CN101993334B - Method for increasing yield of p-xylene in aromatic hydrocarbon production - Google Patents
Method for increasing yield of p-xylene in aromatic hydrocarbon production Download PDFInfo
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Abstract
The invention relates to a method for increasing yield of p-xylene in aromatic hydrocarbon production, and mainly solves the problems of low concentration of p-xylene in mixed xylenes, large aromatic hydrocarbon processing cycle amount, stick requirement on reaction raw materials and high energy consumption during p-xylenes production in the prior art. In the invention, the mixed raw materials separated from a reforming unit are adopted; C9 aromatics and benzene are fed into a benzene and C9 aromatics alkyl transferring process unit for dealkylation reaction to generate the second flow of benzene and the second flow of methylbenzene and the second flow of C8 aromatics; the methylbenzene enters a methylbenzene selective dismutation process unit for methylbenzene selective dismutation reaction to generate the C8 aromatics and benzene flow containing the p-xylene, so as to obtain the third flow of C8 aromatics, methylbenzene and benzene; the C8 aromatics at low concentration are mixed to be fed into a separatography unit to obtain the C8 aromatics containing high concentration p-xylene; the C8 aromatics containing the high concentration p-xylene is fed into a crystallizing separative unit to obtain the p-xylene product and the fourth flow of C8 aromatics. By using the invention, the problem is solved well and the method of the invention can be used for the p-xylene production.
Description
Technical field
The present invention relates to a kind of method of increasing yield of p-xylene in aromatic hydrocarbon production.
Background technology
P-Xylol is one of main basic organic of petrochemical industry, in numerous chemical production field such as chemical fibre, synthetic resins, agricultural chemicals, medicine, plastics, purposes is widely arranged.Typical p-Xylol production method is that the dimethylbenzene containing ethylbenzene of the thermodynamic(al)equilibrium that generates from the petroleum naphtha catalytic reforming is C8 aronmatic, by multistage cryogenic crystallization, to separate or molecular sieve simulated moving bed adsorption separation (abbreviation fractionation by adsorption) technology, and p-Xylol is separated close isomer mixture with it from boiling point.And, for the processing of the dimethylbenzene of ortho position and a position, often take C
8A isomerization (abbreviation isomerization) technology, make it isomery and turn to p-Xylol.For increasing yield of p-xylene, utilize toluene disproportionation or toluene to react and generate benzene and C with transalkylation (being called for short toluene disproportionation and transalkylation) with carbon nine and above aromatic disproportion thereof
8A, thereby volume increase C
8A is the operational path of effective increasing yield of p-xylene.
The MTDP that up to now, in the world more typically, also the technique relevant to toluene disproportionation of comparative maturity has sixties Mo industrialized Tatoray tradition toluene disproportionation process, late nineteen eighties to release reaches S-TDT technique and the TransPlus technique of releasing in recent years.Selective disproportionation of toluene is a new way of producing p-Xylol.Can carry out the C of selective disproportionation generation benzene and high p-Xylol concentration on the ZSM-5 catalyzer through modification due to toluene
8A, therefore only need just can isolate most p-Xylol through a simple step subzero fractionation.In recent years, along with improving constantly of catalyst performance, this technique has obtained considerable progress.Its typical process has oneself industrialized MSTDP selective disproportionation of toluene technique and the pX-Plus technique of release in recent years the late nineteen eighties.
Oneself industrialized selective disproportionation of toluene technique-MSTDP, the treated ZSM-5 type mesoporous molecular sieve of take is the catalyst treatment methylbenzene raw material, can obtain the C of high p-Xylol concentration (85～90%, weight percent, identical except indicating below)
8The benzene of A and nitration grade.There is not yet the PX-plus technique of industrial application report, its main technique index is that under toluene conversion 30% condition, in dimethylbenzene, the selectivity of pX reaches 90%, and the mol ratio of benzene and pX is 1.37.
