CN1377864A - Benzene and heavy arene transalkylation method - Google Patents
Benzene and heavy arene transalkylation method Download PDFInfo
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- CN1377864A CN1377864A CN 01105840 CN01105840A CN1377864A CN 1377864 A CN1377864 A CN 1377864A CN 01105840 CN01105840 CN 01105840 CN 01105840 A CN01105840 A CN 01105840A CN 1377864 A CN1377864 A CN 1377864A
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- benzene
- heavy arene
- arene
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Abstract
The present invention relates to transalkylation process for benezene and heavy arene. Inside one fixed bed reactor, under the hydrogen condition, in the presence of hydrogen type flokite, beta-zeolite or Y-zeolite catalyst with loaded Bi and at least one of optional Fe, Co, Ni and Mo, and at 300-600 deg.c temperature and 1.5-6.0 MPa pressure, benzene, C10 arene and/or C11 arene material are made to react to produce C7-C9 arene and C1-C4 paraffin. The said process is especially suitable for transalkylation reaction of C10 arene and/or C11 arene, and can convert benzene and heavy arene into valuable methyl benzene, C8 arene and C9 arene, and may be used in industrial production.
Description
The present invention relates to benzene and heavy arene transalkylation method, particularly carry out transalkylation reaction generation C about benzene and heavy arene
7~C
9The method of aromatic hydrocarbons.
Past people is usually C
9A, C
10A and C
10Above aromatic hydrocarbons is referred to as heavy aromatics (wherein A is an aromatic hydrocarbons).The oil heavy arene is mainly derived from the byproduct that light oil cracking is produced ethylene unit; The byproduct of refinery catalytic reforming unit; The byproduct of toluene disproportionation and transalkylation unit.Comprehensive Utilization of Heavy Aromatics is the problem that people are concerned about, 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 dimethylbenzene.Therefore, used " heavy arene " term refers in particular to C in present Aromatic Hydrocarbon United Plant
10A and above aromatic hydrocarbons thereof are the heavy arene of main component.At present, the by product heavy arene C of Aromatic Hydrocarbon United Plant
10The 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, also contain tens kinds of C
10A and C
10Above component is as durene, dimethyl ethyl benzene, diethylbenzene, methylnaphthalene, dimethylnaphthalene etc.Heavy arene is complicated owing to forming, the boiling point height, and purposes is less at present.These components are all improper as the blend composition of gasoline or diesel oil, and only some is as solvent oil, and a part is used to tell durol wherein, and all the other major parts act as a fuel and burn, real genus waste.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 course of processing and operating parameters different, the annual heavy aromatics that produces is 2~60,000 tons, this is a kind of resource of preciousness, and present Aromatic Hydrocarbon United Plant is to C
10A fraction heavy arene does not also have appropriate treatment process.
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
10A (benzene 0.81%, toluene 0.26%, C
8A 0.95%, C
9A 80.96%, C
10A 15.23%) be raw material, under 6MPa and 550 ℃ of reaction conditionss, during reaction product is formed by weight percentage for containing benzene 9.74%, toluene 30.27%, dimethylbenzene 32.33%, first and second benzene 5.22% and non-aromatics 0.16%.In U.S. Pat 4172813, with 3%WO
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 1.05~3.5MPa, 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
10Above aromatic hydrocarbons 0.4%.Only contain C in the raw material
10A 10.1%, contains 28.3% toluene again, 46.6% trimethylbenzene, and therefore topmost reaction is the transalkylation of toluene and trimethylbenzene.Narrated a kind of in the U.S. Pat 4341914 from C
9A or C
7A and C
9The A transalkylation is produced C
8The method of A, the C that tells from the transalkylation reaction effluent
9A, C
10The A circulation has improved C as the raw material of transalkylation
8The output of A.
In above-mentioned document, advance C in the raw material of reactor
10A and C
10The content of above aromatic hydrocarbons is lower, is no more than 20% at most, and topmost reaction still is toluene and C
9The toluene disproportionation of A and transalkylation reaction.
