CN102464540A - Method for producing para-alkylated arene - Google Patents
Method for producing para-alkylated arene Download PDFInfo
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- CN102464540A CN102464540A CN2010105528896A CN201010552889A CN102464540A CN 102464540 A CN102464540 A CN 102464540A CN 2010105528896 A CN2010105528896 A CN 2010105528896A CN 201010552889 A CN201010552889 A CN 201010552889A CN 102464540 A CN102464540 A CN 102464540A
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Abstract
The invention relates to a method for producing para-alkylated arene, mainly aiming at solving problems of much side reactions, low raw material use ratio and poor catalyst stability in the traditional olefin alkylating production method. The technical scheme of the invention, which solves the problem well is as follows: the method comprises the following steps of: with arene materials and alkylating reagents as raw materials, contacting the raw material with ZSM type molecular sieve based catalysts to carry out shape-selective alkylating reaction under the condition that the total mole ratio of the arene materials to the alkylating reagents is 1:10-10:1, the weight airspeed is 1-10hr<-1>, the reaction temperature is 300-500 DEG C, the reaction pressure is 0.1-5.0 MPa and the mole ratio of carrier gas to the arene materials is 1-8, wherein the alkylating reagents are divided into at least two material flows. The method disclosed by the invention can be used in industrial production for producing p-xylene by alkylating toluene and methyl alcohol.
Description
Technical field
The present invention relates to a kind of method that is used for production contraposition alkylated aromatic hydrocarbons, particularly use a kind of many bed reactors to carry out the reaction of aromatic hydrocarbons form selected methylation.
Background technology
Alkylating aromatic hydrocarbon is the basic skills of synthesis of alkyl aromatic hydrocarbons, and what, the type of location and alkyl chain of alkyl number on the aromatic ring all have very big influence to the physical and chemical performance and the using value of alkylaromatic hydrocarbon.In alkylation reaction of arene, according to the difference of using catalyst type, the product of generation can be the equilibrium mixture of multiple isomer coexistence, also can be valuable unbalanced type form selected methylation product.Therefore, selecting synthesizing ethyl benzene, p-Xylol, p-methyl-ethylbenzene is very important alkylation reaction of arene process, has important scientific value and practical significance.
In recent years, as important petrochemical complex basic material, p-Xylol all has purposes extremely widely in fields such as trevira, medicine, agricultural chemicals, dye well solvents.Because the trevira excellent property, development leaps to first of the synthon rapidly already, and estimating will have bigger development from now on.According to statistics; The annual growth of p-Xylol demand has surpassed the GNP annual growth in the world wide; Reached 8.5%; Estimate 10 years futures and will increase 1,400 ten thousand tons of p-Xylol yearly capacities newly to satisfy the demand of the whole world to polyester product, this mainly is because p-Xylol is a main raw material of producing polyester product.P-Xylol can obtain terephthalic acid after oxidation, but terephthalic acid and terepthaloyl moietie then polycondensation become polyethylene terephthalate this most important trevira and plastic raw materials.
The p-Xylol market requirement is vigorous, though can from coal tar is reformed oil and pyrolysis gasoline, obtain p-Xylol, its amount is less, far can not satisfy actual needs.The p-Xylol working method of generally using in the industry at present has the xylol isomerizing, toluene and C
9Aromatic disproportion and selective disproportionation of toluene technology.Preceding two kinds of methods all need be from C
8The technology of separating paraxylene in the BTX aromatics, thereby to obtain the p-Xylol of high density, separation condition is very harsh, needs circulation repeatedly, and the material treatment capacity is big.Thereby these two kinds of technology required equipmenies are huge, and efficient is low, and output is few, and cost is very high.The p-Xylol technology that selective disproportionation of toluene generates high density is relatively more novel, and production efficiency is high, and because raw material is single, and flow process is simple, this technology has at home and abroad received widely and having paid close attention to.Yet by reactional equation, in this technology, need can generate with two moles of toluene the p-Xylol of one mole of high density, the toluene utilization ratio is lower.
The alkylation of toluene methanol reaction can change into the higher high density p-Xylol of using value with toluene, has reduced and has separated and isomerized workload, and its economic benefit is considerable, simultaneously also for rationally utilizing methyl alcohol that a valid approach is provided.Be the breakthrough problem of present p-Xylol production technique, get more and more people's extensive concerning.Maximum difficult point is exactly that the problems such as reaction stability of this catalyzer are not resolved in this technology.Stability about catalyzer has more report, generally believes that carbon distribution is the most general and most important deactivation cause of sieve catalyst.
