CN111675593B - C 9 Method for synthesizing sym-tetraalkylbenzene from mixed aromatic hydrocarbon - Google Patents
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
The invention provides a compound C 9 A method for synthesizing sym-tetraalkylbenzene by mixed aromatics. The reactor used in the method is divided into an upper reaction zone and a lower reaction zone, raw materials enter the reactor from the top, methyl ethyl benzene and propyl benzene in the raw materials are subjected to cracking reaction in the upper reaction zone, and the generated light products flow upwards in a gaseous form and flow out from the top of the reactor and enter a light component separation tower; separating to obtain C rich in ethylene and propylene 1 ～C 3 Fraction and C rich in benzene and toluene 4 ～C 8 Fraction of which C 1 ～C 3 Returning the distillate from the bottom of the reactor to the lower reaction zone of the reactor in gaseous form; the trimethylbenzene in the raw material does not react in the upper reaction zone, but flows downwards in liquid form, enters the lower reaction zone and is separated from C in the light component separation tower 1 ～C 3 The ethylene and the propylene in the fraction are subjected to alkylation reaction, the generated tetra-alkylbenzene flows out from the bottom of the reactor in a liquid state, and is separated to obtain a tetra-alkylbenzene product with the purity of 80-99% and the yield of 20-40% (by C) 9 Mixed aromatics based).
Description
Technical Field
The invention belongs to the field of aromatic hydrocarbon synthesis, and particularly relates to C 9 A method for synthesizing sym-tetraalkylbenzene by mixed aromatics.
Background
Pyromellitic dianhydride is a monomer for producing polyimide, which is a high-performance engineering plastic with properties at the top of a pyramid of materials. At present, the development speed of the polyimide industry is slow, mainly because the production cost of pyromellitic dianhydride is too high, the price of polyimide is high, and the cost performance advantage is not obvious. How to reduce the production cost of pyromellitic dianhydride has become the primary problem to be solved in the polyimide industry. At present, the production technology of pyromellitic dianhydride is mainly a gas-phase oxidation method, and the raw material for production is durene.
CN103524288B, CN106565406B, CN106518592B, CN106927990A, CN104557426B, CN110627605A, CN106076404B, and CN107226772A disclose a series of synthetic methods of durene. In general, durene production involves both synthetic and isolated processes. The raw materials for synthesizing the durene comprise synthesis gas, methanol, toluene, xylene or trimethylbenzene, the type of the reactor comprises a fixed bed, a moving bed, a fluidized bed or a slurry bed, and the purity of the durene product is 80-90%. The separation method comprises various modes such as freezing crystallization, melting crystallization and the like, and the production raw material comprises C byproduct of catalytic reforming process 10 Heavy aromatics, heavy aromatics produced as by-product in the methanol-to-gasoline (MTG) process, etc., wherein the purity of durene is 95-98%.
Because the domestic productivity is less than 5 ten thousand tons per year, the durene belongs to a relatively scarce fine chemical product, which is one of the main reasons that the production cost of the downstream product, namely the pyromellitic dianhydride, is higher, and if the durene can be synthesized to be a cheap substitute of the durene, the production cost of the pyromellitic dianhydride is expected to be reduced. Pyromellitic benzenes, such as 5-ethyl (propyl) trimellitbenzene, can be used as a substitute for durene to produce pyromellitic dianhydride.
Few reports are made at home and abroad on the synthesis method of the sym-tetraalkylbenzene. CN108640926A discloses a method for producing pyromellitic dianhydride, wherein the raw material for production is a hydrogenation product of industrial anthracene, namely sym-octahydro-anthracene. The molecular formula of the symmetric octahydro anthracene is C 14 H 18 And the molecular formula of pyromellitic dianhydride is C 10 H 2 O 6 When symmetric octahydro anthracene is used as a raw material to produce pyromellitic dianhydride, the theoretical value of the utilization rate of C atoms is only 71.4%, so the symmetric octahydro anthracene is not an ideal substitute of durene.
Zygophylla et al (petrochemical, 1991, 20 (8), 521-526) reported a method for synthesizing 5-isopropyltrimellitbenzene from trimellitic benzene and propylene. Because the pseudocumene and the propylene are chemical products with high added values, the cost of the sym-tetraalkylbenzene produced by the method is high.