Heavy aromatics, particularly C
10A and C thereof
11The heavy aromatics that A is above, no matter in toluene disproportionation and transalkylation reaction process, perhaps in the hydro-dealkylation reaction process, also follow hydrocracking reaction generation carbon and stable hydrocarbon take place, the aromatic hydrocarbons condensation reaction generates side reactions such as many rings or fused ring compound, and temperature of reaction is high more, side reaction is big more, the macromole condensation product the more, the catalyzer coking also the more, catalyst activity reduction must heal soon.C
10Contain polynuclear compounds such as micro-naphthalene, methylnaphthalene, dimethylnaphthalene in the A fraction, they make catalyst deactivation easily.Therefore, in toluene disproportionation and alkyl transfering process, for slowing down catalyst carbon deposition speed, prolong catalyst life, except that the hydrogen operation was faced in employing, aspect the raw material composition, general requirement was advanced reactor feedstocks C
10A content is no more than 4%, is no more than 8% at most.Indane is the poisonous substance of catalyst for toluene disproportionation and transalkylation, is controlled at below 0.5% usually.
Disclose a kind of heavy arene hydrogenation among the Chinese patent ZL97106718.X and taken off alkyl and alkyl transfering process, with C
10And above heavy arene is raw material, produces C
6~C
9A, with regard to its chemical reaction, the technology of this patent has comprised more rudimentary aromatic hydrocarbons and the C that heavy arene hydrogenation dealkylation and heavy arene hydrogenation reaction generate
10Transalkylation reaction between the A.This is C undoubtedly
10One of and the approach of above heavy arene utilization, but the heavy arene hydrogenation dealkylation has caused the loss of alkyl, thereby from economic angle, reasonable inadequately.
A kind of toluene and heavy arene disproportionation and alkyl transfering process are disclosed among the Chinese patent ZL97106719.8, with toluene, C
10And above aromatic hydrocarbons is raw material, produces benzene, dimethylbenzene, first and second benzene and trimethylbenzene.With regard to its chemical reaction, the main reaction of this technology has comprised toluene disproportionation process, toluene and C
10And above aromatic hydrocarbons transalkylation reaction, certainly, this also is C
10And a kind of approach of above aromatic hydrocarbons utilization, and be one of both economical reasonable use approach.
The objective of the invention is to have aromatic hydrocarbons conversion very flexible in the conventional art, allow heavy arene content lower in the raw material in order to overcome, and the shortcoming that needs to consume a large amount of methylbenzene raw materials, a kind of new benzene and heavy arene transalkylation method are provided.This method has and can generate the characteristics than high value added product such as toluene and dimethylbenzene with a large amount of heavy arenes by carrying out transalkylation reaction with benzene.
The objective of the invention is to realize by following technical scheme: a kind of benzene and heavy arene transalkylation method are that raw material carries out transalkylation reaction with benzene and heavy arene, generate C
7~C
9Aromatic hydrocarbons and C
1~C
4Paraffinic hydrocarbon, wherein heavy arene is C
10Or/and C
11Aromatic hydrocarbons, its reaction conditions is:
A) under hydro condition, benzene feedstock fixes bed bioreactor with heavy arene by gas-solid and contacts with catalyzer, and the weight ratio of benzene and heavy arene is 10~80: 90~20, and temperature of reaction is 300~600 ℃, reaction pressure is 1.5~6.0MPa, and raw material aromatic hydrocarbons weight space velocity is 0.5~2.0 hour
-1, hydrogen hydrocarbon mol ratio is 2~10;
B) used catalyzer contains 20~90 parts in Hydrogen zeolite, SiO in parts by weight
2/ Al
2O
3Mol ratio is 10~50, on h-type zeolite load 0.05~10 part of the metal of bismuth or oxide compound, 0~10 part of the metal of at least a chosen from Fe, cobalt, nickel or molybdenum or oxide compound, the binding agent aluminum oxide is 10~60 parts in catalyzer.
In the technique scheme, when heavy aromatics is C
10During aromatic hydrocarbons, generate C
7~C
9Aromatic hydrocarbons is that toluene, dimethylbenzene, ethylbenzene, first and second benzene are or/and trimethylbenzene.C
1~C
4Paraffinic hydrocarbon be that methane, ethane, propane are or/and butane.In the catalyzer, be 0.1~5 part in the metal or the oxide compound preferable range of parts by weight bismuth, the metal of at least a chosen from Fe, cobalt, nickel or molybdenum or oxide compound preferable range are 0.1~5 part.Used zeolite preferred version is mordenite, β zeolite or Y zeolite in the catalyzer, and more preferably scheme is a mordenite, SiO
2/ Al
2O
3Mol ratio is 10~30.
