CN101734989A - Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics - Google Patents
Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics Download PDFInfo
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- CN101734989A CN101734989A CN200810043976A CN200810043976A CN101734989A CN 101734989 A CN101734989 A CN 101734989A CN 200810043976 A CN200810043976 A CN 200810043976A CN 200810043976 A CN200810043976 A CN 200810043976A CN 101734989 A CN101734989 A CN 101734989A
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Abstract
The invention relates to a method for selective toluene disproportionation and the transalkylation of benzene and C9 aromatics and mainly solves the problems of low paraxylene concentration in mixed xylenes, large aromatic hydrocarbon processing circulating volume, strict reaction raw material requirements and high energy consumption in the production of paraxylene in the prior art. The invention adopts a technical scheme that: in the mixed raw materials separated from a reforming unit, the C9 aromatics and a third fraction of benzene enter a benzene and C9 aromatic transalkylation technical unit to undergo a dealkylation reaction to form a section fraction of benzene, a second fraction of toluene and a second fraction of C8 aromatics; the toluene enters a selective toluene disproportionation unit to undergo a selective disproportionation reaction to form C8 aromatics and benzene homolog flow containing the paraxylene, a third fraction of C8 aromatic, a third fraction of toluene and the third fraction of benzene are obtained, and the third fraction of toluene is returned to the selective toluene disproportionation unit; and the C8 aromatics separated from the reforming unit, the second fraction of C8 aromatics and the third fraction of C8 aromatics are mixed and delivered to a paraxylene separation unit to obtain the paraxylene. According to the technical scheme, the problem is well solved, and the method can be used in the production of the paraxylene.
Description
Technical field
The present invention relates to a kind of selective disproportionation of toluene and benzene and C9 aromatic transalkylation method.
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 that contains ethylbenzene of the thermodynamic(al)equilibrium that generates from the petroleum naphtha catalytic reforming is to separate or molecular sieve simulated moving bed adsorption separation (abbreviation fractionation by adsorption) technology by multistage cryogenic crystallization the C8 aronmatic, and p-Xylol is separated from the close with it isomer mixture of boiling point.And, often take C for the processing of the dimethylbenzene of an ortho position and a position
8A isomerization (abbreviation isomerization) technology makes it isomery and turns to p-Xylol.In order to increase production p-Xylol, utilize toluene disproportionation or toluene and carbon nine and above aromatic disproportion thereof and transalkylation (being called for short toluene disproportionation and transalkylation) reaction to generate benzene and C
8A, thereby volume increase C
8A is the operational path that effectively increases production p-Xylol.
Up to now, in the world more typically, also the technology relevant with toluene disproportionation of comparative maturity has sixties Mo industrialized Tatoray tradition toluene disproportionation process, the MTDP of late nineteen eighties release and S-TDT technology and the TransPlus technology of releasing in recent years.Selective disproportionation of toluene is a new way of producing p-Xylol.Because toluene is at the C that can carry out selective disproportionation generation benzene and high p-Xylol concentration on the ZSM-5 of modification catalyzer
8Therefore A only needs can isolate most p-Xylol through simple once the step subzero fractionation.In recent years, along with improving constantly of catalyst performance, this technology has obtained considerable progress.Its typical process has industrialized MSTDP selective disproportionation of toluene technology and the pX-Plus technology released in recent years the late nineteen eighties.
Industrialized selective disproportionation of toluene technology-MSTDP is the catalyst treatment methylbenzene raw material with treated ZSM-5 type mesoporous molecular sieve, can obtain the C of high p-Xylol concentration (85～90%, weight percent, identical except that indicating below)
8The benzene of A and nitration grade.Do not see the PX-plus technology of industrial application report as yet, its main technique index is that the selectivity of pX reaches 90% in the dimethylbenzene under toluene conversion 30% condition, and the mol ratio of benzene and pX is 1.37.