At present, toluene methylation process generally adopts fixed-bed reactor, and toluene and methyl alcohol are normally according to suitable ratio; Like toluene and methanol=2/1 (mol/mol); Behind the thorough mixing, after certain temperature, introduce in the fixed-bed reactor together in advance through heater heats.In the main reaction that toluene methylation takes place, also many side reactions can take place, form alkene like the methyl alcohol id reaction, become various hydro carbons and even carbon distribution through reaction conversion such as polymerization, cracking, aromizing.The generation of side reaction has also generated a large amount of reaction heat, causes the temperature difference of reactor bed bigger, the catalyst deactivation aggravation.
People such as Kaeding are at " Selectivealkylation of Toluene with Methanol to Produce para-Xylene "; (Journal of Catalysis, Vol.67 (1981) have described through a certain amount of phosphorus of load on ZSM-5 in p159-174) and have prepared modified catalyst; Be applied to the toluene methylation reaction process; Can obtain 85～97% p-Xylol selectivity, yet owing to reasons such as carbon distributions, this catalyzer is active in several hours to be reduced sharply.
USP U4,670,616 relate to use borosilicate zeolite, through preparing catalyzer with kneadings such as sticker such as alumina, silica or alumina-silicas, are applied to toluene methylation and prepare the YLENE reaction.Obtaining the concentration of p-Xylol in Mixed XYLENE is 50～60%, yet in the reaction process, because side reaction is many, use ratio of methanol is low, has produced a large amount of coke, has caused the rapid deactivation of catalyzer.
More than several kinds of methods of producing p-Xylol; It is low all to exist the main reaction selectivity, and dimethylbenzene selective is often 55～60%, and side reaction is many, use ratio of methanol is lower than 55%; And life of catalyst is general all below 300hr, shortcomings such as poor catalyst stability.
Summary of the invention
Technical problem to be solved by this invention is to adopt the existing reactant stream irrational distribution of single bed alkylation reactor in the past; Cause that side reaction increases, use ratio of methanol is low; And the problem of poor catalyst stability; A kind of new method that is used for production contraposition alkylated aromatic hydrocarbons is provided, and this method has that side reaction is few, use ratio of methanol is high, and the good advantage of catalyst stability.
For solving the problems of the technologies described above; The concrete technical scheme that the present invention adopts is following: a kind of method that is used for production contraposition alkylated aromatic hydrocarbons; With aromatic hydrocarbons material and alkylating reagent is raw material, is that 1: 10～10: 1, weight space velocity are 1～10hr in aromatic hydrocarbons material and the total mol ratio of alkylating reagent
-1, temperature of reaction is that 300～500 ℃, reaction pressure 0.1～5.0MPa, carrier gas and aroamtic hydrocarbon raw material mol ratio are under 1～8 the condition; Raw material contacts with ZSM type sieve catalyst and selects shape type alkylated reaction; Alkylating reagent is divided into two bursts of logistics at least, wherein:
(a) arene stream I gets into first beds with after first gang of alkylating reagent stream I I mixes, and obtains gas stream A after the reaction;
(b) gas stream A gets into second beds with after at least the second gang of alkylating reagent stream I II mixes, and obtains gas stream B after the reaction;
(c) gas stream B gets into knockout drum as reaction product, separates the liquid that obtains and gets into the aromatic hydrocarbons fractionating system;
Wherein, alkylating reagent comprises at least a in methyl alcohol, dme, methylamine, ethanol or the ethene, and first strand of alkylating reagent is 10: 1～1: 10 with the mol ratio of at least the second strand of alkylating reagent.
