CN1340489A - Process for preparing p-xylene - Google Patents
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- CN1340489A CN1340489A CN 00119768 CN00119768A CN1340489A CN 1340489 A CN1340489 A CN 1340489A CN 00119768 CN00119768 CN 00119768 CN 00119768 A CN00119768 A CN 00119768A CN 1340489 A CN1340489 A CN 1340489A
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Abstract
A process for preparing P-xylene includes such steps as alkyl transfering reaction of benzene and C9 or higher arylhydrocarbon to obtain toluene and C8 arylhydrocarbon, selectively disproportionating toluene, adsorption separating C8 arylhydrocarbon, and isomerizing to obtain p-xylene. Its advantages are less by-product, and low requirement to raw materials.
Description
The present invention relates to be used to produce the method for p-Xylol.Specifically, be earlier by benzene (Ben) and carbon nine and above aromatic hydrocarbons (C thereof
9 +A) transalkylation reaction generates a large amount of toluene (Tol) and C8 aronmatic (C
8A), and then the selective disproportionation by toluene separate and C with molecular sieve adsorption
8The A isomerization technique, the method for producing p-Xylol.
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 (pX) 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 hydrocarbons (C thereof
9 +A) disproportionation and transalkylation reaction 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 carries out selective disproportionation generation benzene and high p-Xylol concentration on the ZSM-5 of modification catalyzer
8Therefore A only needs can isolate most highly purified 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.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, C
10 +The content of hydrocarbon (carbon ten and above hydrocarbon thereof) must strict control.In order to improve the economic benefit of device, cut down the consumption of energy and material consumption, people have carried out further research and optimization to Tatoray technology, mainly be devoted to its core technology---Study of Catalyst, improve the indicators of overall performance of catalyzer, as improving the molecular-weight average of weight space velocity, prolongation catalyst operation and increase aromatic hydrocarbons reaction raw materials.The raising of molecular-weight average helps increasing C
8A, but when the heavy aromatics too high levels, in order to keep certain transformation efficiency, promptly keep catalyst activity must cause the especially aggravation of hydro-dealkylation reaction of side reaction, thereby makes in the reaction product benzaldehyde product on the high side, causes product C
8A/Ben is on the low side, and the aromatic hydrocarbons loss is bigger, handles equal raw material, the C that obtains
8A is on the low side, the Ben amount is on the high side.And for Aromatic Hydrocarbon United Plant, the toluene disproportionation device is why indispensable to be because it can provide C
8The effect of A.Raising, the C of Ben amount
8The minimizing significant adverse of A amount is in whole Aromatic Hydrocarbon United Plant.These weak points have limited the development of this type of technology.
Document based on Tatoray technology has USP4341914, Chinese patent 98110859.8, USP2795629, USP3551510, Chinese patent 97106719.8 etc.Fig. 1 is the technical process of USP4341914.Wherein 1 is benzenol hydrorefining I, and 2 is the heavy aromatics tower, and 3 is reaction zone, and 4 is the benzene tower, and 5 is toluene tower, and 6 is benzenol hydrorefining II, and 7 is C
9A, 8 is C
8 +The A raw material, 9 and 10 is toluene, and 11 is benzene, and 12 and 13 is C
8A, 17 and 19 for being rich in C
10 +Hydrocarbon stream, 18 for being rich in C
9The A logistics.In this technology, though with the portion C in the reaction product
10A is with circulation C
9A returns reaction zone (logistics 18), the C that has partly utilized reaction itself to generate
10A comes to generate in the inhibited reaction process more substantial C
10 +Hydrocarbon, still, raw material C
8 +C among the A
10 +Hydrocarbon but can't obtain utilizing, and C
8 +Portion C in the A raw material
9A is with C
10 +Hydrocarbon is discharged out-of-bounds (logistics 19) at heavy aromatics Tata still.Because the restriction of catalyst performance, this technology also has exacting terms in the selection of raw material, require heavy aromatics tower (tower 2) cat head effluent---C
9Indane (IND) content in the A logistics (logistics 7) must be lower than below 1%, thereby has caused aforesaid C
9The loss of A and the C that just partly utilizes reaction self to generate
10A, and raw material C
8 +C among the A
10 +Hydrocarbon but can't obtain utilizing.