Yet, in the technology of this class selective disproportionation of toluene, in the harshness of the simultaneous with high para-selectivity to material choice.This type of technology can only be raw material with toluene, and C
9 +A does not have purposes in this technology, can not directly be utilized at least, causes the waste of aromatic hydrocarbon resource.In addition, this technology 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 technology.
The reactor feed of typical Tatoray technology is with toluene and C9 aromatic (C
9A) be reaction raw materials.The dimethylbenzene that is generated by Tatoray technology is to be in the isomer mixture that thermodynamic(al)equilibrium is formed, and has the p-Xylol content of industrial application value generally to have only about 24% most.For the xylol this point that selective disproportionation of toluene can obtain the p-Xylol concentration about 90%, Tatoray technology is in tangible inferior position undoubtedly, but Tatoray technology is exactly that Tatoray technology can be converted into benzene and dimethylbenzene to C9A with respect to one of selective disproportionation of toluene technology very big advantage.Document based on Tatoray technology has USP4341914, Chinese patent 98110859.8, USP2795629, USP3551510, Chinese patent 97106719.8 etc.The technical process that representative USP4341914 proposes is for to carry out the aromatic hydrocarbons fractionation with reformate, toluene that obtains and C
9A enters the Tatoray technique unit and carries out disproportionation and a heatable brick bed group-transfer reaction, 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 from isomerization unit enter the pX tripping device together and isolate highly purified p-Xylol product, and other C8 aronmatic isomer carries out the xylol that xylene isomerization reaction obtains being in thermodynamic(al)equilibrium again to isomerization unit.
Heavy aromatics takes off alkyl and produces C
6～C
8Aromatic hydrocarbons technology caused people's attention gradually along with the rise of selective disproportionation of toluene technology in the last few years.USP5763721 and USP5847256 have proposed to be used for the catalyzer of heavy aromatics dealkylation respectively.Wherein, USP5847256 has announced a kind of mordenite catalyst of rhenium-containing, and this catalyzer is specially adapted to transform and contains the many raw materials of ethyl, can obtain products such as toluene, dimethylbenzene and benzene.
C
8The boiling point of each component of aromatic hydrocarbons is approaching: 136.2 ℃ in 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 bigger 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 bigger 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 that p-Xylol is wherein separated, and is not high as p-Xylol concentration in the raw material, for reaching the acceptable yield of industrial production, generally adopts two sections crystallizations.USP3177255, USP3467724 at first crystallize out most p-Xylol under-80～-60 ℃ low temperature and make productive rate reach theoretical maximum, this moment crystal purity between 65～85%, the crystallization second time is being carried out in the fusing back; Tc can obtain the p-Xylol of 99% above purity generally at-20～0 ℃ for the second time, and p-Xylol content is higher in the mother liquor, can return crystallized region recycle for the first time.
Utilize sorbent material to C
8Each component of aromatic hydrocarbons is difference optionally, can p-Xylol be separated by adsorption method of separation, 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 have described sorbent material that fractionation by adsorption uses X or the Y zeolite as barium type or barium potassium type; USP3558732, USP3686342 use toluene and the p-Diethylbenzene desorbing agent as fractionation by adsorption respectively.
Summary of the invention
Technical problem to be solved by this invention be in the conventional art when producing p-Xylol, exist owing to p-Xylol concentration in the xylol is low, cause problems such as dimethylbenzene separating unit and isomerization unit internal circulating load are big, energy consumption height, a kind of new p-Xylol production method is provided.This 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 the xylol, reduces the scale of p-Xylol separating unit, isomerization unit and aromatic hydrocarbons fractionation unit greatly, 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 selective disproportionation of toluene and benzene and carbon nine transalkylation methods may further comprise the steps:
A. separate the mixing raw material that contains 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 and second strand of toluene enter the selective disproportionation of toluene technique unit together, under hydro condition, carry out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene logistics that contains p-Xylol, 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. send into the p-Xylol separating unit after first strand of C8 aronmatic, second strand of C8 aronmatic and the 3rd strand of C8 aronmatic mix, obtain the p-Xylol product, wherein the p-Xylol separating unit adopts fractionation by adsorption or Crystallization Separation p-Xylol.
