CN1123629C - Disproportionation and transalkylation process of toluene and C9 and heavier aromatic hydrocarbons - Google Patents
Disproportionation and transalkylation process of toluene and C9 and heavier aromatic hydrocarbons Download PDFInfo
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- CN1123629C CN1123629C CN00127434A CN00127434A CN1123629C CN 1123629 C CN1123629 C CN 1123629C CN 00127434 A CN00127434 A CN 00127434A CN 00127434 A CN00127434 A CN 00127434A CN 1123629 C CN1123629 C CN 1123629C
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Abstract
The present invention relates to a disproportionation and transalkylation process of toluene, C9 and heavier aromatic hydrocarbons thereof, which mainly aims to overcome the disadvantage of nonaromatic light hydrocarbon quantity waste or strict raw material composition requirements caused by a small treating capacity of heavy aromatic hydrocarbons or the treatment of the heavy aromatic hydrocarbons only by dealkylation weight lightening in the prior art. The present invention effectively performs a disproportionation reaction and a transalkylation reaction on the toluene, the C9 and the heavier aromatic hydrocarbons thereof to generate a large quantity of benzene product and a large quantity of xylene product by adopting a catalyst prepared by loading a molybdenum oxide and other active constituents on zeolite in the process. The catalyst has the characteristics of high catalytic activity, large treating capacity of Cl0 and heavier aromatic hydrocarbons thereof, high selectivity of the benzene, and high selectivity of a C8 aromatic hydrocarbon product. The catalyst can be used in industrial production.
Description
The present invention relates to toluene and carbon nine and above heavy arene disproportionation and alkyl transfering process, relate in particular to the method that toluene and carbon nine and above heavy arene disproportionation thereof and transalkylation are produced benzene and C8 aronmatic.
P-Xylol in the C8 aronmatic 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 as follows, and at first the dimethylbenzene that contains ethylbenzene by petroleum naphtha catalytic reforming generation thermodynamic(al)equilibrium is C8 aronmatic (C
8A), separate or the molecular sieve simulated Moving Bed Adsorption Separation Technology by multistage cryogenic crystallization then, p-Xylol is separated from the close with it isomer mixture of boiling point.And, often adopt C for the dimethylbenzene of an ortho position and a position and the processing of ethylbenzene
8The A isomerization technique 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 heavy aromatics (C thereof
9 +A) disproportionation and transalkylation reaction generate benzene and C
8A is by volume increase C
8A reaches the purpose of effective volume increase p-Xylol.
People are usually C9 aromatic (C
9A), carbon ten and above heavy aromatics (C thereof
10 +A) be referred to as heavy aromatics.Petroleum Aromatics is mainly derived from the byproduct that light oil cracking is produced ethylene unit; The aromatic hydrocarbons that the refinery catalytic reforming is produced; The byproduct of toluene disproportionation and transalkylation unit.Along with increasing of heavy arene amount, the comprehensive utilization of heavy arene becomes the problem that people are concerned about, wherein C
9The processing and utilization of A has sophisticated method, is widely used as the raw material of toluene disproportionation and transalkylation reaction, is used for making benzene and C
8A.Because the by product C of present Aromatic Hydrocarbon United Plant
10 +The composition complexity of A fraction is except that C such as first and second benzene that contain 5～20% (weight), trimethylbenzenes
9Outside A and the indane (IND), also contain tens kinds of C10 aromartic (C
10A) and carbon 11 and above heavy arene (C thereof
11 +A) component as durene, dimethyl ethyl benzene, diethylbenzene, methylnaphthalene, dimethylnaphthalene etc., is formed complexity, boiling point height, present less application.These components are all improper as the blend composition of gasoline or diesel oil simultaneously, can only partly be used as solvent oil, and part is after telling durol wherein, and all the other major parts act as a fuel and burn, and are not fully utilized.Aromatic Hydrocarbon United Plant of producing 22.5 ten thousand tons of p-Xylol per year according to estimates, because the difference of stock oil, the difference of the course of processing, the annual C that produces
10 +A is 1～30,000 ton, and this is a kind of resource of preciousness, and present Aromatic Hydrocarbon United Plant does not also have suitable processing and utilizes method to this.
