CN102464540B - For the method producing para-alkylated arene - Google Patents
For the method producing para-alkylated arene Download PDFInfo
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- CN102464540B CN102464540B CN201010552889.6A CN201010552889A CN102464540B CN 102464540 B CN102464540 B CN 102464540B CN 201010552889 A CN201010552889 A CN 201010552889A CN 102464540 B CN102464540 B CN 102464540B
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Abstract
The present invention relates to a kind of method for producing para-alkylated arene, the side reaction existing for mainly solving in existing alkylating aromatic hydrocarbon production method is many, raw material availability is low and the problem of poor catalyst stability.The present invention by adopting with aromatic hydrocarbons material and alkylating reagent for raw material, aromatic hydrocarbons material and the total mol ratio of alkylating reagent be 1: 10～10: 1, weight space velocity be 1～10hr-1, reaction temperature is when be 300～500 DEG C, reaction pressure 0.1～5.0MPa, carrier gas and aroamtic hydrocarbon raw material mol ratio being 1～8, raw material contacts with ZSM type molecular sieve catalyst and carries out selecting shape type alkylated reaction, alkylating reagent is at least divided into the technical scheme of two streams, solve this problem preferably, can be used for alkylation of toluene methanol and produce the commercial production of xylol.
Description
Technical field
The present invention relates to a kind of method for producing para-alkylated arene, carry out aromatic hydrocarbons form selected methylation reaction especially with a kind of many bed reactors.
Background technology
Alkylating aromatic hydrocarbon is the basic skills of synthesis of alkyl aromatic hydrocarbons, and the type of the number of alkyl groups, location and alkyl chain on aromatic ring, physical and chemical performance and using value to alkylaromatic hydrocarbon all have a great impact.In alkylation reaction of arene, according to the difference using catalyst type, the product of generation can be the equilibrium mixture that multiple isomer coexists, it is also possible to be valuable unbalanced type form selected methylation product.Therefore, selecting synthesizing ethyl benzene, xylol, p-methyl-ethylbenzene is very important alkylation reaction of arene process, has important scientific value and practical significance.
In recent years, as important basic petrochemical raw material, xylol all has purposes extremely widely in fields such as polyester fiber, medicine, pesticide, dyestuff and solvents.Due to polyester fiber function admirable, quickly grow, leap to first of synthetic fibers already, it is contemplated that will have bigger development from now on.According to statistics, in world wide, the annual rate of growth of xylol demand is more than GNP annual rate of growth, reach 8.5%, estimate coming 10 years by newly-increased 14,000,000 tons of xylol yearly productive capacities with the satisfied whole world demand to polyester product, this is primarily due to xylol is the primary raw material producing polyester product.Can obtaining p-phthalic acid after xylol is oxidized, p-phthalic acid then polycondensation can become polyethylene terephthalate this most important polyester fiber and plastic raw materials with ethylene glycol.
The xylol market demand is vigorous, although can obtain xylol from coal tar reformate and drippolene, but its amount is less, is actually needed far from meeting.The industrial xylol production method commonly used has mixed xylenes isomerization, toluene and C at present9Aromatic disproportion and selective disproportionation of toluene technique.First two method all needs from C8The technology of separating paraxylene in BTX aromatics, thus to obtain the xylol of high concentration, separation condition is extremely harsh, it is necessary to iterative cycles, and material treating capacity is big.Thus, both technique equipment needed therebies are huge, and efficiency is low, and yield is few, costly.The xylol technics comparing that selective disproportionation of toluene generates high concentration is novel, and production efficiency is high, and owing to raw material is single, flow process is simple, and this technique is of great interest at home and abroad.But by reactional equation, in the process, the xylol of one mole of high concentration need to can be generated with two mole toluene, toluene utilization rate is relatively low.
