CN102190553B - Aromatic hydrocarbon alkyl transfer method for producing benzene and p-xylene - Google Patents
Aromatic hydrocarbon alkyl transfer method for producing benzene and p-xylene Download PDFInfo
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Abstract
The invention relates to an aromatic hydrocarbon alkyl transfer method for producing benzene and p-xylene, and the method is mainly used for solving the problems that in the prior art, an isomerization unit and a disproportionation unit of p-xylene just respectively process C8 aromatic hydrocarbon and toluene, and the equipment investment is large. The method comprises the following steps: a) feeding mixed xylene containing o-xylene and m-xylene and a toluene material into an aromatic hydrocarbon alkyl transfer process unit so as to generate an aromatic hydrocarbon alkyl transfer reaction under the hydrogen condition so as to generate an aromatic hydrocarbon material flow containing benzene and p-xylene after reaction; (b) successively passing the aromatic hydrocarbon material flow containing the benzene and the p-xylene through a benzene tower, a toluene tower and a xylene tower so as to separate out the benzene and the mixed xylene; and (c) feeding the mixed xylene in a absorption separation or freezing crystalline separation unit so as to generate the p-xylene, and feeding the unreacted toluene and xylene in the aromatic hydrocarbon alkyl transfer unit, wherein a composite catalyst bed layer is adopted in the aromatic hydrocarbon alkyl transfer process unit, aromatic hydrocarbon alkyl transfer reaction occurs to the upper catalyst bed layer, and toluene selectivity disproportional reaction is carried out on the lower catalyst bed layer with a shape-selective function. By using the technical scheme, the problem can be well solved; and the method can be applied to production of benzene and p-xylene.
Description
Technical field
The present invention relates to a kind of arene transalkylation method of producing benzene and p-Xylol, particularly about a kind of, can process the arene transalkylation method that toluene and C8 aronmatic are produced benzene and p-Xylol simultaneously.
Background technology
P-Xylol (PX) and benzene (B) are the important basic organic chemical industry raw materials involving the interests of the state and the people, can be widely used in the numerous areas such as polyester, chemical fibre, rubber, agricultural chemicals, home consumption amount reaches up to ten million tons, and its output value is huge, and the national economic development is had to material impact.By terephthalic acid (PTA) or diethyl terephthalate (DMT) intermediate, p-Xylol is nearly all for the production of trevira, resin and film.Benzene is the basic petrochemical material of a kind of multi-usage, can produce its derivative many variant productions, comprises ethyl benzene/styrene, cumene/phenol and hexanaphthene/hexanolactam.In petrochemical industry, it is object product that Aromatic Hydrocarbon United Plant be take p-Xylol and benzene conventionally.
P-Xylol that will production maximum, the dimethylbenzene in catalytic reforming and cracking of ethylene gasoline, is mainly to adopt the processing method of disproportionation and transalkylation toluene and C
9aromatic hydrocarbons under molecular sieve catalyst effect, carries out disproportionation and transalkylation reaction generates xylol and benzene, xylol is converted into p-Xylol by dimethylbenzene hydro-isomerization metallization processes again, thereby is high added value aromatic hydrocarbon product low value-added feedstock conversion.In traditional Aromatic Hydrocarbon United Plant, the catalyzer of unit has diverse catalysis, realized respectively disproportionation and reacted with transalkylation reaction, isomerization reaction and heavy aromatics lighting, this has brought that technical process is complicated, facility investment is huge, solid circulating rate is large and the problem such as energy consumption is high.