Yet, in the technique of this class selective disproportionation of toluene, the harshness at the simultaneous with high para-selectivity to material choice.This type of technique can only be take toluene as raw material, and C
9 +A does not have purposes in this technique, at least can not directly be utilized, and causes the waste of aromatic hydrocarbon resource.In addition, this technique is a large amount of benzene of by-product also, causes the p-Xylol yield on the low side, and this is the fatal shortcoming of selective disproportionation technique.
The reactor feed of typical Tatoray technique is with toluene and C9 aromatic (C
9A) be reaction raw materials.The dimethylbenzene generated by Tatoray technique is the isomer mixture formed in thermodynamic(al)equilibrium, has the p-Xylol content of industrial application value generally to only have 24% left and right most.For the xylol this point of p-Xylol concentration that with respect to selective disproportionation of toluene, can obtain 90% left and right, Tatoray technique is in obvious inferior position undoubtedly, but Tatoray technique is exactly that Tatoray technique can be C with respect to one of selective disproportionation of toluene technique very large advantage
9A is converted into benzene and dimethylbenzene.The Tatoray technique of take has USP4341914, Chinese patent 98110859.8, USP2795629, USP3551510, Chinese patent 97106719.8 etc. as basic document.The technical process that representative USP4341914 proposes is for to carry out the aromatic hydrocarbons fractionation by reformate, the toluene obtained and C
9A enters the Tatoray technique unit to carry out disproportionation and reacts with a heatable brick bed group-transfer, and resultant of reaction is toluene and C after separating
9A and part carbon ten (C
10A) circulation, benzene is as the product extraction, C8 aronmatic and the C8 aronmatic come from isomerization unit enter together the pX tripping device and isolate highly purified p-Xylol product, and other C8 aronmatic isomer carries out xylene isomerization reaction to isomerization unit and again obtains the xylol in thermodynamic(al)equilibrium.
The de-alkyl of heavy aromatics is produced C
6～C
8Aromatics process caused people's attention gradually along with the rise of selective disproportionation of toluene technique in the last few years.USP5763721 and USP5847256 have proposed respectively the catalyzer for the heavy aromatics dealkylation.Wherein, USP5847256 has announced a kind of mordenite catalyst of rhenium-containing, and this catalyzer is specially adapted to transform the raw material many containing ethyl, can obtain the products such as toluene, dimethylbenzene and benzene.
C
8The boiling point of each component of aromatic hydrocarbons approaches: 136.2 ℃, ethylbenzene, 138.4 ℃ of p-Xylol, 139.1 ℃ of m-xylenes, 144.4 ℃ of o-Xylols, the o-Xylol that its mid-boiling point is the highest can be separated by rectification method, need up to a hundred theoretical stages and larger reflux ratio, the ethylbenzene that boiling point is minimum also can separate by rectification method, but much more difficult.C
8The fusing point of each component of aromatic hydrocarbons has larger gap: 13.3 ℃ of p-Xylol, o-Xylol-25.2 ℃, m-xylene-47.9 ℃, ethylbenzene-94.95 ℃.Wherein the fusing point of p-Xylol is the highest, can adopt crystallization process general p-xylene separation wherein out, as not high as p-Xylol concentration in raw material, for reaching the acceptable yield of industrial production, generally adopts two sections crystallizations.At first USP3177255, USP3467724 crystallize out most p-Xylol to make productive rate reach theoretical maximum under the low temperature of-80～-60 ℃, and now crystal purity, between 65～85%, is carrying out crystallization for the second time after fusing; Tc, generally at-20～0 ℃, can obtain the p-Xylol of 99% above purity for the second time, and in mother liquor, p-Xylol content is higher, can return to crystallized region recycle for the first time.
Utilize sorbent material to C
8The difference of each compositional selecting of aromatic hydrocarbons, can be by adsorption method of separation by p-xylene separation out, after this method realizes industrialization in nineteen seventies for producing the main method of p-Xylol.USP2985589 has described the method for utilizing the simulation moving-bed separating paraxylene of adverse current; USP3686342, USP3734974, CN98810104.1 has described X or the Y zeolite that sorbent material that fractionation by adsorption used is barium type or barium potassium type; USP3558732, USP3686342 are used respectively toluene and the p-Diethylbenzene desorbing agent as fractionation by adsorption.