Toluene conversion can be become the high concentration xylol that using value is higher by alkylation of toluene methanol reaction, decreases separation and isomerized workload, and its economic benefit is considerable, also provides an effective approach for Appropriate application methanol simultaneously.It is the breakthrough problem of current xylol production technology, gets more and more people's extensive concerning.Difficult point maximum in this technology is exactly that the problems such as the reaction stability of this catalyst are solved.Stability about catalyst has more report, it is common to think that carbon distribution is the most general and most important deactivation cause of molecular sieve catalyst.
At present, the commonly used fixed bed reactors of toluene methylation process, toluene and methanol are usually according to suitable ratio, such as toluene and methanol=2/1 (mol/mol), after being sufficiently mixed in advance, after being heated to uniform temperature by heater, it is concomitantly introduced in fixed bed reactors.While there is the primary response of toluene methylation, it also occur that many side reactions, as methanol id reaction forms alkene, aggregated, cracking, aromatisation etc. are reacted and are changed into various hydro carbons or even carbon distribution.Side reaction also creates substantial amounts of reaction heat, causes that the temperature difference of reactor bed is bigger, and catalysqt deactivation aggravates.
Kaeding et al. is at " SelectivealkylationofToluenewithMethanoltoProducepara-Xy lene ", (JournalofCatalysis, Vol.67 (1981), p159-174) modified catalyst is prepared by a certain amount of phosphorus of load on ZSM-5 described in, it is applied to toluene methylation course of reaction, can obtaining the Selectivity for paraxylene of 85～97%, yet with reasons such as carbon distributions, this catalyst is activity dramatic drop-off within a few hours.
United States Patent (USP) U4,670,616 are directed to use with borosilicate zeolite, prepare catalyst by mediating with binding agent such as Alumina, Silicon stone or silica-alumina etc., are applied to toluene methylation and prepare dimethylbenzene reaction.Obtaining xylol concentration in Mixed XYLENE is 50～60%, but, in course of reaction, owing to side reaction is many, use ratio of methanol is low, creates substantial amounts of coke, causes the rapid deactivation of catalyst.
The method of several production xylol above, all there is primary response selectivity low, dimethylbenzene selective is often 55～60%, and side reaction is many, use ratio of methanol is lower than 55%, and the life-span of catalyst is generally individually in shortcomings such as below 300hr, poor catalyst stability.
Summary of the invention
The technical problem to be solved is those that have previously been reactant stream irrational distribution existing for the single bed alkylation reactor of employing, cause side reaction to increase, use ratio of methanol low, and the problem of poor catalyst stability, a kind of new method for producing para-alkylated arene is provided, the method has that side reaction is few, use ratio of methanol is high, and the advantage that catalyst stability is good.
For solving above-mentioned technical problem, the concrete technical scheme that the present invention adopts is as follows: a kind of method for producing para-alkylated arene, with aromatic hydrocarbons material and alkylating reagent for raw material, aromatic hydrocarbons material and the total mol ratio of alkylating reagent be 1: 10～10: 1, weight space velocity be 1～10hr-1, reaction temperature is when be 300～500 DEG C, reaction pressure 0.1～5.0MPa, carrier gas and aroamtic hydrocarbon raw material mol ratio being 1～8, raw material contacts with ZSM type molecular sieve catalyst and carries out selecting shape type alkylated reaction, alkylating reagent is at least divided into two streams, wherein:
After (a) arene stream I and the first gang alkylating reagent stream I I mixing, enter the first beds, after reaction, obtain gas stream A；
B () gas stream A enters the second beds after mixing with at least the second gang of alkylating reagent stream I II, obtain gas stream B after reaction；
C () gas stream B enters knockout drum as product, separate the liquid obtained and enter aromatic hydrocarbons fractionating system；
Wherein, alkylating reagent includes at least one in methanol, dimethyl ether, methylamine, ethanol or ethylene, and the mol ratio of first strand of alkylating reagent and at least the second strand of alkylating reagent is 10: 1～1: 10.