In technique scheme, the used catalyzer in selective disproportionation of toluene unit is the type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least a metal or its oxide compound that is selected from platinum, molybdenum or the 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
-1The used catalyzer in benzene and C9 aromatic alkyl transfering process unit is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22, and bismuthiferous metal or its oxide compound in the catalyzer, its consumption are 0.005～5% by weight percentage; Benzene and the unitary operational condition of C9 aromatic alkyl transfering process are 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
-1The p-Xylol product purity is weight concentration 〉=99.8% in the p-Xylol separating unit.
Among the present invention, in benzene and C9 aromatic alkyl transfering process unit, owing to use bismuthiferous zeolite to be catalyzer, under hydro condition, by transalkylation reaction, effectively with reaction raw materials benzene and C
9Aromatic hydrocarbons has changed into dimethylbenzene, has realized the raw material processing flexibility, and aromatics conversion rate reaches 64.8%, and selectivity reaches 90%.And toluene selective disproportionation reaction under the effect of platiniferous ZSM-5 catalyzer, takes place in the selective disproportionation of toluene unit, generates benzene and the xylol that contains the high density p-Xylol, and p-Xylol concentration can reach 80～95%.As can be seen, such operational path can allow the concentration of producing p-Xylol in the xylol that obtains significantly improve, and has made full use of C again
9 +The A resource has reduced the treatment scale of isomerization unit and adsorption separation unit, has reduced energy consumption and facility investment scale effectively, and has reduced production cost, has obtained better technical effect.
Description of drawings
Fig. 1 is the technical process of traditional p-Xylol production equipment.
Fig. 2 is the technical process of selective disproportionation of toluene of the present invention and benzene and C9 aromatic transalkylation.
I is the reformer unit deheptanizer among Fig. 1 or Fig. 2; II is aromatic hydrocarbons extracting unit; III is the benzene toluene separating unit after the 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 an adsorption separation unit.1 is the reformation de-pentane oil, and 2 is from deheptanizer cat head distilled C
7 -(comprising that benzene, toluene and carbon six carbon seven are non-aromatic), 3 is carbon eight and the above arene stream that deheptanizer tower still is extracted out, 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 the extracting is extracted, 7 is the toluene that the toluene tower cat head after the extracting is extracted, 8 C for the extraction of the toluene tower still after the 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 portion C
10A, 11 is the xylol of extracting out from the benzenol hydrorefining cat head, 12 is the C that heavy aromatics Tata still is extracted out
10A, 13 is benzene and the unitary product stream of C9 aromatic alkyl transfering process, 14 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 xylol behind the PX, and 17 is the C that isomerization unit deheptanizer tower still is discharged
8 +The A logistics, 18 logistics that contain benzene and toluene of extracting for isomerization unit deheptanizer cat head, 19 is the benzene logistics of disproportionation and transalkylation extraction, the 20 nitrated benzene of extracting for the benzene column overhead of selective disproportionation.
The technological process of tradition paraxylene process units as shown in Figure 1. Enter deheptanizer I from reformation depentanizer tower bottoms 1, cat head is told carbon seven and following aromatic hydrocarbons non-aromatics logistics 2 thereof and is entered 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 after the extracting sent, and the toluene tower tower reactor of mixed xylenes 8 after the extracting extracted out and entered benzenol hydrorefining unit IV. In addition, deheptanizer tower reactor logistics 3 also enters benzenol hydrorefining unit VI, mix carbon eight logistics 11 and distillate p-xylene separation unit IX from cat head, C9 aromatic 10 and from the raw material of the isolated toluene logistics 7 of toluene tower cat head as toluene disproportionation and transalkylation II, C10 +A logistics 12 is sent as byproduct; Disproportionation directly enters unit III with 9 of transalkylation product streams and separates; Adsorption separation unit IX isolates purpose product paraxylene 15, and a small amount of toluene 14 returns toluene disproportionation unit VI, and other mixed xylenes 16 enters xylene isomerization unit VIII and carries out isomerization reaction, the C that isomerization unit deheptanizer tower reactor is discharged8 +A logistics 17 is sent to benzenol hydrorefining unit IV, and the logistics that contains benzene and toluene 18 that the deheptanizer cat head is extracted is sent to the catalytic reforming unit.