Summary of the invention
Technical problem to be solved by this invention be in conventional art when producing p-Xylol, existence is because p-Xylol concentration in xylol is low, the problem such as cause the dimethylbenzene separating unit and the isomerization unit internal circulating load is large, energy consumption is high, provide a kind of new p-Xylol production method.The method is with benzene, toluene, C
8A and C
9 +A is that raw material is produced p-Xylol, improves the concentration of p-Xylol in xylol, reduces greatly the scale of p-xylene separation unit, isomerization unit and aromatic hydrocarbons fractionation unit, thereby reduces the energy consumption of whole device.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of increasing yield of p-xylene in aromatic hydrocarbon production comprises the following steps:
A. separate the mixing raw material containing benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics from reformer unit, isolate first strand of benzene, first strand of toluene, first burst of C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics;
B.a) the isolated C9 aromatic of step and the 3rd strand of benzene enter benzene and C9 aromatic alkyl transfering process unit, carry out dealkylation under hydro condition, generate second strand of benzene, second strand of toluene and second strand of C8 aronmatic;
C. first strand of toluene enters the selective disproportionation of toluene technique unit together with second strand of toluene, carry out toluene selective disproportionation reaction under hydro condition, generate C8 aronmatic and the benzene logistics containing p-Xylol after reaction, after separating, obtain the 3rd strand of C8 aronmatic, the 3rd strand of toluene and the 3rd strand of benzene, wherein the 3rd strand of toluene turns back to the selective disproportionation of toluene technique unit;
D. first strand of C8 aronmatic, second strand of C8 aronmatic and the 3rd strand of C8 aronmatic are sent into adsorption separation unit after mixing, and obtain the C8 aronmatic containing the high density p-Xylol;
E. send into the Crystallization Separation unit containing the C8 aronmatic of high density p-Xylol, obtain the p-Xylol product, and the 4th strand of C8 aronmatic, the 4th strand of C8 aronmatic turns back to adsorption separation unit.
In technique scheme, selective disproportionation of toluene unit catalyzer used is the type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least one metal or its oxide compound be selected from platinum, molybdenum or magnesium, and its consumption is 0.005～5% by weight percentage; The operational condition of selective disproportionation of toluene technique unit is as follows: reaction pressure is 1～4MPa, and temperature of reaction is 300～480 ℃, and hydrogen hydrocarbon mol ratio is 0.5～10, and the liquid weight air speed is 0.8～8 hour
-1.Benzene and C9 aromatic alkyl transfering process unit catalyzer used is at least one molecular sieve be selected from beta-zeolite, mordenite or MCM-22, the metal of bismuth-containing or its oxide compound in catalyzer, and its consumption is 0.005～5% by weight percentage; The operational condition of benzene and C9 aromatic alkyl transfering process unit is as follows: reaction pressure is 1～6MPa, and temperature of reaction is 300～600 ℃, and hydrogen hydrocarbon mol ratio is 2～10, and weight space velocity is 0.5～3 hour
-1.The p-xylene separation unit adopts fractionation by adsorption and the Crystallization Separation separating paraxylene that combines, and Crystallization Separation can adopt film-falling crystallization to separate or suspension crystallization separates; The Tc that film-falling crystallization separates is-30～5 ℃; The Tc that suspension crystallization separates is-15～5 ℃, and washings/crystal weight ratio is 0.05～0.5.In the C8 aronmatic of high density p-Xylol, the weight concentration of p-Xylol is 75～95%; In the p-Xylol product, the weight concentration of p-Xylol is >=99.8%.
