CN101993333B - Combined method for increase production of paraxylene in arene production - Google Patents
Combined method for increase production of paraxylene in arene production Download PDFInfo
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- CN101993333B CN101993333B CN200910057826.0A CN200910057826A CN101993333B CN 101993333 B CN101993333 B CN 101993333B CN 200910057826 A CN200910057826 A CN 200910057826A CN 101993333 B CN101993333 B CN 101993333B
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Abstract
The invention relates to a combined method for increase production of paraxylene in arene production, which is used for solving the problems that the paraxylene has low concentration in mixed paraxylene, circulating volume of arene treatment is large, requirements of reacting materials are rigorous, energy consumption is high and the like in the prior art in the paraxylene producition. The method is realized by comprising the following steps: adopting mixed materials separated by a reforming unit; feeding C9 arene and the third flow of benzene separated by the reforming unit into a benzene and C9 arene alkyl group transfer process unit for carrying out dealkylation reaction so as to generate second flow of benzene, toluene and C8 arene; feeding the second flow of benzene, oluene and C8 arene into a toluene selectivity dismutation process unit for carrying out toluene selectivity dismutation reaction to generate the C8 arene and benzene steam containing the paraxylene, and obtaining third flow of C8 arene, toluene and benzene, wherein the flow of toluene is returned to the toluene selectivity dismutation process unit; delivering mixture of first flow of C8 arene, second flow of C8 arene and fourth flow of C8 arene to an adsorption separation unit with 12-36 adsorbent bed layers to obtain products of first flow of paraxylene; and delivering the third flow of C8 arene to a crystallization separation unit to obtain products of the fourth flow of C8 arene and the second flow of paraxylene. The above problems can be preferably solved by the technical scheme, and the technical scheme can be used for industrial production of the paraxylene.
Description
Technical field
The present invention relates to a kind of combined 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, has purposes widely.Typical p-Xylol production method be the dimethylbenzene containing ethylbenzene of the thermodynamic(al)equilibrium that generates from petroleum naphtha catalytic reforming be C8 aronmatic by multistage cryogenic crystallization separation or molecular sieve simulated moving bed adsorption separation (abbreviation fractionation by adsorption) technology, 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, makes it isomery and turns 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.
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, the MTDP of late nineteen eighties release and S-TDT technique and the TransPlus technique of releasing in recent years.Selective disproportionation of toluene is a new way of producing p-Xylol.Because toluene can carry out the C that selective disproportionation generates benzene and high p-Xylol concentration on the ZSM-5 catalyzer through modification
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 catalyst treatment methylbenzene raw material, can obtain the C of high p-Xylol concentration (85～90%, weight percent, identical below except indicating)
8the benzene of A and nitration grade.The PX-plus technique that there is not yet industrial application report, its main technique index is that under toluene conversion 30% condition, in dimethylbenzene, the selectivity of pX reaches 90%, the mol ratio of benzene and pX is 1.37.
Yet, in the technique of this class selective disproportionation of toluene, there is the harshness of the simultaneous of 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 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 that to take toluene and C9 aromatic (C9A) be reaction raw materials.The dimethylbenzene being generated by Tatoray technique is the isomer mixture forming 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 can obtain 90% left and right with respect to selective disproportionation of toluene, Tatoray technique is in obvious inferior position undoubtedly, but Tatoray technique is exactly that Tatoray technique can be converted into benzene and dimethylbenzene C9A with respect to one of selective disproportionation of toluene technique very large advantage.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 aromatic hydrocarbons fractionation by reformate, the toluene obtaining and C
9a enters 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 separation
9a and part carbon ten (C
10a) circulation, benzene is as product extraction, C8 aronmatic and the C8 aronmatic coming from isomerization unit enter together 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 heavy aromatics dealkylation.Wherein, USP5847256 has announced a kind of mordenite catalyst of rhenium-containing, and this catalyzer is specially adapted to transform containing the many raw materials of 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 be separated 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 by p-xylene separation wherein out, as not high in p-Xylol concentration in raw material, for reaching the acceptable yield of industrial production, generally adopts two sections of crystallizations.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, this method nineteen seventies realize after industrialization 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 p-Diethylbenzene as the desorbing agent of 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 dimethylbenzene separating unit and isomerization unit internal circulating load is large, energy consumption is high, provides 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 combined method of increasing yield of p-xylene in aromatic hydrocarbon production, comprises the following steps:
A. the separated mixing raw material that contains benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics from reformer unit, isolates 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 selective disproportionation of toluene technique unit together with second strand of toluene, under hydro condition, carry out toluene selective disproportionation reaction, after reaction, generate C8 aronmatic and the benzene logistics containing p-Xylol, after separation, 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 selective disproportionation of toluene technique unit;
D. first strand of C8 aronmatic, second strand of C8 aronmatic and the 4th strand of C8 aronmatic are sent into the adsorption separation unit containing 12～36 adsorption bed after mixing, and obtain first strand of p-Xylol product;
E. the 3rd strand of C8 aronmatic sent into Crystallization Separation unit, obtains the 4th strand of C8 aronmatic and second strand of p-Xylol product.
