CN1252009C - Toluene selective disproportionation and carbon 9 and above arene dealkytation method - Google Patents
Toluene selective disproportionation and carbon 9 and above arene dealkytation method Download PDFInfo
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- CN1252009C CN1252009C CN 03141449 CN03141449A CN1252009C CN 1252009 C CN1252009 C CN 1252009C CN 03141449 CN03141449 CN 03141449 CN 03141449 A CN03141449 A CN 03141449A CN 1252009 C CN1252009 C CN 1252009C
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Abstract
The present invention relates to a method for the selective disproportionation of toluene and the dealkylation of the aromatic hydrocarbon of C9 or higher, which mainly solves the problems existing in the prior art for the production of p-xylene, such as low concentration of the p-xylene in mixed xylene, large treatment cycle amount of the aromatic hydrocarbon, high energy consumption or harsh requirements for the raw materials of a reaction, etc. The present invention adopts the technical scheme that the mixed xylene containing the p-xylene with high concentration is produced by the selective disproportionation of the toluene, and the dealkylation of the aromatic hydrocarbon of C9 or higher is carried out for producing benzene, the toluene and mixed xylene combination in thermodynamic equilibrium. Therefore, the problems in the prior art are solved well, and the present invention can be used for the industrial production of the aromatic hydrocarbon.
Description
Technical field
The present invention relates to a kind of selective disproportionation of toluene and carbon nine and above aromatic hydrocarbons thereof and take off alkyl meth.Specifically, be earlier by carbon nine and above aromatic hydrocarbons (C thereof
9 +A) alkyl (be designated hereinafter simply as heavy aromatics and the take off alkyl) reaction of taking off generates benzene (Ben), toluene (Tol) and C8 aronmatic (C
8And then selective disproportionation and p-Xylol fractionation by adsorption or Crystallization Separation and C by toluene A),
8The A isomerization technique, the method for producing p-Xylol (pX).
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 one 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 C with respect to one of selective disproportionation of toluene technology very big advantage
9A is converted into benzene and dimethylbenzene.
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 transalkylation 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.
Based on the Aromatic Hydrocarbon United Plant of selective disproportionation technology representative be PX-Plus technology, the difference of the maximum of it and traditional Aromatic Hydrocarbon United Plant is with the PX-Plus technology generations for Tatoray technology, originally as the C of raw material
9 +A discharges as by-product.
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.
More than each patent can be divided into two classes, one class is to describe toluene disproportionation process, toluene selective disproportionation reaction and heavy aromatics take off these three catalyst for reaction prescriptions of alkyl, though another kind of is to describe technology, but it is just in the limited field of original Tatoray technology thinking, do some rational change on the separation scheme to reaction product, its shortcoming is: utilize toluene or toluene and carbon nine above aromatic hydrocarbons to produce C8 aronmatic and come increasing production of xylol, the content of p-Xylol is low in the xylol that obtains, generally have only about 24%, other xylene isomer can only reach the purpose that is converted into p-Xylol by isomerization, so just cause the dimethylbenzene internal circulating load bigger, promptly cause isomerization unit, the treatment capacity of the xylene separator in PX fractionation unit and the aromatic hydrocarbons fractionation unit etc. is big, and energy consumption is higher.The aromatic hydrocarbons production technique of application choice disproportionation processes technology though obtained the xylol of high density p-Xylol, descends unitary treatment capacity such as isomerization, because this technology can not be handled C greatly
9 +A has caused C
9 +The waste of A raw material resources makes the output of purpose product p-Xylol that by a relatively large margin decline also be arranged.
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, provide a kind of new selective disproportionation of toluene and carbon nine and above aromatic hydrocarbons thereof to take off alkyl meth.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 carbon nine and above aromatic hydrocarbons thereof take off alkyl meth, 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, 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 carbon nine of step and above aromatic hydrocarbons enters carbon nine and above aromatic hydrocarbons takes off the alkyl technique unit carries 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, obtains the 3rd strand of C8 aronmatic and the 3rd burst of benzene logistics;
D) send into the p-Xylol separating unit after first strand of C8 aronmatic and second strand of C8 aronmatic mix, obtain the p-Xylol product.