In the technique scheme, the reactor bed preferable range is 2～15 beds, and the alkylating reagent logistics is corresponding to be divided into 2～15 bursts of logistics, and the preferable range of reactor bed is 2～6 beds, and alkylating reagent logistics preferable range is 2～6 sections logistics; Alkylating reagent logistics distribution at each bed can be a same-size ratio, also can be non-equivalent, and preferred version is that equal proportion is distributed.The alkylating reagent preferred version is the cold burden charging, and the cold burden charging can effectively suppress the beds temperature rise, has improved the effective rate of utilization of methyl alcohol, reduces side reactions such as carbon distribution; The carrier gas preferred version is nitrogen or hydrogen, and more preferably scheme is a hydrogen.The aroamtic hydrocarbon raw material preferred version is at least a in benzene, toluene or the ethylbenzene, and more preferably scheme is a toluene; The alkylating reagent preferred version is at least a in methyl alcohol, dme, methylamine, ethanol or the ethene, and more preferably scheme is a methyl alcohol; The shape-selective catalyst that adopts in weight percent of catalyst, contains Hydrogen ZSM-5 molecular sieve 10～89%, SiO
2/ Al
2O
3Molecular ratio is 20～500; At least a on Hydrogen ZSM-5 molecular sieve among the Mg of load 1～20%, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, the Pb; The used sticker of catalyzer is at least a in silicon-dioxide, titanium oxide, aluminum oxide, the zeyssatite, and its content is 10～80%.
In the prior art, toluene methylation reaction single bed fixed beds or the fluidized-beds of adopting react more, in single bed fixed bed reaction, because methyl alcohol and toluene together gets into by reactor inlet, and the methyl alcohol side reactions such as self-polymerization that mostly occur; And in fluid process, because the carbon deposition quantity relative deficiency of toluene methylation reaction, increase the methyl alcohol add-on in the reaction process keeping certain carbon distribution quantity combusted, thus cause use ratio of methanol on the low side, production cost is higher.
The present invention has adopted many bed reactors to replace existing single bed reactor, makes original methanol reactant logistics change the multiply charging into by the sub-thread charging.Can improve existing fixed-bed reactor; Which floor catalyzer separated into by inert ceramic balls or granulated glass sphere in many bed reactors; Material inlet is installed in marker space at filling inert ceramic balls or granulated glass sphere; After methyl alcohol is separated into a small amount of logistics of multiply through a plurality of inlets, mix, react at beds with big strand hydrogeneous high temperature arene stream.Also can connect overlapping reactor drum more; Every cover reactor drum is one section; The upper and lower of catalyst reactor bed all have inert ceramic balls or granulated glass sphere to carry out the logistics dispersion; Arene stream is introduced by first section reactor drum upper end, and the alkylation material can be divided into the multistage logistics, is introduced by each section reactor drum top respectively.Because the toluene of each bed is all excessive greatly; Thereby improved the chance that methylation reaction takes place methyl alcohol on toluene; The probability that reduced that two or more methyl alcohol take place excessively to methylate on toluene, side reactions such as self condensation and hydrocarbonylation takes place; And because the existence of cold shock material has suppressed the beds temperature rise, improved the generation that methyl alcohol effective rate of utilization to 60% is above, reduced side reactions such as carbon distribution, the reaction life-span of catalyzer extends to 600hr; Improve the stability of catalyzer widely, obtained good effect.
Methylbenzene raw material and liquid reacting product employing model are that the gas chromatograph of HP-5890 is analyzed, and this chromatogram is equipped with flame ionization ditector and polyoxyethylene glycol capillary column, and the material composition carries out quantitatively through proofreading and correct normalization method.
The index of relatively paying close attention in the toluene methylation reaction comprises toluene conversion, dimethylbenzene selective, methyl utilization ratio and X/B value, and wherein toluene conversion is meant methylbenzene raw material single pass reactor drum and the ratio that transforms, and this paper adopts weight percent to represent; Dimethylbenzene selective is meant the weight percent of YLENE in the product; The methyl utilization ratio is meant the ratio that the methyl alcohol of methyl on the aromatic ring accounts for total methanol feeding that is converted into; X/B value representative be the mol ratio of YLENE and benzene in the product.The formula that embodies of each index sees embodiment for details.
Description of drawings
Fig. 1 is typical single bed fixed-bed reactor synoptic diagram.Among the figure,
(1) and (2) be respectively inert material and catalyzer.I represents aroamtic hydrocarbon raw material; II represents alkylating reagent.
Fig. 2 is the synoptic diagram of many beds fixed-bed reactor, and among the figure, (1) and (2) is respectively inert material and catalyzer.I represents aroamtic hydrocarbon raw material; II, III represent alkylating reagent; A then reacts the gas stream A that obtains; B then reacts the gas stream B that obtains.
Fig. 3 is the synoptic diagram of multi-stage type fixed-bed reactor, and among the figure, (1) is carrier gas, and (2) are under meter, and (3) are strainer, and (4) are alkylating reagent, and (5) are aroamtic hydrocarbon raw material, and (6) are water-cooled, and (7) are tail gas, and (8) are sampling.