Fig. 2 is the technical process of Chinese patent 98110859.8.Wherein 1 is benzenol hydrorefining I, and 2 is the heavy aromatics tower, and 3 is reaction zone, and 4 is the benzene tower, and 5 is toluene tower, and 6 is benzenol hydrorefining II, and 7 is ortho-xylene column, and 8 is C
8 +The A raw material, 9 is fresh toluene, 12 and 13 is C
8A, 14 for being rich in C
9The A logistics, 15 is carbon 11 and above hydrocarbon (C thereof
11 +Hydrocarbon), 16 are circulation toluene, and 17 is benzene, and 19 is o-Xylol, and 20 for containing or do not contain the C of o-Xylol
9 +A.This technology has overcome many drawbacks of above-mentioned patent, has high indane content, high C in the raw material of permission
10 +Advantages such as hydrocarbon content, but still a large amount of benzene of by-product.
Summing up above each technology is not difficult to find out: these all patents, all be at a certain specific catalyst for toluene disproportionation and transalkylation a certain or some aspect, as forming, but always do not break through the restriction of original Tatoray technology thinking to doing on the separation scheme of the transalkylation ability of heavy aromatics or reaction product reasonably to change.Its common shortcoming is: utilizes toluene or toluene and carbon nine above aromatic hydrocarbons to produce C8 aronmatic and increases production p-Xylol, want by-product benzene inevitably, and, can not effectively utilize heavy aromatics.
Purpose of the present invention mainly is problems such as carbon ten and above heavy aromatics content thereof is low in a large amount of benzene of by-product, the raw material when solving the production p-Xylol that exists in the conventional art, the method that provides a kind of brand-new more economical being used to produce p-Xylol.This method is with benzene, toluene and C
8 +A is that raw material is produced p-Xylol.By selective disproportionation of toluene technology (being called for short SSTDP) unit is set, and transform original toluene disproportionation unit as aromatic hydrocarbons alkyl transfering process (abbreviate SAT P) unit, reduce production costs significantly, and since benzene also as producing the raw material of p-Xylol, for typical Aromatic Hydrocarbon United Plant, under the constant situation of reformer feed scale, make full use of existing appliance arrangement and technology, just can increase production p-Xylol significantly.
The objective of the invention is to realize by following technical scheme: a kind of method that is used to produce p-Xylol may further comprise the steps:
A). from the de-pentane oil that is rich in aromatic hydrocarbons of reformer unit through deheptanizer, benzenol hydrorefining II, extracting fractionation unit after, isolate benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics, wherein de-pentane oil is meant carbon six and above aromatic hydrocarbons and non-aromatic component;
B). the isolated toluene of extracting fractionation unit enters the selective disproportionation of toluene technique unit of platiniferous ZSM-5 molecular sieve catalyst, under hydro condition, carry out toluene selective disproportionation reaction, reaction back generates p-Xylol and benzene, and wherein the high purity p-Xylol product that obtains after Crystallization Separation of p-Xylol is discharged out-of-bounds;
C). the isolated benzene of extracting fractionation unit, the isolated carbon nine of benzenol hydrorefining II and above aromatic hydrocarbons thereof and enter aromatic hydrocarbons alkyl transfering process unit with the bismuth-containing macro-porous zeolite catalyst from the unitary part or all of benzene of selective disproportionation of toluene, under hydro condition, carry out the transalkylation reaction of aromatic hydrocarbons, generate toluene and C8 aronmatic, the toluene that generates enters the selective disproportionation of toluene technique unit, C8 aronmatic advances molecular sieve adsorption to be separated and the isomerization of C-8 aromatics unit, produces p-Xylol.
In technique scheme, the logistics of benzenol hydrorefining II cat head extraction C8 aronmatic, carbon nine and C10 aromartic logistics are rich in the line extraction of tower bottom side, extraction of tower still or not extraction carbon 11 and above hydrocarbon thereof; The reaction pressure of selective disproportionation of toluene technique unit reaction zone is 1～4MPa, and temperature of reaction is 300～480 ℃, and hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour-1; The raw material of selective disproportionation of toluene technique unit is for to be rich in the toluene logistics: the reaction pressure in aromatic hydrocarbons alkyl transfering process unit process district is 1～5MPa, temperature of reaction is 250～480 ℃, hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour-1; In the unitary reactor feed of aromatic hydrocarbons alkyl transfering process, by weight percentage, contain indane 0～5%, carbon ten and above hydrocarbon thereof are 0～20%.