In technique scheme, the operational condition of selective disproportionation of toluene technique unit reaction zone is as follows: 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 of selective disproportionation of toluene technique 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 that carbon nine and above aromatic hydrocarbons thereof take off alkyl technique unit reaction zone is as follows: reaction pressure is 1～5MPa, and temperature of reaction is 250～480C, and hydrogen-hydrocarbon ratio is 0.5～8 moles/mole, and weight space velocity is 0.8～10 hour
-1It is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22 that carbon nine and above aromatic hydrocarbons thereof take off the used catalyzer of alkyl technique unit, its preferred version is bismuthiferous metal or its oxide compound in the used catalyzer, and its consumption is 0.005～5% by weight percentage.P-Xylol separating unit preferred version is for adopting fractionation by adsorption or freezing and crystallizing separating paraxylene.First kind of scheme of the 3rd strand of C8 aronmatic for adopt separately the freezing and crystallizing separation method and separate or with send into the p-Xylol separating unit, recovery part p-Xylol product after first strand of C8 aronmatic and second strand of C8 aronmatic mix; Second kind of scheme of the 3rd strand of C8 aronmatic is that its raffinate mixes with first strand of C8 aronmatic and second strand of C8 aronmatic after adopting freezing and crystallizing to separate separately, enters adsorption separation unit together and produces the p-Xylol product.
Among the present invention, take off the alkyl technique unit at carbon nine and above aromatic hydrocarbons thereof, under hydro condition, catalyzer has and carbon nine and above aromatic hydrocarbons thereof are taken off alkyl becomes benzene, toluene and C
8The function of A.The toluene that carbon nine and above aromatic hydrocarbons thereof take off the generation of alkyl technique unit enters the selective disproportionation of toluene unit; The benzene that reaction generates does not have the benzene of unnecessary extraction at this unit internal recycle, can reduce the generation of by-product benzene so as far as possible; The C that reaction generates
8A then enters fractionation by adsorption and isomerization unit is produced pX.Toluene other toluene in Aromatic Hydrocarbon United Plant that carbon nine and above aromatic hydrocarbons thereof take off the generation of alkyl technique unit enters the selective disproportionation of toluene unit, under the effect of platiniferous ZSM-5 catalyzer, toluene selective disproportionation reaction takes place, generate benzene and the xylol that contains high density pX, pX 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 that traditional aromatic hydrocarbons is produced the machinery technical process.
Fig. 2 takes off the alkyl technical process for selective disproportionation of toluene of the present invention and carbon nine and above aromatic hydrocarbons thereof.
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; IV is the benzenol hydrorefining unit, and the heavy aromatics tower can be established also as the case may be and can not establish; V is toluene disproportionation and alkyl transfering process unit; VI is the selective disproportionation technique unit; VII is that heavy aromatics takes off the alkyl technique unit; VIII is the xylene isomerization process unit; IX is p-Xylol separating technology unit.Whether V and VI set up independently aromatic hydrocarbons tripping device of own unit in these two unit as the case may be.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, the 6 high purity product benzene of extracting for the benzene column overhead, 7 toluene of extracting for the toluene tower cat head, 8 C that extract out for the toluene tower still
8 +A, 9 is that disproportionation and transalkylation are stablized the still liquid that the Tata still is extracted out, 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
10 +A, 13 for heavy aromatics takes off the still liquid that alkyl unit benzene Tata still is extracted out, 14 small amount of toluene of separating for the PX separating unit, 15 be highly purified product p-Xylol, and 16 is the xylol of isolating behind the PX, and 17 is the C of isomerization unit deheptanizer tower still discharge
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 20th, the benzene of selective disproportionation unit extraction.
The technological process of tradition aromatic hydrocarbons production combined unit 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, aromatic hydrocarbons fractionation unit III is removed in benzene toluene logistics 4, products benzene 6 is sent from the benzene column overhead, and mixed xylenes 8 enters benzenol hydrorefining unit IV from the extraction of toluene tower tower reactor. 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 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; Toluene disproportionation and transalkylation can determine whether to set up the aromatic hydrocarbons separator as the case may be, when setting up the aromatic hydrocarbons separator, and disproportionation unit extraction benzaldehyde product 19, toluene self circulation, C8 +A logistics 9 enters the PX separative element and carries out the pX separation; And when the aromatic hydrocarbons fractionation unit was not established in the toluene disproportionation unit, 9 of stripper tower reactor Produced Liquids directly enter the aromatic hydrocarbons fractionation unit to be separated; P-xylene separation unit IV 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 the aromatic hydrocarbons fractionation unit, and the logistics that contains benzene and toluene 18 that the deheptanizer cat head is extracted is sent to the catalytic reforming unit.