C
8aromatic hydrocarbons is the mixture of p-Xylol (PX), m-xylene (MX), o-Xylol (OX) and the ethylbenzene (EB) etc. that obtain from catalytic reforming, petroleum cracking process.The boiling point of ethylbenzene and dimethylbenzene is close, although can carry out separation by superfractionation, due to the requirement that device is large, recycle ratio is high, ethylbenzene purity does not reach vinylbenzene industry, therefore must be by ethylbenzene conversion in xylene isomerization process.Xylene isomerization is exactly by the C containing poor PX
8aromatic hydrocarbons mixture is converted into and is approached the C that thermodynamic(al)equilibrium forms by catalyst action
8aromatic hydrocarbons mixture, in conjunction with PX separating technology, by cyclical operation, progressively by OX, MX and EB are all converted into PX, reach the object of volume increase PX.The isomerization process of the isomerization process that wherein ethylbenzene isomerization is dimethylbenzene and ethylbenzene dealkylation volume increase benzene can be selected according to product requirement and turn of the market.Isomerization unit has determined the economy of Aromatic Hydrocarbon United Plant.Owing to being subject to the restriction of thermodynamic(al)equilibrium, the content by p-Xylol in isomerization unit gained dimethylbenzene generally only has 24% left and right, causes like this treatment capacity of aromatic hydrocarbons fractionation unit and PX separating unit large, energy consumption is higher.
Methylbenzene shape selective disproportionation is that toluene reacts and generates the C of benzene and high PX concentration on the ZSM-5 catalyzer through modification
8aromatic hydrocarbons is a new way of producing PX and benzene.Methylbenzene shape selective disproportionation generates the process of PX, is subject to the acting in conjunction of acid catalysis and diffusion control.There is disproportionation reaction in the toluene molecule that enters ZSM-5 duct, generate the xylol of benzene and thermodynamic(al)equilibrium on acid sites.Under the sieving action of molecular sieve pore passage, preferentially diffusion effusion from zeolite cavity of benzene and PX, and m-xylene and o-Xylol are limited in molecular sieve pore passage, through isomerization reaction, generate PX.In recent years, along with improving constantly of catalyst performance, this technique has obtained considerable progress.Its typical process has the SD-01 technique of industrialized MSTDP technique the late nineteen eighties, the PX-Plus technique of releasing in recent years and the exploitation of Sinopec Shanghai Petroleum Chemical Engineering Institute.Its representative processes index is as follows: toluene conversion 30%, and in dimethylbenzene, the selectivity of PX reaches 90%, and the mol ratio of benzene and PX is about 1.4.Yet, in the technique of this class selective disproportionation of toluene, thering is the harshness of the simultaneous of high para-selectivity to material choice, this technique can only be take pure toluene as raw material.
The main chemical reactions occurring from Aromatic Hydrocarbon United Plant, by disproportionation and transalkylation reaction, two contraposition methyl to PX transform methyl on side chain aromatic hydrocarbons, there is dealkylation in the ethyl on side chain aromatic hydrocarbons, propyl group etc., finally realizes the maximization of B and PX and produce.If the catalyzer of these features can be integrated in a reactor, the height of realizing disproportionation and transalkylation, isomerization unit is integrated, and High-efficient Production benzene and p-Xylol will have very important significance, and is also an important developing direction.The exploitation of many beds catalyst system that function matches is expected to realize this target.The key of many beds catalyst system exploitation is, the reasonable coupling of the appropriate combination of reaction raw materials, the exploitation of performance function beds and a plurality of beds.
In recent years, even outstanding advantage and the exploitation thereof of many beds fixed-bed process have caused that people pay close attention to greatly to dual bed.United States Patent (USP) (USP 7314601) has been introduced the p-Xylol production technology of a kind of integrated disproportionation and transalkylation, isomerization unit function, upper strata catalyzer or upstream reactor performance disproportionation and transalkylation function, lower floor's catalyzer or downstream reactor performance xylene isomerization function, the object that improve dimethylbenzene yield to reach, reduces facility investment and energy consumption.But, the toluene in raw material and C
9aromatic hydrocarbons is when disproportionation and transalkylation Partial Conversion are benzene and dimethylbenzene, inevitably can on the disproportionation of strong solid acidity and transalkylation catalyst, there is disproportionation reaction in the dimethylbenzene in logistics, cause a large amount of losses of dimethylbenzene, this will reduce the economy of reaction.