The present invention adopts the hydrogen zeolite catalyst of one or more promotors of bismuth-containing and chosen from Fe, cobalt, nickel, molybdenum, and reaction raw materials is benzene and C
10The A fraction.C
10C in the A cut
9A content is no more than 10% usually (can certainly contain higher C
9A), C
10A content also contains more C up to more than 70%
11A, i.e. C
10C in the A cut
10A adds C
11A can be up to more than 90%, and indane content can be up to 2%.The present invention benzene and cheap C
10The A fraction by transalkylation reaction, makes C
10A, C
11A is converted into the C of higher-value
7A~C
9The more rudimentary aromatic hydrocarbons of A, C
10The A transformation efficiency can be up to more than 80%, C
11The A transformation efficiency also can generate toluene, C near more than 40%
8A, C
9The weight yield of A can reach 88%, and all the other are C
1~C
5Alkane and naphthenic hydrocarbon, and mainly be C
1~C
4Alkane.Therefore, the present invention is that comprehensive utilization contains C
10A and C
11The heavy aromatics of A particularly fully utilizes with C
10A is the cheap C of main component
10The A fraction is made toluene, C
8A and C
9The effective ways of A have been obtained effect preferably.
Use method of the present invention,, can make inexpensive C by means of benzene
10The A heavy aromatics (is mainly C
10A and C
11A), make toluene, dimethylbenzene and C by transalkylation reaction
9A.Dimethylbenzene is the important source material of polyester and synthon; Toluene is the important source material of making trotyl (explosive).
The catalyzer that uses in the inventive method can be by the method preparation of Chinese patent ZL97106719.8.
The present invention is further elaborated below by embodiment.
The reaction raw materials benzene, the C that are used for benzene of the present invention and heavy arene alkyl transfering process
10A all derives from the petrochemical complex Aromatic Hydrocarbon United Plant.
Carry out above-mentioned aroamtic hydrocarbon raw material transalkylation reaction performance evaluation with fixed-bed reactor, 20 millimeters of reactor inside diameter φ, 1200 millimeters of length are made with stainless steel tube.Adopt electrically heated, temperature is controlled automatically.Filling 20 gram catalyzer in 5 millimeters granulated glass spherees of reactor bottom filling φ, reaction zone, 5 millimeters granulated glass spherees of top filling φ are as the usefulness of raw material preheating, vaporization.Benzene feedstock, C
10A and C
11A mixes with hydrogen, pass through reactor from top to bottom, transalkylation reaction takes place, and generates toluene, ethylbenzene, dimethylbenzene or generates more rudimentary aromatic hydrocarbons such as toluene, ethylbenzene, dimethylbenzene, first and second benzene, trimethylbenzene, and alkane such as a small amount of methane, ethane, propane, butane.This technology is used hydrogen, is side reaction on the one hand---and the aromatic hydrogenation dealkylation need consume hydrogen, and on the other hand, the existence of hydrogen is mainly in order to suppress catalyst carbon deposition, in order to prolong the running period of catalyzer.
Benzene and C
10And above aromatic hydrocarbons transalkylation reaction data are handled as follows:
The invention will be further elaborated below by embodiment.[embodiment 1]
Na
2O content less than 0.15%, SiO
2/ Al
2O
3The ammonium type mordenite powder of 12,550 ℃ of calcination losses 10% of mol ratio or beta-zeolite, Y-zeolite and Na
2O content less than 0.15%, the pseudo-boehmite (α-Al of calcination loss 30%
2O
3H
2O) mix.With chemical pure Bismuth trinitrate [Bi (NO
3)
35H
2O], chemical pure nitric acid, water, be made into mixing solutions with at least a metal or oxide compound in chosen from Fe, cobalt, nickel or the molybdenum.This mixing solutions is added in the mixture of ammonium type mordenite or beta-zeolite, Y-zeolite and pseudo-boehmite, thorough mixing, kneading are evenly carried out extruded moulding, oven dry, pelletizing, calcination activation, make catalyst A, B, C, D respectively.Concrete table composed as follows:
[embodiment 2]
Catalyzer | ????A | ????B | ????C | ????D |
Bi Fe Co Mo zeolite type | 1.0 ///mordenite | 0.5 // 0.5 beta-zeolite | 0.1 0.1/0.5 beta-zeolite | 5.0/0.1 0.1 Y-zeolite |
With benzene/C
10The A weight ratio is about 40/60 raw material, under hydro condition, selects the catalyst A of embodiment 1 for use, carries out benzene and C
10The A transalkylation reaction, raw material aromatic hydrocarbons weight space velocity 2.0 hours
-1, hydrogen hydrocarbon mol ratio 4.0, reaction pressure 4.0MPa reacts under 400 ℃ of conditions of temperature of reaction, and raw material composition and product liquid are composed as follows, weight %:
??NA | ????B | ????T | ??C 8A | ??C 9A | ??C 10A | ??C 11 +A | ??IND | |
The raw material liq product | ??0.05 ??3.40 | ??39.90 ??18.00 | ??0.05 ??17.25 | ??0.02 ??30.09 | ??4.60 ??18.00 | ??52.33 ??11.47 | ??2.32 ??1.75 | ??0.73 ??0.03 |
Annotate: C
11 +A is carbon 11 and above aromatic hydrocarbons thereof.
