CN1193967C - Benzene and C9 and more than that arene transalkylation method - Google Patents
Benzene and C9 and more than that arene transalkylation method Download PDFInfo
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- CN1193967C CN1193967C CNB021110042A CN02111004A CN1193967C CN 1193967 C CN1193967 C CN 1193967C CN B021110042 A CNB021110042 A CN B021110042A CN 02111004 A CN02111004 A CN 02111004A CN 1193967 C CN1193967 C CN 1193967C
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Abstract
The present invention relates to a method for the transalkylation of benzene and C9 and C9+ arenes, which mainly solves the problem of no method for the transalkylation of benzene and C9 and C9+ arenes or no method for converting C10 and C9+ arenes into useful toluene and C8 arenes in the prior art. The present invention has the technical scheme that benzene and C9 and C9+ arenes are adopted as raw reaction materials, a composition of zeolite with the silica alumina ratio of 3 to 500 and aluminum oxide is used as a catalyst in a fixed bed reactor and under the condition of hydrogenation, and the zeolite is loaded with metal molybdenum and/or an oxide thereof, at least one metal selected from iron, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium and silver and/or an oxide thereof added in a non-compulsory mode; under the technological conditions that reaction temperature is from 300 to 600 DEG C, pressure is from 1.0 to 6.0MPa, the molar ratio of hydrogen to arenes is 1 to 15 and weight hourly space velocity (WHSV) is from 0.5 to 5.0/h, toluene and C8 arenes are produced by the reaction. The benzene and the C9 and C9+ arenes are effectively converted into toluene and C8 arenes; the present invention has the characteristics of high catalyst activity, high stability, and high selectivity of target products. The method can be applied to the industrial production of arenes.
Description
Technical field
The present invention relates to benzene and carbon nine and above arene transalkylation method thereof.Specifically, be by benzene (Ben) and carbon nine and above aromatic hydrocarbons (C thereof
9 +A) transalkylation reaction generates toluene (Tol) and C8 aronmatic (C
8A), supply with selective disproportionation of toluene unit and C
8The A isomerization unit is used to increase production p-Xylol.
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 (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 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.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 aromatic hydrocarbons thereof) must strict control.Document based on Tatoray technology has USP4341914, Chinese patent 98110859.8, USP2795629, USP3551510, Chinese patent 97106719.8 etc.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.
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: utilize toluene or toluene and carbon nine above aromatic hydrocarbons to produce C8 aronmatic and increase production p-Xylol, want by-product benzene inevitably, and can not effectively utilize heavy arene.
Traditional arene transalkylation catalyst and technology mainly are with toluene and C
9 +A is that raw material is produced benzene and dimethylbenzene, and a large amount of benzene that generate often belong to the product of slack market.
Methylbenzene shape selective disproportionation is produced the catalyzer and the technology of p-Xylol, because can not utilize C
9 +A can only have stronger competitive power in limited range.
Hydro-dealkylation technology can be from C
9 +A obtains benzene,toluene,xylene, generates side reactions such as many rings or fused ring compound but the aromatic hydrocarbons condensation takes place easily, and temperature of reaction is high more, and side reaction is big more, the macromole condensation product the more, the catalyzer coking also the more, catalyst activity reduction must heal soon.
The legislation of various countries aspect environment is strict day by day, and particularly the content of aromatics will have to reduce gradually in the gasoline, and like this, the oil company, various countries will have to consider to extract out unnecessary benzene to meet environmental legislation.Along with the oil company, various countries carries out ethylene unit capacity expansion revamping engineering energetically, also will get more and more as the benzene of by product.Though benzene occupies very important effect in petrochemical industry, be the basic raw material of synthesizing styrene, phenols and Maleic Acid, Anhydrous etc., these fields are difficult to increase to the demand of benzene from now on.Therefore, be necessary for benzene and open up a new market, seek new Application Areas.