Along with the rapid increase of the aromatic hydrocarbon productivity in China and the down-regulation of the aromatic hydrocarbon content in the motor gasoline, C 9 The application space of mixed aromatics is continuously reduced, and the future domestic C 9 The mixed aromatics must present the situation of over-supply, so C with low added value 9 The mixed aromatic hydrocarbon is used as a raw material to produce the sym-tetraalkylbenzene, so that the method has good industrial application prospect.
Disclosure of Invention
Aiming at the problems of durene resource shortage and high durene substitute production cost at present, the invention provides a C with low added value as a byproduct of catalytic reforming process 9 The method for synthesizing the sym-tetraalkylbenzene by using the mixed aromatic hydrocarbon as the raw material has low production cost and is an ideal substitute of the sym-tetramethylbenzene.
The invention is realized by the following technical scheme:
c 9 The method for synthesizing the sym-tetraalkylbenzene by the mixed aromatic hydrocarbon comprises the following steps:
(1) Raw material C 9 Preheating mixed aromatic hydrocarbon, feeding the preheated mixed aromatic hydrocarbon into a reactor from top, said reactor is divided into upper and lower reaction zones, in the upper reaction zone the methyl ethyl benzene and propyl benzene are undergone the process of cracking reaction, the produced light product can be upwards flowed from top of reactor, and fed into light component separation tower, and separated so as to obtain C rich in ethylene and propylene 1 ～C 3 Fraction and C rich in benzene and toluene 4 ～C 8 Fraction in which C 1 ～C 3 The fraction enters a lower reaction zone of the reactor from the bottom of the reactor together with fresh carrier gas in a gaseous state; the trimethylbenzene component which has not reacted in the upper reaction zone flows downward in liquid form into the lower reaction zone together with C from the light component separation column 1 ～C 3 Performing alkylation reaction on ethylene and propylene in the fraction, and enabling the tetraalkylbenzene generated by the alkylation reaction to flow out from the bottom of the reactor in a liquid form and enter a heavy component separation system; the low carbon hydrocarbon generated by the alkylation reaction and the carrier gas flow upwards in a gaseous form and flow out from the top of the reactor to enter a light component separation tower;
(2) The effluent at the bottom of the reactor is separated by a separating tank to obtain a catalyst and an alkylation product, the catalyst enters a regenerator and returns to the reactor from the top after being regenerated; the alkylated product is separated by a heavy component separation tower to obtain trimethylbenzene, pyromellitic alkylbenzene and high-boiling-point aromatic solvent oil, wherein the trimethylbenzene returns to the reactor from the upper edge position of the lower reaction zone;
wherein the catalyst consists of 20-80% of active component and 20-80% of binder by mass percentage, wherein the active component is at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve, NU-9 molecular sieve and IM-5 molecular sieve; c 9 The weight ratio of the aromatic hydrocarbon raw material to the catalyst is 0.1-100, and the carrier gas is at least one of nitrogen and hydrogen; c 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.5 to 5.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 1.0-10.0, the pressure is 7.0-10.0 MPa, and the upper part is reverseThe temperature of the reaction zone is 400-450 ℃, and the temperature of the lower reaction zone is 350-380 ℃.
In the above technical solution of the present invention, the reactor is preferably a moving bed, slurry bed or fluidized bed reactor equipped with a catalyst regeneration system; more preferably a slurry bed reactor.
In the above technical solution of the present invention, the binder is preferably at least one of pseudo-boehmite, alumina sol, and silica sol.
In the technical scheme of the invention, the active component is preferably at least one of a NU-9 molecular sieve and an IM-5 molecular sieve, and accounts for 30-70% of the catalyst by mass percent.
In the above technical solution of the present invention, the reaction conditions are preferably: the weight ratio of the aromatic hydrocarbon raw material to the catalyst in the reactor is 1.0-90 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.8 to 4.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 2.0-8.0, the pressure is 8.0-9.0 MPa, the temperature of the upper reaction zone is 430-440 ℃, the temperature of the lower reaction zone is 360-370 ℃, and the carrier gas is nitrogen.