Benzenol hydrorefining II tower still produced quantity described in the such scheme is means of control SATP technique unit raw material molecular-weight average.In the normal running, not extraction of tower still C
11 +Hydrocarbon is to increase production more pX; Have only when catalyzer be in the latter stage in operational cycle and be difficult to synchronous situation of factory's turnaround under, can be by the extraction portion C
11 +Hydrocarbon with the raw material molecular-weight average of reduction SATP technique unit, thereby reduces the severity that reacts, and makes the unitary operation of SATP not influence the turnaround plans of factory.
The reaction pressure in SSTDP selective disproportionation of toluene unit process district is 1～4MPa, and temperature of reaction is 300～480 ℃, and hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour
-1, in the raw material toluene, by weight percentage, toluene level is 90～100%
The reaction pressure in SATP unit process district is 1～5MPa, and temperature of reaction is 250～480 ℃, and hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour
-1In the unitary reactor feed of SATP, by weight percentage, contain indane 0～5%, carbon ten and above hydrocarbon thereof are 0～20%.
In the technology patent of the present invention, in the SATP unit, owing to use bismuthiferous macro-porous zeolite catalyst, under hydro condition, it is toluene and C that catalyzer has benzene and carbon nine above aromatic hydrocarbons transalkylations
8The function of A.After the toluene that SATP generates enters the selective disproportionation of toluene unit, under the effect of platiniferous ZSM-5 catalyzer, toluene selective disproportionation reaction taking place, generates the pX of benzene and high density.The benzene that generates is as the unitary raw material of SATP, and the pX of the high density of generation reclaims after a simple step or two-step crystallization separation and obtains most highly purified pX product, and by extraction out-of-bounds.Isolate the C behind the pX
8 +A enters the benzenol hydrorefining II of whole aromatic device or directly enters the fractionation by adsorption isomerization unit.Because this C
8 +PX concentration in the A logistics still is much higher than thermodynamic equilibrium value, has improved the C of benzenol hydrorefining II cat head extraction
8The concentration of pX among the A, thus the rate of recovery of the pX of pX adsorption unit improved effectively, reduced separation costs.The C that SATP generates
8A then enters fractionation by adsorption and isomerization unit is produced pX.
As can be seen, such operational path, make the aromatic hydrocarbons of carbon more than six all be transformed into the p-Xylol of high added value, after setting up a cover SSTDP device and original toluene disproportionation plant modification become the SATP device, function between fully perfect each device, increase production pX effectively, and reduced the running cost of device.Therefore patent technology of the present invention can be to greatest extent and is produced p-Xylol economically.
Fig. 3 is used to produce the selective disproportionation and the alkyl transfering process flow process of p-Xylol for the present invention.
I is a deheptanizer among the figure, and II is benzenol hydrorefining II, and III is the fractionation by adsorption isomerization unit, and IV is the SSTDP unit, and V is the SATP unit, and VI is the extracting fractionation unit.The de-pentane oil (carbon six and above hydrocarbon thereof) 4 of reformer unit depentanize Tata still extraction advances deheptanizer, and the logistics 5 of benzene and toluene is rich in the cat head extraction, the extracting fractionation unit of going forward side by side.Extraction is rich in C at the bottom of the deheptanizer tower
8 +Benzenol hydrorefining II is advanced in A logistics 6, the C of cat head extraction
8The fractionation by adsorption isomerization unit is advanced in A logistics 7, and C is rich in the line extraction of tower bottom side
9The SATP unit is entered in A logistics 8, tower still C
11 +Hydrocarbon 9 is by extraction or not extraction.Enter the C of fractionation by adsorption isomerization unit
8A is after processing, and non-aromatics (NA) 10 and p-Xylol product 11 by direct extraction out-of-bounds contain C
9Benzenol hydrorefining II and SSTDP unit are entered in the logistics 12 of A and toluene logistics 13 respectively.Toluene logistics 14 is carried out toluene selective disproportionation reaction after entering the SSTDP unit with toluene logistics 19 under hydro condition, the p-Xylol 16 that the non-aromatics 15 that reaction generates and separating obtains by extraction out-of-bounds, the C behind the separation pX
8 +A logistics 22 enters benzenol hydrorefining II or directly enters the fractionation by adsorption isomerization unit.The benzene logistics 17 that SSTDP generates and from the benzene logistics 18 of extracting fractionation unit, and from benzenol hydrorefining II tower bottom side line be rich in carbon nine, the SATP unit is entered in C10 aromartic logistics 8, carry out transalkylation reaction under hydro condition after, the toluene 19 that reaction generates enters the SSTDP unit, the C of generation
8The fractionation by adsorption isomerization unit is advanced in A logistics 20, and non-aromatics 21 extraction out-of-bounds.23 for the non-aromatics of extracting fractionation unit extraction.