In the present invention, in benzene and C9 aromatic alkyl transfering process unit, because the zeolite that uses bismuth-containing is catalyzer, under hydro condition, by transalkylation reaction, effectively by reaction raw materials benzene and C
9Aromatic hydrocarbons has changed into dimethylbenzene, has realized the handiness of Raw material processing, and aromatics conversion rate reaches 64.8%, and selectivity reaches 90%.And the selective disproportionation of toluene unit, under the effect of platiniferous ZSM-5 catalyzer, toluene selective disproportionation reaction occurs, generate benzene and containing the xylol of high density p-Xylol, p-Xylol concentration can reach 80～95%, and the C8 aronmatic that this xylol and toluene and carbon nine and above aromatic disproportion thereof and alkyl transfering process unit generate is sent to absorption-Crystallization Separation assembled unit and obtains the p-Xylol product.Can find out, such operational path, can allow the concentration of producing p-Xylol in the xylol obtained significantly improve, and takes full advantage of again C
9 +The A resource, reduced the treatment scale of isomerization unit and adsorption separation unit, effectively reduced energy consumption and facility investment scale, and reduced production cost, obtained technique effect preferably.
The accompanying drawing explanation
The technical process that Fig. 1 is traditional p-Xylol production equipment.
The technical process that Fig. 2 is increasing yield of p-xylene in aromatic hydrocarbon production of the present invention.
In Fig. 1 or Fig. 2, I is the reformer unit deheptanizer; II is the Aromatics Extractive Project unit; III is the benzene toluene separating unit after extracting; IV is the benzenol hydrorefining unit; V is toluene disproportionation and alkyl transfering process unit; VI is the selective disproportionation technique unit; VII is benzene and C9 aromatic alkyl transfering process unit; VIII is the xylene isomerization process unit; IX is adsorption separation unit; X is the Crystallization Separation unit.1 is the reformation de-pentane oil, and 2 is the C distillated from the deheptanizer tower top
7 -(comprising that benzene, toluene and carbon six carbon seven are non-aromatic), 3 carbon eight and above arene streams for the extraction of deheptanizer tower reactor, 4 for extracting benzene and the toluene logistics after non-aromatic, 5 is non-aromatic, 6 is the high purity product benzene that the benzene column overhead after extracting is extracted, 7 is the toluene that the toluene tower tower top after extracting is extracted, 8 C for the extraction of the toluene tower reactor after extracting
8 +A, 9 is disproportionation and transalkylation product stream, 10 is C
8 +The C that heavy aromatics column overhead in the A fractionation unit is extracted out
9A and part C
10A, 11 is the xylol of extracting out from the benzenol hydrorefining tower top, 12 is the C that heavy aromatics tower tower reactor is extracted out
10A, 13 product streams that are benzene and C9 aromatic alkyl transfering process unit, 14 a small amount of toluene of separating for adsorption separation unit, the 15 pure p-Xylol of separating for adsorption separation unit, 16 for fractionation by adsorption goes out the xylol after PX, and 17 is the C that isomerization unit deheptanizer tower reactor is discharged
8 +The A logistics, 18 logistics that contain benzene and toluene of extracting for isomerization unit deheptanizer tower top, the 19 benzene logistics that are disproportionation and transalkylation extraction, the 20 nitrated benzene of extracting for the benzene column overhead of selective disproportionation, the 21 p-Xylol products of separating for the Crystallization Separation unit, 22 for Crystallization Separation goes out the C8 aronmatic after PX, and 23 is adsorption separation unit high density p-Xylol out.
The technical process of tradition p-Xylol production equipment as shown in Figure 1.Enter deheptanizer I from reformation depentanizer tower bottoms 1, tower top separates carbon seven and following aromatic hydrocarbons non-aromatics logistics 2 thereof and enters Aromatics Extractive Project unit II and carry out separating of aromatic hydrocarbons and non-aromatics, isolated non-aromatic 5 discharge, unit III is removed in benzene toluene logistics 4, the benzene column overhead of products benzene 6 from extracting sent, and the toluene tower tower reactor of xylol 8 from extracting extracted out and entered benzenol hydrorefining unit IV.In addition, deheptanizer tower reactor logistics 3 also enters benzenol hydrorefining unit IV, mix carbon eight logistics 11 and distillate p-xylene separation unit IX from tower top, C9 aromatic 10 and from the isolated toluene logistics 7 of toluene tower tower top the raw material as toluene disproportionation and transalkylation II, C
10 +A logistics 12 is sent as byproduct; Disproportionation directly enters unit III with 9 of transalkylation product streams and is separated; Adsorption separation unit IX isolates purpose product p-Xylol 15, and a small amount of toluene 14 returns to toluene disproportionation unit VI, and other xylol 16 enters xylene isomerization unit VIII and carries out isomerization reaction, the C that isomerization unit deheptanizer tower reactor is discharged
8 +A logistics 17 is sent to benzenol hydrorefining unit IV, and the logistics that contains benzene and toluene 18 that the deheptanizer tower top is extracted is sent to the catalytic reforming unit.