Compared with the prior art, the invention has the following advantages: (1) C with rich resources and low additional value 9 The mixed aromatic hydrocarbon is used as raw material, the synthesis cost is low, the purity of the obtained product, namely the tetra-alkyl benzene, is high, the yield is high (80-99 percent, the yield is 20-40 percent), the preferred scheme can reach 85-99 percent, the yield is 30-40 percent, and C is used 9 Mixed aromatic hydrocarbon based); (2) The ethyl and the propyl on the aromatic ring in the raw material are effectively utilized as the alkylating reagent, so that the utilization rate of the raw material is high; (3) The efficient coupling of the cracking reaction and the alkylation reaction is realized in the same reactor, and the reaction efficiency is high.
Drawings
FIG. 1 shows a block C of the present invention 9 The process flow of the method for synthesizing the sym-tetraalkylbenzene by the mixed aromatics is shown in the schematic diagram.
In fig. 1: 1 is a reactor; 2 is a light component separation tower; 3 is a solid-liquid separation tank; 4 is a catalyst regenerator; and 5, a heavy component separation tower.
Detailed Description
The technical scheme of the invention is further illustrated by the following embodiments in combination with the attached drawings of the specification.
As shown in FIG. 1, the reactor 1 is divided into an upper reaction zone and a lower reaction zone, and the raw material C 9 The mixed aromatic hydrocarbon enters a reactor 1 from the top, methyl ethyl benzene and propyl benzene in the raw materials undergo cracking reaction in an upper reaction zone to generate ethylene, propylene, benzene and toluene, the products flow upwards in a gaseous form and flow out from the top of the reactor 1, and C rich in ethylene and propylene is obtained after separation in a separation tower 2 1 ～C 3 Fraction and C rich in benzene and toluene 4 ～C 8 Fraction in which C 1 ～C 3 The distillate enters the lower reaction zone of the reactor 1 in gaseous form from the bottom of the reactor 1 together with fresh carrier gas. The trimethylbenzene in the feed does not react in the upper reaction zone but flows down in liquid form into the lower reaction zone with the C from the separation column 2 1 ～C 3 The fraction ethylene and propylene are alkylated, the produced tetraalkyl benzene flows out from the bottom of the reactor 1 in liquid form, and the produced lower hydrocarbon and the carrier gas flow upward in gaseous form and flow out from the top of the reactor 1 to enter a separation tower 2. The bottom effluent of the reactor 1 is separated by a knockout drum 3 to obtain the catalyst and the alkylation product, the catalyst enters a regenerator 4, and the catalyst returns to the reactor 1 from the top after regeneration. The alkylated product is separated by a separation tower 5 to obtain trimethylbenzene, pyromellitic alkylbenzene and high boiling point aromatic solvent oil, wherein the trimethylbenzene returns to the reactor 1 and enters the reactor 1 from the upper edge position of the lower reaction zone.
In the upper reaction area of the reactor, methyl ethyl benzene and propyl benzene are subjected to cracking reaction to remove ethyl and propyl side chains on a benzene ring, and ethylene, propylene, benzene and toluene are generated. In the lower reaction zone of the reactor, trimethylbenzene, ethylene and propylene are alkylated to produce 5-ethyltrimethylbenzene and 5-isopropyltrimethylbenzene, which are collectively referred to as sym-tetraalkylbenzene.
The byproduct C of the raw material catalytic reforming process in the embodiment of the patent application 9 The composition of the mixed aromatics is given in Table 1.
TABLE 1C 9 Composition statistical table of mixed aromatics
Example 1
The catalyst is prepared by taking the NU-9 molecular sieve as an active component and the pseudo-boehmite as a binder, wherein the weight percentages of the two components in the catalyst are 30% and 70% in sequence.
As shown in FIG. 1, the reactor is a slurry bed, and C is arranged in the reactor 9 The weight ratio of the mixed aromatic hydrocarbon to the catalyst is 1.0 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.8h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 2.0, the pressure is 9.0MPa, the temperature of the upper reaction zone is 440 ℃, the temperature of the lower reaction zone is 370 ℃, and the carrier gas is nitrogen.