All take strict restriction indane content in related process in early days, catalyzer patent and the document, purpose selectivity of product, the prolongation running operation time of improving toluene disproportionation and transalkylation catalyst.Because the boiling point of indane is between C
9A and C
10Between the A, thereby directly cause early stage technology can't utilize C
10A.Along with the development of catalyst technology, can adopt the C that sneaks into certain content in the reaction raw materials at present
10The method of A improves the yield of purpose product, pursues under high conversion, the high-speed to remedy, and the deficiency that product yield is on the low side, but still can not utilize C
11 +A.C in the reaction raw materials
11 +The introducing of A will have a strong impact on the stability of its employed catalyzer, thereby can't realize stable operation on technology.Because C
10The component complexity of A, boiling range wide ranges, the C of quite a few
10The boiling point of A has surpassed C
11 +The boiling point of A is in separation of C
10Must the strict operational condition of controlling the heavy aromatics tower during A.Therefore, for fear of C
11 +A enters reaction raw materials, in fact C
10Have only about 20～30% to be utilized among the A, and about 80～70% C
10A is with C
11 +A discharges at the bottom of the heavy aromatics Tata.
Contain about 60～65% C in typical carbon ten and the above heavy arene thereof
10A and 40～35% C
11 +Can A as can be seen, utilize C
11 +Can A will badly influence carbon ten above heavy arenes and fully be utilized.
Because benzene and C
8The purposes of A is wider relatively, and its price is also higher relatively, simultaneously a large amount of C
10 +A still is underutilized, so toluene and carbon nine and above heavy arene disproportionation and transalkylation reaction production benzene and C
8A more and more has been subjected to people's attention.
At present by toluene and/or carbon nine and above heavy arene disproportionation and transalkylation reaction production benzene and C
8The method of A mainly contains following three kinds:
First kind is that mixture with toluene and an amount of heavy arene is a raw material, produces benzene and C by toluene disproportionation and transalkylation process
8A.This method is that traditional technological process is a Tatoray technology.Because 95% (weight) all is C in the heavy arene that is mentioned in this technology
9A, so actual industrial is united the C of relative low price in the aromatic device
10 +A is not effectively used at all.In this processing method, though C in the raw material
10A can exist, but can not handle C
11 +A, and must strict control C
10A content: toluene and C
9The content sum of A aromatic hydrocarbons requires to reach 97% (weight) or higher scope, allows C
10The content of A only is 3% (weight) or lower.C in raw material
10A content is higher than at 3% o'clock, will badly influence the normal running of this technology.
In U.S. Pat P 4172813,3%WO by weight percentage
3, 5%MoO
3-60% mordenite-40%Al
2O
3Be catalyzer, make heavy reformation liquid that hydro-dealkylation and transalkylation reaction take place to select.Its temperature of reaction is 315～538 ℃, and reaction pressure is 150～500Psig, and reaction raw materials contains non-aromatics 0.5%, C
8A 0.4%, toluene 28.3%, and trimethylbenzene 46.6%, the first and second benzene 11.6%, indane adds propyl benzene 2.1%, durene 10.1%, C
11 +A only is 0.4%.Its purpose product mainly is to realize by the dealkylation generation light aromatics of heavy arene.Generated a large amount of non-aromaticss in this technology, aromatics yield is lower.
Second kind of technological process is to obtain the purpose product by heavy aromatic hydrocarbon light fully.As in the public clear 51-29131 patent of spy, use MoO
3-NiO/Al
2O
3(13 weight %Mo, 5 weight %Ni) catalyzer is with C
9A～C
10 +(weight percent consists of A: benzene 0.81%, toluene 0.26%, C
8A 0.95%, C
9A 80.96%, C
10 +A 15.23%) be raw material, under 6MPa and 550 ℃ of reaction conditionss, react, during reaction product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, C
8A 32.23% and non-aromatics 0.16%.Though this second kind of processing method can be handled high-load C
10 +A, but its purpose product is to realize that by the dealkylation generation light hydrocarbons of heavy arene like this, the lighter hydrocarbons amount of system will roll up.Device is that the unnecessary flare system of delivering to is burnt as combustion gas to the general processing mode of lighter hydrocarbons at present.Clearly, this technology can cause a large amount of wastings of resources.
The third technology is to be the selectivity toluene disproportionation process that material choice ground produces p-Xylol with the pure toluene.This technology is active constituent with the ZSM-5 zeolite mainly.ZSM-5 zeolite catalyst with central hole structure, common in recent years report mostly are the selective disproportionation process that is applied to toluene, as USP 5403800 (1995), USP 5633417 (1997).
