CN104557437B - Produce the method for isopropyl benzene - Google Patents
Produce the method for isopropyl benzene Download PDFInfo
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- CN104557437B CN104557437B CN201310512503.2A CN201310512503A CN104557437B CN 104557437 B CN104557437 B CN 104557437B CN 201310512503 A CN201310512503 A CN 201310512503A CN 104557437 B CN104557437 B CN 104557437B
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Abstract
The present invention relates to a kind of method producing isopropyl benzene, mainly solving prior art, to there is propylene conversion low, positive propyl benzene content height in isopropyl benzene product, the problem that device production efficiency is low. The present invention arranges at least two reaction zones by employing, solves this problem preferably by the technical scheme of the blocked operation of two reaction zones and process combination, can be used in the industrial production of benzene and production of propylene isopropyl benzene.
Description
Technical field
The present invention relates to a kind of method producing isopropyl benzene.
Background technology
Isopropyl benzene is a kind of important Organic Chemicals, is the main intermediate compound producing phenol, acetone and alpha-methyl styrene. Industrially isopropyl benzene be by propylene and benzene alkylated reaction prepare, its by product is mainly polyisopropylbenzene. Just disclose in the presence of acidic as far back as UOP in 1945, the method (SPA method) (USP2382318) of isopropyl benzene is prepared with propylene and benzene reaction, SPA method take solid phosphoric acid as alkylation catalyst, due to solid phosphoric acid not can catalysis transalkylation reaction, so there is no transalkylation portion in technical process. Therefore, SPA method can only be run under high benzene alkene mol ratio (5��7) condition, and the receipts rate of its isopropyl benzene is only about 95%. In the 80's of last century, Monsanto company develops with AlCl3For the isopropyl benzene production technique of alkylation catalyst, and realize industrial application. Due to AlCl3Equally can not catalysis transalkylation reaction, therefore, with AlCl3It is still lower in the receipts rate of isopropyl benzene that method produces isopropyl benzene, also there is serious pollution problem and corrosion of equipment problem simultaneously.
In the 90's of last century, it is catalyzer that Dow, CDTech, Mobil-Badger, Enichem and UOP etc. (US4992606, US5362697, US5453554, US5522984, US5672799, US6162416, US6051521) company discloses in succession taking micro-pore zeolite, has the fixed-bed process flow process of transalkylation ability. In the prior art, first benzene and propylene carry out alkylated reaction in alkylation reaction device, the polysubstituted isopropyl benzene that alkylated reaction generates is after distillation system is separated, and polysubstituted isopropyl benzene enters a single bed with benzene transalkylation reaction zone after mixing again carries out transalkylation reaction.
In existing disclosed isopropyl benzene technology, the alkylation of benzene and propylene is all adopt single, multistage layer formula fixed-bed reactor, propylene sectional feeding pattern and reaction solution outer circulation technology, its object is to: 1, reduces the propylene content in reactor, to reduce catalyst deactivation rate; 2, by reducing the temperature of beds, the generation of the positive propyl benzene of impurity is reduced, to improve the quality of products. In fact, avoid the inactivation of catalyzer, to reduce impurity positive propyl benzene content be the most important research direction of isopropyl benzene technical field. Recently, document US6835862B1 discloses by process optimization, adopts higher reaction solution outer circulation amount can reduce the deactivation rate of catalyzer.Document US7790939B2 also discloses by increasing pre-reactor before alkylation reactor, to improve the ability of the anti-impurity of main reactor catalyzer. But, adopt single reactor and conventional multistage outer circulation isopropyl benzene Technology, even if being difficult to solve catalyzer smaller inactivation occurs, also the remarkable reduction of propylene conversion can be caused, and when catalyzer generation serious inactivation, just must stop more catalyst changeout, causes the problem that production efficiency is low. In addition, prior art is also difficult to greatly by regulating temperature of reaction to promote reactivity worth. Because reduction temperature of reaction, the activity of catalyzer will certainly be reduced, thus the transformation efficiency making propylene reduces; But improving temperature can cause propylene vaporization to cause catalyst deactivation.