Example 2
The catalyst is prepared by taking IM-5 molecular sieve as an active component and alumina sol as a binder, wherein the weight percentage of the two components in the catalyst is 50%.
As shown in FIG. 1, the reactor is a slurry bed, and C is arranged in the reactor 9 The weight ratio of the mixed aromatic hydrocarbon to the catalyst is 45,C 9 The weight space velocity of the mixed aromatic hydrocarbon is 2.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 5.0, the pressure is 8.5MPa, the temperature of the upper reaction zone is 430 ℃, the temperature of the lower reaction zone is 360 ℃, and the carrier gas is nitrogen.
Example 3
The catalyst is prepared by taking the NU-9 molecular sieve and the IM-5 molecular sieve as active components and taking pseudo-boehmite and alumina sol as binders. In the catalyst, the weight percentage of the two molecular sieves is 35 percent, and the weight percentage of the two binders is 15 percent.
As shown in FIG. 1, the reactor is a slurry bed, and C is arranged in the reactor 9 The weight ratio of the mixed aromatic hydrocarbon to the catalyst is 90,C 9 The weight space velocity of the mixed aromatic hydrocarbon is 4.0h -1 Carrier gas and C 9 Mixed aromatic hydrocarbonThe hydrocarbon molar ratio was 8.0, the pressure was 8.0MPa, the temperature in the upper reaction zone was 450 deg.C, the temperature in the lower reaction zone was 380 deg.C, and the carrier gas was nitrogen.
Example 4
The catalyst is prepared by taking a ZSM-5 molecular sieve as an active component and silica sol as a binder. The weight percentage of the molecular sieve in the catalyst is 20 percent, and the weight percentage of the binder is 80 percent.
As shown in FIG. 1, the reactor is a fluidized bed, and C is arranged in the reactor 9 The weight ratio of the mixed aromatic hydrocarbon to the catalyst is 0.1,C 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.5h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 1.0, the pressure is 10.0MPa, the temperature of the upper reaction zone is 420 ℃, the temperature of the lower reaction zone is 350 ℃, and the carrier gas is hydrogen.
Example 5
The catalyst is prepared by taking a ZSM-11 molecular sieve as an active component and silica sol as a binder. The weight percentage of the molecular sieve in the catalyst is 80 percent, and the weight percentage of the binder is 20 percent.
As shown in FIG. 1, the reactor is a moving bed, and C is arranged in the reactor 9 The weight ratio of the mixed aromatic hydrocarbon to the catalyst is 100,C 9 The weight space velocity of the mixed aromatic hydrocarbon is 5.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 10.0, the pressure is 7.0MPa, the temperature of the upper reaction zone is 420 ℃, and the temperature of the lower reaction zone is 350 ℃. The carrier gas is hydrogen.
The evaluation results of the examples are shown in Table 2.
Table 2 statistical table of evaluation results of examples
Claims (6)
1. C 9 The method for synthesizing the sym-tetraalkylbenzene by the mixed aromatic hydrocarbon is characterized by comprising the following steps of:
(1) Raw material C 9 Preheating mixed aromatic hydrocarbon, feeding the preheated mixed aromatic hydrocarbon into a reactor from top, dividing said reactor into upper portion and lower portion,In the next two reaction zones, the methyl ethyl benzene and propyl benzene in the raw materials are subjected to cracking reaction in the upper reaction zone, the generated light products flow upwards in a gaseous form and flow out from the top of the reactor, and the light products enter a light component separation tower to be separated to obtain C rich in ethylene and propylene 1 ～C 3 Fraction and C rich in benzene and toluene 4 ～C 8 Fraction of which C 1 ～C 3 The fraction enters a lower reaction zone of the reactor from the bottom of the reactor together with fresh carrier gas in a gaseous state; the trimethylbenzene raw material which does not react in the upper reaction zone flows down in liquid form into the lower reaction zone together with C from the light component separation column 1 ～C 3 The ethylene and the propylene in the fraction undergo alkylation reaction, and the tetraalkylbenzene generated by the alkylation reaction flows out from the bottom of the reactor in a liquid state and enters a heavy component separation system; the low carbon hydrocarbon generated by the alkylation reaction and the carrier gas flow upwards in a gaseous form and flow out from the top of the reactor to enter a light component separation tower;
(2) The effluent at the bottom of the reactor is separated by a separating tank to obtain a catalyst and an alkylation product, the catalyst enters a regenerator and returns to the reactor from the top after being regenerated; the alkylated product is separated by a heavy component separation tower to obtain trimethylbenzene, pyromellitic alkylbenzene and high-boiling-point aromatic solvent oil, wherein the trimethylbenzene returns to the reactor from the upper edge position of the lower reaction zone;
wherein the catalyst consists of 20 to 80 mass percent of active component and 20 to 80 mass percent of binder, wherein the active component is at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve, NU-9 molecular sieve and IM-5 molecular sieve; c 9 The weight ratio of the mixed aromatic hydrocarbon raw material to the catalyst is 0.1-100, and the carrier gas is at least one of nitrogen and hydrogen; c 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.5 to 5.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 1.0-10.0, the pressure is 7.0-10.0 MPa, the temperature of the upper reaction zone is 400-450 ℃, and the temperature of the lower reaction zone is 350-380 ℃.
