM-12 crystallized mixed growth is (as the United States Patent (USP) 5 of Ghosh, 907,703 is described).But, do not use the disclosed alumina adhesive of Ghosh, and be to use silica binder described herein.For further describing the method that preparation is used for β zeolite of the present invention, can be with reference to people's such as Wadlinger noted earlier patent 3,308,069, people's such as Calvert 4,642,226 and Ghosh 5,907,073, and the EPA communique No.507 of Shamshoum, 761, these documents are in full with reference to being incorporated into this.
Also use based on silica/alumina ratio and carry out the present invention greater than the β zeolite of the silica bound of the β zeolite of routine.For example,, disclose in 447, can make incinerating β zeolite dealuminzation by steaming process, to improve the silica/alumina ratio of this zeolite at the EPA of Keennedy communique No.186.Therefore, disclose as Kennedy, make silica/alumina ratio be after 30: 1 the calcining β zeolite under 650 ℃ and environmental stress through 100% steam treatment 24 hours.As a result, the silica/alumina ratio of this catalyzer is about 228: 1, cleans through acid then, generates 250: 1 β zeolite.As described above, various β zeolites by using nitric acid extraction, extract aluminium from Beta zeolite structures through leaching process.The cleaning of initial β zeolitic acid proceeds to the β zeolite that reaches high silicon dioxide/alumina ratio.Carry out ion-exchange subsequently, lanthanum enters zeolite structured.Do not answer pickling afterwards, to avoid removing lanthanum from zeolite.
In the alkylating aromatic hydrocarbon method, after catalyst activity descends in time in alkylation process, require regenerated catalyst.In carrying out test work of the present invention, find, with the reproducibility of the β zeolite of silica binder preparation significantly better than according to the ordinary method of prior art β zeolite with the alumina adhesive preparation.In alkylation process, usually fresh catalyzer has high relatively initial activity, and the ethylbenzene percentage ratio that produces under benzene/ethylene molar ratio that can be on request and the benzene air speed is measured.Requirement keeps geostationary activity in the initial stage, but at certain a bit, because catalyzer coking in alkylation process, its activity descends gradually.Catalyst activity reduction or after at least can not economical operation, be cut off the logistics of reactor after can not further operate, and catalyzer carries out regenerative process.Typical regenerative process relates to and begins to inject nitrogen, is increased in the air capacity that adds in the nitrogen subsequently gradually, up to meeting the requirements of oxygen level.For example, when injecting for about 500 ℃, initial oxygen level is about 0.5% (volume) of the regeneration gas of injection.Increase gradually with oxygen level, the coking on the catalyzer is by burning-off, reaches ecological up to catalyzer again, and this moment, its activity was approaching, sometimes even equal the initial activity of catalyzer.In the regeneration of β zeolite, requirement begins to provide the nitrogen atmosphere near 500 ℃, so that discharged nearly all hydrogen before feeding oxygen, to avoid producing water.
Catalyst regeneration can characterize with gain factor, and gain factor refers to that from an alkylation process to another alkylation process, catalyzer can regenerated degree (comparing with its initial activity).Like this, when considering a plurality of alkylations and regenerative process, if catalyzer is during first alkylation process, an activity of overlapping under the standard conditions that shows 10% ethylbenzene, if under the similarity condition of activity when second alkylation process begins of this catalyzer when first regeneration step finishes is 9% ethylbenzene, then gain factor is 90%.If to second regeneration step to the trialkyl process, observe same gain factor from second alkylation process, the catalyst activity when then the trialkyl process begins is 8.1% ethylbenzene.
Describe when of the present invention, term " gain factor " is characterized with following standard conditions.Catalyzer is used under 300 ℃ and the 650psig, and benzene/ethylene molar ratio is 10 o'clock liquid-phase alkylation processes of being carried out.Carry out ethylation reaction, descend 0.5% up to catalyst activity (pressing conversion of ethylene (%) measures).This catalyzer slowly increases the oxygen level in the nitrogen subsequently by injecting nitrogen 24 hours at 500 ℃ at first then, increases to 10% in 24 hours.Afterwards, be determined at the catalyzer initial activity in second alkylation process, so that obtain being used to measure second alkylation activity of gain factor.