Calculation result: benzene transformation efficiency 56.92% (weight)
C
10A transformation efficiency 79.08% (weight)
C
11 +A transformation efficiency 28.02% (weight)
Total conversion rate 68.47% (weight)
C
7A~C
9A selectivity 89.17% (weight) [embodiment 3]
With benzene/C
10The A weight ratio is about 20/80 raw material, under hydro condition, selects the catalyst B of embodiment 1 for use, carries out benzene and C
10The A transalkylation reaction, raw material aromatic hydrocarbons weight space velocity 0.5 hour
-1, hydrogen hydrocarbon mol ratio 8.0, reaction pressure 3.0MPa reacts under 360 ℃ of conditions of temperature of reaction, and reaction raw materials composition and product liquid are composed as follows, weight %:
??NA | ????B | ????T | ??C 8A | ??C 9A | ??C 10A | ??C 11 +A | ??IND | |
The raw material liq product | ??0.03 ??3.90 | ??19.95 ??5.01 | ??0.02 ??16.97 | ??0.03 ??18.00 | ??6.13 ??22.06 | ??69.77 ??31.84 | ??3.09 ??2.17 | ??0.98 ??0.05 |
Calculation result: benzene transformation efficiency 76.39% (weight)
C
10A transformation efficiency 57.10% (weight)
C
11 +A transformation efficiency 33.98% (weight)
Total conversion rate 60.48% (weight)
Toluene+C
8A+C
9A selectivity 84.50% (weight) [embodiment 4]
With benzene/C
10The A weight ratio is about 70/30 raw material, under hydro condition, selects the catalyzer C of embodiment 1 for use, carries out benzene and C
10The A transalkylation reaction, raw material aromatic hydrocarbons weight space velocity 2.0 hours
-1, hydrogen hydrocarbon mol ratio 5.0, reaction pressure 1.5MPa reacts under 450 ℃ of conditions of temperature of reaction, and reaction raw materials composition and product liquid are composed as follows, weight %:
??NA | ????B | ????T | ??C 8A | ??C 9A | ??C 10A | ??C 11 +A | ??IND | |
The raw material liq product | ??0.08 ??0.70 | ??69.90 ??55.65 | ??0.05 ??11.00 | ??0.02 ??12.01 | ??2.56 ??15.23 | ??26.50 ??5.00 | ??0.66 ??0.40 | ??0.23 ??0.01 |
Calculation result: benzene transformation efficiency 23.18% (weight)
C
10A transformation efficiency 81.77% (weight)
C
11 +A transformation efficiency 40.91% (weight)
Total conversion rate 39.30% (weight)
Toluene+C
8A+C
9A selectivity 89.88% (weight) [embodiment 5]
With the raw material of embodiment 4, under hydro condition, select the catalyzer D of embodiment 1 for use, carry out benzene and C
10The A transalkylation reaction, raw material aromatic hydrocarbons weight space velocity 2.0 hours
-1, hydrogen hydrocarbon mol ratio 5.0, reaction pressure 1.8MPa reacts under 420 ℃ of conditions of temperature of reaction, and reaction raw materials composition and product liquid are composed as follows, weight %:
??NA | ????B | ????T | ??C 8A | ??C 9A | ??C 10A | ??C 11 +A | ??IND | |
The raw material liq product | ??0.08 ??0.70 | ??69.90 ??48.23 | ??0.05 ??12.89 | ??0.02 ??13.32 | ??2.56 ??16.48 | ??26.50 ??7.85 | ??0.66 ??0.52 | ??0.23 ??0.01 |
Calculation result: benzene transformation efficiency 34.11% (weight)
C
10A transformation efficiency 71.71% (weight)
C
11 +A transformation efficiency 24.76% (weight)
Total conversion rate 44.31% (weight)
Toluene+C
8A+C
9A selectivity 88.68% (weight)
Conventional toluene disproportionation and alkyl transfering process have been realized with toluene and C
9A is the process of raw material production benzene and dimethylbenzene; Chinese patent ZL97106719.8 has realized with toluene and C by toluene and heavy aromatics disproportionation and alkyl transfering process
9A, C
10A is the process of raw material production benzene and dimethylbenzene.The present invention realizes with benzene and C then by benzene and heavy aromatics alkyl transfering process
10A is the process of raw material production toluene and dimethylbenzene.