Summary of the invention
Technical problem to be solved by this invention is that C can only be processed respectively in the xylene isomerization unit and the disproportionation unit that in prior art, exist
8aromatic hydrocarbons and toluene, the problem that facility investment is large, provides a kind of new production benzene and the arene transalkylation method of p-Xylol.The method, for the production of Aromatic Hydrocarbon United Plant benzene and PX, has and can process C simultaneously
8aromatic hydrocarbons and toluene material, the advantages such as low equipment investment.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of arene transalkylation method of producing benzene and p-Xylol, comprise the following steps: the xylol and the toluene material that a) contain o-Xylol and m-xylene enter aromatic hydrocarbons alkyl transfering process unit, under hydro condition, there is transalkylation, after reaction, generate the arene stream containing benzene and p-Xylol; B) arene stream containing benzene and p-Xylol that reaction generates, successively by benzene tower, toluene tower and benzenol hydrorefining, is isolated benzene and xylol; C) elder brother closes dimethylbenzene and removes fractionation by adsorption or freezing and crystallizing separating unit production p-Xylol, and unreacted toluene and dimethylbenzene are to aromatic hydrocarbons alkyl transfering process unit feed; Wherein, aromatic hydrocarbons alkyl transfering process unit adopts composite catalyst bed, on upper catalyst bed layer, xylene isomerization reaction occurs, and has on the lower catalyst bed layer of shape selecting function toluene selective disproportionation reaction occurs.
In technique scheme, aromatic hydrocarbons alkyl transfering process unit adopts axial restraint bed bioreactor, and in upper catalyst bed layer and lower catalyst bed layer, the mass ratio of catalyzer is between 1/10 to 10/1, and preferable range is between 1/3 to 3/1; In xylol, p-Xylol content from 0 to 15%, and preferred version is for containing p-Xylol, and wherein the xylol of extraction p-Xylol and toluene material comprise not the toluene higher than 90 % by weight of material gross weight; Aromatic hydrocarbons alkyl transfering process unit generation isomery turns to the reaction of dimethylbenzene or de-ethyl generation benzene; Adopt many beds fixed bed catalyst technique, on upper catalyst bed layer, xylene isomerization reaction occurs, have on the lower catalyst bed layer of shape selecting function toluene selective disproportionation reaction occurs.Using the xylol that contains o-Xylol and m-xylene and toluene mixing of materials dimethylbenzene and toluene as raw material, by this unique aromatic hydrocarbons transalkylation, through aromatic hydrocarbons fractionation is separated with PX, can obtain benzene and PX again, technique integrated level is high, facility investment saving.And, owing to having passed through modification, outside surface is by effectively passivation, the dimethylbenzene molecule that kinetic diameter is greater than 10 ring molecular sieve pore passages cannot enter zeolite granular inside and react, it is minimum that this has dropped to the disproportionation reaction of dimethylbenzene molecule on toluene selective disproportionation catalyst, solved the excessive problem of xylene loss.