In technique scheme, reactor bed preferably ranges from 2～15 beds, and alkylating reagent logistics is divided into 2～15 bursts of logistics accordingly, reactor bed preferably range from 2～6 beds, alkylating reagent logistics preferably ranges from 2～6 sections of logistics；Alkylating reagent flow distribution at each bed can be same-size ratio, it is also possible to be non-equivalent, it is preferable that scheme is proportional allocations.Alkylating reagent preferred version is cold burden charging, and cold burden charging can effectively suppress beds temperature rise, improves the effective rate of utilization of methanol, reduces the side reactions such as carbon distribution；Carrier gas preferred version is nitrogen or hydrogen, and more preferably scheme is hydrogen.Aroamtic hydrocarbon raw material preferred version is at least one in benzene, toluene or ethylbenzene, and more preferably scheme is toluene；Alkylating reagent preferred version is at least one in methanol, dimethyl ether, methylamine, ethanol or ethylene, and more preferably scheme is methanol；The shape-selective catalyst adopted, in weight percent of catalyst, containing Hydrogen ZSM-5 molecular sieve 10～89%, SiO2/Al2O3Molecular proportion is 20～500, the at least one in Mg, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, Pb of load 1～20% on Hydrogen ZSM-5 molecular sieve, binding agent used by catalyst is at least one in silicon dioxide, titanium dioxide, aluminium oxide, kieselguhr, and its content is 10～80%.
In the prior art, toluene methylation reaction adopts the fixing bed of single bed or fluid bed to react, and in single bed fixed bed reaction, owing to methanol and toluene together enter by reactor inlet, methanol relatively mostly occurs the side reactions such as self-polymerization；And in fluid-bed process, due to the carbon deposition quantity relative deficiency of toluene methylation reaction, course of reaction increases methanol addition to maintain certain carbon distribution quantity combusted, thus causing use ratio of methanol on the low side, production cost is higher.
Present invention employs many bed reactors and replace existing single bed reactor, make original methanol reactant logistics be changed into multiply charging by sub-thread charging.Existing fixed bed reactors can be improved, in many bed reactors, catalyst is by which floor inert ceramic balls or bead separate into, in the marker space of filling inert ceramic balls or bead, material inlet is installed, after methanol is separated into a small amount of logistics of multiply by multiple inlets, mix homogeneously with the hydrogeneous high temperature arene stream of big stock, react at beds.Can also connect overlapping reactor more, often set reactor is one section, the upper and lower of catalyst reactor bed all have inert ceramic balls or bead to carry out logistics dispersion, arene stream introduces by first paragraph reactor upper end, alkylation material can be divided into multistage logistics, is introduced by each section of reactor top respectively.Owing to the toluene of each bed is all significantly excessive, thus improve methanol and the chance of methylation reaction occurs on toluene, decrease the probability that two or more methanol occurs the side reactions such as Hypermethylation, self-condensation and hydrocarbonylation to occur on toluene, and owing to the existence of cold shock material inhibits beds temperature rise, improve methanol effective rate of utilization to more than 60%, decrease the generation of the side reactions such as carbon distribution, the reaction life of catalyst is to 600hr, greatly increase the stability of catalyst, achieve good effect.
The gas chromatograph that methylbenzene raw material and liquid reacting product adopt model to be HP-5890 is analyzed, and this chromatograph is equipped with flame ionization ditector and polyethylene glycol capillary column, and material composition is undertaken quantitatively by correcting normalization method.
The index comparing concern in toluene methylation reaction includes toluene conversion, dimethylbenzene selective, methyl utilization rate and X/B value, and wherein toluene conversion refers to the ratio that methylbenzene raw material is once converted by reactor, adopts percentage by weight to represent herein；Dimethylbenzene selective refers to the percentage by weight of dimethylbenzene in product；Methyl utilization rate refers to that the methanol being converted on aromatic ring methyl accounts for the ratio of total methanol feeding；What X/B value represented is the mol ratio of dimethylbenzene and benzene in product.The expression detailed in Example of each index.
Accompanying drawing explanation
Fig. 1 is typical single bed fixed bed reactors schematic diagram.In figure,
And (2) respectively inert material and catalyst (1).I represents aroamtic hydrocarbon raw material；II represents alkylating reagent.