Selective disproportionation of toluene of the present invention and carbon nine and above aromatic hydrocarbons thereof take off the alkyl technological process 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, to some process flow to having done corresponding change. The place that Fig. 2 is identical with Fig. 1 is no longer narrated, and the below only elaborates with regard to difference. In the technique of the present invention former carbon nine and the above aromatic hydrocarbons 10 thereof that is used as toluene disproportionation and transalkylation raw material is taken off the raw material of alkyl unit as heavy aromatics, the benzene that reaction generates circulates C in the unit7 +A logistics 13 separates to the toluene tower in the aromatic hydrocarbons fractionation unit; All as the raw material of selective disproportionation unit, the selective disproportionation unit can determine whether to set up the aromatic hydrocarbons separator as the case may be in toluene logistics 7 (comprise the toluene of bringing in the raw material and react the toluene that generates). When setting up the aromatic hydrocarbons separator, the benzaldehyde product 20 of selective disproportionation unit extraction nitration grade is rich in the C of paraxylene8A logistics 9 enters the PX separative element and carries out the pX separation; And when the aromatic hydrocarbons fractionation unit was not established in the selective disproportionation unit, 9 of stripper tower reactor Produced Liquids directly enter the aromatic hydrocarbons fractionation unit to be separated, and did not also have the extraction of benzene logistics 20 simultaneously.
The present invention is further elaborated below by embodiment.
Specific implementation method
[embodiment 1]
The mixing raw material that will contain benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons thereof and non-aromatics separates, obtain carbon nine and above aromatic hydrocarbons thereof, as raw material, under hydro condition, in fixed-bed reactor, carry out carbon nine and above aromatic hydrocarbons dealkylation performance thereof and investigate.25 millimeters of reactor inside diameter φ, 1000 millimeters of length, stainless steel.The equal up and down 3 millimeters granulated glass spherees of filling φ of beds play air-flow and distribute and supporting role, and filling 20 gram bismuth-containings are 0.05% beta-zeolite catalyzer in the reactor.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, temperature of reaction is 425 ℃, and pressure is 3.0Mpa, and weight space velocity is 2.0 hours
-1, hydrogen hydrocarbon mol ratio is 5.0.
C in the raw material
9 +A derives from petrochemical complex Aromatic Hydrocarbon United Plant, H
2Be electrolysis hydrogen, through dehydrating processing, reaction result is listed in the table 1.
Table 1 C9 aromatic dealkylation raw material and product compositional analysis
| Component | NA | Ben | Tol | C 8A | C 9 +A | C 10 +A | ∑ |
| Raw material, weight % | 0.00 | 0.00 | 0.01 | 0.82 | 93.24 | 5.93 | 100.00 |
| Product, weight % | 6.13 | 1.92 | 11.89 | 19.22 | 57.82 | 3.02 | 100.00 |
Wherein: NA is a non-aromatics, C
10 +A is carbon ten and above aromatic hydrocarbons thereof.
From embodiment 1 as can be seen: raw material C
9 +A has generated benzene, toluene and C after reacting
8A.
The mixing raw material that will contain benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons thereof and non-aromatics separates, and obtains toluene, is raw material with toluene, under hydro condition, carries out toluene selective disproportionation reaction on fixed-bed reactor.25 millimeters of reactor inside diameter φ, 1000 millimeters of length, stainless steel.The equal up and down 3 millimeters granulated glass spherees of filling φ of beds play air-flow and distribute and supporting role, and filling 20 grams contain 0.05% platinum ZSM-5 molecular sieve catalyst in the reactor.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.
Raw material toluene derives from petrochemical complex Aromatic Hydrocarbon United Plant, H
2Be electrolysis hydrogen, through dehydrating processing, temperature of reaction is 420 ℃, and reaction pressure is 1.5MPa, and air speed is 4.0 hours
-1, hydrogen-hydrocarbon ratio is 3.0 moles/mole.The result is as shown in table 2.