Above-mentioned several technology all is to face hydrogen and fixed bed reaction technology.The existence of hydrogen is operational cycle and the guard catalyst for the coking that suppresses catalyzer, prolongation catalyzer.
Under identical working condition, carbon nine and above heavy arene (C thereof in the common reaction raw materials
9 +A) content is high more, especially C
10 +The content of A is high more, the easy more coking of catalyzer, therefore, in traditional technology to the C in the reaction raw materials
10 +The all strict restriction of A.
Be raw material with toluene and carbon nine and above heavy arene thereof at present, produce benzene and C by disproportionation and transalkylation reaction
8The device of A uses traditional Tatoray technology mostly.This technology is normally under hydro condition, with toluene and C
9A is a raw material, uses fixed-bed reactor, and reaction generates C in the presence of mordenite catalyst
6～C
10Aromatic hydrocarbons and C
1～C
5Alkane and a small amount of C
11 +A.Toluene in the reaction effluent and C
9A circulates fresh toluene and the fresh C external with the battery limit (BL) after separating
9A converges as reactor feed.Owing to be subjected to the restriction of catalyst performance, the C that device itself generates
10A and C
11 +A can not discharge out-of-bounds by heavy arene tower still as the raw material circulation.Because be subjected to the restriction of catalyst performance, the technical indicator of technology is lower, typical operational condition is: toluene and C in the reaction raw materials
9The weight ratio of A is 80: 20 to 60: 40, and reaction pressure is 3.0MPa (G), and the molecular ratio of hydrogen and aromatic hydrocarbons (abbreviation hydrogen-hydrocarbon ratio) is not less than 6, is generally 8～10, and weight space velocity WHSV is 1.0～1.5hr
-1, be generally 1.1～1.3hr
-1, (toluene+C
9A) total conversion rate is 40～43%, is generally 40～41%, (benzene+C
8A) selectivity is no more than 94%.
With the mordenite catalyst is the toluene disproportionation and the alkyl transfering process of feature, relevant report is also more relatively with relevant patent, as: transalkylation catalyst, reaction mass composition and reaction conditions have been described among U.S. Pat P 2795629, USP 3551510, USP 3701813 and the USP 3729521.The catalyzer patent that is used for alkyl transfering process has USP2795629, USP 3780122 and USP 3849340.In fact above patent can not make full use of C owing to be subjected to the influence of catalyst performance
9A and above heavy arene thereof, the yield of purpose product is all lower, and economic and technical norms are uneconomical.
USP 4341914 discloses a kind of improved Tatoray processing method.Though the C that this method can partly utilize reaction itself to generate
10A circulates, and introduce in the reaction raw materials, but it just plays inhibition generation C
10 +The effect of A reaction, thus C reduced
10 +The turnout of A, the yield of raising benzene and C8 aronmatic.In fact, this technology can not utilized C
10 +A.In addition, because the restriction of catalyst performance, this technology also has exacting terms in the selection of raw material, must strict control reaction raw materials in the content of indane, thereby make it can't be with C
10 +A is as reaction raw materials.
USP 4665258 (1987) has proposed a kind of new for improved toluene disproportionation process, is feature to lack aluminium wire geolyte catalyzer.Its reaction can carried out under the exacting terms relatively.The mordenite silica alumina ratio of catalyst system therefor is preferably 40～60 greater than 30.But it is active and stability is not ideal enough, and the raw materials used C that do not relate to
10 +A.
Disclose a kind of catalyzer method for preparing alkylbenzene among the clear 49-46295 of Japanese Patent, its catalyzer is to be active main body with the mordenite, and load zirconium and the promotor that is selected from silver, bismuth, copper, antimony carry out disproportionation reaction.Do not relate in this patent and whether can process heavy aromatics and be used for toluene disproportionation and the reactivity worth of transalkylation.
Disclose a kind of synthetic method of high silicon mordenite among the Chinese patent ZL89106793.0, it is with cheap industrial raw material such as water glass, mineral acid, mineral alkali, aluminium salt or aluminate directly synthetic SiO in the presence of ammonia
2/ Al
2O
3Molecular ratio is 15～30 high silicon mordenite, but this patent is not mentioned this mordenite as toluene disproportionation and C
9 +Reactivity worth during the A transalkylation catalyst.