Principal reaction involved in the technology of the present invention comprises:
(I) .SSTDP unit:
(II) .SATP unit:
In technology of the present invention, the unitary transalkylation reaction of SATP is different with traditional transalkylation notion, and it is with benzene and carbon nine and above aromatic hydrocarbons (C thereof
9 +A) be raw material, reaction generates toluene and C
8A, through simple fractionation, the toluene that obtains promptly can be used as the unitary raw material of SSTDP, and the C that obtains
8A enters the fractionation by adsorption isomerization unit, unreacted benzene and C
9 +The A circulation.Enter the SSTDP unit from the toluene of unitary toluene of SATP and extracting fractionation unit and carry out toluene selective disproportionation reaction, generate the dimethylbenzene of benzene and high p-Xylol concentration.The benzene that SSTDP generates enters the SATP unit, and the dimethylbenzene of the high pX concentration of generation is after simple Crystallization Separation reclaims most pX, and raffinate enters the benzenol hydrorefining II of whole aromatic device or directly advances the fractionation by adsorption isomerization unit, the C in the raffinate
9 +A has finally also entered the SATP unit.Because benzene and heavy aromatics be also as producing the raw material of p-Xylol, thereby under the constant situation of reformation scale, just can improve the throughput of p-Xylol significantly.
Technology patent of the present invention, owing to there is a cover SSTDP technique unit, this unit has the ability of the independent pX of production, therefore, factory can increase production pX and a large amount of high-quality nitration grade benzene of coproduction by outsourcing toluene.Also can co-production of high-quality benzene after satisfying the unitary benzene demand of SATP.Therefore, this patent not only has unique pX and expands the energy potentiality, and bigger handiness is arranged in the device product variation.
The invention will be further elaborated by the following examples.[embodiment 1～7]
Under the hydro condition, in fixed-bed reactor, carry out benzene and C
9 +A transalkylation reaction performance is investigated.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, the bismuthiferous macro-porous zeolite catalyst of filling 20 grams in the reactor.Aroamtic hydrocarbon raw material with after hydrogen mixes from top to bottom by beds, carry out benzene and C
9 +The transalkylation reaction of A generates toluene and C
8A.