Adopt technical scheme of the present invention, the reaction pressure of aromatic hydrocarbons transalkylation is 0.6～3.0MPa, and temperature of reaction is 380～450 ℃, and hydrogen/hydrocarbon mol ratio is 0.5～10.0, and weight space velocity is 0.8～10.0 hour
-1.Upper catalyst bed layer catalyzer molecular sieve preferred version used is selected from ZSM-5, its silica alumina ratio between 200～300, ZSM-11, its silica alumina ratio between 30～210, Y zeolite, its silica alumina ratio is between 4～15 or mordenite, its silica alumina ratio is between 10～45, lower catalyst bed layer catalyzer molecular sieve preferred version used is selected from ZSM-5, and its silica alumina ratio is between 12～50.The xylol that contains o-Xylol and m-xylene is in catalyzer upper bed layer generation isomerization reaction, dimethylbenzene reaches thermodynamic(al)equilibrium, if ethylbenzene occur reaction that isomery turns to dimethylbenzene transformation efficiency be greater than 25%, if the reaction conversion ratio that de-alkyl generates benzene occurs ethylbenzene, reach more than 60%.A small amount of toluene that toluene in raw material and isomerization reaction produce generates benzene and containing the xylol of high density PX at catalyzer lower bed layer generation shape-selective disproportionation reaction.In product, PX content is much higher than thermodynamic equilibrium value, and this is all very favorable for absorption and Crystallization Separation.Can find out, such operational path, can allow the PX concentration of producing in the xylol obtaining significantly improve, and has improved the efficiency of PX separating unit, effectively reduces again facility investment scale, has reduced production cost, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is that traditional aromatic hydrocarbons is produced machinery technical process.
Fig. 2 is the technical process that comprises aromatic hydrocarbons transalkylation of the present invention.
Fig. 3 is the dual bed reactor schematic diagram of aromatic hydrocarbons transalkylation of the present invention.
In Fig. 1: I. reformer unit deheptanizer; II. Aromatics Extractive Project unit; III. benzene toluene separating unit; IV. benzenol hydrorefining unit; V. toluene disproportionation and transalkylation; VI. xylene isomerization process unit; VII. dimethylbenzene separating technology unit.1. reformation de-pentane oil; 2. the C distillating from deheptanizer tower top
7 -(comprising that benzene, toluene and carbon six carbon seven are non-aromatic); 3. carbon eight and the above arene stream for deheptanizer tower reactor, extracted out; 4. for extracting non-aromatic benzene and toluene logistics; 5. non-aromatic; 6. the high-purity benzene product that benzene column overhead is extracted; 7. the toluene that toluene tower tower top is extracted; 8. toluene tower tower reactor is extracted out carbon eight and above aromatic hydrocarbons; 9. the still liquid that disproportionation and transalkylation stabilizer tower tower reactor are extracted out; 10. the heavy aromatics tower top in dimethylbenzene separating unit is extracted out carbon nine and part C10 aromartic; The xylol that 11. benzenol hydrorefining tower tops are extracted out; Carbon ten and above aromatic hydrocarbons that 12. heavy aromatics tower tower reactors are extracted out; A small amount of toluene that 13. dimethylbenzene separating units separate; 14; Highly purified p-Xylol product; 15. isolate the xylol of p-Xylol; The above arene stream of carbon eight that 16. isomerization unit deheptanizer tower reactors are discharged; The logistics that contains benzene and toluene that 17. isomerization unit deheptanizer tower tops are extracted; The benzene logistics of 18. disproportionations and transalkylation extraction.
In this traditional technology route, by unit processes such as reformation, extracting, fractionation, disproportionation and transalkylations, obtain the mixed C 8 aromatics (C8A) that PX concentration is less than 20%, then produce PX through unit processes such as isomerization and fractionation by adsorption.
In Fig. 2: A. transalkylation reactor; B. gas stripping column; C. benzene tower; D. toluene tower; E. benzenol hydrorefining; F. dimethylbenzene separating technology unit.
1. toluene and dimethylbenzene parallel feeding; 2. pass through the product of transalkylation reactor; 3. gas stripping column materials at bottom of tower; 4. benzene tower materials at bottom of tower; 5. toluene tower materials at bottom of tower; 6. circulation toluene material; 7. heavy aromatics material at the bottom of benzenol hydrorefining tower; 8. xylol material; 9. p-Xylol material; 10. the dimethylbenzene material of poor p-Xylol; 11. high purity p-Xylol products.