In technique scheme, selective disproportionation of toluene unit catalyzer used is type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least one metal or its oxide compound being 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 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 being 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.P-xylene separation unit adopts fractionation by adsorption and the Crystallization Separation separating paraxylene that combines, Crystallization Separation can adopt film-falling crystallization separation or suspension crystallization separated.The adsorption bed number of plies of adsorption separation unit is preferably 20～30.The Tc of film-falling crystallization separation is-30～5 ℃; The Tc of suspension crystallization separation is-15～5 ℃, and washings/crystal weight ratio is 0.05～0.5; The purity of p-Xylol product is p-Xylol weight concentration >=99.8%.
In the present invention, in benzene and C9 aromatic alkyl transfering process unit, owing to using the zeolite of bismuth-containing, be 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%, the C that reaction generates
8a enters fractionation by adsorption and isomerization unit is produced pure p-Xylol.The toluene that the de-alkyl technique unit of carbon nine and above aromatic hydrocarbons thereof generates enters selective disproportionation of toluene unit together with other toluene in Aromatic Hydrocarbon United Plant, under the effect of platiniferous ZSM-5 catalyzer, there is toluene selective disproportionation reaction, generate benzene and containing the xylol of high density p-Xylol, p-Xylol concentration can reach 80～95%, this xylol is sent to Crystallization Separation unit and obtains pure p-Xylol, and residue xylol also enters fractionation by adsorption and isomerization unit is produced pure p-Xylol.Can find out, such operational path, can allow the concentration of producing p-Xylol in the xylol obtaining significantly improve, and takes full advantage of again C
9 +a resource, has reduced the treatment scale of isomerization unit and adsorption separation unit, has effectively reduced energy consumption and facility investment scale, and has reduced production cost, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the technical process of traditional p-Xylol production equipment.
Fig. 2 is the combination process flow process of increasing yield of p-xylene in aromatic hydrocarbon production of the present invention.
In Fig. 1 or Fig. 2, I is reformer unit deheptanizer; II is Aromatics Extractive Project unit; III is the benzene toluene separating unit after extracting; IV is benzenol hydrorefining unit; V is toluene disproportionation and alkyl transfering process unit; VI is selective disproportionation technique unit; VII is benzene and C9 aromatic alkyl transfering process unit; VIII is xylene isomerization process unit; IX is adsorption separation unit; X is the aromatic hydrocarbons fractionation unit of selective disproportionation; XI is Crystallization Separation unit.1 is reformation de-pentane oil, and 2 is the C distillating from 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 toluene tower reactor extraction after extracting
8 +a, 9 is disproportionation and transalkylation product stream, 10 is C
8 +the C that heavy aromatics column overhead in A fractionation unit is extracted out
9a and part C
10a, 11 is the xylol of extracting out from benzenol hydrorefining tower top, 12 is the C that heavy aromatics tower tower reactor is extracted out
10a, the 13 still liquid of extracting out for the de-alkyl unit benzene tower tower reactor of heavy aromatics, 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 +a logistics, 18 logistics that contain benzene and toluene of extracting for isomerization unit deheptanizer tower top, 19 is the benzene logistics of disproportionation and transalkylation extraction, the 20 nitrated benzene of extracting for the benzene column overhead of selective disproportionation aromatic hydrocarbons fractionation unit, 21 toluene of extracting for the toluene tower tower top of selective disproportionation aromatic hydrocarbons fractionation unit, 22 C that extract for the benzenol hydrorefining tower top of selective disproportionation aromatic hydrocarbons fractionation unit
8 +a, 23 is the still liquid that the benzenol hydrorefining tower reactor of selective disproportionation aromatic hydrocarbons fractionation unit is extracted out, the 24 pure p-Xylol of separating for Crystallization Separation unit, 25 go out the xylol after PX for Crystallization Separation.
The technical process of tradition p-Xylol production equipment as shown in Figure 1.From reformation depentanizer tower bottoms 1, enter deheptanizer I, tower top separates carbon seven and following aromatic hydrocarbons non-aromatics logistics 2 thereof and enters Aromatics Extractive Project unit II and carry out the separated 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 carries out separated; Adsorption separation unit IX isolates object 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 deheptanizer tower top is extracted is sent to catalytic reforming unit.