β zeolite with macroporous structure has CN1108214A, CN1108213A and CN1105646A etc. as the synthetic patent of catalytic activity main body.But these patents do not relate to the reactivity worth when being used for toluene disproportionation and transalkylation.Compare with mordenite, because the three-dimensional open-framework of β zeolite and bigger aperture, the reaction back generates C
10 +The amount of A is bigger, thereby has caused the purpose product selectivity to descend.Therefore, when the β zeolite is used for toluene disproportionation and heavy arene alkyl transfering process, need carry out modification to it.
In petroleum chemical industry, the core of various Technologies is catalyst technologies.Article one, very sophisticated operational path tends to change because of the industrialization of a raw catalyst.The exploitation of a petrochemical process and to improve be because succeeding in developing with improving constantly of its performance of associated catalysts promotes after all.In order to improve disproportionation device processing toluene and C
9The ability of A, reduce device energy consumption and material consumption, reach the working condition requirement of scale economics, people have developed the catalyst for toluene disproportionation and transalkylation of high-speed and high conversion in succession.But, along with the raising of catalyzer transformation efficiency, the C of generation
10 +The amount of A has also increased, thereby has caused the decline of purpose selectivity of product.
The objective of the invention is in order to overcome in the existing Technology, it is lower that device is handled the aroamtic hydrocarbon raw material ability, to carbon ten and above heavy arene processing power difference thereof or only by taking off the alkyl lighting, causes system's lighter hydrocarbons amount to increase the wasting of resources and benzene and C
8The shortcoming that the A yield is lower provides a kind of toluene and carbon nine and above heavy arene disproportionation and alkyl transfering process, and technology of the present invention is being carried out toluene and C
9When disproportionation and transalkylation reaction take place A, carbon ten and above heavy aromatics thereof are transformed into benzene and C effectively
8A, carbon ten and above heavy aromatics processing power thereof are big, have high purpose selectivity of product under high-speed, high conversion.
The objective of the invention is to realize by following technical scheme: a kind of toluene and carbon nine and above heavy arene disproportionation and alkyl transfering process comprise:
A) be reaction raw materials with toluene and carbon nine and above heavy arene thereof, use fixed-bed reactor, raw material toluene and C
9 +A mixes with hydrogen, from top to bottom by beds, disproportionation and transalkylation reaction takes place, and wherein wt is than toluene: C
9 +A=95: 5～5: 95, be preferably 90: 10～30: 70, more preferably 80: 20～40: 60; C in the reaction raw materials
10 +The A weight percentage is 0～30%, wherein, and C
9 +A is carbon nine and above heavy arene thereof, C
10 +A is carbon ten and above heavy arene thereof;
B) weight space velocity is 0.8～8.0 hour
-1, be preferably 1.5～4.5 hours
-1
C) temperature of reaction is 300～500 ℃, is preferably 350～450 ℃;
D) under the hydro condition, in gauge pressure reaction pressure 1.0～5.0MPa, be preferably 2.0～3.5MPa, hydrogen-hydrocarbon ratio is 1～10, is preferably 3～7;
E) catalyzer is toluene and carbon nine and above heavy arene disproportionation and transalkylation catalyst, wherein comprises in parts by weight:
1) SiO
2/ Al
2O
3Mol ratio is 20～90 parts of 10～50 h-type zeolites; Be stated from the zeolite
2) oxide compound of molybdenum is 0.05～10 part; Preferred 0.1～5 part;
3) at least a oxide compound that is selected from nickel or bismuth is 0～10 part; Preferred 0～5 part; More preferably 0.1～5 part;
4) at least a oxide compound that is selected from lanthanum, silver or rhenium is 0～10 part; Preferred 0.1～5 part;
5) the binding agent aluminum oxide is 10～60 parts.
The weight content of carbon ten and above heavy arene thereof can be preferably 3～20% up to 0～30% in the reaction raw materials of the present invention, more preferably 5～15% (weight).H-type zeolite is selected from mordenite, β zeolite or its miscellany in the catalyzer, and preferred version is for being selected from the β zeolite; In parts by weight, preferred version is that the preferable range that contains bismuth oxide compound or nickel oxide is 0～5 part in the catalyzer, and more preferably scope is 0.1～5 part.H-type zeolite SiO
2/ Al
2O
3Mol ratio is preferably 15～35.
Catalyzer used in the present invention by h-type zeolite, aluminum oxide and employed metal-salt through dipping or mix or mediate extrusion after 350～600 ℃ of roastings make.