Benzene and 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. benzene and C9 aromatic transalkylation reaction raw material and product compositional analysis (1～7)
| Embodiment | ????1 | ???2 | ????3 | ????4 | ???5 | ????6 | ????7 | |
| Catalyst activity main body * temperature of reaction, ℃ reaction pressure, the MPa weight space velocity, hour -1Hydrogen hydrocarbon molecule ratio, moles/mole | ????A ????325 ????1.5 ????0.8 ????3 | ?B ?365 ?1.5 ?1.3 ?2 | ??B ??440 ??4 ??4.5 ??8.5 | ??A ??460 ??4 ??6 ??10 | ?A ?410 ?2.5 ?3.5 ?5 | ??B ??420 ??3 ??3 ??6 | ??B ??380 ??3 ??2 ??6 | |
| Reaction raw materials is formed weight % | ????NA ????Ben ????Tol ????C 8A ????C 9A ????IND ????C 10 +The hydrocarbon ∑ | ????0.01 ????73.98 ????0.01 ????0.26 ????19.13 ????0.61 ????6.00 ????100.00 | ?0.01 ?73.98 ?0.01 ?0.26 ?19.13 ?0.61 ?6.00 ?100.00 | ??0.10 ??64.00 ??0.19 ??0.29 ??22.01 ??3.49 ??9.92 ??100.00 | ??0.10 ??64.00 ??0.19 ??0.29 ??22.01 ??3.49 ??9.92 ??100.00 | ?0.01 ?50.91 ?0.01 ?0.26 ?34.22 ?1.56 ?13.03 ?100.00 | ??0.01 ??50.91 ??0.01 ??0.26 ??34.22 ??1.56 ??13.03 ??100.00 | ??0.01 ??66.62 ??0.01 ??0.26 ??23.38 ??0.30 ??9.43 ??100.00 |
| Reaction product is formed weight % | ????NA ????Ben ????Tol ????C 8A ????C 9A ????C 10 +The hydrocarbon ∑ | ????2.51 ????49.57 ????25.72 ????13.11 ????5.86 ????3.23 ????100.00 | ?3.01 ?50.31 ?25.33 ?12.67 ?5.06 ?3.62 ?100.00 | ??4.01 ??40.48 ??27.91 ??14.96 ??6.21 ??6.43 ??100.00 | ??5.21 ??40.96 ??25.31 ??14.42 ??8.03 ??6.07 ??100.00 | ?6.09 ?30.52 ?29.05 ?17.43 ?9.57 ?7.34 ?100.00 | ??5.6 ??29.53 ??30.91 ??18.55 ??8.39 ??7.02 ??100.00 | ??2.94 ??39.30 ??30.01 ??16.21 ??5.76 ??5.78 ??100.00 |
Annotate: A represents the bismuth-containing mordenite; B represents bismuth-containing β zeolite.
From embodiment 1～7 as can be seen: benzene and C the raw material
9 +A has generated toluene and C after reacting
8A.[embodiment 8]
Under the hydro condition, on fixed-bed reactor, carry out toluene selective disproportionation reaction.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, filling 20 gram platiniferous ZSM-5 molecular sieve catalysts 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%, with MSTDP technology industrial application report data basically identical.[Comparative Examples 1]
With reformer de-pentane oil C in the typical Aromatic Hydrocarbon United Plant
6A～C
10 +The flow rate of hydrocarbon stream is basic data (seeing Table 3), investigates the ability that this patent is produced pX.
Table 3. reformation de-pentane oil aromatic hydrocarbons is formed and flow rate
| Form | ??Ben | ??Tol | ??C 8A | ??C 9A | ??C 10 +Hydrocarbon | ???∑ |
| Relative quantity *，W/T | ??44.4 | ??100.0 | ??132.6 | ??115.9 | ??24.9 | ??417.8 |
Annotate: with the Tol flow rate is that 100W/T is a benchmark.W/T is meant unit weight/unit time.
Form and flow rate (fresh feed) and embodiment 8 toluene selective disproportionation reaction results carry out computer Simulation according to the aromatic hydrocarbons in aforesaid this patent technical process and the table 3, unitary material charging of SSTDP and SATP and extraction data are listed in table 4.
In this patent technology, when fresh feed amount (aromatic hydrocarbons in the reformation de-pentane oil) is 417.8W/T (seeing Table 3), the produced quantity of SSTDP p-Xylol is 117.4W/T, enters the C of fractionation by adsorption isomerization unit
8The A total amount is:
132.6+20.4+109.9＝262.9(W/T)
As calculated, the molar ratio of the fresh feed aromatic hydrocarbons (the aromatic hydrocarbons amount that promptly reacts away) that whole device is total and total extraction aromatic hydrocarbons is 1.13, the molar ratio of the aromatic hydrocarbons of SATP unit fresh feed and extraction aromatic hydrocarbons is 1.10, do not have aromatization process in the reaction, computer is rational to the turnover situation simulation of each supplies of unit in this patent technical process.
262.9 C (W/T)
8The amount that A enters each product that generates behind the fractionation by adsorption isomerization unit sees Table 5.