In Fig. 1, reactor drum has two opening for feeds of gas-liquid, the total logistics of aromatic hydrocarbons and alkylating reagent; The common reactor drum liquid phase inlet of introducing; After inert material district, the upper strata of reactor drum vaporizes dispersion, get into beds, carry out the toluene methylation reaction; Reacted product feeds gas-liquid separator through overcooling to be separated, and product liquid and gaseous product can be distinguished sampling analysis.
In Fig. 2, reactor drum has two opening for feeds of gas-liquid, after aromatic hydrocarbons and first part's alkylating reagent logistics mix; The common reactor drum liquid phase inlet of introducing after the first layer inert material district of reactor drum vaporizes dispersion, gets into first beds; Carry out the toluene methylation reaction, reacted then product and the logistics of second section alkylating reagent are after the vaporization of second layer inert material district disperses; Get into second beds, the toluene methylation reaction takes place, after the multistage reaction; Reaction product feeds gas-liquid separator through overcooling separates, and product liquid and gaseous product can be distinguished sampling analysis.
In Fig. 3; Reactor feed comprises a kind of gas and two kinds of liquid, and wherein a kind of charging is divided into the multistage feeding of equivalent or inequality, hop count equal the to connect number of used reactor drum; 4 reactors in series are just done a signal shown in the figure; The actual series connection evaluating apparatus that adopts can contain 2～15 reactor drums, and reaction product feeds gas-liquid separator equally after overcooling separates, and gas and product liquid be sampling analysis respectively.
Turn to example with the methylbenzene methanol alkylation selectivity, each catalytic performance index calculating method is following:
We can find that this index has comprised the methyl in YLENE and the trimethylbenzene in the expression formula of above-mentioned methyl utilization ratio; The mole proportion of deduction benzene is to have lost a methyl because of comparing with initial aroamtic hydrocarbon raw material toluene; It is because trimethylbenzene has increased by two methyl that the trimethylbenzene expression formula multiply by coefficient 2, and its composition more complicated of aromatic hydrocarbons that durene etc. are heavier is difficult to accurate analysis; And this part material growing amount is less, thereby ignores when calculating the methyl utilization ratio.
Through specific embodiment the present invention is done further elaboration below.
Embodiment
[Comparative Examples 1]
Use Na
2O content is less than 0.15% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 molecular sieve powder 66.7 grams and the Na of molecular ratio 260
2O content is less than the α-Al of 0.15% (weight)
2O
3H
2O 57.1 gram uniform mixing; Powder behind the dipping adds the CP dilute nitric acid solution again; Fully mediate evenly, carry out extruded moulding, roasting, be made into the aqueous solution with CP Lanthanum trinitrate, titanium sulfate and nitrate of baryta then and flood; Process catalyst A, wherein lanthanum content is 2%, titanium content is 1%, barium content is 1%.
The conventional fixed-bed reactor that Fig. 1 describes in the working instructions accompanying drawing, filling 10g catalyst A, during evaluation with toluene and 2: 1 in molar ratio mixed of methanol liquid; After stirring, after vaporization, introduce reactor head, after dispersion of upper strata porcelain ball and preheating; Get into beds, at weight space velocity WHSV4.0hr-1,420 ℃ of temperature of reaction; React under the condition of pressure 0.5Mpa, reaction product is fed gas-liquid separator through overcooling and is separated by the reactor drum lower end; The product liquid sampling analysis, its technical indicator is listed in table 1, and its stability test data are seen chart 2.
[Comparative Examples 2]
Use Na
2O content is less than 0.15% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 powder 66.7 grams and the Na of molecular ratio 20
2O content is less than the silicon sol 57.1 gram uniform mixing of 0.15% (weight); Add iron nitrate solution, bismuth nitrate solution; Fully mediate evenly, carry out extruded moulding, roasting, carry out aqueous solution dipping respectively with magnesium nitrate, Xiao Suangu and platinum acid chloride solution again; Process catalyst B, wherein Mg content is 1%, cobalt contents is 2%, platinum content is 1%.