The present invention uses fixed-bed reactor to carry out toluene and C
9 +The disproportionation of A and transalkylation reaction performance are investigated, 25 millimeters of reactor inside diameter φ, 1200 millimeters of length, stainless steel.Adopt electrically heated, temperature is controlled automatically.5 millimeters granulated glass spherees of reactor bottom filling φ are as upholder, filling catalyzer 20 grams in the reactor, and 5 millimeters granulated glass spherees of top filling φ are made for the usefulness of raw material preheating and vaporization.Raw material toluene and C
9 +A mixes with hydrogen, from top to bottom by beds, disproportionation and transalkylation reaction takes place, and generates benzene, C
8More rudimentary aromatic hydrocarbons such as A, and alkane such as a small amount of methane, ethane, propane, butane.
Raw material toluene and C
9 +A derives from the petrochemical complex Aromatic Hydrocarbon United Plant, and testing data is calculated as follows.
Below by description, further specify but do not limit the present invention: [embodiment 1～5] embodiment
Use Na
2O content is less than 0.15% (weight), SiO
2/ Al
2O
3Ammonium type mordenite powder 66.7 gram and the Na of molecular ratio 15～35
2O content is less than the α-Al of 0.15% (weight)
2O
3H
2O 57.1 gram uniform mixing are made into the aqueous solution with the chemical pure ammonium molybdate then and flood.Powder behind the dipping adds the chemical pure dilute nitric acid solution again, fully mediates evenly, carries out extruded moulding, catalyzer is made in roasting.The consumption that changes ammonium molybdate makes the molybdenum oxide weight content and is respectively 0.1%, 1.0%, 2.0%, 3.0%, 5.0% different catalysts A, B, C, D, E.[embodiment 6～10]
Prepare catalyzer with method identical among the embodiment 1, use Na
2The O weight content is less than 0.15% SiO
2/ Al
2O
3Molecular ratio is 15～40 β zeolite replacement mordenite.Make the molybdenum oxide weight content and be respectively 0.1%, 1.0%, 2.0%, 3.0%, 5.0% catalyst A
1, B
1, C
1, D
1, E
1[Comparative Examples 1]
The preparation method does not just add ammonium molybdate with embodiment 1, makes catalyzer G.[embodiment 11]
Catalysts containing molybdenum A～the E, the A that make with embodiment 1～10
1～E
1With the catalyzer G that Comparative Examples 1 makes, on the fixed bed reaction evaluating apparatus, carry out the active investigation of toluene disproportionation and transalkylation reaction.Loaded catalyst is 20 grams, and weight space velocity is 2.5 hours
-1, 390 ℃ of temperature of reaction, reaction pressure 3.0MPa (G), hydrogen hydrocarbon molecule are than 3.5, and raw material is toluene: C
9 +A=60: 40 (w/w), wherein, C
9 +Contain 12.5% (weight) C among the A
10 +A.C in the raw material wherein
9A weight consists of: propyl benzene 3.45%, first and second benzene 33.14%, trimethylbenzene 63.40%, C
10 +A weight consists of: diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene 28.84%, methylnaphthalene 14.49%, dimethylnaphthalene 11.16%, other C
11 +A12.90%, evaluation result such as table 1.
Table 1 evaluation result
| Catalyzer | Former powder | SiO 2/Al 2O 3(mol ratio) | MoO 3% (weight) | (toluene+C 9A) total conversion rate % | C 10 +A transformation efficiency % | (benzene+C 8A) selectivity % |
| A | Mordenite | 33.0 | 0.1 | 30.2 | 22.8 | 98.2 |
| B | 22.3 | 1.0 | 35.6 | 24.6 | 97.8 | |
| C | 15.0 | 2.0 | 28.4 | 24.2 | 98.5 | |
| D | 25.4 | 3.0 | 41.8 | 22.6 | 96.4 | |
| E | 22.3 | 5.0 | 46.0 | 30.4 | 95.3 | |
| A 1 | The β zeolite | 28.0 | 0.1 | 29.6 | 12.2 | 97.7 |
| B 1 | 15.6 | 1.0 | 34.3 | 14.0 | 97.6 | |
| C 1 | 24.6 | 2.0 | 40.2 | 14.2 | 96.8 | |
| D 1 | 31.4 | 3.0 | 42.4 | 18.0 | 96.1 | |
| E 1 | 28.0 | 5.0 | 46.8 | 22.3 | 94.8 | |
| G | Mordenite | 33.0 | 0 | 24.5 | / | 97.5 |
The present invention makes contains molybdenum filament geolyte, beta-zeolite catalyst, no matter the height of its molybdenum content, compare with the catalyzer that does not add molybdenum, has all presented higher activity.[embodiment 12]
Prepare catalyzer with method identical among the embodiment 1 and 9.Change the ratio of molecular sieve and aluminum oxide, the ammonium molybdate dilute nitric acid solution with among the dilute nitric acid solution replacement embodiment 1 and 9 of ammonium molybdate, Bismuth trinitrate makes MoO
3And Bi
2O
3Weight content is respectively 1.0% and 0.5% catalyzer H.Make catalyzer L, N, O, R, the S of one or more metals in bismuth-containing, nickel, lanthanum, silver, the rhenium with similar method.Form with the activity rating device among the embodiment 11 and reaction conditions and raw material and to carry out catalyst activity evaluation, result such as table 2.