Summary of the invention
It is low that technical problem to be solved by this invention is that prior art exists propylene conversion, positive propyl benzene content height in isopropyl benzene product, and the problem causing device production efficiency low because of more catalyst changeout, it is provided that a kind of method of production isopropyl benzene newly. The method has propylene conversion height, and in product isopropyl benzene, positive propyl benzene content is low, the feature that device stable operation, efficiency are high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method producing isopropyl benzene, comprises the following steps:
A) device at least comprising the first reaction zone and second reaction zone is provided;
B) valve (6), (7), (28), (29), (30), (31) and (32) are opened, first burst of benzene logistics and first strand of propylene stream is made to enter the first reaction zone, contact with catalyzer, generate first strand of cumene stream; First strand of cumene stream is divided into two portions, and a part loops back the first reaction zone, and another part enters second reaction zone; The logistics entering second reaction zone contacts with catalyzer, generates the product stream containing isopropyl benzene; Wherein, valve (10), (11), (23), (24), (25), (26) and (27) are in cut-out state or only allow less logistics to pass through;
C) the first reaction zone catalyst activity reduces or after inactivation, open valve (10), (11), (23), (24), (25), (26) and (27), the 2nd burst of benzene logistics and the 2nd strand of propylene stream is made to enter second reaction zone, contact with catalyzer, generate the 2nd strand of cumene stream; 2nd strand of cumene stream is divided into two portions, and a part loops back second reaction zone, and another part enters the first reaction zone; The logistics entering the first reaction zone contacts with catalyzer, generates the product stream containing isopropyl benzene; Wherein, valve (6), (7), (28), (29), (30), (31) and (32) are in cut-out state or only allow less logistics to pass through;
D) second reaction zone catalyst activity reduces or after inactivation, repeating step b) and c).
In technique scheme, preferably, described first reaction zone and second reaction zone are all the reactors of at least one section, or the reaction zone become by least two single section of reactors in series, or at least one single section of reactor and at least one reactors in series of at least two sections and the reaction zone that becomes.
In technique scheme, it may be preferred that in step b), the operational condition of described first reaction zone is: the mol ratio of first burst of benzene logistics and first strand of propylene stream is 1��10, first strand of propylene stream weight space velocity is 0.2 ~ 10 hour-1, recycle ratio is 2 ~ 50, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa.More preferably, the mol ratio of first burst of benzene logistics and first strand of propylene stream is 1.5��4, first strand of propylene stream weight space velocity is 0.3 ~ 5 hour-1, recycle ratio is 3 ~ 25, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa. Most preferably, temperature of reaction is 100��160 DEG C, and first strand of propylene stream weight space velocity is 0.4 ~ 3.0 hour-1��
In technique scheme, it may be preferred that in step b), the operational condition of described second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 0��10, two strand of propylene stream weight space velocity is 0 ~ 2 hour-1, recycle ratio is 0 ~ 10, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa. More preferably, the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 0��5, two strand of propylene stream weight space velocity is 0 ~ 1.5 hour-1, recycle ratio is 0 ~ 5, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa. Most preferably, temperature of reaction is 100��160 DEG C, and the 2nd strand of propylene stream weight space velocity is 0 ~ 1.0 hour-1��
In technique scheme, it may be preferred that in step b), the recycle ratio of the first reaction zone is greater than the recycle ratio of second reaction zone.
In technique scheme, it may be preferred that in step c), the operational condition of described first reaction zone is: the mol ratio of first burst of benzene logistics and first burst of phenylallene logistics is 0��10, first strand of propylene stream weight space velocity is 0 ~ 2 hour-1, recycle ratio is 0 ~ 10, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa. More preferably, the mol ratio of first burst of benzene logistics and first strand of propylene stream is 0��5, first strand of propylene stream weight space velocity is 0 ~ 1.5 hour-1, recycle ratio is 0 ~ 5, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa. Most preferably, temperature of reaction is 100��160 DEG C, and first strand of propylene stream weight space velocity is 0 ~ 1.0 hour-1��
In technique scheme, it may be preferred that in step c), the operational condition of second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 1��10, two strand of propylene stream weight space velocity is 0.2 ~ 10 hour-1, recycle ratio is 2 ~ 50, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa. More preferably, the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 1.5��4, two strand of propylene stream weight space velocity is 0.3 ~ 5 hour-1, recycle ratio is 3 ~ 25, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa. Most preferably, temperature of reaction is 100��160 DEG C, and the 2nd strand of propylene stream weight space velocity is 0.4 ~ 3.0 hour-1��
In technique scheme, it may be preferred that in step c), the recycle ratio of second reaction zone is greater than the recycle ratio of the first reaction zone.