The technical process of increasing yield of p-xylene in aromatic hydrocarbon production of the present invention as shown in Figure 2.Be that with the improvements of traditional technology technique of the present invention changes the toluene disproportionation process unit in traditional technology into C9 aromatic de-alkyl technique unit, in addition, has increased a set of selective disproportionation of toluene unit VI and Crystallization Separation unit X.The place that Fig. 2 is identical with Fig. 1 is no longer narrated, and below only with regard to difference, elaborates.The benzene 20 in technique of the present invention, the former carbon nine that is used as toluene disproportionation and transalkylation raw material and above aromatic hydrocarbons 10 thereof and selective disproportionation unit generated is as the raw material of benzene and C9 aromatic alkyl transfering process unit, benzene logistics 7 (comprising the toluene that the toluene brought in raw material and reaction generate) is all as the raw material of selective disproportionation unit, product stream 9 is separated with the toluene tower in benzene toluene tower unit after thing 13 flows to extracting, the logistics 8 of isolating after benzene and toluene is sent into benzenol hydrorefining unit IV, dimethylbenzene tower top extraction C
8 +A logistics 11, logistics 11 is sent into adsorption separation unit and is isolated high density p-Xylol 23, and high density p-Xylol 23 is sent into Crystallization Separation unit X, isolates pure p-Xylol 21, and other xylol 22 turns back to adsorption separation unit IX.
Below by specific embodiment, the present invention is further illustrated, and still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
Press flow process shown in Fig. 2, with C in the de-pentane oil of typically reforming
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate the present invention and produce the ability of p-Xylol and benzene and the treatment scale situation of each unit.Typical reformer is sent the flow rate of the composition distribution of aromatic hydrocarbons and each component that the present embodiment adopts in Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the beta-zeolite catalyzer that in reactor, the filling bismuth-containing is 0.05%, and reaction conditions is: 385 ℃ of temperature of reaction, pressure is 3.0MPa, weight space velocity is 2.0 hours
-1, hydrogen/hydrocarbon mol ratio is 3.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A, generate benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and in reactor, filling is containing 0.05% platinum ZSM-5 molecular sieve catalyzer, and reaction conditions is: 385 ℃ of temperature of reaction, and pressure is 3.0MPa, weight space velocity is 2.0 hours
-1, hydrogen/hydrocarbon mol ratio is 3.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
6 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts film-falling crystallization to separate, and Crystallization Separation is divided crystallization, sweating and three steps of melting, and wherein Tc is-20 ℃, and sweating temperature is 15 ℃, and melt temperature is 30 ℃.
Table 1 reformation de-pentane oil aromatic hydrocarbons forms and flow rate
| Form | Ben | Tol | C 8A | C 9A | C 10 + | ∑ |
| Form % by weight | 14.41 | 26.79 | 33.53 | 24.02 | 1.25 | 100.00 |
| Flow, kg/hr | 12673 | 23560 | 29482 | 21122 | 1095 | 87932 |
Wherein: NA is non-aromatics, and Ben is benzene, and Tol is toluene, C
8A is C8 aronmatic, C
9A is C9 aromatic, C
10 +A is carbon ten and above aromatic hydrocarbons thereof, below identical.