Relate to benzene and C at present
9 +The document of transalkylation reaction seldom between the A.Japanese Patent JP10158201 has introduced a kind of technology, and its purpose is by benzene or toluene to make polyalkylbenzene with the transalkylation between many alkyl aromatic compounds.The catalyzer that this patent is used is a kind of without metal-modified Hydrogen DGA zeolite, does not have the report of and catalyst stability not metal-modified about this kind zeolite.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the above-mentioned document to exist not relate to benzene and carbon nine and above arene transalkylation method thereof or do not relate to the problem that carbon ten and above heavy aromatics thereof can be changed into useful toluene and C8 aronmatic, providing a kind of is reaction raw materials with benzene and carbon nine and above aromatic hydrocarbons thereof, produce toluene and a spot of C8 aronmatic of coproduction, thereby can be selective disproportionation unit supply toluene, be aromatics isomerization unit supply C8 aronmatic, by the aromatic hydrocarbons transalkylation, the unitary acting in conjunction of selective disproportionation of toluene and aromatics isomerization reaches that to make full use of benzene and carbon nine and above aromatic hydrocarbons thereof be the purpose that raw material increases production p-Xylol (pX).Benzene provided by the invention in addition and carbon nine and above arene transalkylation method thereof have the processing condition, activity of such catalysts height, good stability of suitable broad, the characteristics that target product selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of benzene and carbon nine and above arene transalkylation method thereof, with benzene and carbon nine and above aromatic hydrocarbons thereof is that reaction raw materials carries out transalkylation reaction, generates toluene and C8 aronmatic, and its reaction conditions is:
A) under hydro condition, benzene feedstock and carbon nine and above aromatic hydrocarbons thereof fix bed bioreactor by gas-solid and contact with catalyzer, the weight ratio of benzene and carbon nine and above aromatic hydrocarbons thereof is 10～90: 90～10, temperature of reaction is 300～600 ℃, reaction pressure is 1.0～6.0MPa, and raw material aromatic hydrocarbons weight space velocity WHSV is 0.5～5.0 hour
-1, H
2/ hydrocarbon mol ratio is 1～15;
B) used catalyzer contains 10～90 parts in Hydrogen zeolite, the SiO of zeolite in parts by weight
2/ Al
2O
3Mol ratio is 3～500, and the metal of load molybdenum on zeolite is or/and 0.01～20 part of oxide compound, and the binding agent aluminum oxide is 10～90 parts in catalyzer.
The parts by weight preferable range of the metal of molybdenum and/or metal oxide is 0.1～10.0 part in the technique scheme, the SiO of zeolite
2/ Al
2O
3The mol ratio preferable range is 15～100, and h-type zeolite can be direct synthetic, also can be dealuminated zeolite, and the restricted index of zeolite is 0.1～15.Restricted index and measuring method thereof are described in detail in U.S. Pat P4016218.Used zeolite preferred version is selected from least a in ZSM-5 zeolite, Y zeolite, mordenite, β zeolite, MCM-22 zeolite, MCM-49 zeolite or the MCM-56 zeolite, and more preferably scheme is that mordenite is or/and the β zeolite.In parts by weight on zeolite also load at least a metal in chosen from Fe, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium or the silver or/and 0.01～20 part of oxide compound, its consumption preferable range is 0.1～5 part.Carbon nine in the raw material and above aromatic hydrocarbons preferred version thereof are to be selected from least a in trimethylbenzene, first and second benzene, propyl benzene, indane, carbon ten or the carbon ten above heavy arenes, and the C8 aronmatic preferred version is dimethylbenzene, ethylbenzene or their mixture.
The catalyzer that the present invention uses, owing on h-type zeolite, carried out metal-modified, the antigen material moisture ability of catalyzer is increased greatly, and can keep higher activity and stability, promptly can use the raw material of moisture 500ppm, that is to say under quite harsh reaction conditions and use,, can remove raw material Ben and C from full scale plant
9 +The drying and dehydrating operation of A.
The main component of the catalyzer that the present invention uses as load molybdenum metal or/and at least a metal at least a chosen from Fe, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium or the silver of 0.01～20 part of oxide compound and non-imposed adding or/and the h-type zeolite of 0.01～20 part of oxide compound.H-type zeolite can be the dealuminated zeolite that the low silica-alumina ratio zeolite obtains through acid treatment, it also can be the Hydrogen supersiliceous zeolite that sodium type supersiliceous zeolite that natural zeolite or direct crystallization obtain obtains through inorganic ammonium ion exchange, drying, roasting, its sodium content should be lower than 0.2 weight %, and the most suitable with direct crystallization synthetic supersiliceous zeolite.The premium properties of catalyzer of the present invention is the coefficient result of katalysis by the metal of load on katalysis of Hydrogen supersiliceous zeolite and the zeolite and/or metal oxide.