In this operational path, the xylol that contains o-Xylol and m-xylene and toluene material enter aromatic hydrocarbons alkyl transfering process unit, under hydro condition, there is transalkylation, the arene stream containing benzene and p-Xylol that reaction generates is successively by benzene tower, toluene tower and benzenol hydrorefining, isolate benzene and xylol, xylol goes fractionation by adsorption or freezing and crystallizing separating unit to produce p-Xylol, and unreacted toluene and dimethylbenzene are to aromatic hydrocarbons alkyl transfering process unit feed.The operational condition of benzene tower, toluene tower, benzenol hydrorefining and dimethylbenzene separating unit is with traditional Aromatic Hydrocarbon United Plant.
In Fig. 3: 1. toluene and dimethylbenzene parallel feeding; A. arene transalkylation catalyst constituent element; B. selective disproportionation catalyst constituent element.
The xylol that contains o-Xylol and m-xylene enters aromatic hydrocarbons alkyl transfering process unit together with toluene material, respectively at upper bed layer and lower bed layer generation transalkylation and methylbenzene shape-selective disproportionation reaction.
Below by example, further illustrate the present invention, but the present invention is not limited to this.
Embodiment
[embodiment 1]
Get silica alumina ratio and be 150 grams of 180 high silica alumina ratio Hydrogen ZSM-5 molecular sieves, 70 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, the platinum acid chloride solution of take obtains platinum content as the platinum of 0.05 % by weight by incipient impregnation, can obtain the de-ethyl type C of ethylbenzene after oven dry roasting
8a arene transalkylation catalyst.Get silica alumina ratio and be 160 grams of 15 low silica-alumina ratio Hydrogen ZSM-5 molecular sieves, adding dioxide-containing silica is 100 grams of 40 silicon sol, after kneading, extrusion, oven dry, roasting obtain catalyst body, with polymethylphenyl siloxane fluid, flood this catalyst body, dry rear roasting, carry out so more silicon oil modified process twice, obtain toluene selective disproportionation catalyst.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 8 grams of C into
8a arene transalkylation catalyst, bottom packs 12 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.Wherein temperature of reaction is 415 ℃, weight space velocity 2h
-1, reaction pressure 1.2MPa, hydrogen hydrocarbon mol ratio is 3.0.
Raw material toluene and C8A aromatic hydrocarbons derive from petrochemical complex Aromatic Hydrocarbon United Plant, H
2for electrolysis hydrogen, through dehydrating processing, the results are shown in Table 1 for raw material and product analysis.
Table 1 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 1.03 | 1.21 |
| Benzene | 0 | 8.73 |
| Toluene | 50.10 | 35.42 |
| Ethylbenzene | 5.81 | 1.74 |
| P-Xylol | 0 | 17.59 |
| M-xylene | 29.73 | 22.87 |
| O-Xylol | 13.32 | 11.36 |
| C 9A aromatic hydrocarbons | 0.10 | 1.08 |
Wherein, toluene conversion is 29.31%, and conversion of ethylbenzene is 70.05%, Selectivity for paraxylene 33.94%.
[embodiment 2]
Get silica alumina ratio and be 160 grams of 45 Hydrogen ZSM-5 molecular sieves, 80 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, and the platinum acid chloride solution of take obtains platinum content as the platinum of 0.06 % by weight by incipient impregnation, can obtain the de-ethyl type C of ethylbenzene after oven dry roasting
8a arene transalkylation catalyst.Get silica alumina ratio and be 160 grams of 25 low silica-alumina ratio Hydrogen ZSM-5 molecular sieves, adding dioxide-containing silica is 100 grams of 40 silicon sol, after kneading, extrusion, oven dry, roasting obtain catalyst body, with polymethylphenyl siloxane fluid, flood this catalyst body, dry rear roasting, carry out so more silicon oil modified process twice, obtain toluene selective disproportionation catalyst.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 12 grams of C into
8a arene transalkylation catalyst, bottom packs 8 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.Wherein temperature of reaction is 390 ℃, weight space velocity 1h
-1, reaction pressure 1.5MPa, hydrogen hydrocarbon mol ratio is 1.0.