Table 2 catalyst activity evaluation result
*M represents mordenite;
*β represents the β zeolite.
Evaluation result shows the catalyzer of one or more metal oxides in load molybdenum that the present invention makes and lanthanum, bismuth, nickel, silver, the rhenium, and toluene disproportionation and transalkylation reaction are had good catalytic activity.[embodiment 13～22]
With the catalyzer in the foregoing description, with the reaction raw materials of embodiment 11, suitably adjust the content of each component, and add indane (IND), change other appreciation condition, reaction result sees Table 3 and table 4.
The technical indicator of technology of the present invention under the table 3 differential responses condition
| Embodiment | 13 | 14 | 15 | 16 | 17 |
| Catalyzer | C 1 | D | E | E 1 | N |
| Reaction raw materials is formed (weight) %: toluene | 90.0 | 75.0 | 60.0 | 56.0 | 40.0 |
| C 9A IND | 5.0 0.4 | 10.0 0.8 | 36.3 0.6 | 35.0 0.6 | 48.0 0.7 |
| C 10 +A | 4.6 | 14.2 | 3.1 | 8.4 | 11.3 |
| Total amount | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Weight space velocity, (whsv) hr -1 | 4.5 | 4.0 | 3.0 | 2.5 | 1.5 |
| Reaction pressure, MPa (G) | 3.5 | 2.5 | 2.8 | 3.0 | 2.1 |
| Hydrogen hydrocarbon molecule ratio, mol/mol | 3.1 | 4.0 | 5.0 | 5.5 | 8.0 |
| Temperature of reaction, ℃ | 450 | 440 | 380 | 390 | 330 |
| Reaction result: % (toluene+C 9A) total conversion rate C 10 +A transformation efficiency (benzene+C 8A) selectivity | 40.0 40.1 97.0 | 40.2 35.0 99.5 | 42.0 6.1 95.1 | 46.0 32.0 96.0 | 43.3 40.0 98.0 |
The technical indicator of technology of the present invention under the table 4 differential responses condition
[embodiment 23]
| Embodiment | 18 | 19 | 20 | 21 | 22 |
| Catalyzer | H | L | R | S | O |
| Reaction raw materials is formed (weight) %: | |||||
| Toluene | 63.0 | 64.6 | 60.0 | 54.6 | 55.0 |
| C 9A IND | 36.6 0.4 | 30.0 0.4 | 32.5 0.5 | 38.0 0.4 | 37.1 0.8 |
| C 10 +A | / | 5.0 | 7.0 | 7.0 | 7.1 |
| Total amount | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Weight space velocity, (whsv) hr -1 | 2.5 | 2.5 | 2.0 | 1.0 | 3.0 |
| Reaction pressure, MPa (G) | 3.0 | 2.6 | 3.0 | 1.5 | 3.0 |
| Hydrogen hydrocarbon molecule ratio, mol/mol | 3.5 | 3.5 | 4.2 | 8.5 | 5.5 |
| Temperature of reaction, ℃ | 390 | 395 | 400 | 340 | 410 |
| Reaction result %:(toluene+C 9A) total conversion rate C 10 +A transformation efficiency (benzene+C 8A) selectivity | 42.0 / 94.8 | 45.1 30.2 95.0 | 46.2 42.3 97.5 | 40.4 40.5 98.5 | 45.5 40.1 97.4 |
The catalyzer E that makes with embodiment 5 uses different C respectively
10 +The raw material of A content carries out toluene disproportionation and transalkylation reaction, wherein toluene and C in the raw material
9 +The ratio of A and C
9A and C
10 +A forms with embodiment 11, investigates the ability that it handles carbon ten and carbon ten above aromatic hydrocarbons.All the other investigation conditions are investigated and be the results are shown in Table 5 with embodiment 11.