Ben and C that the present invention uses
9 +The preparation method of A transalkylation catalyst is by the method preparation of general solution impregnation load, and drying, roasting get catalyzer then.Have technical maturity, equipment simple, easy to operate, be easy to realize characteristics such as industrialization.
The present invention is used for the transalkylation method of benzene and carbon nine and above aromatic hydrocarbons thereof, its toluene adds the C8 aronmatic selectivity and is up to 94.1%, benzene adds carbon nine and above aromatics conversion rate is up to 64%, and has good stability, allow water content higher in the raw material, and carbon ten and above aromaticity content thereof are higher, can be converted into useful benzene and C8 aronmatic, have obtained better technical effect.
Benzene and carbon nine and above aromatic hydrocarbons transalkylation reaction data thereof are handled as follows:
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
Make sodium type mordenite, sodium type β zeolite and sodium type ZSM-5 zeolite by ZL89106793.0, USP3308069 and USP4441991 respectively.Three kinds of na-pretreated zeolites respectively with ammonium chloride or aqueous ammonium nitrate solution 90～98 ℃ of ion-exchanges 1～8 hour, the elimination mother liquor repeats ion-exchange for several times, washing then, 110 ℃ of oven dry obtain ammonium type zeolite.The SiO of three kinds of ammonium type zeolites
2/ Al
2O
3Be respectively 25,25 and 500.Three kinds of ammonium type zeolites respectively with pseudo-boehmite (α-Al
2O
3H
2O) mixed, add rare nitric acid, ammonium molybdate and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 550 ℃ of roastings obtain catalyst A 1, A2, A3, and three kinds of catalyst metal molybdenum content are 4.0 weight %.
[embodiment 4]
Get commercially available sodium type Y zeolite (SiO
2/ Al
2O
3=4), carry out ion-exchange, kneading, moulding, roasting by the method for embodiment (1～3), make catalyst A 4, the metal molybdenum content of catalyst A 4 is 4.0 weight %.
[embodiment 5～7]
Make sodium type MCM-22 zeolite, sodium type MCM-49 zeolite and sodium type MCM-56 zeolite by USP4956514, USP5264643 and USP5453554 respectively.Three kinds of na-pretreated zeolites respectively with ammonium chloride or aqueous ammonium nitrate solution 90～98 ℃ of ion-exchanges 1～8 hour, the elimination mother liquor repeats ion-exchange for several times, washing then, 110 ℃ of oven dry obtain ammonium type zeolite.The SiO of three kinds of ammonium type zeolites
2/ Al
2O
3Be respectively 30,138 and 18.Three kinds of ammonium type zeolites respectively with pseudo-boehmite (α-Al
2O
3H
2O) mixed, add rare nitric acid, ammonium molybdate and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 550 ℃ of roastings obtain catalyst A 5, A6, A7, and three kinds of catalyst metal molybdenum content are 4.0 weight %.
[embodiment 8～13]
Prepare SiO by USP3308069
2/ Al
2O
3Be respectively four kinds of β zeolites of 25.7,35.1,40.2 and 44.0, after ammonium exchange, drying, with commercially available pseudo-boehmite (α-Al
2O
3H
2O) mixed by 50/50 (weight ratio), add rare nitric acid and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 400 ℃ of roastings obtain cylinder thing.This cylinder thing impregnated in the ammonium molybdate aqueous solution and spends the night, and then 110 ℃ of oven dry, obtains catalyst B 1, B2, B3, the B4 of containing metal molybdenum 4.0 weight % again in 540 ℃ of roastings.Be respectively 70/30,30/70 catalyst B 5 and B6 by obtain H β zeolite and commercially available pseudo-boehmite weight ratio with quadrat method.