The conventional fixed-bed reactor that Fig. 1 describes in the working instructions accompanying drawing, filling 10g catalyst B compares 3: 1 mixed with toluene and dme massage with fluid that during evaluation; After stirring, after vaporization, introduce reactor head, after dispersion of upper strata porcelain ball and preheating; Get into beds, at weight space velocity WHSV2.0hr-1,400 ℃ of temperature of reaction; React under the condition of pressure 1.2Mpa, reaction product is fed gas-liquid separator through overcooling and is separated by the reactor drum lower end; The product liquid sampling analysis, its technical indicator is listed in table 3, and the stability test data are seen table 4.
[embodiment 1～4]
Many beds fixed-bed reactor that Fig. 2 describes in the working instructions accompanying drawing; The catalyst A that makes in the filling 10g comparative example 1; The alkylating reagent logistics is separated into the multistage logistics of equivalent or inequality, under the normal temperature, is got into the different beds of fixed-bed reactor respectively by a plurality of inlets.Promptly; Behind first section inert material layer thorough mixing, get into the first layer beds of reactor drum through first section alkylating reagent logistics (II) of the arene stream (I) of hydrogen after the heat exchange and normal temperature, obtain after the reaction gas stream with by the methanol stream (III) of second strand of normal temperature of second section inlet introducing after second section inert material layer mixes, gasifies, is uniformly dispersed; Get into second beds of reactor drum; The methanol stream (IV) that obtains the normal temperature that gas stream introduces with the 3rd section inlet again after the reaction gets into the 3rd beds of reactor drum after mixing, gasify, be uniformly dispersed at the 3rd section inert material layer, react the gas stream that obtains; Feeding gas-liquid separator through overcooling separates; The product liquid sampling analysis, its technical indicator is listed in table 1, and the stability test data of embodiment 4 are seen table 2.
[embodiment 5～8]
The placed in-line fixed-bed reactor of multistage that Fig. 3 describes in the working instructions accompanying drawing; The catalyst B that filling 10g comparative example 2 makes; The multiply normal temperature logistics that the alkylating reagent logistics is separated into equivalent or inequality gets into multistage series connection fixed-bed reactor respectively by a plurality of inlets; With after first burst of alkylating reagent logistics (II) of normal temperature mixes at the inert layer of first section reactor drum, vaporizes, get into the beds of first section reactor drum through the arene stream (I) of hydrogen after the heat exchange, obtain after the reaction gas stream with by the normal temperature alkylating reagent logistics (III) of the inlet introducing on second section reactor drum top after porcelain ball layer mixes, gasifies, is uniformly dispersed; Get into the beds of second section reactor drum; The alkylating reagent logistics (IV) that obtains the normal temperature that gas stream introduces with the inlet on the 3rd section reactor drum top again after the reaction gets into the beds of the 3rd section reactor drum after porcelain ball layer mixes, gasifies, is uniformly dispersed, react the gas stream that obtains; Feeding gas-liquid separator through overcooling separates; The product liquid sampling analysis, its technical indicator is listed in table 3, and the stability test data of embodiment 8 are seen table 4.
Table 1
Table 2
Table 3
Table 4
Claims (7)
1. a method that is used for production contraposition alkylated aromatic hydrocarbons is a raw material with aromatic hydrocarbons material and alkylating reagent, is that 1: 10～10: 1, weight space velocity are 1～10hr in aromatic hydrocarbons material and the total mol ratio of alkylating reagent
-1, temperature of reaction is that 300～500 ℃, reaction pressure 0.1～5.0MPa, carrier gas and aroamtic hydrocarbon raw material mol ratio are under 1～8 the condition; Raw material contacts with ZSM type sieve catalyst and selects shape type alkylated reaction; Alkylating reagent is divided into two bursts of logistics at least, wherein:
(a) arene stream I gets into first beds with after first gang of alkylating reagent stream I I mixes, and obtains gas stream A after the reaction;
(b) gas stream A gets into second beds with after at least the second gang of alkylating reagent stream I II mixes, and obtains gas stream B after the reaction;
(c) gas stream B gets into knockout drum as reaction product, separates the liquid that obtains and gets into the aromatic hydrocarbons fractionating system;
Wherein, alkylating reagent comprises at least a in methyl alcohol, dme, methylamine, ethanol or the ethene, and first strand of alkylating reagent is 10: 1～1: 10 with the mol ratio of at least the second strand of alkylating reagent.
2. according to the claim 1 said method that is used for production contraposition alkylated aromatic hydrocarbons; It is characterized in that reactor drum contains 2～15 beds; The alkylating reagent logistics is corresponding to be divided into 2～15 bursts of logistics; The alkylating reagent logistics is got into by the inert layer of reactor drum, at beds and arene stream or reacting gas stream generation alkylated reaction.
