CN102464559A - Method for producing alkylated aromatic hydrocarbon - Google Patents
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Abstract
The invention relates to a method for producing alkylated aromatic hydrocarbon. The problems of many side reactions, high yield of benzene, low utilization rate of methanol and relatively low objective product in a traditional method for producing the aromatic hydrocarbon through alkylation are solved. The method comprises the following steps that: an alkylating reagent is fed in multiple sections, an aromatic hydrocarbon material and the alkylating reagent serve as raw materials, and under the condition that the molar ratio between the aromatic hydrocarbon material and the alkylating reagent is 1:10-10:1, the weight space velocity is 1 to 10 hr<-1,the reaction temperature is 300 to 500 DEG C, the reaction pressure is 0.1 to 5.0MPa and the molar ratio between carrier gas and the raw materials is 0 to 8, the raw materials are subjected to alkylation reaction on a balanced catalyst, and the alkylating reagent is at least divided into two material flows. The problems are better solved through the technical scheme and the method can be applied to the industrial production of mixed dimethylbenzene through methylbenzene and methanol alkylation.
Description
Technical field
The present invention relates to a kind of method that is used to produce alkylated aromatic hydrocarbons.
Background technology
Alkylating aromatic hydrocarbon is the basic skills of synthesis of alkyl aromatic hydrocarbons.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%, but use ratio of methanol is low, and side reaction is many, has produced a large amount of coke, has caused the rapid deactivation of catalyzer.
More than several kinds of methods of producing p-Xylol, exist that side reaction is many, benzene content is 3～15% in the product, use ratio of methanol is low, generally all is lower than 55%, and dimethylbenzene selective is lower than 60%, shortcoming such as purpose product output is lower.
Because the topmost problem of toluene methylation system p-Xylol technology; Be to improve p-Xylol and optionally can reduce toluene per pass conversion and catalyst stability significantly simultaneously; In addition, the conversion of methyl alcohol can discharge a large amount of reaction heat, and the inactivation of meeting accelerator activator.Therefore, the catalyst stability deficiency is the main difficult problem of this technical development of restriction and popularization.
During end of the year to 2,009 2008 year, receive the receding economy environmental influence, great change appears in domestic aromatic hydrocarbons market, and gliding by a relatively large margin all appears in each aromatic hydrocarbon product price, and that the benzene price hangs down is particularly serious.Under this background, the present invention proposes and use the modified version fixed-bed reactor, do not produce benzene and the balanced type toluene methylation technology of voluminous xylol.
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, causes that side reaction is many, use ratio of methanol is low, and the lower problem of purpose product output; A kind of new method that is used to produce alkylated aromatic hydrocarbons is provided; This method is used many bed reactors, can effectively distribute reactant stream, reduces side reaction; Use ratio of methanol is high, the advantage that title product output is high.
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 to produce 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 the mol ratio of 300～500 ℃, reaction pressure 0.1～5.0MPa, carrier gas and raw material is that raw material carries out alkylated reaction under 0～8 the condition on equilibrium catalyst, alkylating reagent is divided into two bursts of logistics at least, wherein:
(a) arene stream (I) gets into first beds with after first burst of alkylating reagent logistics (II) mixes, and obtains gas stream A after the reaction;
(b) gas stream A gets into second beds with after at least the second burst of alkylating reagent logistics (III) 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 bursts of 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 equilibrium catalyst that adopts, wherein in weight percent of catalyst, SiO
2/ Al
2O
3Molecular ratio is that 20～500 Hydrogen ZSM-5 molecular sieve content preferable range are 20～90%; The preferable range of at least a element on Hydrogen ZSM-5 molecular sieve among load Mg, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, the Pb is 0～20%; The used sticker preferred version of catalyzer is at least a in silicon-dioxide, titanium oxide, aluminum oxide, the zeyssatite, and its content preferable range 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.
In the present technique scheme, adopt many beds fixed-bed reactor, all toluene are introduced by reactor inlet, and methyl alcohol divides multistage to introduce each bed.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, thus improved methyl alcohol effective rate of utilization, reduced the generation of side reactions such as carbon distribution, improved the stability of catalyzer.
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.Contained non-virtue (C in the reaction end gas product
1～C
5) analysis formed also is on the HP-5890 gas chromatograph, to carry out, and is equipped with hydrogen flame ionization detector and aluminum oxide capillary column, adopt external standard method to tail gas form carry out quantitative.
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.Each index to embody formula 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.
Description of drawings
Fig. 1 is typical single bed fixed-bed reactor synoptic diagram,
Among the figure, (1) and (2) is respectively inert material and catalyzer, and I represents aroamtic hydrocarbon raw material; II represents alkylating reagent.