Fig. 2 is the schematic diagram of many beds fixed bed reactors, in figure, and (1) and (2) respectively inert material and catalyst.I represents aroamtic hydrocarbon raw material；II, III represent alkylating reagent；The gas stream A that A is then obtained by reacting；The gas stream B that B is then obtained by reacting.
Fig. 3 is the schematic diagram of multisection type fixed bed reactors, in figure, (1) for carrier gas, (2) for effusion meter, (3) are filter, and (4) are alkylating reagent, (5) for aroamtic hydrocarbon raw material, (6) for water-cooled, (7) are tail gas, and (8) are sampling.
In FIG, reactor has two charging apertures of gas-liquid, aromatic hydrocarbons and the total logistics of alkylating reagent, it is collectively incorporated into reactor liquid phase entrance, after the inert material district, upper strata of reactor is vaporized dispersion, enters beds, carry out toluene methylation reaction, reacted product passes into gas-liquid separator through supercooling and is easily separated, and product liquid and gaseous product can separately sampled be analyzed.
In fig. 2, reactor has two charging apertures of gas-liquid, after aromatic hydrocarbons and Part I alkylating reagent logistics mixing, it is collectively incorporated into reactor liquid phase entrance, after the ground floor inert material district of reactor is vaporized dispersion, enter the first beds, carry out toluene methylation reaction, then reacted product and Part II alkylating reagent logistics, after the vaporization dispersion of second layer inert material district, enter the second beds, there is toluene methylation reaction, after multistage reacts, product passes into gas-liquid separator through supercooling and is easily separated, product liquid and gaseous product can separately sampled be analyzed.
In figure 3, reactor feed includes a kind of gas and two kinds of liquid, one of which charging is divided into the multistage feeding of equivalent or inequality, the number of the reactor that hop count is used equal to series connection, shown in figure, 4 reactors in series simply do a signal, the actual series connection evaluating apparatus adopted can contain 2～15 reactors, and product passes into gas-liquid separator after also passing through cooling and is easily separated, gas and the separately sampled analysis of product liquid.
Turning to example with methylbenzene methanol alkylation selectivity, each catalytic performance index calculating method is as follows:
In the expression formula of above-mentioned methyl utilization rate, we are it appeared that this index contains the methyl in dimethylbenzene and trimethylbenzene, mole proportion of deduction benzene is because compared with initial aroamtic hydrocarbon raw material toluene to lose a methyl, trimethylbenzene expression formula is multiplied by coefficient 2 and is because trimethylbenzene and adds two methyl, its composition of aromatic hydrocarbons that durene etc. are heavier is more complicated, it is difficult to accurate analysis, and this moieties growing amount is less, thus it is omitted when calculating methyl utilization rate.
Below by specific embodiment, the invention will be further elaborated.
Detailed description of the invention
[comparative example 1]
Use Na2O content is less than 0.15% (weight), SiO2/Al2O366.7 grams of the ammonium type ZSM-5 molecular sieve powder of molecular proportion 260 and Na2O content is less than the α-Al of 0.15% (weight)2O3·H2O57.1 gram of Homogeneous phase mixing, powder after dipping adds chemical pure dilute nitric acid solution again, fully mediate uniformly, carry out extruded moulding, roasting, then it is made into aqueous solution with chemical pure Lanthanum (III) nitrate, titanium sulfate and barium nitrate to impregnate, make catalyst A, wherein lanthanum content be 2%, Ti content be 1%, barium content be 1%.
The conventional fixed bed reactors that in operation instructions accompanying drawing, Fig. 1 describes, filling 10g catalyst A, during evaluation by toluene and methanol liquid in molar ratio 2: 1 ratio mixing, after stirring, reactor head is introduced after vaporization, after disperseing by upper strata porcelain ball and preheat, enter beds, at weight space velocity WHSV4.0hr-1, reaction temperature 420 DEG C, react when pressure 0.5Mpa, product is by reactor lower end, pass into gas-liquid separator through supercooling to be easily separated, product liquid sample analysis, its technical specification is listed in table 1, its stability test data are shown in chart 2.