According to the aromatic hydrocarbons flow rate (fresh feed) in the described technical process of the present invention of accompanying drawing 2 and table 1 and the operation of the parameter in embodiment, material feeding and the discharging data of selective disproportionation of toluene unit, benzene and C9 aromatic transalkylation and isomerization unit are listed in table 2.The treatment scale of p-Xylol production equipment unit is in Table 3, and the output of product p-Xylol and benzene is in Table 4, and wherein the p-Xylol product increases by 19% with respect to Comparative Examples.
Table 2 embodiment 1 process stream table
Annotate: C
8A
*Refer to other C8 aronmatic except PX, as follows.
Table 3 embodiment 1 each cell processing scale table
| The unit title | Benzene and carbon nine transalkylation | Isomerization unit | Adsorption separation unit | The Crystallization Separation unit | The dimethylbenzene fractionation unit |
| Scale, kg/hr | 54810 | 168667 | 211965 | 65101 | 235861 |
Table 4 embodiment 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kg/hr | 58591 | 13060 | 71651 |
| Purity, % | 99.80 | 99.94 |
Result shows, uses the technology of the present invention, the listed aroamtic hydrocarbon raw material with table 1, and the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 71651 kg/hrs.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended respectively 25%, 23% and 27%, and this has obviously reduced the design scale of device.Plant energy consumption is 21000 * 10
6Joule/ton (p-Xylol+benzene), with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), Energy Intensity Reduction 21%.Therefore, the problem such as when patent of the present invention has overcome the production p-Xylol existed in the conventional art, xylol concentration is low, internal circulating load is large, energy consumption is high, provide a kind of brand-new more economical method for increasing yield of p-xylene.
[embodiment 2]
Press flow process shown in Fig. 2, with C in the de-pentane oil of typically reforming
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate the present invention and produce the ability of p-Xylol and benzene and the treatment scale situation of each unit.Typical reformer is sent the flow rate of the composition distribution of aromatic hydrocarbons and each component that the present embodiment adopts in Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the Hydrogen MCM-22 zeolite catalyst of filling bismuth-containing 0.30% in reactor, and reaction conditions is: 460 ℃ of temperature of reaction, pressure is 41.0MPa, weight space velocity is 3.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A, generate benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and in reactor, filling is containing platiniferous 0.2% and 0.5% magnesium ZSM-5 molecular sieve catalyzer, and reaction conditions is: 450 ℃ of temperature of reaction, and pressure is 6.0MPa, weight space velocity is 6.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
3 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is 5 ℃.
According to the parameter provided in the described technical process of the present invention of accompanying drawing 2 and example, operated, the treatment scale of p-Xylol production equipment unit is in Table 5, and the output of product p-Xylol and benzene is in Table 6.
Table 5 embodiment 2 each cell processing scale tables
| The unit title | Heavy aromatics takes off alkyl unit | Isomerization unit | Adsorption separation unit | The Crystallization Separation unit | The dimethylbenzene fractionation unit |
| Scale, kg/hr | 54810 | 166773 | 214166 | 65101 | 245876 |
Table 6 embodiment 2 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kg/hr | 58591 | 13060 | 71651 |
| Purity, % by weight | 99.80 | 99.94 |
Result shows, uses the technology of the present invention, the listed aroamtic hydrocarbon raw material with table 1, and the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 71651 kg/hrs.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended respectively 24%, 22% and 24%, has obviously reduced the design scale of device.Plant energy consumption is 20465 * 10
6Joule/ton (p-Xylol+benzene), with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), Energy Intensity Reduction 23%.
[embodiment 31]
Press flow process shown in Fig. 2, with C in the de-pentane oil of typically reforming
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate the present invention and produce the ability of p-Xylol and benzene and the treatment scale situation of each unit.Typical reformer is sent the flow rate of the composition distribution of aromatic hydrocarbons and each component that the present embodiment adopts in Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the h-mordenite of filling bismuth-containing 0.10% in reactor, and reaction conditions is: 320 ℃ of temperature of reaction, pressure is 1.0MPa, weight space velocity is 0.8 hour
-1, hydrogen/hydrocarbon mol ratio is 2.0.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A, generate benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and in reactor, filling is containing 0.3% molybdenum and 0.8% magnesium ZSM-5 molecular sieve catalyzer, and reaction conditions is: 320 ℃ of temperature of reaction, and pressure is 1.0MPa, weight space velocity is 0.8 hour
-1, hydrogen/hydrocarbon mol ratio is 1.0.Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A.
