CN1340490A - Selective disproportionation and alkyl transfer process for preparing p-xylene - Google Patents

Abstract

A process for preparing p-xylene by selective disproportionating and alkyl transferring reaction includes alkyl transferring reaction of benzene and C8 or higher arylhydrocarbon to obtain toluene, selective disproportionating reaction to obtain benzene and p-xylene, and cyclic use of benzene in the said alkyl transferring reaction. Its advantages are little by-products and low requirement to raw materials.

Description

Be used to produce the selective disproportionation and the transalkylation method of p-Xylol

The present invention relates to be used to produce the selective disproportionation and the transalkylation method of p-Xylol (pX).Specifically earlier by benzene (Ben) and carbon eight and above aromatic hydrocarbons (C thereof ₈ ⁺A) transalkylation reaction generates a large amount of toluene, and then the selective disproportionation by toluene, 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 production method is that the dimethylbenzene that contains ethylbenzene of the thermodynamic(al)equilibrium that generates from the petroleum naphtha catalytic reforming is C8 aronmatic (C ₈A) separate or molecular sieve simulated moving bed adsorption separation (abbreviation fractionation by adsorption) technology by multistage cryogenic crystallization in, 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 of the nineties later stage 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.

The objective of the invention is to exist in the document when producing p-Xylol in order to overcome in the past, a large amount of benzene of by-product and heavy aromatics, reaction raw materials require harshness and complete assembly that problems such as the fractionation by adsorption of p-Xylol and isomerization of C-8 aromatics device must be arranged, and provide a kind of new more economical being used to produce the selective disproportionation and the transalkylation method of p-Xylol.It is unrestricted that this method has ingredient requirement, with benzene, toluene and C ₈ ⁺A is that raw material is produced p-Xylol, can save the adsorption separation device and the isomerization unit of p-Xylol, 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, just can increase production p-Xylol significantly.

The objective of the invention is to realize by following technical scheme: a kind of selective disproportionation and transalkylation 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, extracting fractionation unit after, isolate benzene, toluene and carbon eight 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 selective disproportionation of toluene technique unit that the isolated toluene of extracting fractionation unit enters platiniferous ZSM-5 molecular sieve catalyst carries out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene that is rich in p-Xylol, the C8 aronmatic that is rich in p-Xylol that generates obtains highly purified p-Xylol product and discharges out-of-bounds after Crystallization Separation, the benzene of generation and the carbon after the separating paraxylene eight and above aromatic hydrocarbons raffinate thereof enter aromatic hydrocarbons alkyl transfering process unit;

C). the isolated benzene of extracting fractionation unit, the isolated carbon eight of deheptanizer and above aromatic hydrocarbons thereof and to enter with the bismuth-containing large pore zeolite from the carbon eight after unitary part or all of benzene of selective disproportionation of toluene and the separating paraxylene and above aromatic hydrocarbons raffinate thereof be the aromatic hydrocarbons alkyl transfering process unit of catalyzer, carry out the aromatic hydrocarbons transalkylation reaction and generate toluene under hydro condition, the toluene of generation enters the selective disproportionation of toluene technique unit.

In technique scheme, benzene and toluene logistics are rich in the extraction of deheptanizer cat head, and carbon eight, carbon nine and C10 aromartic logistics are rich in the line extraction of tower bottom side, and carbon 11 and above hydrocarbon thereof are discharged or do not discharged to the tower still; During selective disproportionation of toluene unit production high purity p-Xylol, the purification of p-Xylol is to separate by a step or two-step crystallization to obtain; Selective disproportionation of toluene technique unit reaction zone pressure 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 ^-1The raw material of selective disproportionation of toluene technique unit is for being rich in the toluene logistics; The reaction pressure in aromatic hydrocarbons alkyl transfering process 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 aromatic hydrocarbons alkyl transfering process, by weight percentage, contain indane 0～5%, carbon ten and above hydrocarbon thereof are 0～20%.