[comparative example 2]
Use Na2O content is less than 0.15% (weight), SiO2/Al2O366.7 grams of the ammonium type ZSM-5 powder of molecular proportion 20 and Na2O content is less than 57.1 grams of Homogeneous phase mixing of Ludox of 0.15% (weight), add iron nitrate solution, bismuth nitrate solution, fully mediate uniformly, carry out extruded moulding, roasting, aqueous impregnation is carried out respectively again with magnesium nitrate, cobalt nitrate and platinum acid chloride solution, make catalyst B, wherein content of magnesium be 1%, cobalt content be 2%, platinum content be 1%.
The conventional fixed bed reactors that in operation instructions accompanying drawing, Fig. 1 describes, filling 10g catalyst B, by the ratio mixing of toluene and your ratio 3: 1 of dimethyl ether massage with fluid during evaluation, after stirring, reactor head is introduced after vaporization, after disperseing by upper strata porcelain ball and preheat, enter beds, at weight space velocity WHSV2.0hr-1, reaction temperature 400 DEG C, react when pressure 1.2Mpa, product is by reactor lower end, pass into gas-liquid separator through supercooling to be easily separated, product liquid sample analysis, its technical specification is listed in table 3, stability test data are in Table 4.
[embodiment 1～4]
Many beds fixed bed reactors that in operation instructions accompanying drawing, Fig. 2 describes, the catalyst A prepared in filling 10g comparative example 1, alkylating reagent logistics is separated into the multistage logistics of equivalent or inequality, under room temperature, multiple inlets respectively enters the different beds of fixed bed reactors.nullNamely，After heat exchange, the arene stream (I) of hydrogen and first paragraph alkylating reagent logistics (II) of room temperature are after first paragraph inert material layer is sufficiently mixed，Enter the ground floor beds of reactor，Obtain gas stream after reaction to mix at second segment inert material layer with the methanol stream (III) of the second strand of room temperature introduced by second segment inlet、Gasification、After being uniformly dispersed，Enter the second beds of reactor，The methanol stream (IV) obtaining the room temperature that gas stream introduces with the 3rd section of inlet again after reaction is mixing at the 3rd section of inert material layer、Gasification、After being uniformly dispersed，Enter the 3rd beds of reactor，The gas stream being obtained by reacting，Pass into gas-liquid separator through supercooling to be easily separated，Product liquid sample analysis，Its technical specification is listed in table 1，The stability test data of embodiment 4 are in Table 2.
[embodiment 5～8]
nullThe fixed bed reactors of the multi-stage series that Fig. 3 describes in operation instructions accompanying drawing，The catalyst B that filling 10g comparative example 2 prepares，Alkylating reagent logistics is separated into the multiply room temperature logistics of equivalent or inequality and is respectively enterd multi-stage series fixed bed reactors by multiple inlets，After heat exchange, the arene stream (I) of hydrogen mixes at the inert layer of first paragraph reactor with first burst of alkylating reagent logistics (II) of room temperature、After vaporization，Enter the beds of first paragraph reactor，Obtain gas stream after reaction to mix at porcelain ball layer with room temperature alkylating reagent logistics (III) introduced by the inlet on second segment reactor top、Gasification、After being uniformly dispersed，Enter the beds of second segment reactor，The alkylating reagent logistics (IV) obtaining the room temperature that gas stream introduces with the inlet on the 3rd section of reactor top again after reaction mixes at porcelain ball layer、Gasification、After being uniformly dispersed，Enter the beds of the 3rd section of reactor，The gas stream being obtained by reacting，Pass into gas-liquid separator through supercooling to be easily separated，Product liquid sample analysis，Its technical specification is listed in table 3，The stability test data of embodiment 8 are in Table 4.