2. The process of claim 1 wherein the reactor is a moving bed, slurry bed, or fluidized bed reactor equipped with a catalyst regeneration system.
3. The method of claim 1, wherein the binder is at least one of pseudoboehmite, alumina sol, and silica sol.
4. The method according to claim 1, wherein the active component is at least one of NU-9 molecular sieve and IM-5 molecular sieve, and the active component accounts for 30-70% of the catalyst by mass.
5. The method of claim 1, wherein the reaction conditions are: said C 9 The weight ratio of the mixed aromatic hydrocarbon raw material to the catalyst is 1.0-90 9 The weight space velocity of the mixed aromatic hydrocarbon is 0.8 to 4.0h -1 Carrier gas and C 9 The molar ratio of the mixed aromatic hydrocarbon is 2.0-8.0, the pressure is 8.0-9.0 MPa, the temperature of the upper reaction zone is 430-440 ℃, the temperature of the lower reaction zone is 360-370 ℃, and the carrier gas is nitrogen.
6. The method of claim 1, wherein C is 9 The mixed arene is used as the raw material, the purity of the sym-tetraalkylbenzene is 80 to 99 percent, and the yield is 20 to 40 percent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155533A (en) * | 1996-11-25 | 1997-07-30 | 中国科学院山西煤炭化学研究所 | Synthesis of sym-tetramethylbenzene |
| CN101037439A (en) * | 2007-04-23 | 2007-09-19 | 东北师范大学 | Production technique of benzenetetracarboxylic dianhydride by catalyzing carrier-type polyoxometalates |
| CN104557426A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation slurry bed reaction method |
| CN107226772A (en) * | 2017-06-19 | 2017-10-03 | 中海油天津化工研究设计院有限公司 | One kind is by C9+The method that heavy aromatics prepares dimethylbenzene coproduction durol |
| CN107365240A (en) * | 2017-06-19 | 2017-11-21 | 中海油天津化工研究设计院有限公司 | One kind is by C9+The method that heavy aromatics prepares BTX coproduction durols |
-
2020
- 2020-06-24 CN CN202010590475.6A patent/CN111675593B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155533A (en) * | 1996-11-25 | 1997-07-30 | 中国科学院山西煤炭化学研究所 | Synthesis of sym-tetramethylbenzene |
| CN101037439A (en) * | 2007-04-23 | 2007-09-19 | 东北师范大学 | Production technique of benzenetetracarboxylic dianhydride by catalyzing carrier-type polyoxometalates |
| CN104557426A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation slurry bed reaction method |
| CN107226772A (en) * | 2017-06-19 | 2017-10-03 | 中海油天津化工研究设计院有限公司 | One kind is by C9+The method that heavy aromatics prepares dimethylbenzene coproduction durol |
| CN107365240A (en) * | 2017-06-19 | 2017-11-21 | 中海油天津化工研究设计院有限公司 | One kind is by C9+The method that heavy aromatics prepares BTX coproduction durols |
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| CN111675593A (en) | 2020-09-18 |
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