In the test work of the present invention,, carry out alkylation with the lanthanum β zeolite (catalyst A) of alumina adhesive preparation and the lanthanum β zeolite of preparing with silicon-dioxide (catalyst B).Method according to EPO 507761 prepares lanthanum β zeolite, and the silica/alumina ratio of this catalyzer is about 100, and lanthanum content is about 1% (weight).In single pass reactors, under 300 ℃ and 650psig, carry out this test work.Benzene raw materials purity is about 99%, feeds with 70/ hour air speed (LHSV).Carry out two groups of tests, one group is used the 5ml catalyzer on catalyst bed, and another group is used the 10ml catalyzer.
(with the lanthanum β zeolite of alumina adhesive) measures two continuous alkylation process in the initial battery of tests that the use catalyst A is carried out, and the centre is inserted with the time dependent fluctuation of reaction bed temperature of a regenerative process.Battery of tests is to the 5ml catalyst bed, and another is organized the 10ml catalyst bed, measures active.
The 5ml catalyst bed is carried out 5 days alkylation operation, the 10ml catalyst bed is carried out alkylation in 4 days, with the thermocouple measurement temperature that is positioned at bed.The result of first shaker test that catalyst A is carried out is marked in Fig. 1, among the figure, is marked in the longitudinal axis at the bed volume %V of top temperature (490 ℃), and operation fate (D) is marked in transverse axis.Among Fig. 1, the result of first journey of curve 2 expression 5ml catalyst beds, the result of second journey of curve 3 expression 5ml catalyst beds.Curve 5 and curve 6 are represented first journey of 10ml catalyst bed and the result of second journey respectively.Regeneration period, temperature are controlled at 490 ℃ of top temperatures.To the test of 5ml and 10ml, lanthanum β zeolite shows deactivation rate high when comparing beginning behind primary recycling.After the regeneration, recover active for the second time, show that the lanthanum β zeolite of preparing with aluminum oxide is stable inadequately, can not bear repeatedly regeneration.
Under the critical phase condition, use the lanthanum β zeolite of the silica binder of 20% amount (identical with the amount of binder of using in the lanthanum βYang Hualv catalyst composition approximately), carry out second cover and test.At this, carry out alkylation operation being higher than under the benzene critical temperature (289 ℃).Temperature of reactor is 300 ℃, and pressure is 650psig, and the benzene air speed is 70/ hour (LHSV).Find, catalyzer benzene/ethylene molar ratio be 10: 1 times stable.After carrying out 4 days initial manipulation, adopt following regenerative process regenerated catalyst:
1. flow down at minimum benzene and be cooled to envrionment temperature;
2. use the 240sccm nitrogen purging; Keeping reactor is to downflow mode;
3. make temperature rise to 400 ℃ with 100 ℃/speed at one hour rating, and kept 3 hours;
4. be cooled to 250 ℃;
5. under minimum mass flow control rate, slowly add air; Make heat release be no more than 490 ℃;
In a single day 6. finish initial rapid burning, in 2 hours, slowly increase air, reduce nitrogen simultaneously to 0sccm to 240sccm;
7. temperature is increased to 485 ℃, and keeps this temperature 3 hours;
8. be cooled to envrionment temperature with fluidizing air.
Use regenerated catalyst, the benzene air speed remained on 70/ hour, carried out the operation of second journey, improved ethene speed gradually, produced the benzene/ethylene ratio of 20: 1,10: 1 and 7.9: 1.The result of this test work is plotted in Fig. 2, and wherein, the bed volume %V of top temperature (490 ℃) is marked in the longitudinal axis, and catalyst bed fate (D) in steam is marked in transverse axis.Among Fig. 2, it is 20: 1 data that curve 8 is drawn benzene/ethylene molar ratio, and curve 9 is that benzene/ethylene molar ratio is 9: 1 data.Curve 10 is that benzene/ethylene molar ratio is 7.9: 1 data.By test-results shown in Figure 2 as can be known, catalyzer is 10: 1 and 7.9: 1 in benzene/ethylene molar ratio, even 20: 1 times complete stabilities, show benzene/ethylene molar ratio be 10: 1 o'clock should stability significantly better than the catalyzer of alumina adhesive.At the 10th day, reduce the benzene air speed, the ethene flow also reduces, and about 3: 5 benzene/ethylene ratio is provided, at the very fast demonstration inactivation of this site catalyst, shown in curve 11.