Deheptanizer tower still produced quantity described in the technique scheme is means of control aromatic hydrocarbons alkyl transfering process (abbreviate SAT P) 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 satisfy factory's turnaround plans arrangement.

In the patent technology of the present invention, in the SATP unit, owing to use bismuthiferous macro-porous zeolite catalyst, under hydro condition, catalyzer has the function that benzene and carbon eight and above aromatic hydrocarbons thereof is generated toluene by transalkylation reaction, therefore a whole set of technology can make full use of raw material, and farthest generates the required methylbenzene raw material of toluene selective disproportionation reaction.After the toluene that generates enters the selective disproportionation of toluene unit, under the effect of platiniferous ZSM-5 catalyzer, toluene selective disproportionation reaction takes place, highly selective changes p-Xylol into, and the benzene of coproduction is then as the unitary raw material of SATP.Such operational path makes the aromatic hydrocarbons of carbon more than six all be transformed into the p-Xylol of high added value, and therefore patent technology of the present invention can be increased production p-Xylol significantly.Because toluene disproportionation process is a selective disproportionation reaction, the dimethylbenzene that reaction generates is almost pure p-Xylol, therefore can save the adsorption separation device and the C of p-Xylol ₈The A isomerization unit only needs simply to go out highly purified p-Xylol once step or two step freezing and crystallizings are separable.

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, II is selective disproportionation of toluene technology (being called for short SSTDP) unit, III is the SATP unit, IV is the extracting fractionation unit, 4 is carbon six and above aromatic hydrocarbons and the non-aromatic component behind the depentanize, 5 is the logistics that is rich in benzene and toluene of extracting from the deheptanizer cat head, and 6 is the C that extracts out from deheptanizer tower still ₁₁ ⁺Hydrocarbon, 7 are the C that is rich in from the line extraction of tower bottom side ₈ ⁺The A logistics, 8 toluene logistics for SATP unit process generation, 9 is from SSTDP unit extraction p-Xylol out-of-bounds, 10 is from SSTDP unit extraction non-aromatics (NA) out-of-bounds, 11 and 12 are respectively toluene and the benzene from the extracting fractionation unit, 13 is from the unitary benzene logistics of SSTDP, and 14 for from the unitary C that isolates behind the pX of SSTDP ₈ ⁺A, 15 is from SATP unit extraction NA out-of-bounds, 16 is the NA from the extraction of extracting fractionation unit.

Involved main reaction comprises in the patent technology of the present invention:

(I) .SSTDP unit:

(II) .SATP unit:

In patent technology of the present invention, the unitary transalkylation reaction of SATP is different with traditional transalkylation notion, and it is with benzene and C ₈ ⁺A is a raw material, and reaction generates toluene, and through simple fractionation, the toluene that obtains promptly can be used as the unitary raw material of SSTDP, unreacted benzene and C ₈ ⁺The A circulation.Toluene from unitary toluene of SATP and extracting fractionation unit enters the C that the SSTDP unit carries out toluene selective disproportionation reaction generation benzene and high p-Xylol concentration ₈A.

Patent technology of the present invention is being produced in the middle of the process of pX, has saved that all produce tripping device (multistage cryogenic crystallization separates or adsorption separation device) and the isomerization unit of the pX that must establish in pX machinery in the past.Why this patent technology can accomplish this point, is that the ingenious collocation and the reasonable combination of the catalyzer by two excellent performances realizes fully: will to enter all kinds of feedstock conversion of this technique unit effectively be toluene to employed catalyzer in the SATP unit; And the toluene selective disproportionation reaction that the SSTDP unit carries out generates the p-Xylol of high density, thereby there is no need to be provided with again isomerization unit, and, also there is no need to be set to obtain highly purified p-Xylol required multistage cryogenic crystallization or adsorption separation device.This has not only greatly reduced the one-time construction investment cost of device, but also has saved regular job expenses such as operation a large amount of general facilitiess that isomerization unit and multistage cryogenic crystallization or adsorption separation device consumed and manpower.And the most important thing is, 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.