Table 4. this patent process stream equilibrium criterion
| Component | The reformation de-pentane oil | The SSTDP unit | The SATP unit | |
| Fresh feed W/T | ??NA | ????/ | ????/ | ????/ |
| ??Ben | ????44.4 | ????/ | ????186.3 | |
| ??Tol | ????100.0 | ????303.5 | ????/ | |
| ??C 9A * | ????115.9 | ????/ | ????122.2 | |
| ??C 10 +A | ????24.9 | ????/ | ????24.9 | |
| ??∑ | ????285.2 | ????303.5 | ????333.4 | |
| Product extraction W/T | ??NA | ????/ | ????17.6 | ????20.0 |
| ??Ben | ????/ | ????141.9 | ||
| ??Tol | ????/ | ????/ | ????203.5 | |
| ??pX | ???132.6 | ????117.4 | ????109.9 | |
| ??C 8A * | ????20.4 | |||
| ??C 9A | ????/ | ????6.3 | ????/ | |
| ??C 10 +A | ????/ | ????/ | ????/ | |
| ??∑ | ???132.6 | ????303.6 | ????333.4 | |
Annotate: a small amount of indane has been included into C
9Among the A, C
8A
*Be meant other C except pX
8A.
Table 5.C
8Each product amount that A changes into
*(unit: W/T)
| Component | ????NA | ????pX | ???Tol | ????C 9 +A | Add up to |
| Output | ????23.7 | ????226.1 | ????2.6 | ????10.5 | ??262.9 |
Annotate: C
8A is when the final extraction pX of fractionation by adsorption and isomerization, and by weight percentage, the yield of pX is 86%,
The yield of non-aromatics (NA) is 9%, and the yield of toluene is 1% and C
9 +The yield of A is 4%; Below identical.
Therefore, react away each aroamtic hydrocarbon raw material in the table 3, this patent can generate pX:
226.1+117.4＝343.5(W/T)
And also have the toluene of 2.6W/T and the C of 10.5W/T
9 +A can be used to produce pX (seeing Table 5).
On this basis, carried out a series of laboratory test work, the simulated data of the experimental data among the embodiment 7 that obtains and unitary fresh feed of SATP and product extraction is coincide.
In sum, react away the listed aroamtic hydrocarbon raw material of table 3, it is 343.5W/T that technology of the present invention can be produced pX.[Comparative Examples 2]
Still with typical Aromatic Hydrocarbon United Plant reformation de-pentane oil C in the table 3
6A～C
10 +The flow rate of A logistics is a basic data, investigates the ability that traditional Aromatic Hydrocarbon United Plant that contains toluene disproportionation and transalkylation (abbreviation toluene disproportionation) technique unit is produced pX.Concrete material data sees the following form 6.
Table 6. adopts the Aromatic Hydrocarbon United Plant of toluene disproportionation process to produce the amount (unit: W/T) of pX
| Component | Fresh feed | Processing mode | The extraction of processing mode I product | The extraction of processing mode II product | The extraction of processing mode III product * | The extraction of machinery product |
| ??NA | ????/ | ????/ | ????/ | ????11.9 | ????23.6 | ??35.5 |
| ??Ben | ??44.4 | Extraction is (I) out-of-bounds | ????44.4 | ????/ | ????45.8 | ??90.2 |
| ??PX | ????/ | ????/ | ????/ | ????114.0 | ????130.1 | ??244.1 |
| ??C 8A | ??132.6 | Go fractionation by adsorption and isomerization (II) | ????/ | ????/ | ????/ | ????/ |
| ??Tol | ??100.0 | Carry out typical toluene disproportionation process (III) | ????/ | ????1.3 | ????1.5 | ??2.8 |
| ??C 9A | ??115.9 | ????/ | ????5.3 | ????6.0 | ??11.3 | |
| ??C 10 +A | ??24.9 | Extraction is (I) out-of-bounds | ????24.9 | ????/ | ????8.9 | ??33.8 |
| ??∑ | ??417.8 | ????/ | ????69.3 | ????132.5 | ????215.9 | ??417.7 |
Annotate: the C that * toluene disproportionation and transalkylation generate
8A is calculated to be pX and other aromatic hydrocarbons by processing mode II;
" fresh feed " expression is from each aromatic component flow rate in the upstream reformation de-pentane oil in the last table; " processing mode " represents the processing mode of each component; The finished product amount that " extraction of machinery product " expression fresh feed obtains after treatment.Wherein, the method for calculation of processing mode II are consistent with table 5, when processing mode III promptly carries out traditional toluene disproportionation and alkyl transfering process, non-aromatic yield is 4.62%, the yield of benzene is 21.21%, and the yield of C8 aronmatic is 70.05%, and the yield of carbon ten is 4.12%.