The technological 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 handicraft technique of the present invention changes the toluene disproportionation process unit in the traditional handicraft into C9 aromatic and takes off the alkyl technique unit, in addition, increased by a cover selective disproportionation of toluene unit VI. The place that Fig. 2 is identical with Fig. 1 is no longer narrated, and the below only elaborates with regard to difference. The benzene 20 that in the technique of the present invention the former C9 aromatic 10 that is used as toluene disproportionation and transalkylation raw material and selective disproportionation unit is 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 the raw material and reaction generate) is all as the raw material of selective disproportionation unit, product stream 9 separates with toluene tower in the benzene toluene tower unit after thing 13 flows to extracting, the logistics 8 of isolating behind benzene and the toluene is sent into benzenol hydrorefining unit IV, dimethylbenzene cat head extraction C8 +A logistics 11, logistics 11 are sent into adsorption separation unit IX and are isolated pure paraxylene 21.
The present invention is further illustrated below by specific embodiment, and still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, and the filling bismuth-containing is 0.05% beta-zeolite catalyzer in the reactor, and reaction conditions is: 385 ℃ of temperature of reaction, pressure are 3.0MPa, and 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 generates benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and filling contains 0.05% platinum ZSM-5 molecular sieve catalyst in the reactor, and reaction conditions is: 385 ℃ of temperature of reaction, pressure are 3.0MPa, and 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.
24 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
Table 1 reformation de-pentane oil aromatic hydrocarbons is formed and flow rate
| Form | ??Ben | ??Tol | ??C 8A | ??C 9A | ??C 10 + | ??∑ |
| Form weight % | ??14.41 | ??26.79 | ??33.53 | ??24.02 | ??1.25 | ??100.00 |
| Form | ??Ben | ??Tol | ??C 8A | ??C 9A | ??C 10 + | ??∑ |
| Flow, kilogram/hour | ??12673 | ??23560 | ??29482 | ??21122 | ??1095 | ??87932 |
Wherein: NA is a non-aromatics, and Ben is a benzene, and Tol is a toluene, C
8A is a C8 aronmatic, C
9A is a C9 aromatic, C
10 +A is carbon ten and above aromatic hydrocarbons thereof, below identical.
According to aromatic hydrocarbons flow rate (fresh feed) in accompanying drawing 2 described technical process of the present invention and the table 1 and the operation of the parameter among the embodiment, the material charging and the discharging data of selective disproportionation of toluene unit, benzene and C9 aromatic transalkylation and isomerization unit are listed in table 2.Each unitary treatment scale of p-Xylol production equipment sees Table 3, and the output of product p-Xylol and benzene sees 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
*Be meant other C8 aronmatic except that 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 dimethylbenzene fractionation unit |
| Scale, kilogram/hour | ??54810 | ??168667 | ??211965 | ??252149 |
Table 4 embodiment 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | ??58591 | ??13060 | ??71651 |
| Purity, % | ??99.80 | ??99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 71651 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 23%, 23% and 22% respectively, and this has obviously reduced the Design of device scale.Plant energy consumption is 21529 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 19%.Therefore, problems such as xylol concentration was low when patent of the present invention had overcome the production p-Xylol that exists in the conventional art, internal circulating load is big, energy consumption height provide a kind of brand-new more economical being used to increase production the method for p-Xylol.
[embodiment 2]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees 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 the reactor, and reaction conditions is: 460 ℃ of temperature of reaction, pressure are 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 generates 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 catalyst in the reactor, and reaction conditions is: 450 ℃ of temperature of reaction, pressure are 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.
6 grades of adsorption separation unit employings are simulation moving-bed, filling sorbent material in the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is 5 ℃.