Patent technology 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 1～8]

Carry out benzene and be rich in C with fixed-bed reactor ₈ ⁺The raw material of A carries out the transalkylation reaction performance and investigates.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 bismuthiferous β zeolite of gram or mordenite catalysts in the reactor.Aroamtic hydrocarbon raw material (benzene and C ₈ ⁺A) with after hydrogen mixes pass through beds from top to bottom, carry out benzene and C ₈ ⁺The transalkylation reaction of A generates the arene stream that is rich in toluene.

Benzene and C in the raw material ₈ ⁺A derives from petrochemical complex Aromatic Hydrocarbon United Plant, H ₂Be electrolysis hydrogen, through dehydrating processing, reaction result is listed in the table 1.

Embodiment 1～7 explanation, bismuthiferous β zeolite or mordenite catalyst have excellent transalkylation function.In the presence of this catalyzer, with benzene and C ₈ ⁺A is a raw material, can carry out transalkylation reaction, generates toluene.

Table 1. transalkylation reaction raw material and product compositional analysis (1～8)

Embodiment		????1	????2	????3	????4	????5	????6	????7	????8
										The catalyst activity body temperature, ℃ pressure, the MPa air speed, hour -1Hydrogen-hydrocarbon ratio, moles/mole		??A *(1)??450 ??1.0 ??5.0 ??9.0	??B *(2)??420 ??3.0 ??3.0 ??4.0	??A ??355 ??5.0 ??1.5 ??10	??B ??380 ??2.0 ??1.6 ??6.0	??A ??320 ??3.0 ??0.8 ??3.0	????B ????400 ????4.0 ????2.0 ????1.5	????A ????365 ????3.0 ????1.5 ????5.0	????A ????375 ????3.0 ????1.6 ????5.0
Feed composition ' weight %	????NA ????Ben ????Tol ????C 8A ????C 9A ????IND ????C 10 +A adds up to	????????0.01 ????????42.23 ????????0.22 ????????37.99 ????????13.84 ????????3.18 ????????2.53 ????????100.00		???????0.01 ???????46.99 ???????0.21 ???????32.30 ???????14.32 ???????1.16 ???????5.01 ???????100.00		????????0.01 ????????50.95 ????????0.49 ????????25.63 ????????20.36 ????????0.43 ????????2.13 ????????100.00		??0.01 ??55.75 ??0.23 ??25.77 ??14.35 ??0.16 ??3.73 ??100.00	??0.01 ??55.87 ??0.23 ??27.75 ??12.85 ??0.16 ??3.13 ??100.00
										Product is formed ' weight %	????NA ????Ben ????Tol ????C 8A ????C 9A ????IND ????C 10 +A adds up to	??3.15 ??26.11 ??36.78 ??24.00 ??7.62 ??0.04 ??2.30 ??100.00	??3.05 ??26.63 ??35.60 ??24.49 ??7.93 ??0.05 ??2.25 ??100.00	??3.23 ??28.13 ??38.97 ??20.47 ??7.01 ??0.04 ??2.15 ??100.00	??3.15 ??27.89 ??37.69 ??21.19 ??7.56 ??0.04 ??2.48 ?100.00	?2.98 ?30.91 ?37.73 ?16.23 ?9.85 ?0.04 ?2.36 ?100.00	??2.89 ??31.26 ??38.37 ??15.48 ??9.69 ??0.05 ??2.26 ??100.00	??2.87 ??32.75 ??39.33 ??16.22 ??6.54 ??0.05 ??2.24 ??100.00	??3.01 ??33.52 ??38.10 ??17.48 ??5.91 ??0.01 ??1.97 ??100.00

Annotate: A represents bismuthiferous β zeolite; B represents bismuthiferous mordenite.[embodiment 9]

Carry out toluene selective disproportionation reaction with 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, 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 arene stream that is rich in benzene and p-Xylol.