10 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is-15 ℃.
According to the parameter provided in the described technical process of the present invention of accompanying drawing 2 and example, operated, the treatment scale of p-Xylol production equipment unit is in Table 7, and the output of product p-Xylol and benzene is in Table 8.
Table 7 embodiment 3 each cell processing scale tables
| The unit title | Heavy aromatics takes off alkyl unit | Isomerization unit | Adsorption separation unit | The Crystallization Separation unit | The dimethylbenzene fractionation unit |
| Scale, kg/hr | 54810 | 161532 | 203754 | 65101 | 245876 |
Table 8 embodiment 3 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kg/hr | 58624 | 13060 | 71684 |
| Purity, % by weight | 99.80 | 99.94 |
Result shows, uses the technology of the present invention, the listed aroamtic hydrocarbon raw material with table 1, and the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 71684 kg/hrs.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended respectively 26%, 26% and 24%, has obviously reduced the design scale of device.Plant energy consumption is 21530 * 10
6Joule/ton (p-Xylol+benzene), with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), Energy Intensity Reduction 19%.
[comparative example 1]
Press flow process shown in Fig. 1, still with typical reformation de-pentane oil C in table 1
6A～C
10 +The flow rate of A logistics is basic data, investigates the ability that traditional Aromatic Hydrocarbon United Plant containing toluene disproportionation and alkyl transfering process unit is as shown in Figure 1 produced p-Xylol and benzene.The material feeding of its disproportionation and transalkylation, isomerization unit and extraction situation are in Table 9, and the treatment scale of each unit is in Table 10, and the output of product p-Xylol and benzene is in Table 11.
Table 9 comparative example 1 process stream table
Table 10 comparative example 1 each cell processing scale table
| The unit title | Disproportionation and transalkylation | Isomerization unit | Adsorption separation unit | The dimethylbenzene fractionation unit |
| Scale, kg/hr | 111988 | 219438 | 274572 | 323269 |
Table 11 comparative example 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kg/hr | 54316 | 22751 | 77067 |
| Purity, % | 99.80 | 99.94 |
Result shows, traditional aromatic hydrocarbons production technique reaction aroamtic hydrocarbon raw material as listed as table 1, and the total amount that work has been produced p-Xylol and benzene is 77067 kg/hrs, plant energy consumption is 26579 * 10
6Kilojoule/ton (p-Xylol+benzene).
Claims (1)
1. the method for an increasing yield of p-xylene in aromatic hydrocarbon production, enter deheptanizer I from reformation depentanizer tower bottoms (1), tower top separates carbon seven and following aromatic hydrocarbons non-aromatics logistics (2) thereof and enters Aromatics Extractive Project unit II and carry out separating of aromatic hydrocarbons and non-aromatics, isolated non-aromatics (5) is discharged, unit III is removed in benzene toluene logistics (4), the benzene column overhead of products benzene (6) from extracting sent, and the toluene tower tower reactor of xylol (8) from extracting extracted out and entered benzenol hydrorefining unit IV; In addition, deheptanizer tower reactor logistics (3) also enters benzenol hydrorefining unit IV, mix carbon eight logistics (11) and distillate p-xylene separation unit IX from tower top, C9 aromatic (10) and from the isolated toluene logistics of toluene tower tower top (7) raw material as toluene disproportionation and transalkylation II, C
10 +A logistics (12) is sent as byproduct; Disproportionation directly enters unit III with transalkylation product stream (9) and is separated; Adsorption separation unit IX isolates purpose product p-Xylol (15), and a small amount of toluene (14) returns to toluene disproportionation unit VI, other xylol (16) enters xylene isomerization unit VIII and carries out isomerization reaction, the C that isomerization unit deheptanizer tower reactor is discharged