With the lanthanum β zeolite of silica binder, be 20: 1 and 10: 1 in benzene/ethylene molar ratio, the centre is situated between has four successive processess of regenerated to test.With the silica/alumina ratio is that 50: 1 lanthanum β zeolite carries out this test.Temperature is controlled at and is up to 490 ℃, and pressure is 650psig, and in the supercritical range operation, therefore the reaction conditions that provides is severeer than conventional alkylating demulcent temperature and pressure condition.Carried out each process at 70/ hour under the benzene raw materials LHSV.Between each process according to renovation process regenerated catalyst recited above.
This test the results are shown in table 1.As shown in table 1, show EB content to each process, in the logistics that produces with respect to the diethylbenzene amount of the mensuration of ethylbenzene, based on the butylbenzene amount of ethyl-benzene level (per 1,000,000/part).By the test of table 1 as can be known, the catalyzer after each regeneration keeps excellent activity, and the activity of the 4th process approximates initial activity.In the regeneration of carrying out between the second and the 3rd process second time, unexpected high coking burning causes that catalyst bed temperature surpasses the top temperature that requires and reaches 40 minutes for 490 ℃, is up to 550 ℃.This makes the propyl benzene of generation increase an order of magnitude, and is as shown in table 1.Yet, thus Shi Yan description obviously as seen, much more stable with the β zeolite of silica binder than the β zeolite of using alumina adhesive mutually, have obviously better gain factor.
Table 1
| La-β????50/1?Sil 20/1 | ?La-β????50/1 ?10/1 | |||||||
| Fate | Fate | |||||||
| 1 | ?2 | ?3 | ?4 | ?1 | ?2 | ?3 | ||
| The EB equivalent | First journey | 7.32 | ?7.49 | ?7.58 | ?7.56 | ?14.01 | ?14.17 | ?13.54 |
| Second journey | 7.61 | ?7.20 | ?7.16 | ?7.24 | ?14.11 | ?13.21 | ?13.05 | |
| The 3rd journey | 7.22 | ?7.38 | ?7.46 | ?13.04 | ?13.20 | ?14.12 | ||
| Quadruple pass | 8.18 | ?7.18 | ?7.43 | ?14.47 | ?13.70 | ?13.71 | ||
| ????DEB/EB％ | First journey | 4.61 | ?4.9 | ?4.96 | ?5.01 | ?8.23 | ?8.21 | ?8.11 |
| Second journey | 4.61 | ?4.47 | ?4.44 | ?4.64 | ?6.53 | ?7.24 | ?7.71 | |
| The 3rd journey | 4.2 | ?4.3 | ?4.34 | ?6.45 | ?6.49 | ?6.73 | ||
| Quadruple pass | 4.53 | ?4.29 | ?4.31 | ?6.88 | ?6.8 | ?6.77 | ||
| Bu-benzene/EB equivalent (ppm) | First journey | 338 | ?449 | ?470 | ?471 | ?939 | ?942 | ?929 |
| Second journey | 468 | ?426 | ?420 | ?424 | ?1258 | ?1050 | ?929 | |
| The 3rd journey | 508 | ?510 | ?504 | ?1203 | ?1211 | ?1131 | ||
| Quadruple pass | 544 | ?538 | ?546 | ?1250 | ?1200 | ?1192 | ||
| Propyl group-benzene/EB equivalent (ppm) | First journey | 189 | ?185 | ?235 | ?429 | ?628 | ?642 | ?608 |
| Second journey | 286 | ?220 | ?208 | ?164 | ?1949 | ?889 | ?505 | |
| The 3rd journey | 2908 | ?2683 | ?2494 | ?2257 | ?2755 | ?3309 | ||
| Quadruple pass | 7651 | ?7270 | ?6731 | ?3488 | ?3182 | ?3088 | ||
As noted, according to the present invention, the beta-zeolite catalyst of silica binder is designed for liquid-phase alkylation.Implement among the present invention, under the pressure that is higher than the vapour pressure that aromatic hydrocarbons substrate reactions temperature relates to, carry out alkylated reaction, in whole reactor, guarantee liquid phase.For complete liquid phase reaction is provided, adopt the fluidized-bed type that overflows, catalyzer is immersed in the liquid fully.Adopt the flow pattern that makes progress as adopting in the test of front, can reach overflow type easily, the present invention should adopt this mode.Yet, by the control rate of discharge, guarantee that catalyst bed is covered by liquid benzene or other aromatic hydrocarbons substrate, can implement downward fluidized bed operation.