Raw material toluene and C
8a aromatic hydrocarbons derives from petrochemical complex Aromatic Hydrocarbon United Plant, H
2for electrolysis hydrogen, through dehydrating processing, in raw material and product analysis result table 2.
Table 2 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 1.03 | 1.09 |
| Benzene | 0 | 10.48 |
| Toluene | 48.05 | 35.54 |
| Ethylbenzene | 7.86 | 1.92 |
| P-Xylol | 0 | 16.46 |
| M-xylene | 26.38 | 23.61 |
| O-Xylol | 16.54 | 9.62 |
| C 9A aromatic hydrocarbons | 0.23 | 1.37 |
Wherein, toluene conversion is 28.25%, and conversion of ethylbenzene is 76.32%, Selectivity for paraxylene 33.13%.
[embodiment 3]
Get silica alumina ratio and be 150 grams, 110 high silica alumina ratio Hydrogen ZSM-11 molecular sieve, 70 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, the platinum acid chloride solution of take obtains platinum content as the platinum of 0.05 % by weight by incipient impregnation, can obtain the de-ethyl type C of ethylbenzene after oven dry roasting
8a aromatic hydrocarbons ten thousand group-transfer catalyzer.Get silica alumina ratio and be 160 grams of 37 low silica-alumina ratio Hydrogen ZSM-5 molecular sieves, adding dioxide-containing silica is 100 grams of 40 silicon sol, after kneading, extrusion, oven dry, roasting obtain catalyst body, with polymethylphenyl siloxane fluid, flood this catalyst body, dry rear roasting, carry out so more silicon oil modified process twice, obtain toluene selective disproportionation catalyst.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 10 grams of C into
8a arene transalkylation catalyst, bottom packs 10 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.
Raw material toluene and C8A aromatic hydrocarbons derive from petrochemical complex Aromatic Hydrocarbon United Plant, H
2for electrolysis hydrogen, through dehydrating processing, the results are shown in Table 3 for raw material and product analysis.Wherein temperature of reaction is 425 ℃, weight space velocity 3.5h
-1, reaction pressure 2.1MPa, hydrogen hydrocarbon mol ratio 5.0.
Table 3 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 0.94 | 1.07 |
| Benzene | 0 | 12.55 |
| Toluene | 39.78 | 27.31 |
| Ethylbenzene | 14.76 | 4.94 |
| P-Xylol | 1.37 | 22.97 |
| M-xylene | 29.73 | 20.00 |
| O-Xylol | 13.32 | 9.95 |
| C 9A aromatic hydrocarbons | 0.10 | 1.21 |
Wherein, toluene conversion is 33.4%, and conversion of ethylbenzene is 67.99%, and Selectivity for paraxylene is 43.41%.
[embodiment 4]
Get silica alumina ratio and be 100 grams, 9 y-type zeolite molecular sieve, 140 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, and the platinum acid chloride solution of take obtains platinum content as 0.5 % by weight by incipient impregnation, and after oven dry roasting, can obtain ethylbenzene isomerization is xylol type C
8a arene transalkylation catalyst.Toluene selective disproportionation catalyst is with embodiment 1.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 6 grams of C into
8a arene transalkylation catalyst, bottom packs 14 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons, the results are shown in Table 4 for raw material and product analysis.Wherein temperature of reaction is 440 ℃, weight space velocity 1.5h
-1, reaction pressure 1.8MPa, hydrogen hydrocarbon mol ratio 3.0.
Table 4 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 1.03 | 1.75 |
| Benzene | 0 | 7.65 |
| Toluene | 50.10 | 31.56 |
| Ethylbenzene | 5.81 | 3.78 |
| P-Xylol | 0 | 18.75 |
| M-xylene | 29.73 | 23.96 |
| O-Xylol | 13.32 | 10.52 |
| C 9A aromatic hydrocarbons | 0.10 | 2.03 |
Wherein, toluene conversion is 37.01%, and conversion of ethylbenzene is 34.94%, and Selectivity for paraxylene is 35.22%.