Operate according to the parameter that provides in accompanying drawing 2 described technical process of the present invention and the example, each unitary treatment scale of p-Xylol production equipment sees Table 5, and the output of product p-Xylol and benzene sees Table 6.
Table 5 embodiment 2 each cell processing scale table
| The unit title | Heavy aromatics takes off alkyl unit | Isomerization unit | Adsorption separation unit | The dimethylbenzene fractionation unit |
| Scale, kilogram/hour | ??54810 | ??166371 | ??205929 | ??235986 |
Table 6 embodiment 2 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | ??58591 | ??13060 | ??71651 |
| Purity, weight % | ??99.80 | ??99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 78340 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 23%, 25% and 27% respectively, has obviously reduced the Design of device scale.Plant energy consumption is 20465 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 23%.
[embodiment 3]
By flow process shown in Figure 2, with C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate ability and each unitary treatment scale situation that the present invention produces p-Xylol and benzene.Typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted sees Table 1.
Benzene and C9 aromatic alkyl transfering process unit adopt fixed-bed reactor, the h-mordenite catalyzer of filling bismuth-containing 0.10% in the reactor, and reaction conditions is: 320 ℃ of temperature of reaction, pressure are 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 generates benzene, toluene and C
8A.
The selective disproportionation of toluene technique unit adopts fixed-bed reactor, and filling contains 0.3% molybdenum and 0.8% magnesium ZSM-5 molecular sieve catalyst in the reactor, and reaction conditions is: 320 ℃ of temperature of reaction, pressure are 1.0MPa, and 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 the moving-bed, and the fractionation by adsorption service temperature is 130 ℃.
The Crystallization Separation unit adopts suspension crystallization to separate, and Tc is-15 ℃.
Operate according to the parameter that provides in accompanying drawing 2 described technical process of the present invention and the example, each unitary treatment scale of p-Xylol production equipment sees Table 7, and the output of product p-Xylol and benzene sees Table 8.
Table 7 embodiment 3 each cell processing scale table
| The unit title | Heavy aromatics takes off alkyl unit | Isomerization unit | Adsorption separation unit | The Crystallization Separation unit | The dimethylbenzene fractionation unit |
| Scale, kilogram/hour | ??54810 | ??161532 | ??203754 | ??65101 | ??245876 |
Table 8 embodiment 3 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | ??58624 | ??13060 | ??71684 |
| Purity, weight % | ??99.80 | ??99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 1, the ultimate production that technology of the present invention can be produced p-Xylol and benzene is 71684 kilograms/hour.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 26%, 26% and 24% respectively, has obviously reduced the Design of device scale.Plant energy consumption is 21530 * 10
6Joule/ton (p-Xylol+benzene) is with respect to 26579 * 10 of Comparative Examples
6Joule/ton (p-Xylol+benzene), energy consumption has reduced by 19%.
[comparative example 1]
By flow process shown in Figure 1, still with typical reformation de-pentane oil C in the table 1
6A～C
10 +The flow rate of A logistics is a basic data, investigates traditional ability that contains toluene disproportionation and unitary Aromatic Hydrocarbon United Plant production p-Xylol of alkyl transfering process and benzene as shown in Figure 1.The material charging and the extraction situation of its disproportionation and transalkylation, isomerization unit see Table 9, and each unitary treatment scale sees Table 10, and the output of product p-Xylol and benzene sees 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, kilogram/hour | ??111988 | ??219438 | ??274572 | ??323269 |
Table 11 comparative example 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | ??54316 | ??22751 | ??77067 |
| Purity, % | ??99.80 | ??99.94 |
The result shows, traditional aromatic hydrocarbons production technique reaction aroamtic hydrocarbon raw material listed as table 1, and the total amount that the worker has produced p-Xylol and benzene is 77067 kilograms/hour, plant energy consumption is 26579 * 10
6Kilojoule/ton (p-Xylol+benzene).