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 ^*Expression other C8 aronmatic except that pX.

PX is at C ₈Weight percentage among the A is 89%, with MSTDP technology industrial application report data basically identical.[Comparative Examples 1]

With reformation de-pentane oil C in the typical Aromatic Hydrocarbon United Plant ₆A～C ₁₀ ⁺The flow rate of hydrocarbon stream is a basic data, investigates the ability that this patent is produced pX.

The composition that below is aromatic hydrocarbons in the typical reformer de-pentane oil distributes, and is 100 unit weights (W)/unit time (T) with the toluene flow rate relatively, and other component and flow rate see Table 3.

Table 3. reformation de-pentane oil aromatic hydrocarbons is formed and flow rate

Component	??Ben	??Tol	??C 8A	??C 9A	??C 10 +Hydrocarbon	???∑
							Form W/T	??44.4	??100.0	??132.6	??115.9	??24.9	?417.8

According to aforesaid this patent technical process and above-mentioned fresh feed situation, and toluene selective disproportionation reaction result among the embodiment 9, carry out computer Simulation, the material charging and the extraction situation of SSTDP unit, SATP unit and patent technology of the present invention see Table 4.

Be in this patent technology, when the fresh feed amount is 417.7W/T, the produced quantity of p-Xylol is 313.6W/T, and the molar ratio of the aromatic hydrocarbons of fresh feed and extraction aromatic hydrocarbons is 1.37, the molar ratio of the aromatic hydrocarbons of SATP unit feed and extraction aromatic hydrocarbons is 1.09, do not have aromatization process in the reaction, computer is rational to the turnover digital simulation of each supplies of unit in this patent technical process.

Table 4. this patent process stream is accounted

Component		Patent technology	The SSTDP unit	The SATP unit
					Fresh feed, W/T	??Ben ??Tol ??C 8A ??C 9A *??C 10 +The hydrocarbon ∑	????44.4 ????100.0 ????132.6 ????115.9 ????24.9 ????417.8	????/ ????825.3 ????/ ????/ ????/ ????825.3	????426.8 ????/ ????195.8 ????132.4 ????24.9 ????779.9
The product extraction, W/T	??NA ??Ben ??Tol ??PX ??C 8A *??C 9A ??C 10 +The hydrocarbon ∑	????104.2 ??????/ ??????/ ????313.6 ??????/ ??????/ ??????/ ????417.8	????49.5 ????382.4 ????/ ????313.6 ????63.3 ????16.5 ????/ ????825.3	????54.6 ????/ ????725.8 ????/ ????/ ????/ ????/ ????780.4

* annotate: IND has been included into C ₉Among the A, C ₈A is meant other C8 aronmatic except pX.

On this basis, carried out a series of laboratory test work, the simulated data of the experimental data among the embodiment 8 that obtains and unitary fresh feed of SATP and product extraction (i.e. data in the table 4) is coincide.Therefore can think that computer simulation results is accurately.

In sum, react away the listed aroamtic hydrocarbon raw material of table 3, it is 313.6W/T that technology of the present invention can generate pX.[Comparative Examples 2]

Still with reformation de-pentane oil C in the above-mentioned typical Aromatic Hydrocarbon United Plant ₆A～C ₁₀ ⁺The flow rate of hydrocarbon stream is basic data (table 3 data), investigates traditional ability that contains toluene disproportionation and the unitary Aromatic Hydrocarbon United Plant production of alkyl transfering process pX.Concrete material balance data sees the following form 5.