The combination process flow process that p-Xylol of the present invention is produced 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 as the de-alkyl technique unit of C9 aromatic into, in addition, a set of selective disproportionation of toluene unit VI, corresponding aromatic hydrocarbons fractionation unit X and Crystallization Separation unit XI have been increased.The place that Fig. 2 is identical with Fig. 1 is no longer narrated, and only with regard to difference, elaborates below.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 being 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, from the nitrated benzene 20 of benzene column overhead extraction, toluene tower overhead extraction toluene 21 turns back to selective disproportionation unit VI, the still liquid 23 that benzenol hydrorefining tower reactor is extracted out is sent into benzenol hydrorefining unit IV, dimethylbenzene tower top extraction C
8 +a logistics 22, Crystallization Separation unit XI is sent in logistics 22, isolates pure p-Xylol 24, and other xylol 25 is delivered 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.The composition that typical reformer is sent aromatic hydrocarbons distribute and the flow rate of 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, 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 from top to bottom by beds, carries out C after mixing with hydrogen
9 +the dealkylation of A, generates benzene, toluene and C
8a.
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 from top to bottom by beds, carries out toluene selective disproportionation reaction after mixing with hydrogen, generates the C of benzene and high p-Xylol concentration
8a.
24 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and fractionation by adsorption service temperature is 130 ℃.
Crystallization Separation unit adopts film-falling crystallization separated, 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, 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 technical process of the present invention described in accompanying drawing 2 and the aromatic hydrocarbons flow rate (fresh feed) in 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 p-Xylol product increases by 19% with respect to comparative example.
Table 2 embodiment 1 process stream table
Note: C
8a
*refer to other C8 aronmatic except PX, as follows.
Table 3 embodiment 1 each cell processing scale table
| Unit title | Benzene and carbon nine transalkylation | Isomerization unit | Adsorption separation unit | Crystallization Separation unit | Dimethylbenzene fractionation unit |
| Scale, kg/hr | 54810 | 168667 | 200437 | 65101 | 235986 |
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, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 78324 kgs/hr.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has declined respectively 26%, 27% and 27%, and this has obviously reduced the design scale of device.Plant energy consumption is 19890 * 10
6joule/ton (p-Xylol+benzene), with respect to 26579 * 10 of comparative example
6joule/ton (p-Xylol+benzene), Energy Intensity Reduction 25%.Therefore, the problem such as when patent of the present invention has overcome the production p-Xylol existing in conventional art, xylol concentration is low, internal circulating load is large, energy consumption is high, provides a kind of brand-new more economical method for the production of p-Xylol.
[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.The composition that typical reformer is sent aromatic hydrocarbons distribute and the flow rate of 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 from top to bottom by beds, carries out C after mixing with hydrogen
9 +the dealkylation of A, generates benzene, toluene and C
8a.
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 from top to bottom by beds, carries out toluene selective disproportionation reaction after mixing with hydrogen, generates the C of benzene and high p-Xylol concentration
8a.
30 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and fractionation by adsorption service temperature is 130 ℃.
Crystallization Separation unit adopts suspension crystallization separated, and Tc is 5 ℃.
According to the parameter providing in the technical process of the present invention described in accompanying drawing 2 and example, operate, 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
| Unit title | Benzene and carbon nine transalkylation | Isomerization unit | Adsorption separation unit | Crystallization Separation unit | Dimethylbenzene fractionation unit |
| Scale, kg/hr | 54810 | 166773 | 203183 | 65101 | 245684 |
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, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 78340 kgs/hr.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has declined respectively 26%, 26% 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 example
6joule/ton (p-Xylol+benzene), Energy Intensity Reduction 23%.
[embodiment 3]
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.The composition that typical reformer is sent aromatic hydrocarbons distribute and the flow rate of 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 from top to bottom by beds, carries out C after mixing with hydrogen
9 +the dealkylation of A, generates benzene, toluene and C
8a.
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 from top to bottom by beds, carries out toluene selective disproportionation reaction after mixing with hydrogen, generates the C of benzene and high p-Xylol concentration
8a.
18 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and fractionation by adsorption service temperature is 130 ℃.
Crystallization Separation unit adopts suspension crystallization separated, and Tc is-15 ℃.
According to the parameter providing in the technical process of the present invention described in accompanying drawing 2 and example, operate, 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
| Unit title | Heavy aromatics takes off alkyl unit | Isomerization unit | Adsorption separation unit | Crystallization Separation unit | 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, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technique of the present invention can be produced p-Xylol and benzene is 71684 kgs/hr.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has declined 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 example
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
| Unit title | Disproportionation and transalkylation | Isomerization unit | Adsorption separation unit | 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 in table 1, and the total amount that work has been produced p-Xylol and benzene is 77067 kgs/hr, plant energy consumption is 26579 * 10
6kilojoule/ton (p-Xylol+benzene).