For guaranteeing the fine benzene (or other aromatic hydrocarbons substrate) that is dissolved in of ethene (or other alkylating agent), should adopt the segmentation reaction pattern, entire reaction is carried out in liquid phase.By a plurality of catalyst beds in the reactor or by a plurality of reactors that are linked in sequence (as the United States Patent (USP) 5,073 of Butler, described in 653), provide the segmentation reaction pattern.Multi-stage type provides interlude refrigerative chance, can use insulating reactor or allow to use several isothermal reaction sections.Refer back to Fig. 3, Fig. 3 is a synoptic diagram of producing the multistage reactor of ethylbenzene by ethene and benzene reaction, and this reactor includes the intercooling section and injects a plurality of insulating reactors of ethene.Describe in detail according to this figure, by pipeline 12 and 14 inlet pipes 15 ethene and benzene supply dewatering unit 16.The effect of dewatering unit is the water that removes the alkylation reactor charging, makes the charging substantially dry, requires the charging water content less than 100ppm, better less than 50ppm.For example, water trap 16 can be desiccant-filled packed tower or azeotropic cryogenic columns form as silica gel or other suitable moisture absorption medium.
Water trap effluent liquid supply response device 18, i.e. first of the alkylation reactor of a plurality of connections is according to upwards flow pattern operation.Reactor 18 is operated down for 150-250 ℃ more fortunately 350 ℃ or lower medial temperature.To liquid-phase operation, reactor 18 should keep enough pressure to make benzene be in liquid phase, and pressure is advisable at the high 50psig of the vapour pressure under the temperature of reactor than benzene at least.Reactor pressure is usually in about 500-850psig scope.Remaining reactor is generally downward flow pattern operation, with the basic identical condition of first reactor under operate.The effluent liquid of the reactor 18 of beginning is drawn by pipeline 19, and supplies with second section reactor 24 by heat exchanger 22 cooling backs.Supply with ethene by pipeline 21, ethene and mix in pipeline 21 from the effluent liquid of first reactor 18.As shown in the figure, ethene should be supplied with the reactor stream fluid before the cooling, is beneficial to ethylene distribution in all liquid benzene.Cooling step is carried out in requirement, and the raw mix temperature of supplying with second reactor 24 is reduced to and the essentially identical temperature of first reactor, 18 imports.Medial temperature in second reactor usually and basic identical in first reactor.Pressure must be lower slightly, provides sufficient pressure gradient to make and flow through this system.Supply with second intercooler unit 29 together from the effluent liquid of second reactor with by the ethene that pipeline 27 provides, the incoming mixture of supplying with the 3rd reactor 30 is cooled to approximate two reactor inlet temperatures of beginning again.