Claims (6)
1. a selective disproportionation of toluene and benzene and C9 aromatic transalkylation method may further comprise the steps:
A. separate the mixing raw material that contains 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 and second strand of toluene enter the selective disproportionation of toluene technique unit together, under hydro condition, carry out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene logistics that contains p-Xylol, 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. send into the p-Xylol separating unit after first strand of C8 aronmatic, second strand of C8 aronmatic and the 3rd strand of C8 aronmatic mix, obtain the p-Xylol product, wherein the p-Xylol separating unit adopts fractionation by adsorption or Crystallization Separation p-Xylol.
2. according to the described selective disproportionation of toluene of claim 1 and benzene and C9 aromatic transalkylation method, it is characterized in that the used catalyzer in selective disproportionation of toluene unit is the type ZSM 5 molecular sieve catalyzer, type ZSM 5 molecular sieve contains at least a metal or its oxide compound that is selected from platinum, molybdenum or the magnesium, and its consumption is 0.005～5% by weight percentage.
3. according to the described selective disproportionation of toluene of claim 1 and benzene and C9 aromatic transalkylation method, the operational condition that it is characterized in that the selective disproportionation of toluene technique unit is as follows: reaction pressure is 1～4MPa, temperature of reaction is 300～480 ℃, hydrogen/hydrocarbon mol ratio is 0.5～10, and the liquid weight air speed is 0.8～8 hour
-1
4. according to the described selective disproportionation of toluene of claim 1 and benzene and C9 aromatic transalkylation method, it is characterized in that the used catalyzer in benzene and C9 aromatic alkyl transfering process unit is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22, bismuthiferous metal or its oxide compound in the catalyzer, its consumption are 0.005～5% by weight percentage.
5. according to the described selective disproportionation of toluene of claim 1 and benzene and C9 aromatic transalkylation method, it is characterized in that benzene and the unitary operational condition of C9 aromatic alkyl transfering process are as follows: reaction pressure is 1～6MPa, temperature of reaction is 300～600 ℃, hydrogen/hydrocarbon mol ratio is 2～10, and weight space velocity is 0.5～3 hour
-1
6. according to the described selective disproportionation of toluene of claim 1 and benzene and C9 aromatic transalkylation method, it is characterized in that the p-Xylol product purity is weight concentration 〉=99.8% in the p-Xylol separating unit.
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| CN103845915A (en) * | 2014-02-15 | 2014-06-11 | 中山大学 | Multi-stage flash evaporation separation equipment of toluene disproportionation reaction effluent and separation method thereof |
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| CN1141277C (en) * | 2000-08-29 | 2004-03-10 | 中国石油化工集团公司 | Process for preparing p-xylene |
| CN1193967C (en) * | 2002-03-13 | 2005-03-23 | 中国石油化工股份有限公司 | Benzene and C9 and more than that arene transalkylation method |
| CN1216020C (en) * | 2002-12-11 | 2005-08-24 | 中国石油化工股份有限公司 | Transalkylation process between benzene and C9 arene |
| CN1252009C (en) * | 2003-07-09 | 2006-04-19 | 中国石油化工股份有限公司 | Toluene selective disproportionation and carbon 9 and above arene dealkytation method |
| CN100531907C (en) * | 2006-06-21 | 2009-08-26 | 中国石油化工股份有限公司 | Catalyst for alkyl transfer of polyalkylbenzene |
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| CN104107717A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Toluene disproportionation catalyst for improving selectivity of xylene, and its use |
| CN104107717B (en) * | 2013-04-16 | 2016-12-28 | 中国石油化工股份有限公司 | Improve toluene disproportionation catalyst of dimethylbenzene selective and application thereof |
| CN103845915A (en) * | 2014-02-15 | 2014-06-11 | 中山大学 | Multi-stage flash evaporation separation equipment of toluene disproportionation reaction effluent and separation method thereof |
| CN109803944A (en) * | 2016-10-04 | 2019-05-24 | 埃克森美孚化学专利公司 | The disproportionation and transalkylation of heavy arene |
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