Claims (1)
1. the combined method of an increasing yield of p-xylene in aromatic hydrocarbon production, from reformation depentanizer tower bottoms, enter deheptanizer I, tower top separates carbon seven and the logistics of following aromatic hydrocarbons non-aromatics thereof and enters Aromatics Extractive Project unit II and carry out the separated of aromatic hydrocarbons and non-aromatics, isolated non-aromatics is discharged, unit III is removed in benzene, toluene logistics, the benzene column overhead of products benzene from extracting sent, and the toluene tower tower reactor of xylol from extracting extracted out and entered benzenol hydrorefining unit IV; In addition, the logistics of deheptanizer tower reactor also enters benzenol hydrorefining unit IV, mix carbon eight logistics and distillate p-xylene separation unit IX from tower top, C9 aromatic and from the isolated toluene logistics of toluene tower tower top the raw material as toluene disproportionation and transalkylation II, C
10 +a logistics is sent as byproduct; Disproportionation directly enters unit III with transalkylation product stream and carries out separated; Adsorption separation unit IX isolates object product p-Xylol, and a small amount of toluene returns to toluene disproportionation unit VI, and other xylol enters xylene isomerization unit VIII and carries out isomerization reaction, the C that isomerization unit deheptanizer tower reactor is discharged
8 +a logistics is sent to benzenol hydrorefining unit IV, and the logistics that contains benzene and toluene that deheptanizer tower top is extracted is sent to catalytic reforming unit;
In aforesaid method, the benzene that the former carbon nine that is used as toluene disproportionation and transalkylation raw material and above aromatic hydrocarbons thereof and selective disproportionation unit are generated is as the raw material of benzene and C9 aromatic alkyl transfering process unit, benzene logistics, comprise the toluene of bringing in raw material and react the toluene generating, all as the raw material of selective disproportionation unit, from the nitrated benzene of benzene column overhead extraction, toluene tower overhead extraction toluene turns back to selective disproportionation unit VI, the still liquid that benzenol hydrorefining tower reactor is extracted out is sent into benzenol hydrorefining unit IV, dimethylbenzene tower top extraction C
8 +a logistics, C
8 +crystallization Separation unit XI is sent in A logistics, isolates pure p-Xylol, and other xylol is delivered to adsorption separation unit IX;
With C in the de-pentane oil of typically reforming
6a～C
10 +each material of hydrocarbon consist of basic data, investigate p-Xylol and the ability of benzene and the treatment scale situation of each unit of producing; The composition that typical reformer is sent aromatic hydrocarbons distributes and the weight of each component of adopting forms and flow is as follows:
Ben:14.41 % by weight, flow, 12673 kgs/hr,
Tol:26.79 % by weight; Flow, 23560 kgs/hr,
C
8a:33.53 % by weight; Flow, 29482 kgs/hr,
C
9a:24.02 % by weight; Flow, 21122 kgs/hr,
C
10 +a:1.25 % by weight; Flow, 1095 kgs/hr,
∑: 100.00 % by weight; Flow, 87932 kgs/hr;
Wherein, C
8a is C8 aronmatic, C
9a is C9 aromatic, C
10 +a is carbon ten and above aromatic hydrocarbons thereof, and Ben is benzene, and Tol is toluene;
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 from top to bottom by beds, carries out C after mixing with hydrogen
9 +the dealkylation of A, generates benzene, toluene and C
8a;
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 from top to bottom by beds, carries out toluene selective disproportionation reaction after mixing with hydrogen, generates the C of benzene and high p-Xylol concentration
8a;
30 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in moving-bed, and fractionation by adsorption service temperature is 130 ℃;
Crystallization Separation unit adopts suspension crystallization separated, and Tc is 5 ℃;
According to above-mentioned technical process and the parameter that provides, operate, the treatment scale of p-Xylol production equipment unit is as follows:
Benzene and carbon nine transalkylation: 54810 kgs/hr,
Isomerization unit: 166773 kgs/hr,
Adsorption separation unit: 203183 kgs/hr,
Crystallization Separation unit: 65101 kgs/hr,
Dimethylbenzene fractionation unit: 245684 kgs/hr,
The output of product p-Xylol and benzene:
P-Xylol output, 58591 kgs/hr; Purity, 99.80 % by weight;
Benzene yield, 13060 kgs/hr; Purity, 99.94 % by weight;
71651 kgs/hr of output summations.
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