3. according to the said method that is used for production contraposition alkylated aromatic hydrocarbons of claim 2, it is characterized in that reactor bed is 2～6 beds, the alkylating reagent logistics is 2～6 bursts of logistics.
4. according to the said method that is used for production contraposition alkylated aromatic hydrocarbons of claim 1, it is characterized in that carrier gas in the reaction process is at least a in nitrogen or the hydrogen.
5. according to the said method that is used for production contraposition alkylated aromatic hydrocarbons of claim 1, it is characterized in that aroamtic hydrocarbon raw material comprises at least a in benzene, toluene or the ethylbenzene; Alkylating aromatic product is at least a in p-Xylol, p-methyl-ethylbenzene or the p-Diethylbenzene of toluene, ethylbenzene, high density.
6. according to the said method that is used for production contraposition alkylated aromatic hydrocarbons of claim 6, it is characterized in that aroamtic hydrocarbon raw material is a toluene; Alkylating reagent is a methyl alcohol, and alkylating aromatic product is the p-Xylol of high density.
7. according to the said method that is used for production contraposition alkylated aromatic hydrocarbons of claim 1, it is characterized in that used many beds catalyzer is the form selected methylation catalyzer, wherein in weight percent of catalyst, SiO
2/ Al
2O
3Molecular ratio is that the content of 20～500 Hydrogen ZSM-5 molecular sieve is 10～89%; Load 1～20% is selected from least a among Mg, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, the Pb on Hydrogen ZSM-5 molecular sieve; The used sticker of catalyzer is selected from least a in silicon-dioxide, titanium oxide, aluminum oxide, the zeyssatite, and its content is 10～80%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8969643B2 (en) | 2013-05-23 | 2015-03-03 | Saudi Basic Industries Corporation | Method for conversion of aromatic hydrocarbons |
| CN104557375A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for co-producing p-methyl-ethylbenzene in production of p-xylene |
| CN105646132A (en) * | 2014-11-20 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparing xylene through arene alkylation |
| CN107913731A (en) * | 2017-11-14 | 2018-04-17 | 江苏师范大学 | A kind of preparation method of amino modified methanol paraxylene catalyst |
| CN108786671A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | The fluidized bed plant and method of methanol and/or dimethyl ether and benzene paraxylene co-producing light olefins |
| CN109824468A (en) * | 2019-03-11 | 2019-05-31 | 中国科学院大连化学物理研究所 | Alkylation of toluene prepares the moving bed process method of paraxylene co-producing light olefins |
| CN114349589A (en) * | 2021-12-30 | 2022-04-15 | 江苏常青树新材料科技股份有限公司 | Method for preparing p-methyl ethyl benzene by using toluene and ethylene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8969643B2 (en) | 2013-05-23 | 2015-03-03 | Saudi Basic Industries Corporation | Method for conversion of aromatic hydrocarbons |
| CN104557375A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for co-producing p-methyl-ethylbenzene in production of p-xylene |
| CN104557375B (en) * | 2013-10-28 | 2016-07-13 | 中国石油化工股份有限公司 | The method producing xylol co-production p-methyl-ethylbenzene |
| CN105646132A (en) * | 2014-11-20 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparing xylene through arene alkylation |
| CN108786671A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | The fluidized bed plant and method of methanol and/or dimethyl ether and benzene paraxylene co-producing light olefins |
| US11161085B2 (en) | 2017-04-27 | 2021-11-02 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and benzene |
| CN107913731A (en) * | 2017-11-14 | 2018-04-17 | 江苏师范大学 | A kind of preparation method of amino modified methanol paraxylene catalyst |
| CN109824468A (en) * | 2019-03-11 | 2019-05-31 | 中国科学院大连化学物理研究所 | Alkylation of toluene prepares the moving bed process method of paraxylene co-producing light olefins |
| CN114349589A (en) * | 2021-12-30 | 2022-04-15 | 江苏常青树新材料科技股份有限公司 | Method for preparing p-methyl ethyl benzene by using toluene and ethylene |
| CN114349589B (en) * | 2021-12-30 | 2024-05-14 | 江苏常青树新材料科技股份有限公司 | Method for preparing p-methyl ethylbenzene by using toluene and ethylene |
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