[embodiment 5]
Get silica alumina ratio and be 100 grams, 25 high silica alumina ratio h-mordenite molecular sieve, 140 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, the platinum acid chloride solution of take obtains platinum content as 0.8 % by weight by incipient impregnation, and after oven dry roasting, can obtain ethylbenzene isomerization is xylol type C
8a arene transalkylation catalyst.Toluene selective disproportionation catalyst is with embodiment 2.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 11 grams of C into
8a arene transalkylation catalyst, bottom packs 9 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.Raw material and product analysis the results are shown in Table 5.Wherein temperature of reaction is 430 ℃, weight space velocity 2h
-1, reaction pressure 1.2MPa, hydrogen hydrocarbon mol ratio 4.0.
Table 5 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 1.03 | 1.48 |
| Benzene | 0.56 | 6.01 |
| Toluene | 40.35 | 30.23 |
| Ethylbenzene | 7.56 | 5.15 |
| P-Xylol | 0.3 | 14.54 |
| M-xylene | 32.05 | 29.15 |
| O-Xylol | 18.03 | 11.87 |
| C 9A aromatic hydrocarbons | 0.12 | 1.57 |
Wherein, toluene conversion is 27.31%, and conversion of ethylbenzene is 33.91%, and Selectivity for paraxylene is 26.17%.
[embodiment 6]
Get silica alumina ratio and be 37 grams, 16 high silica alumina ratio h-mordenite molecular sieve, 140 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, the platinum acid chloride solution of take obtains platinum content as 0.3 % by weight by incipient impregnation, and after oven dry roasting, can obtain ethylbenzene isomerization is xylol type C
8a arene transalkylation catalyst.Toluene selective disproportionation catalyst bed preparation method is with embodiment 1.
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 6 grams of C into
8a arene transalkylation catalyst, bottom packs 14 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.Raw material and product analysis the results are shown in Table 6.Wherein temperature of reaction is 450 ℃, weight space velocity 4h
-1, reaction pressure 0.8MPa, hydrogen hydrocarbon mol ratio 4.0.
Table 6 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 1.82 | 1.85 |
| Benzene | 0.50 | 8.72 |
| Toluene | 50.56 | 33.95 |
| Ethylbenzene | 4.20 | 3.22 |
| P-Xylol | 0.1 | 15.36 |
| M-xylene | 30.31 | 24.50 |
| O-Xylol | 12.35 | 10.98 |
| C 9A aromatic hydrocarbons | 0.16 | 1.42 |
Wherein, toluene conversion is 34.87%, and conversion of ethylbenzene is 25.63%, and Selectivity for paraxylene is 30.21%.
[embodiment 7]
Upper bed layer transalkylation catalyst preparation method is with embodiment 1, and toluene selective disproportionation catalyst bed preparation method is also with embodiment 1.Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons.25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel.Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 2 grams of C into
8a arene transalkylation catalyst, bottom packs 18 grams of toluene selective disproportionation catalysts into.Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons.Raw material and product analysis the results are shown in Table 7.Wherein temperature of reaction is 450 ℃, weight space velocity 2h
-1, reaction pressure 1.5MPa, hydrogen hydrocarbon mol ratio 4.0.
Table 7 raw material and product weight percent form
| Component title | Raw material weight percentage composition, % | Product weight percentage, % |
| Non-aromatic | 0.23 | 0.21 |
| Benzene | 0 | 15.47 |
| Toluene | 88.65 | 59.98 |
| Ethylbenzene | 1.25 | 0.42 |
| P-Xylol | 0 | 14.97 |
| M-xylene | 5.91 | 5.84 |
| O-Xylol | 3.86 | 2.46 |
| C 9A aromatic hydrocarbons | 0.10 | 0.65 |
Wherein, toluene conversion is 30.25%, and conversion of ethylbenzene is 65.07%, and Selectivity for paraxylene is 64.33%.