Generally be to adopt toluene disproportionation and alkyl transfering process, toluene and heavy arene disproportionation and alkyl transfering process are by toluene and C
9A, C
10A produces benzene and dimethylbenzene; In particular cases, promptly in benzene and heavy aromatics surplus and toluene and dimethylbenzene when under-supply, available benzene and heavy arene alkyl transfering process solve.Like this, the present invention has not only realized particularly C of heavy aromatics
10And above Comprehensive Utilization of Heavy Aromatics, also realized the handiness of aroamtic hydrocarbon raw material and the handiness of product, can satisfy the different demands in market.
Claims (7)
1, a kind of benzene and heavy arene transalkylation method are that raw material carries out transalkylation reaction with benzene and heavy arene, generate C
7~C
9Aromatic hydrocarbons and C
1~C
4Paraffinic hydrocarbon, wherein heavy arene is C
10Or/and C
11Aromatic hydrocarbons, its reaction conditions is:
A) under hydro condition, benzene feedstock fixes bed bioreactor with heavy arene by gas-solid and contacts with catalyzer, and the weight ratio of benzene and heavy arene is 10~80: 90~20, and temperature of reaction is 300~600 ℃, reaction pressure is 1.5~6.0MPa, and raw material aromatic hydrocarbons weight space velocity is 0.5~2.0 hour
-1, hydrogen hydrocarbon mol ratio is 2~10;
B) used catalyzer contains 20~90 parts in Hydrogen zeolite, SiO in parts by weight
2/ Al
2O
3Mol ratio is 10~50, on h-type zeolite load 0.05~10 part of the metal of bismuth or oxide compound, 0~10 part of the metal of at least a chosen from Fe, cobalt, nickel or molybdenum or oxide compound, the binding agent aluminum oxide is 10~60 parts in catalyzer.
2,, it is characterized in that heavy arene is C according to described benzene of claim 1 and heavy arene transalkylation method
10Aromatic hydrocarbons generates C
7~C
9Aromatic hydrocarbons is that toluene, dimethylbenzene, ethylbenzene, first and second benzene are or/and trimethylbenzene.
3, according to described benzene of claim 1 and heavy arene transalkylation method, it is characterized in that C
1~C
4Paraffinic hydrocarbon be that methane, ethane, propane are or/and butane.
4,, it is characterized in that metal or the oxide compound in the parts by weight bismuth is 0.1~5 part according to described benzene of claim 1 and heavy arene transalkylation method.
5,, it is characterized in that metal or the oxide compound at least a chosen from Fe of parts by weight, cobalt, nickel or molybdenum is 0.1~5 part according to described benzene of claim 1 and heavy arene transalkylation method.
6,, it is characterized in that zeolite is mordenite, β zeolite or Y zeolite according to described benzene of claim 1 and heavy arene transalkylation method.
7,, it is characterized in that zeolite is a mordenite, SiO according to described benzene of claim 1 and heavy arene transalkylation method
2/ Al
2O
3Mol ratio is 10~30.
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CNB011058404A CN1164540C (en) | 2001-04-04 | 2001-04-04 | Benzene and heavy arene transalkylation method |
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CNB011058404A CN1164540C (en) | 2001-04-04 | 2001-04-04 | Benzene and heavy arene transalkylation method |
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Publication Number | Publication Date |
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CN1377864A true CN1377864A (en) | 2002-11-06 |
CN1164540C CN1164540C (en) | 2004-09-01 |
Family
ID=4654905
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2001
- 2001-04-04 CN CNB011058404A patent/CN1164540C/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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