[embodiment 14～16]
Present embodiment is the scarce aluminium wire geolyte catalyzer that preparation adds molybdenum.Lack the preparation of aluminium wire geolyte: commercially available sodium type mordenite (SiO
2/ Al
2O
3=10), reflux down at 90 ℃, make the mordenite dealuminzation, filter with rare nitric acid, washing, 110 ℃ of oven dry obtain SiO
2/ Al
2O
3=15.2 scarce aluminium wire geolyte.Repeat aforesaid operations for several times, obtain SiO respectively
2/ Al
2O
3It is 20.4 and 26.7 scarce aluminium wire geolyte.Three kinds of scarce aluminium wire geolytes are mixed by 50/50 (weight ratio) with commercially available pseudo-boehmite respectively, add rare nitric acid, ammonium molybdate and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 550 ℃ of roastings obtain catalyzer C1, C2, C3, and three kinds of catalyst metal molybdenum content are 4.0 weight %.
[embodiment 17～19]
Method SiO according to embodiment (8～13)
2/ Al
2O
3=25.7 β zeolite and pseudo-boehmite are mediated, and extrusion is shaped, and the dipping ammonium molybdate aqueous solution obtains catalyzer D1, D2, D3 that metal molybdenum content is respectively 1.0,3.0 and 8.0 weight %.
[embodiment 20～22]
With the ammonium type mordenite among the embodiment (1～3), with commercially available pseudo-boehmite (α-Al
2O
3H
2O) press different ratios and mix, add rare nitric acid and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 400 ℃ of roastings obtain cylinder thing.This cylinder thing impregnated in the ammonium molybdate aqueous solution and spends the night, and then 110 ℃ of oven dry, obtains catalyzer E1, E2, the E3 that the containing metal molybdenum is respectively 1.0,3.0,8.0 weight % in 540 ℃ of roastings again.
[comparative example 1]
According to the method for embodiment (1～3), obtaining metal molybdenum content is the HM zeolite catalyst F1 of 0.0 weight %.
[comparative example 2]
According to the method for embodiment (13～15), obtaining metal molybdenum content is the H beta-zeolite catalyst F2 of 0.0 weight %.
[embodiment 23]
With the various catalyzer that embodiment (1～22) and Comparative Examples 1～2 make, examination catalyzer transalkylation activity on pressurized stream dynamic formula fixed bed reaction evaluating apparatus.Loaded catalyst 20 grams, 380 ℃ of temperature of reaction, reaction pressure 3.0MPa (table), the hydrogen hydrocarbon divides mol ratio 5.3, raw material Ben/C
9A/C
10 +The A weight ratio is 57/43/5, water content 500ppm, weight space velocity WHSV2.5 hour
-1, result such as table 1.The result shows that the h-type zeolite load molybdenum catalyst that the present invention makes has good transalkylation reaction activity.
[embodiment 24～28]
With the ammonium type mordenite among the embodiment (1～3), mix by weight 70/30 with pseudo-boehmite, add rare nitric acid and water, mediate evenly extrusion, 110 ℃ of oven dry, pelletizing, dipping ammonium molybdate aqueous solution and cobalt nitrate aqueous solution, 110 ℃ of oven dry, 550 ℃ of roastings obtain the catalyzer G1 that metal molybdenum and cobalt metal content are respectively 4.0 weight % and 0.6 weight %.Make with similar method and to contain molybdenum and at least a catalyzer G2～G5 that is selected from metals such as cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium, silver or its compound.
[embodiment 29]
Catalyzer G1～G5 with embodiment (24～28) makes carries out the investigation of catalyzer transalkylation activity, result such as table 2 with activity rating device and the condition of embodiment 23.The result shows that the present invention makes contains the catalyzer of metals such as molybdenum and at least a chosen from Fe, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium, silver or its compound, has good transalkylation reaction activity.
[embodiment 30]
Catalyzer G3 with embodiment (24～28) makes with activity rating device and the condition of embodiment 23, selects the different reaction raw materials of forming for use, carries out the catalyzer transalkylation activity and investigates result such as table 3.The result shows, under the condition with different anabolic reaction raw materials, the catalyzer that the present invention makes has good transalkylation reaction activity, selectivity and adaptability to different constitutive materials.