Table 1
Table 2
Table 3
Table 4
Claims (7)
1. for the method that produces para-alkylated arene, with aromatic hydrocarbons material and alkylating reagent for raw material, aromatic hydrocarbons material and the total mol ratio of alkylating reagent be 1: 10～10: 1, weight space velocity be 1～10hr-1, reaction temperature is when be 300～500 DEG C, reaction pressure 0.1～5.0MPa, carrier gas and aroamtic hydrocarbon raw material mol ratio being 1～8, raw material contacts with ZSM type molecular sieve catalyst and carries out selecting shape type alkylated reaction, alkylating reagent is at least divided into two streams, wherein:
After (a) arene stream I and the first gang alkylating reagent stream I I mixing, enter the first beds, after reaction, obtain gas stream A；
B () gas stream A enters the second beds after mixing with at least the second gang of alkylating reagent stream I II, obtain gas stream B after reaction；
C () gas stream B enters knockout drum as product, separate the liquid obtained and enter aromatic hydrocarbons fractionating system；
Wherein, alkylating reagent is at least one in methanol, dimethyl ether and methylamine, and the mol ratio of first strand of alkylating reagent and at least the second strand of alkylating reagent is 10: 1～1: 10；
Described alkylating reagent is cold burden charging.
2. the method being used for according to claim 1 producing para-alkylated arene, it is characterized in that reactor contains 2～15 beds, alkylating reagent logistics is divided into 2～15 bursts of logistics accordingly, alkylating reagent logistics is entered by the inert layer of reactor, at beds and arene stream or reacting gas stream generation alkylated reaction.
3. the method being used for according to claim 2 producing para-alkylated arene, it is characterised in that reactor bed is 2～6 beds, and alkylating reagent logistics is 2～6 bursts of logistics.
4. the method being used for according to claim 1 producing para-alkylated arene, it is characterised in that in course of reaction, carrier gas is at least one in nitrogen or hydrogen.
5. the method being used for according to claim 1 producing para-alkylated arene, it is characterised in that aroamtic hydrocarbon raw material includes at least one in benzene, toluene or ethylbenzene；Alkylating aromatic product is at least one in toluene, ethylbenzene, the xylol of high concentration, p-methyl-ethylbenzene or p-Diethylbenzene.
6. the method being used for according to claim 1 producing para-alkylated arene, it is characterised in that aroamtic hydrocarbon raw material is toluene；Alkylating reagent is methanol, and alkylating aromatic product is the xylol of high concentration.
7. the method being used for according to claim 1 producing para-alkylated arene, it is characterised in that many bed catalyst used are form selected methylation catalyst, wherein in weight percent of catalyst, SiO2/Al2O3Molecular proportion is the content of the Hydrogen ZSM-5 molecular sieve of 20～500 is 10～89%；At least one in Mg, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, Pb of load 1～20% on Hydrogen ZSM-5 molecular sieve；At least one in silicon dioxide, titanium dioxide, aluminium oxide, kieselguhr of the binding agent used by catalyst, its content is 10～80%.
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| US8969643B2 (en) | 2013-05-23 | 2015-03-03 | Saudi Basic Industries Corporation | Method for conversion of aromatic hydrocarbons |
| 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 |
| CN108786671B (en) * | 2017-04-27 | 2021-04-23 | 中国科学院大连化学物理研究所 | Fluidized bed device and method for preparing p-xylene and co-producing low-carbon olefin by methanol and/or dimethyl ether and benzene |
| CN107913731B (en) * | 2017-11-14 | 2020-04-07 | 江苏师范大学 | Preparation method of catalyst for preparing p-xylene from methanol |
| 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 |
| 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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| US5196623A (en) * | 1989-06-23 | 1993-03-23 | Fina Technology, Inc. | Aromatic alkylation process employing zeolite omega catalyst |
| CN1428319A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Production method of alkylbenzene |
| CN1505546A (en) * | 1999-05-14 | 2004-06-16 | 埃克森化学专利公司 | Catalyst selectivation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5196623A (en) * | 1989-06-23 | 1993-03-23 | Fina Technology, Inc. | Aromatic alkylation process employing zeolite omega catalyst |
| CN1505546A (en) * | 1999-05-14 | 2004-06-16 | 埃克森化学专利公司 | Catalyst selectivation |
| CN1428319A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Production method of alkylbenzene |
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