Table 2 toluene selective disproportionation reaction result
| Component | NA | Ben | Tol | PX | C 8A * | C 9 +A | ∑ |
| Form weight % | 1.74 | 14.05 | 69.95 | 11.62 | 2.02 | 0.62 | 100.00 |
Annotate: C
8A
*Be meant other C8 aronmatics except that pX.
The content of pX in dimethylbenzene is 89%.
[embodiment 2]
With C in the typical reformation de-pentane oil
6A～C
10 +Each material of hydrocarbon consist of basic data, investigate the present invention and press the technical process production pX shown in the accompanying drawing 2 and ability and each unitary treatment scale situation of benzene.
Table 3 is that typical reformer is sent the composition distribution of aromatic hydrocarbons and the flow rate of each component that present embodiment adopted.
Table 3 reformation de-pentane oil aromatic hydrocarbons is formed and flow rate
| Form | Ben | Tol | C 8A | C 9A | C 10 +Hydrocarbon | ∑ |
| Form weight % | 14.41 | 26.79 | 33.53 | 24.02 | 1.25 | 100.00 |
| Flow rate, kilogram/hour | 12673 | 23560 | 29482 | 21122 | 1095 | 87932 |
According to the aromatic hydrocarbons flow rate (fresh feed) in accompanying drawing 2 described technical process of the present invention and the table 3 and embodiment 1 carbon nine and above aromatic hydrocarbons dealkylation result and toluene selective disproportionation reaction result, the unitary reaction product of selective disproportionation of toluene also enters adsorption separation device separates, and selective disproportionation of toluene unit, heavy aromatics take off the material charging and the discharging data of alkyl unit and isomerization unit and list in table 4.Each unitary treatment scale of Aromatic Hydrocarbon United Plant sees Table 5, and the output of product p-Xylol and benzene sees Table 6.
Table 4 embodiment 2 process stream tables
| Component | The selective disproportionation unit | Heavy aromatics takes off alkyl unit | Isomerization unit | |
| Unit feed, kilogram/hour | Ben | 14 | 0 | |
| Tol | 97617 | / | 108 | |
| C 8A | 92 | 211 | 161632 | |
| C 9A | / | 36715 | 87 | |
| C 10 +A | / | 1824 | ||
| ∑ | 97723 | 38750 | 161827 | |
| The unit discharging, kilogram/hour | Ben | 13502 | 2 | 2069 |
| Tol | 67233 | 5900 | 1038 | |
| pX | 12086 | 12011 | 155995 | |
| C 8A * | 1622 | |||
| C 9A | 791 | 14020 | 869 | |
| C 10 +A | / | 3036 | ||
| ∑ | 95234 | 34969 | 157902 | |
C wherein
9A is a C9 aromatic, C
8A
*Be meant other C8 aronmatics except that pX.
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 | 38750 | 161827 | 211070 | 252165 |
Table 6 embodiment 2 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 49258 | 29066 | 78324 |
| Purity, % | 99.8 | 99.94 |
The result shows, utilization the technology of the present invention, and with the listed aroamtic hydrocarbon raw material of table 3, the ultimate production that technology of the present invention can be produced pX and benzene is 78324 kilograms/hour.The concentration that enters p-Xylol in the xylol raw material of adsorption separation unit is 24.0%, and the concentration of p-Xylol has only 19.5% in the comparative example, that is to say, the concentration of p-Xylol has improved 4.5%.The treatment scale of xylene isomerization unit, adsorption separation unit and dimethylbenzene fractionation unit has descended 26%, 23% and 22% respectively, and this has obviously reduced the Design of device scale.Plant energy consumption is 21840 * 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 21.7%.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, the method that provides a kind of brand-new more economical being used to produce p-Xylol.For typical Aromatic Hydrocarbon United Plant, under the situation that device is not done to change, newly-built one overlaps the selective disproportionation device, just can improve the processing power of raw material, increases production p-Xylol significantly.
[embodiment 3]
Still adopt technical process, processing condition and the catalyzer of embodiment 2, consist of benchmark with the raw material shown in the table 3, improve 29% raw material treatment capacity, the flow rate of raw material is as shown in table 7.Again investigate the ability of explained hereafter pX of the present invention and benzene based on this.Each unitary treatment scale of Aromatic Hydrocarbon United Plant sees Table 8, and the output of product p-Xylol and benzene sees Table 9.