Table 5 is investigated the result
Annotate
*: refer to C in the 100 gram reaction product
5And C
5The growing amount of following hydrocarbon.
| C 9 +C among the A 10 +A content % (weight) | (toluene+C 9A) total conversion rate % | C 10 +A transformation efficiency % | (benzene+C 8A) selectivity % | Lighter hydrocarbons *G (gram) |
| 12.5 | 46.0 | 30.4 | 95.3 | 4.7 |
| 17.5 | 44.5 | 36.6 | 97.0 | 4.7 |
| 25.0 | 43.2 | 38.0 | 99.5 | 4.8 |
Table 5 data show that adopting technology of the present invention to handle contains higher C
10 +The raw material of A amount, as can be seen from Table 5, along with C in the raw material
10 +The increase of A content, purpose product (benzene+C
8A) selectivity increases, and the lighter hydrocarbons amount that generates is constant substantially, illustrates to transform the C of falling
10 +A mainly is by transalkylation process, changes into benzene and C
8Purpose products such as A.
Adopt method of the present invention,, generated a large amount of C because the excellent properties of employed catalyzer has had the function of toluene and carbon nine and above heavy arene generation transalkylation thereof
8A, disproportionation reaction takes place in toluene itself more in addition, generates benzene and C
8A has generated purpose product benzene and C in a large number thereby make in the product composition
8A.Therefore mainly be that disproportionation and transalkylation reaction take place in the technology of the present invention, rather than the hydro-dealkylation reaction, thereby avoided generating a large amount of light hydrocarbons, causing the wastage of material problem.
Catalyzer used in the present invention is owing to have disproportionation and transalkylation function simultaneously, make reaction raw materials break the restriction of pure toluene, catalyzer of the present invention in addition adopts the technical scheme that adds molybdenum and other active constituent in zeolite, especially on mordenite or β zeolite the load molybdenum oxide or/and nickel oxide or/and the oxide compound that is selected from lanthanum, silver or rhenium of bismuth oxide and non-imposed adding, more make the catalyzer that makes possess high catalytic activity, thereby make the content of carbon ten in the reaction raw materials and above aromatic hydrocarbons thereof can be up to 30% (weight), benzene adds C in the product simultaneously
8The selectivity of A makes carbon ten and above aromatic hydrocarbons thereof be transformed into benzene and C effectively up to 99.5%
8A has obtained effect preferably.Employed catalyzer in the technology of the present invention, by on mordenite or β zeolite or its mixture, introducing the load molybdenum oxide or/and nickel oxide or/and bismuth oxide, the sour intensity that improved the sour total amount of catalyzer and modulation effectively, thereby when improving catalyst activity, fully avoid the generation of side reaction, the processing power and the purpose product selectivity of catalyzer have been improved effectively, thereby make the inventive method have extraordinary technico-economical comparison, under high-speed, high conversion, have high purpose selectivity of product, have good industrial prospect.
The invention is not restricted to above embodiment, those skilled in the art can make various changes and distortion according to the present invention, only otherwise break away from spirit of the present invention, all should belong to scope of the present invention.
Claims (13)
1, a kind of toluene and carbon nine and above heavy arene disproportionation and alkyl transfering process comprise:
A) be reaction raw materials with toluene and carbon nine and above heavy arene thereof, use fixed-bed reactor, raw material toluene and C
9 +A mixes with hydrogen, from top to bottom by beds, disproportionation and transalkylation reaction takes place, and wherein wt is than toluene: C
9 +A=95: 5～5: 95, C in the reaction raw materials
10 +The A weight percentage is 0～30%, wherein C
9 +A is carbon nine and above heavy arene thereof, C
10 +A is carbon ten and above heavy arene thereof;
B) weight space velocity is 0.8～8.0 hour
-1
C) temperature of reaction is 300～500 ℃;
D) under the hydro condition, in gauge pressure reaction pressure 1.0～5.0MPa, hydrogen hydrocarbon molecule ratio is 1～10;
E) catalyzer is toluene and carbon nine and above heavy arene disproportionation and transalkylation catalyst, wherein comprises in parts by weight:
1) SiO
2/ Al
2O
3Mol ratio is 20～90 parts of 10～50 h-type zeolites; Be stated from the zeolite
2) oxide compound of molybdenum is 0.05～10 part;
3) at least a oxide compound that is selected from nickel or bismuth is 0～10 part;
4) at least a oxide compound that is selected from lanthanum, silver or rhenium is 0～10 part;
5) the binding agent aluminum oxide is 10～60 parts.
2, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, wherein
A) the ratio weight ratio of described toluene and carbon nine and above heavy arene thereof is toluene: C
9 +A=90: 10～30: 70, C in the reaction raw materials
10 +The A weight percentage is 3～20%;
B) described weight space velocity is 1.5～4.5 hours
-1
C) described temperature of reaction is 350 ℃～450 ℃;
D) described reaction pressure is 2.0～3.5MPa, and hydrogen hydrocarbon molecule ratio is 3～7.
3, according to the described toluene of claim 2 and carbon nine and above heavy arene disproportionation and alkyl transfering process, wherein
A) the ratio weight ratio of described toluene and carbon nine and above aromatic hydrocarbons thereof is toluene: C
9 +A=80: 20～40: 60; C in the reaction raw materials
10 +The A weight percentage is 5～15%.
4, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, h-type zeolite is selected from mordenite, β zeolite or its miscellany in the wherein said catalyzer.
5, according to the described toluene of claim 4 and carbon nine and above heavy arene disproportionation and alkyl transfering process, wherein said h-type zeolite is selected from the β zeolite.
6, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, the oxide amount in the parts by weight molybdenum in the wherein said catalyzer is 0.1～5 part.
7,, in parts by weight, contain 0～5 part of at least a oxide compound that is selected from nickel or bismuth in the wherein said catalyzer according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process.
8,, in parts by weight, contain 0.1～5 part of at least a oxide compound that is selected from nickel or bismuth in the wherein said catalyzer according to the described toluene of claim 7 and carbon nine and above heavy arene disproportionation and alkyl transfering process.
9, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, in parts by weight, contain 0～5 part of nickel oxide in the wherein said catalyzer.
10, according to the described toluene of claim 9 and carbon nine and above heavy arene disproportionation and alkyl transfering process, in parts by weight, contain 0.1～5 part of nickel oxide in the wherein said catalyzer.
11, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, in the wherein said catalyzer in parts by weight, 0～5 part of bismuth oxide.
12, according to the described toluene of claim 11 and carbon nine and above heavy arene disproportionation and alkyl transfering process, in the wherein said catalyzer in parts by weight, 0.1～5 part of bismuth oxide.
13, according to the described toluene of claim 1 and carbon nine and above heavy arene disproportionation and alkyl transfering process, in the wherein said catalyzer in parts by weight, 0.1～5 part of at least a oxide compound that is selected from lanthanum, silver or rhenium.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| CN100376658C (en) * | 2004-09-02 | 2008-03-26 | 中国石油天然气集团公司 | Catalytic gasoline hydrogenation modifying catalyst and its preparing method |
| 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 |
| CN101172251B (en) * | 2006-11-02 | 2010-05-12 | 中国石油化工股份有限公司 | Arene alkyl transfer and dealkylation catalyst for increasing production of xylol |
| CN101190866B (en) * | 2006-11-21 | 2011-08-17 | 中国石油化工股份有限公司 | Arene alkyl transferring and dealkylation reaction method of low ethyl benzene by-product |
| CN101554591B (en) * | 2008-04-08 | 2011-08-31 | 中国科学院大连化学物理研究所 | Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof |
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| CN110180581B (en) * | 2018-02-22 | 2021-11-30 | 中国石油化工股份有限公司 | Catalysts and their use in C11+Application in reaction for converting heavy aromatics into light aromatics |
| CN110075912A (en) * | 2019-05-20 | 2019-08-02 | 南京工业大学 | A kind of C10+Heavy arene hydrogenation takes off the catalyst and preparation method thereof that alkyl prepares low-carbon aromatic hydrocarbons |
| CN110075911A (en) * | 2019-05-20 | 2019-08-02 | 南京工业大学 | One kind being used for C10+Heavy arene hydrogenation takes off the catalyst and preparation method thereof of alkyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Assignee: China Petrochemical Science and Technology Development Co Ltd Assignor: Shanghai Petrochemical Research Institute|China Petroleum Chemical Co, China Petroleum Chemical Co Contract record no.: 2010990000343 Denomination of invention: Disproportionation and transalkylation process of toluene and C9 and heavier aromatic hydrocarbons Granted publication date: 20031008 License type: Exclusive License Open date: 20020605 Record date: 20100603 |
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