Table 5. adopts the Aromatic Hydrocarbon United Plant material balance data (W/T of unit) of toluene disproportionation process

Component	Fresh feed	Processing mode	The extraction of processing mode I product	The extraction of processing mode II product	Processing mode III *The product extraction	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 +Hydrocarbon	??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 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 flow rate that " extraction of machinery product " expression fresh feed obtains after treatment.Wherein, the method for calculation of processing mode II: C ₈A is when the final extraction pX of fractionation by adsorption and isomerization, and by weight percentage, the yield of pX is 86%, and the yield of NA is 9%, and the yield of toluene is 1% and C ₉ ⁺The yield of A is 4%; When processing mode III promptly carried out traditional toluene disproportionation and alkyl transfering process, non-aromatic yield was 4.62%, and the yield of benzene is 21.21%, and the yield of C8 aronmatic is 70.05%, and the yield of carbon ten and above hydrocarbon thereof 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 252.6W/T.

Therefore, patent of the present invention had overcome in the past and to have existed when producing p-Xylol in the document, a large amount of benzene of by-product and heavy aromatics, reaction raw materials require harshness and complete assembly that problems such as the fractionation by adsorption of p-Xylol and isomerization of C-8 aromatics device must be arranged, and provide a kind of new more economical being used to produce the selective disproportionation and the transalkylation method of p-Xylol.It is unrestricted that this method has ingredient requirement, with benzene, toluene and C ₈ ⁺A is that raw material is produced p-Xylol, and because SATP unit and SSTDP unit are integrated together, can save the adsorption separation device and the isomerization unit of p-Xylol, reduces production costs significantly.Simultaneously, because benzene is also as producing the raw material of p-Xylol,, under the constant situation of reformer feed scale, just can increase production p-Xylol significantly for typical Aromatic Hydrocarbon United Plant.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 24%.

Claims (7)

1. a selective disproportionation and transalkylation 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, extracting fractionation unit after, isolate benzene, toluene and carbon eight 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 selective disproportionation of toluene technique unit that the isolated toluene of extracting fractionation unit enters platiniferous ZSM-5 molecular sieve catalyst carries out toluene selective disproportionation reaction, the reaction back generates C8 aronmatic and the benzene that is rich in p-Xylol, the C8 aronmatic that is rich in p-Xylol that generates obtains highly purified p-Xylol product and discharges out-of-bounds after Crystallization Separation, the benzene of generation and the carbon after the separating paraxylene eight and above aromatic hydrocarbons raffinate thereof enter aromatic hydrocarbons alkyl transfering process unit;

C). the isolated benzene of extracting fractionation unit, the isolated carbon eight of deheptanizer and above aromatic hydrocarbons thereof and to enter with the bismuth-containing large pore zeolite from the carbon eight after unitary part or all of benzene of selective disproportionation of toluene and the separating paraxylene and above aromatic hydrocarbons raffinate thereof be the aromatic hydrocarbons alkyl transfering process unit of catalyzer, carry out the aromatic hydrocarbons transalkylation reaction and generate toluene under hydro condition, the toluene of generation enters the selective disproportionation of toluene technique unit.

2. according to described selective disproportionation and the transalkylation method that is used to produce p-Xylol of claim 1, it is characterized in that the extraction of deheptanizer cat head is rich in benzene and toluene logistics, carbon eight, carbon nine and C10 aromartic logistics are rich in the line extraction of tower bottom side, and carbon 11 and above hydrocarbon thereof are discharged or do not discharged to the tower still;

3. according to described selective disproportionation and the transalkylation method that is used to produce p-Xylol of claim 1, when it is characterized in that selective disproportionation of toluene unit production high purity p-Xylol, the purification of p-Xylol is to separate by a step or two-step crystallization to obtain;

4. according to described selective disproportionation and the transalkylation method that is used to produce p-Xylol of claim 1, it is characterized in that selective disproportionation of toluene technique unit reaction zone pressure is 1～4MPa, temperature of reaction is 300～480 ℃, hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour ^-1

5. according to described selective disproportionation and the transalkylation 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;

6. according to described selective disproportionation and the transalkylation 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 ℃, hydrogen-hydrocarbon ratio is 0.5～10 moles/mole, and weight space velocity is 0.8～8 hour ^-1

7. according to described selective disproportionation and the transalkylation method that is used to produce p-Xylol of claim 1, it is characterized in that 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%.