Table 7 reformation de-pentane oil aromatic hydrocarbons is formed and flow rate
| Form | Ben | Tol | C 8A | C 9A | C 10 +Hydrocarbon | ∑ |
| Form weight % | 14.41 | 26.79 | 33.53 | 24.02 | 1.25 | 100.00 |
| Flow rate, kilogram/hour | 16348 | 30392 | 38032 | 27247 | 1413 | 113432 |
Table 8 embodiment 3 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 | 49987 | 208731 | 272263 | 323145 |
Table 9 embodiment 3 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 63535 | 37610 | 101145 |
| Purity, % | 99.8 | 99.94 |
Compare with embodiment 2, embodiment 3 has increased by 29% unit capacity, the ultimate production of p-Xylol and benzene has increased by 31.2%, and each unitary treatment scale, except the selective disproportionation unit of not establishing in the comparative example, other each unitary treatment scale does not increase, and treatment scale is immediate to be xylene separator, only is 99.9% of comparative example xylene separator treatment scale yet.Therefore, use the technology of the present invention and produce p-Xylol, can improve the processing power of device, increase the output of product p-Xylol and benzene.
[embodiment 4]
Adopt technical process, processing condition and the catalyzer of embodiment 2, consist of benchmark with the raw material shown in the table 3, the xylol logistics of the unitary reaction product of selective disproportionation of toluene after separating enters the crystallization freezing separating unit and separates, after the one-level freezing and crystallizing separates, the rate of recovery of p-Xylol is 67%, and the raffinate after the separation enters adsorption separation unit and continues to reclaim p-Xylol.Each unitary treatment scale of Aromatic Hydrocarbon United Plant sees Table 10, and the output of product p-Xylol and benzene sees Table 11.
Table 10 embodiment 4 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 | 38743 | 161451 | 202640 | 243724 |
Table 11 embodiment 4 product productions and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 49273 | 29067 | 78340 |
| Purity, weight % | 99.8 | 99.94 |
The result shows, utilization the technology of the present invention, and the PX that adopts freezing and crystallizing isolation technique separation of methylbenzene selective disproportionation to produce, the ability that machinery generates product pX and benzene is suitable with Comparative Examples 1.But the treatment scale of adsorption separation unit and dimethylbenzene separating unit further descends, and energy consumption decreases again.
[comparative example 1]
Still with typical reformation de-pentane oil C in the table 3
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 pX 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 12, and each unitary treatment scale sees Table 13, and the output of product p-Xylol and benzene sees Table 14.
Table 12 comparative example 1 process stream table
| Component | Disproportionation and transalkylation | Isomerization unit | ||
| Unit feed, kilogram/ | Ben | 12 | 0 | |
| Tol | 65630 | 0 | ||
| C 8A | 332 | 219340 | ||
| C 9A | 42789 | 98 | ||
| C 10 +A | 3225 | |||
| ∑ | 111988 | 219438 | ||
| The unit discharging, kilogram/hour | Ben | 9035 | 420 | |
| Tol | 40223 | 1883 | ||
| C 8A | 33919 | 210585 | ||
| C 9A | 18590 | 3175 | ||
| C 10 +A | 4527 | |||
| ∑ | 106294 | 216063 | ||
Table 13 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 14 comparative example 1 product production and purity table
| Product | P-Xylol | Benzene | Summation |
| Output, kilogram/hour | 54316 | 22751 | 77067 |
| Purity, weight % | 99.8 | 99.94 |
The result shows that traditional aromatic hydrocarbons production technique reacts away the listed aroamtic hydrocarbon raw material of table 1, and it is 77067 kilograms/hour that symbiosis has become the total amount of pX and benzene, and plant energy consumption is 26579 * 10
6Joule/ton (p-Xylol+benzene), the concentration that enters p-Xylol in the xylol raw material of adsorption separation unit is 19.5%.
Claims (10)
1, a kind of selective disproportionation of toluene and carbon nine and above aromatic hydrocarbons thereof take off alkyl meth, 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, 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 carbon nine of step and above aromatic hydrocarbons enters carbon nine and above aromatic hydrocarbons takes off the alkyl technique unit carries 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, obtains the 3rd strand of C8 aronmatic and the 3rd burst of benzene logistics;
D) send into the p-Xylol separating unit after first strand of C8 aronmatic and second strand of C8 aronmatic mix, obtain the p-Xylol product.
2, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that the used catalyzer in selective disproportionation of toluene unit is the type ZSM 5 molecular sieve catalyzer.
3, take off alkyl meth according to the described selective disproportionation of toluene of claim 2 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that type ZSM 5 molecular sieve contains at least a metal or its oxide compound that is selected from platinum, molybdenum or the magnesium, its consumption is 0.005～5% by weight percentage.
4, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, the operational condition that it is characterized in that selective disproportionation of toluene technique unit reaction zone 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
5, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that it is at least a molecular sieve that is selected among beta-zeolite, mordenite or the MCM-22 that carbon nine and above aromatic hydrocarbons thereof take off the used catalyzer of alkyl technique unit.
6, take off alkyl meth according to the described selective disproportionation of toluene of claim 5 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that bismuthiferous metal or its oxide compound in the used catalyzer, its consumption is 0.005～5% by weight percentage.
7, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, it is as follows to it is characterized in that carbon nine and above aromatic hydrocarbons thereof take off the operational condition of alkyl technique unit reaction zone: reaction pressure is 1～5MPa, temperature of reaction is 250～480 ℃, hydrogen-hydrocarbon ratio is 0.5～8 moles/mole, and weight space velocity is 0.8～10 hour
-1
8, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that the p-Xylol separating unit adopts fractionation by adsorption or freezing and crystallizing separating paraxylene.
9, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, it is characterized in that the 3rd strand of C8 aronmatic adopt the freezing and crystallizing separation method to separate separately or with send into the p-Xylol separating unit, recovery part p-Xylol product after first strand of C8 aronmatic and second strand of C8 aronmatic mix.
10, take off alkyl meth according to the described selective disproportionation of toluene of claim 1 and carbon nine and above aromatic hydrocarbons thereof, after it is characterized in that the 3rd strand of C8 aronmatic adopts freezing and crystallizing to separate separately, its raffinate mixes with first strand of C8 aronmatic and second strand of C8 aronmatic, enters adsorption separation unit together and produces the p-Xylol product.
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| CN101735003A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Combined method for production of paraxylene |
| CN101735000B (en) * | 2008-11-21 | 2013-06-05 | 中国石油化工股份有限公司 | Combination method for producing p-xylene |
| CN101734989B (en) * | 2008-11-21 | 2013-10-30 | 中国石油化工股份有限公司 | Method for selective toluene disproportionation and transalkylation of benzene and C9 aromatics |
| CN101811926B (en) * | 2009-02-19 | 2013-06-05 | 中国石油化工股份有限公司 | Method for aromatic co-production |
| CN101811927B (en) * | 2009-02-19 | 2013-03-06 | 中国石油化工股份有限公司 | Method for producing paraxylene |
| CN101830772B (en) * | 2009-03-09 | 2013-03-06 | 中国石油化工股份有限公司 | Combined method for producing p-xylene |
| CN101885661B (en) * | 2009-05-13 | 2013-09-18 | 中国石油化工股份有限公司 | Combination method for joint production of arene |
| CN101993332B (en) * | 2009-08-31 | 2013-06-19 | 中国石油化工股份有限公司 | Combined method for joint production of aromatic hydrocarbon |
| CN101993335B (en) * | 2009-08-31 | 2013-12-04 | 中国石油化工股份有限公司 | Combination method for increasing yield of p-xylene in aromatic hydrocarbon production |
| CN101993334B (en) * | 2009-08-31 | 2013-12-04 | 中国石油化工股份有限公司 | Method for increasing yield of p-xylene in aromatic hydrocarbon production |
| CN102040461B (en) * | 2009-10-13 | 2014-07-02 | 中国石油化工股份有限公司 | Combined method for increasing yield of paraxylene in production of aromatic hydrocarbons |
| CN112661588A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Method and system for increasing yield of p-xylene |
| CN114456035A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Aromatic hydrocarbon transalkylation method and system |
| TW202242079A (en) * | 2021-04-23 | 2022-11-01 | 大陸商中國石油化工科技開發有限公司 | Method for producing light aromatic hydrocarbons |
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