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.
Fig. 2 is the synoptic diagram of many beds fixed-bed reactor,
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.
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.
Fig. 3 is the synoptic diagram of multi-stage type fixed-bed reactor,
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. 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.
Through embodiment the present invention is done further elaboration below.
Embodiment
[Comparative Examples 1]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type ZSM-5 molecular sieve 20 gram and and the Na of molecular ratio 22
2O content is less than the Al of 0.1% (weight)
2O
351 gram uniform mixing are made into the aqueous solution with ammonium molybdate then and flood; Powder behind the dipping adds the dilute nitric acid solution of Bismuth trinitrate, iron nitrate, cerous nitrate again, fully mediates evenly, carries out extruded moulding, balanced type sieve catalyst A is processed in 500 ℃ of roastings, and wherein bi content is 1%, and iron level is 2%, and cerium content is 1%.
The conventional fixed-bed reactor that Fig. 1 describes in the working instructions accompanying drawing, filling 10g self-control balanced type sieve 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]
Adopt Na
2O content is less than 0.1% (weight), SiO
2/ Al
2O
3Ammonium type mordenite 39 grams and the Na of molecular ratio 490
2O content is less than the Al of 0.1% (weight)
2O
336 gram uniform mixing are made into the aqueous solution with ammonium molybdate then and flood; Powder behind the dipping adds a certain amount of dilute nitric acid solution, nickelous nitrate, Lanthanum trinitrate, iron nitrate, zirconium oxychloride and Palladous chloride; Fully mediate evenly; Carry out extruded moulding, balanced type sieve catalyst B is processed in 500 ℃ of roastings, wherein nickel content is 2%, lanthanum content is 5%; Zirconium content is 5%, and palladium content is 1%.
The conventional fixed-bed reactor that Fig. 1 describes in the working instructions accompanying drawing, filling 10g self-control balanced type sieve catalyst B, during evaluation with 3: 1 mixed of your ratio of toluene and dme massage with fluid; 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 its stability test data are seen chart 4.
[embodiment 1～4]
Many beds fixed-bed reactor that Fig. 2 describes in the working instructions accompanying drawing; Filling 10g self-control balanced type sieve catalyst A; 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 its stability test data are seen chart 2.
[embodiment 5～8]
The placed in-line fixed-bed reactor of multistage that Fig. 3 describes in the working instructions accompanying drawing; Filling 10g self-control balanced type sieve catalyst B; 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 its stability test data are seen chart 4.
Table 1
Table 2
Table 3
Table 4
Claims (7)
1. a method that is used to produce 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 the mol ratio of 300～500 ℃, reaction pressure 0.1～5.0MPa, carrier gas and raw material is that raw material carries out alkylated reaction under 0～8 the condition on equilibrium catalyst, alkylating reagent is divided into two bursts of logistics at least, wherein:
(a) arene stream (I) gets into first beds with after first burst of alkylating reagent logistics (II) mixes, and obtains gas stream A after the reaction;
(b) gas stream A gets into second beds with after at least the second burst of alkylating reagent logistics (III) 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 method for claim 1 said production 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 method for the said production alkylated aromatic hydrocarbons of claim 2, it is characterized in that reactor bed is 2～6, the alkylating reagent logistics is 2～6 strands.
4. according to the method for the said production alkylated aromatic hydrocarbons of claim 1, it is characterized in that carrier gas is selected from least a in nitrogen or the hydrogen.
5. according to the method for the said production alkylated aromatic hydrocarbons of claim 1, it is characterized in that aroamtic hydrocarbon raw material is selected from least a in benzene, toluene or the ethylbenzene; Alkylating aromatic product is selected from least a in the diethylbenzene of first and second benzene or thermodynamic(al)equilibrium of YLENE, thermodynamic(al)equilibrium of toluene, ethylbenzene, thermodynamic(al)equilibrium.
6. according to the method for the said production alkylated aromatic hydrocarbons of claim 5, it is characterized in that aroamtic hydrocarbon raw material is preferably toluene; Alkylating reagent is preferably methyl alcohol, and alkylating aromatic product is the xylol of thermodynamic(al)equilibrium.
7. according to the method for the said production alkylated aromatic hydrocarbons of claim 1, it is characterized in that equilibrium catalyst, wherein in weight percent of catalyst, SiO
2/ Al
2O
3Molecular ratio is that 20～500 Hydrogen ZSM-5 molecular sieve content is 20～90%; At least a constituent content that is selected among Mg, Ca, Ba, Zr, Ti, Co, Mo, Ni, Pt, Pd, La, Ce, Cu, Fe, B, Si, P, Sn, the Pb of load is 0～20% on the 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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