The discharging of reactor 30 is supplied with downstream separation and processing unit 34 by pipeline 32.In unit 34, isolate ethylbenzene, and extract out as the product of alkyl plant.Usually, ethylbenzene will be as the charging of dehydrogenation system, producing phenyl ethylene by ethyl benzene catalytic dehydrogenation in dehydrogenation system.Benzene separates in unit 34 usually with ethene, and circulation is used for alkylation process.Heavy multi-ethyl phenenyl and benzene produce other ethylbenzene through transalkylation.Suitable multistage separation system and trans alkylation system can adopt one of association system of EPA 467,007 disclosures, and the document is in full with reference to being incorporated into this.With the raw material supplying alkylation reactor of benzene stoichiometry, to improve the selectivity of monoalkylation above ethene.Reactor is operated under the relative mitigation condition of liquid-phase alkylation is provided and is not only made the dimethylbenzene that produces in the alkylated reaction minimum, and benzene/ethylene molar ratio of using is lower than regular situation.Use is low to moderate about 2: 1 benzene/ethylene molar ratio, although also can use about 4: 1 benzene/ethylene molar ratio.Yet, seldom to agree with using very high mol ratio, in the practice, benzene/ethylene molar ratio is hardly above 15: 1.Benzene/ethylene molar ratio is about 4: 1 preferably.Above-mentioned benzene/ethylene molar ratio is according to total system, and to the multistage reactor as shown in the figure, the benzene/ethylene molar ratio of each section raw material will be less than total ratio.Be dissolved in the ethene amount of supplying with in each stage reactor benzene raw materials and depend in part on the reactor hop count of use.Usually, use at least three sections reactor.Although hop count is no more than 8 usually, can provide the reactor of extra segment.The pressure of each conversion zone and the ethene amount that provides are preferably and provide at least 1% (mole) to be dissolved in the ethene of benzene.Generally in the raw material of supplying with each reactor, be dissolved with 2% (mole) ethene at least.Unless use more multiple reactor section, the ethene amount that generally is dissolved in the liquid phenenyl of each reactor is at least 4% (mole).
Can also ethylize according to the multistage that the present invention uses the isothermal reaction district to carry out benzene.Isothermal reactor can be a shell-and-tube type heat exchanger form, deposition alkylation catalyst in pipe, and heat exchange medium is by the circulation of the shell around the catalyst filling pipe.Certainly provide heat exchange medium to make by reactor, it is constant relatively that its speed should keep traversing the temperature of each conversion zone.In this case, the interlude cooling is optional, although should inject ethene in each conversion zone front.
As previously described, in liquid phase alkylation reaction, should use β-SiO 2 catalyst under the mitigation condition relatively.But, can carry out the present invention at the alkylation reactor of similar liquid-phase operation with the benzene substrate, its temperature and pressure all is higher than under the severe condition of ceitical region of benzene.As noted, in this case, alkylation reactor can be operated under about 290 ℃ and 700psig pressure.Usually adopt higher temperature and pressure.At this, benzene adopts the alkylation reactor of supercritical region to operate under 300-600 ℃ and about 650-850psig pressure.
Specifically described embodiment of the present invention, one skilled in the art should appreciate that and can change the present invention, all these change all within the scope of claims.
Claims (16)
1. alkylating aromatic hydrocarbon method, this method comprises the following steps:
(a) will contain benzene raw materials supply response district, and contact with comprising the molecular sieve catalyst with the β zeolite alkylated catalyst of silica binder preparation, this catalyzer carries out under 500 ℃ of temperature at least that the average gain factor of tertiary recycling is at least 95% not being higher than;
(b) provide C at described reaction zone
2-C
4Alkylating agent;
(c) described reaction zone makes described benzene be operated under effective alkylating temperature and pressure condition by alkylating agent in liquid phase or supercritical region;
(d) reclaim alkylating benzene from described reaction zone.
2. the method for claim 1 is characterized in that described alkylating agent is an ethylating agent.
3. method as claimed in claim 2 is characterized in that described ethylating agent is an ethene.
4. the method for claim 1 is characterized in that described reaction zone is at described benzene under the temperature and pressure condition of liquid phase to operate.
5. method as claimed in claim 4 is characterized in that making described benzene and alkylating agent to supply with described reaction zone, and its flow is for making the benzene that provides and described alkylating agent mol ratio less than 15.
6. method as claimed in claim 5, the mol ratio that it is characterized in that described benzene and described alkylating agent is less than 10.
7. method as claimed in claim 5, the mol ratio that it is characterized in that described benzene and described alkylating agent is in the 4-10 scope.