[embodiment 31]
Catalyzer G3 with embodiment (24～28) makes with the activity rating device of embodiment 23, selects different processing condition for use, carries out the catalyzer transalkylation activity and investigates result such as table 4.The result shows, in the processing condition scope of broad, the catalyzer that the present invention makes has good transalkylation reaction activity, selectivity and to the adaptability of different technology conditions.
[embodiment 32]
The catalyst A 1, B1 and Comparative Examples F1, the F2 that make with embodiment (1～13) carry out the active further evaluation of catalyzer transalkylation reaction, purpose is to investigate their stability, reaction conditions is substantially the same manner as Example 23, but the initial reaction temperature of catalyst A 1, B1 is 380 ℃, and the initial reaction temperature of comparative catalyst F1, F2 is 410 ℃.About transformation efficiency 61～63 weight % of control catalyst A1, B1, the method for taking progressively to improve temperature of reaction is kept transformation efficiency about 61～63 weight %.About transformation efficiency 48～51 weight % of control catalyst F1, F2, the method for taking progressively to improve temperature of reaction is kept transformation efficiency about 48～51 weight %.Test-results such as table 5.As can be seen, catalyst A of the present invention 1 reaction 1000 hours, the temperature of reaction all-the-time stable is at 380 ℃, average conversion 62.2 weight %, average (Tol+C
8A) selectivity 93.0 weight %; Average conversion 48.0 weight % are kept in comparative catalyst F1 reaction 500 hours, average (Tol+C
8A) selectivity 84.5 weight %, temperature of reaction is by 410 ℃ of 445 ℃ of being promoted at the end.Catalyst B of the present invention 1 reaction 1000 hours, temperature of reaction be by 380 ℃ of 392 ℃ of being promoted at the end, average conversion 63.2 weight %, average (Tol+C
8A) selectivity 90.4 weight %; Average conversion 50.3 weight % are kept in comparative catalyst F2 reaction 500 hours, average (Tol+C
8A) selectivity 82.9 weight %, temperature of reaction is by 410 ℃ of 438 ℃ of being promoted at the end.The catalyst stability test-results shows that catalyzer of the present invention has high reactivity, highly selective and satisfactory stability.
Table 1 catalyst activity evaluation result
| Catalyzer | Ben+C 9 +A transformation efficiency/(weight %) | Tol+C 8 +A selectivity/(weight %) | Tol selectivity/C 8A selectivity (mol ratio) | |||||
| Numbering | Zeolite type | The SiO of zeolite 2/Al 2O 3Mol ratio | The Zeolite/alumina weight ratio | Metal molybdenum content weight % | Add the molybdenum method | |||
| A1 A2 A3 A4 A5 A6 A7 | HM Hβ HZSM-5 HY HMCM-22 HMCM-49 HMCM-56 | 25 25 500 4 30 138 18 | 50/50 50/50 50/50 50/50 50/50 50/50 50/50 | 4.0 4.0 4.0 4.0 4.0 4.0 4.0 | Knead | 62.5 63.7 42.6 51.1 64.0 58.2 64.3 | 93.1 90.6 74.4 76.4 91.6 92.6 91.9 | 3.4 3.0 0.8 1.0 3.2 3.3 3.3 |
| B1 B2 B3 B4 B5 B6 | Hβ Hβ Hβ Hβ Hβ Hβ | 25.7 35.1 40.2 44.0 25.7 25.7 | 50/50 50/50 50/50 50/50 70/30 30/70 | 4.0 4.0 4.0 4.0 4.0 4.0 | Dipping dipping dipping dipping dipping dipping | 63.3 63.5 62.7 62.6 64.1 57.6 | 90.7 90.4 90.8 90.8 90.2 90.0 | 3.0 2.9 2.9 2.9 3.1 2.5 |
| C1 C2 C3 | Dealuminzation MOR *Dealuminzation MOR dealuminzation MOR | 15.2 20.4 26.7 | 50/50 50/50 50/50 | 4.0 4.0 4.0 | Knead | 53.6 53.9 55.7 | 77.6 80.4 80.8 | 1.0 1.1 1.3 |
| D1 D2 D3 | Hβ Hβ Hβ | 25.7 25.7 25.7 | 50/50 50/50 50/50 | 1.0 3.0 8.0 | Dipping dipping dipping | 55.0 60.7 66.4 | 84.6 88.2 87.1 | 2.3 2.8 3.1 |