8 +A logistics (17) is sent to benzenol hydrorefining unit IV, and the logistics that contains benzene and toluene (18) that the deheptanizer tower top is extracted is sent to the catalytic reforming unit;
By in above-mentioned technique, the benzene (20) that the former carbon nine that is used as toluene disproportionation and transalkylation raw material and above aromatic hydrocarbons (10) thereof and selective disproportionation unit are generated is as the raw material of benzene and C9 aromatic alkyl transfering process unit, benzene logistics (7), toluene comprising the toluene of bringing in raw material and reaction generation, all as the raw material of selective disproportionation unit, product stream (9) is separated with the toluene tower in benzene toluene tower unit after thing (13) flows to extracting, the logistics (8) of isolating after benzene and toluene is sent into benzenol hydrorefining unit IV, dimethylbenzene tower top extraction C
8 +A logistics (11), C
8 +A logistics (11) is sent into adsorption separation unit and is isolated high density p-Xylol (23), high density p-Xylol (23) is sent into Crystallization Separation unit X, isolate pure p-Xylol (21), other xylol (22) turns back to adsorption separation unit IX;
According to above-mentioned flow process, with C in the de-pentane oil of typically reforming
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate the present invention and produce the ability of p-Xylol and benzene and the treatment scale situation of each unit; The composition that typical reformer is sent aromatic hydrocarbons distribute and the flow rate of each component of adopting as follows:
The Ben:14.41 % by weight, flow is 12673 kg/hrs;
The Tol:26.79 % by weight, flow is 23560 kg/hrs;
C
8The A:33.53 % by weight, flow is 29482 kg/hrs;
C
9The A:24.02 % by weight, flow is 21122 kg/hrs;
C
10 +: 1.25 % by weight, flow is 1095 kg/hrs;
∑: 100.00 % by weight, flow is 87932 kg/hrs;
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the Hydrogen MCM-22 zeolite catalyst of filling bismuth-containing 0.30% in reactor, and reaction conditions is: 460 ℃ of temperature of reaction, pressure is 41.0MPa, weight space velocity is 3.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0; Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out C
9 +The dealkylation of A, generate benzene, toluene and C
8A;
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, filling platiniferous 0.2% and 0.5% magnesium ZSM-5 molecular sieve catalyzer in reactor, and reaction conditions is: 450 ℃ of temperature of reaction, pressure is 6.0MPa, weight space velocity is 6.0 hours
-1, hydrogen/hydrocarbon mol ratio is 8.0; Toluene with after hydrogen mixes from top to bottom by beds, carry out toluene selective disproportionation reaction, generate the C of benzene and high p-Xylol concentration
8A;
3 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and the fractionation by adsorption service temperature is 130 ℃;
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is 5 ℃;
The treatment scale of p-Xylol production equipment unit is as follows:
54810 kg/hrs of the de-alkyl unit of heavy aromatics;
Isomerization unit: 166773 kg/hrs;
Adsorption separation unit: 214166 kg/hrs;
Crystallization Separation unit: 65101 kg/hrs;
Dimethylbenzene fractionation unit: 245876 kg/hrs;
Output and the purity of product p-Xylol and benzene are as follows:
P-Xylol: 58591 kg/hrs; Purity is 99.80 % by weight;
Benzene: 13060 kg/hrs; Purity is 99.94 % by weight;
Summation: 71651 kg/hrs.
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| FR3090414B1 (en) * | 2018-12-19 | 2022-07-29 | Ifp Energies Now | Selective catalyst in hydrogenolysis of ethyl-aromatics by conservation of methyl-aromatics. |
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| CN1340489A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Process for preparing p-xylene |
| CN1566046A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工股份有限公司 | Toluene selective disproportionation and carbon 9 and above arene dealkytation method |
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| CN1566046A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工股份有限公司 | Toluene selective disproportionation and carbon 9 and above arene dealkytation method |
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