8. method for preparing ethylbenzene, this method comprises the following steps:
(a) will contain benzene raw materials supply response district, contact with the molecular sieve catalyst that comprises the β zeolite alkylated catalyst of preparing with silica binder;
(b) provide ethene at described reaction zone;
(c) described reaction zone is at described benzene under the temperature and pressure condition of liquid phase or supercritical phase and operates, and described benzene is ethylized with initial activity in the presence of described alkylation catalyst;
(d) reclaim the alkylate that contains ethylbenzene from described reaction zone;
(e) operation of the described reaction zone of continuation descends 0.1% up to the described activity of such catalysts that is used for styroylization from its initial activity;
(f) stop the operation in benzene alkylation reaction district, the beginning regenerative process, described catalyzer is regenerated in well-oxygenated environment, and medial temperature is not higher than 500 ℃ in the described regenerative process;
(g) after described regenerative process, by providing benzene to set up the operation of described alkylation reaction zone again to described alkylation reaction zone;
(h) described reaction zone is operated under liquid phase or the effective ethylating temperature and pressure condition of the described benzene of the overcritical mutual-assistance, and described benzene is ethylized in the presence of described regenerated catalyzer, with the active preparation of at least 95% the secondary ethylbenzene of initial activity;
(i) operation of the described alkylation reaction zone of continuation drops to secondary active at least 0.1% up to the described styroyl activity of such catalysts that is used for;
(j) stop the operation of alkylation reaction zone, be not higher than 500 ℃ of described catalyzer of regeneration down at well-oxygenated environment and medial temperature;
(k) provide benzene and ethene to described alkylation reaction district;
(l) described reaction zone is operated under liquid phase or the effective ethylating temperature and pressure condition of the described benzene of the overcritical mutual-assistance, and described benzene is ethylized in the presence of described regenerated alkylation catalyst, styroylization is provided the initial activity of secondary active at least 95%.
9. method as claimed in claim 8 is characterized in that described beta-zeolite catalyst comprises the β zeolite that adds the lanthanum modification of lanthanum ion by ion-exchange in the β zeolite.
10. method as claimed in claim 8 is characterized in that the silicon-dioxide/aluminum ratio value of described β zeolite is at least 40.
11. method as claimed in claim 8 is characterized in that described beta-zeolite catalyst is included in the β zeolite of the modification that the ZSM-12 of intergrowth crystalline structure is arranged in the β zeolite crystal structure.
12. method as claimed in claim 8, after it is characterized in that described β zeolite regeneration at least three times, its gain factor for and the beta-zeolite catalyst gain factor prepared of the alumina adhesive of the silica binder same amount that uses of described β zeolite at least 105%.
13. method as claimed in claim 8 is characterized in that described reaction zone is at described benzene under the temperature and pressure condition of liquid phase to operate.
14. method as claimed in claim 13 is characterized in that described benzene and alkylating agent are supplied with described reaction zone, its flow for mol ratio that the benzene that provides and described alkylating agent are provided less than 15.
15. method as claimed in claim 14, the mol ratio that it is characterized in that described benzene and described alkylating agent is less than 10.
16. method as claimed in claim 14, the mol ratio that it is characterized in that described benzene and described alkylating agent is 4-10.
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| IT1237198B (en) * | 1989-11-16 | 1993-05-26 | Eniricerche Spa | PROCESS FOR THE ALKYLATION OF AROMATIC COMPOUNDS. |
| JPH06239771A (en) * | 1989-12-22 | 1994-08-30 | Dow Chem Co:The | Method and catalytic composition for alkylation of benzene or substituted benzene or transalkylation of alkylated benzene |
| IT1290846B1 (en) * | 1996-12-12 | 1998-12-14 | Enichem Spa | CATALYTIC COMPOSITION AND PROCESS FOR THE AKYLATION AND / OR TRANSALKYLATION OF AROMATIC COMPOUNDS |
| CN1110364C (en) * | 1999-03-30 | 2003-06-04 | 中国石油化工集团公司 | Catalyst for producing ethylbenzene and its preparation method |
| CN1116931C (en) * | 2000-02-24 | 2003-08-06 | 中国石油化工集团公司 | Method of raising the stability of catalyst for benzene and ethylene alkylation |
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