| E1 E2 E3 | HM HM HM | 25.2 25.2 25.2 | 50/50 50/50 50/50 | 1.0 3.0 8.0 | Dipping dipping dipping | 54.3 60.4 65.2 | 91.4 92.9 90.8 | 3.0 3.2 3.6 |
| F1 F2 | HM Hβ | 25.2 25.7 | 50/50 50/50 | 0.0 0.0 | - - | 49.0 48.7 | 87.7 78.5 | 1.3 0.9 |
*Mordenite
Table 2 catalyst activity evaluation result
| The catalyzer numbering | A1 | G1 | G2 | G3 | G4 | G5 | |
| Loaded metal kind and content/(weight %) | Mo Co Ni Cr Zr Ag | 4.0 - - - - - | 4.0 0.6 - - - - | 4.0 - 1.2 - - - | 4.0 - - 1.1 - - | 4.0 - - - 0.8 - | 4.0 - - - - 0.4 |
| (Ben+C 9 +A) transformation efficiency/(weight %) | 62.6 | 63.3 | 62.7 | 63.1 | 62.7 | 62.1 | |
| (Tol+C 8A) selectivity/(weight %) | 93.1 | 93.2 | 93.3 | 94.1 | 92.4 | 93.3 | |
| Tol selectivity/C 8A selectivity (mol ratio) | 3.4 | 3.4 | 3.3 | 3.7 | 3.4 | 3.2 | |
Table 3 catalyst activity evaluation result (one)
| The catalyzer numbering | Ben/C in the raw material 9A/C 10 +A (weight ratio) | Total conversion rate/(weight %) | (Tol+C 8A) selectivity/(weight %) | Tol selectivity/C 8A selectivity (mol ratio) |
| G3 G3 G3 G3 G3 | 40/60/5 45/55/5 50/50/5 55/45/5 60/40/5 | 55.6 60.7 62.4 63.2 60.6 | 90.6 93.0 93.3 93.9 94.2 | 2.7 3.1 3.5 3.7 3.8 |
Table 4 catalyst activity evaluation result (two)
| The catalyzer numbering | Temperature of reaction/℃ | Reaction pressure/MPa | Weight hourly space velocity WHSV/ hour -1 | H 2/ hydrocarbon mol ratio | Total conversion rate/(weight %) | (Tol+C 8A) selectivity/(weight %) | Tol selectivity/C 8A selectivity (mol ratio) |
| G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 G3 | 300 350 400 480 380 380 380 380 380 380 380 380 380 380 380 380 380 | 3.0 3.0 3.0 3.0 2.0 2.5 3.0 4.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 | 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.0 2.0 3.0 4.0 5.0 2.5 2.5 2.5 2.5 | 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 2.5 4.0 5.5 7.0 | 42.8 57.4 64.6 62.4 55.3 60.6 63.1 63.3 63.9 63.5 62.9 55.1 50.6 51.3 56.7 63.2 65.4 | 72.4 88.7 91.4 84.6 89.6 91.8 94.1 93.3 93.6 93.8 94.2 94.4 94.7 74.1 85.6 94.4 94.6 | 1.8 2.8 3.7 4.0 2.7 3.1 3.7 3.8 4.0 3.8 3.6 2.8 2.1 1.7 2.1 3.7 3.8 |
The test of table 5 catalyst stability
| The catalyzer numbering | Reaction times/hour | Temperature of reaction, beginning → end/℃ | Average conversion/(weight %) | (Tol+C 8A) average selectivity/(weight %) | Tol selectivity/C 8A selectivity (mol ratio) |
| A1 | 1000 | 380→380 | 62.2 | 93.0 | 3.2 |
| F1 | 500 | 410→445 | 48.0 | 84.5 | 1.2 |
| B1 | 1000 | 380→392 | 63.2 | 90.4 | 3.0 |
| F2 | 500 | 410→438 | 50.3 | 82.9 | 0.8 |
Claims (9)
1, a kind of benzene and carbon nine and above arene transalkylation method thereof are that reaction raw materials carries out transalkylation reaction with benzene and carbon nine and above aromatic hydrocarbons thereof, generate toluene and C8 aronmatic, and its reaction conditions is:
A) under hydro condition, benzene feedstock and carbon nine and above aromatic hydrocarbons thereof fix bed bioreactor by gas-solid and contact with catalyzer, the weight ratio of benzene and carbon nine and above aromatic hydrocarbons thereof is 10～90: 90～10, temperature of reaction is 300～600 ℃, reaction pressure is 1.0～6.0MPa, and raw material aromatic hydrocarbons weight space velocity WHSV is 0.5～5.0 hour
-1, H
2/ hydrocarbon mol ratio is 1～15;
B) used catalyzer contains 10～90 parts in Hydrogen zeolite, the SiO of zeolite in parts by weight
2/ Al
2O
3Mol ratio is 3～500, and the metal of load molybdenum on zeolite is or/and 0.01～20 part of oxide compound, and the binding agent aluminum oxide is 10～90 parts in catalyzer.