Claims (1)
1. an arene transalkylation method of producing benzene and p-Xylol, get silica alumina ratio and be 150 grams, 110 high silica alumina ratio Hydrogen ZSM-11 molecular sieve, 70 grams of pseudo-boehmites, after kneading, extrusion, oven dry, roasting obtain catalyst body, the platinum acid chloride solution of take obtains platinum content as the platinum of 0.05 % by weight by incipient impregnation, can obtain the de-ethyl type C of ethylbenzene after oven dry roasting
8a arene transalkylation catalyst; Get silica alumina ratio and be 160 grams of 37 low silica-alumina ratio Hydrogen ZSM-5 molecular sieves, adding dioxide-containing silica is 100 grams of 40 silicon sol, after kneading, extrusion, oven dry, roasting obtain catalyst body, with polymethylphenyl siloxane fluid, flood this catalyst body, dry rear roasting, carry out so more silicon oil modified process twice, obtain toluene selective disproportionation catalyst;
Under hydro condition, in multi-stage fixed-bed reactor, carry out toluene and C
8the transalkylation reaction Performance of A aromatic hydrocarbons; 25 millimeters of reactor inside diameter Φ, 1000 millimeters of length, stainless steel; Beds up and down equal 3 millimeters of granulated glass spherees of filling Φ plays air-flow distribution and supporting role, and top packs 10 grams of C into
8a arene transalkylation catalyst, bottom packs 10 grams of toluene selective disproportionation catalysts into; Aroamtic hydrocarbon raw material from top to bottom by beds, carries out toluene and C after mixing with hydrogen
8the transalkylation reaction of A aromatic hydrocarbons;
Raw material toluene and C8A aromatic hydrocarbons derive from petrochemical complex Aromatic Hydrocarbon United Plant, H
2for electrolysis hydrogen, through dehydrating processing, wherein temperature of reaction is 425 ℃, weight space velocity 3.5h
-1, reaction pressure 2.1MPa, hydrogen hydrocarbon mol ratio 5.0; Raw material and product analysis result are as follows:
In raw material, each composition weight percentage composition is as follows: non-aromatics is 0.94%, and benzene is 0, and toluene is 39.78%, and ethylbenzene is 14.76%, and p-Xylol is 1.37%, and m-xylene is 29.73%, and o-Xylol is 13.32%, C
9a aromatic hydrocarbons is 0.10%;
In product, each composition weight percentage composition is as follows: non-aromatics is 1.07%, and benzene is 12.55%, and toluene is 27.31%, and ethylbenzene is 4.94%, and p-Xylol is 22.97%, and m-xylene is 20.00%, and o-Xylol is 9.95%, C
9a aromatic hydrocarbons is 1.21%;
Wherein, toluene conversion is 33.4%, and conversion of ethylbenzene is 67.99%, and Selectivity for paraxylene is 43.41%.
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| CN108430958B (en) | 2015-12-16 | 2021-01-01 | 环球油品公司 | Method and apparatus for toluene methylation in aromatic compound compounding equipment |
| US10501389B1 (en) * | 2018-10-25 | 2019-12-10 | Saudi Arabian Oil Company | Process and system for the production of para-xylene and benzene from streams rich in C6 to C12+ aromatics |
| EP3921296A1 (en) * | 2019-02-04 | 2021-12-15 | China Petroleum & Chemical Corporation | Process for making phenol and xylenes |
| CN112824364B (en) * | 2019-11-21 | 2023-01-03 | 中国石化工程建设有限公司 | Process for disproportionating alkyl aromatic hydrocarbon |
| CN114426456A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Combined process for benzene and heavy aromatic transalkylation and toluene methylation |
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