The toluene of the 2.8W/T that generates and the carbon nine of 11.3W/T can be converted into the p-Xylol of 8.5W/T at most, and promptly the maximum yield through typical toluene disproportionation and alkyl transfering process p-Xylol is:
244.1+8.5＝252.6W/T。
By as seen above-mentioned, problems such as carbon ten and above heavy aromatics content thereof is low in a large amount of benzene of by-product, raw material when patent of the present invention has overcome the production p-Xylol that exists in the conventional art, the method that provides a kind of brand-new more economical being used to produce p-Xylol.And, because benzene is also as producing the raw material of p-Xylol,, under the constant situation of reformer feed scale, make full use of existing appliance arrangement and technology for typical Aromatic Hydrocarbon United Plant, just can increase production p-Xylol significantly.By Comparative Examples 1 and 2 as seen, this patent technology is compared with alkyl transfering process with typical toluene disproportionation, and p-Xylol can increase production 36%.
Claims (6)
1, a kind of method that is used to produce p-Xylol may further comprise the steps:
A). from the de-pentane oil that is rich in aromatic hydrocarbons of reformer unit through deheptanizer, benzenol hydrorefining II, extracting fractionation unit after, isolate benzene, toluene, C8 aronmatic, carbon nine and above aromatic hydrocarbons and non-aromatics, wherein de-pentane oil is meant carbon six and above aromatic hydrocarbons and non-aromatic component;
B). the isolated toluene of extracting fractionation unit enters the selective disproportionation of toluene technique unit of platiniferous ZSM-5 molecular sieve catalyst, under hydro condition, carry out toluene selective disproportionation reaction, reaction back generates p-Xylol and benzene, and wherein the high purity p-Xylol product that obtains after Crystallization Separation of p-Xylol is discharged out-of-bounds;
C). the isolated benzene of extracting fractionation unit, the isolated carbon nine of benzenol hydrorefining II and above aromatic hydrocarbons thereof and enter aromatic hydrocarbons alkyl transfering process unit with the bismuth-containing macro-porous zeolite catalyst from the unitary part or all of benzene of selective disproportionation of toluene, under hydro condition, carry out the transalkylation reaction of aromatic hydrocarbons, generate toluene and C8 aronmatic, the toluene that generates enters the selective disproportionation of toluene technique unit, C8 aronmatic advances molecular sieve adsorption to be separated and the isomerization of C-8 aromatics unit, produces p-Xylol.
2, according to the described method that is used to produce p-Xylol of claim 1, it is characterized in that the logistics of benzenol hydrorefining II cat head extraction C8 aronmatic, carbon nine and C10 aromartic logistics are rich in the line extraction of tower bottom side, extraction of tower still or not extraction carbon 11 and above hydrocarbon thereof;
3, according to the described method that is used to produce p-Xylol of claim 1, the reaction pressure that it is characterized in that selective disproportionation of toluene technique unit reaction zone is 1～4MPa, temperature of reaction is 300～480 ℃, and hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour
-1
4, according to the described method that is used to produce p-Xylol of claim 1, the raw material that it is characterized in that the selective disproportionation of toluene technique unit is for being rich in the toluene logistics;
5, according to the described method that is used to produce p-Xylol of claim 1, the reaction pressure that it is characterized in that aromatic hydrocarbons alkyl transfering process unit process district is 1～5MPa, temperature of reaction is 250～480 ℃, and hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour
-1
6, according to the described method that is used to produce p-Xylol of claim 1, it is characterized in that by weight percentage, containing indane 0～5% in the unitary reactor feed of aromatic hydrocarbons alkyl transfering process, carbon ten and above hydrocarbon thereof are 0～20%.
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| EP1447395A1 (en) * | 2001-10-22 | 2004-08-18 | China Petroleum & Chemical Corporation | THE SELECTIVE DISMUTATION PROCESS OF TOLUENE AND THE DISMUTATION AND TRANSALKYLATION PROCESS OF TOLUENE AND AROMATIC HYDROCARBONS OF C9 AND C9&plus |
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