2,, it is characterized in that carbon nine in the raw material and above aromatic hydrocarbons thereof are to be selected from least a in trimethylbenzene, first and second benzene, propyl benzene, indane, carbon ten or the carbon ten above heavy arenes according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof.
3,, it is characterized in that C8 aronmatic is dimethylbenzene, ethylbenzene or their mixture according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof.
4,, it is characterized in that containing the metal of molybdenum or/and the amount of oxide compound is 0.1～10.0 part in the parts by weight catalyst system therefor according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof.
5,, it is characterized in that the SiO of used zeolite according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof
2/ Al
2O
3Mol ratio is 15～100.
6,, it is characterized in that used zeolite is selected from least a in ZSM-5 zeolite, Y zeolite, mordenite, β zeolite, MCM-22 zeolite, MCM-49 zeolite or the MCM-56 zeolite according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof.
7,, it is characterized in that used zeolite is that mordenite is or/and the β zeolite according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof.
8, according to the described benzene of claim 1 and carbon nine and above arene transalkylation method thereof, it is characterized in that in parts by weight on zeolite also load at least a metal in chosen from Fe, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium or the silver or/and oxide compound, its consumption is 0.01～20 part.
9, described according to Claim 8 benzene and carbon nine and above arene transalkylation method thereof, it is characterized in that in parts by weight on zeolite also load at least a metal in chosen from Fe, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium or the silver or/and the consumption of oxide compound is 0.1～5 part.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021110042A CN1193967C (en) | 2002-03-13 | 2002-03-13 | Benzene and C9 and more than that arene transalkylation method |
| AU2003211667A AU2003211667A1 (en) | 2002-03-13 | 2003-02-25 | The transalkylation method of benzene and c9+ aromatic hydrocarbons |
| PCT/CN2003/000146 WO2003076372A1 (en) | 2002-03-13 | 2003-02-25 | The transalkylation method of benzene and c9+ aromatic hydrocarbons |
| TW092104390A TW200502207A (en) | 2002-03-13 | 2003-03-03 | Benzene and C9 and above arene transalkylation method |
| US10/385,988 US20030181774A1 (en) | 2002-03-13 | 2003-03-11 | Process for the transalkylation of benzene and C9+ aromatics |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021110042A CN1193967C (en) | 2002-03-13 | 2002-03-13 | Benzene and C9 and more than that arene transalkylation method |
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| CN1193967C true CN1193967C (en) | 2005-03-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336790C (en) * | 2004-07-12 | 2007-09-12 | 中国石油化工股份有限公司 | Process for preparing p-xylene |
| CN101172924B (en) * | 2006-11-02 | 2010-09-01 | 中国石油化工股份有限公司 | High selectivity arene alkyl transfer and dealkylation xylol production increase reaction method |
| CN101607207B (en) * | 2008-06-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Heavy aromatic hydrocarbon light catalyst, preparation method and application thereof |
| 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 |
| CN101768039B (en) * | 2009-01-07 | 2012-09-05 | 中国石油化工股份有限公司 | Method for lightening and transalkylation of C9 and heavier aromatic hydrocarbons |
| CN102925211A (en) * | 2012-11-15 | 2013-02-13 | 中国海洋石油总公司 | Method for lightening MTG (Methanol to Gasoline) heavy aromatics |
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