In technique scheme, it may be preferred that described catalyzer is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.
In technique scheme, it may be preferred that propylene segmentation enters reaction zone.
In technique scheme, it may be preferred that benzene enters from the top of reaction zone.
In technique scheme, it may be preferred that the logistics looping back reaction zone enters from the top of reaction zone.
In the inventive method, described pressure refers to gauge pressure. Described recycle ratio refers to that the weight ratio of logistics is flowed out in the logistics looping back reaction zone and reaction zone.
The catalyzer used in the inventive method is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.Wherein, described in there is MWW laminate structure zeolite can be selected from MCM-22, MCM-56, MCM-49, and according to having the zeolite of MWW structure disclosed in document CN200410066636.2 and CN200610029979.0.
For reducing positive propyl benzene content in product, usually adopting the means reducing reactor service temperature and high outer circulation ratio, low temperature and high recycle ratio will certainly cause the transformation efficiency of propylene to reduce. For overcoming this contradiction, the inventive method is provided with primary and secondary two reaction zones, and main reaction region is run than under condition in higher outer circulation, and secondary response district runs in lower recycle ratio or under almost not having outer circulation material existent condition. Propylene is in the first reaction zone almost complete reaction, first reaction zone (main reaction region) effluent flows to the 2nd reaction zone (secondary response district) into the logistics that almost do not circulate and continues reaction, this substantially extends the residence time, make to continue reaction at the first unreacted a small amount of propylene of reactor, thus ensure that the high conversion of propylene. Simultaneously, when reaction starts, first reaction zone is main reaction region, second reaction zone is secondary response district, when, after the catalyst activity reduction or inactivation of the first reaction zone, by valve transfer, now the first reaction zone has become secondary response district, and second reaction zone becomes main reaction region, it is achieved that the steady production of device. The present invention is by adopting the combination of at least two reactors, it is achieved that by adjustment temperature by a relatively large margin, reduces the positive propyl benzene content of impurity, improves propylene conversion, it is achieved that the blocked operation of reactor and process combination, it is to increase device operational stability. The temperature of reaction of alkylation in the prior art is usually at about 150 DEG C, and the setting range up and down of temperature of reaction, within 10 DEG C, is even less than 5 DEG C. The change of temperature seriously can affect the transformation efficiency of propylene and the content of the positive propyl benzene of impurity. In the present invention, by adopting the scheme of primary and secondary reaction zone, the temperature of primary and secondary reaction zone can independent variation, the temperature of single reaction zone, especially main reactor can adjust as required within the scope of 90��180 DEG C simultaneously, and can ensure transforming completely and low foreign matter content of propylene. Meanwhile, according to the running condition of reactor catalyst, it is possible to realize switchover operation, the even on-line regeneration of a reactor: even only a reactor puts into operation, and the reactor that another catalyst activity reduces carries out the on-line regeneration of catalyzer. Adopting the inventive method, do not need whole device to stop more catalyst changeout, positive propyl benzene content can lower than 200 mg/kg isopropyl benzenes, and propylene conversion can be greater than 99.99%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention, so that containing two reaction zones, each reaction zone is two beds.
Fig. 2 is the process flow diagram of prior art.
In Fig. 1, 1 is the first reaction zone, 2 is second reaction zone, 3 is recycle pump, 4 is first strand of benzene raw materials, 5 is first burst of propylene feedstocks, 6 for controlling to enter the valve of the first reaction zone first bed propylene feed, 7 for controlling to enter the valve of the first reaction zone the 2nd bed propylene feed, 8 is the 2nd strand of benzene raw materials, 9 is the 2nd burst of propylene feedstocks, 10 for controlling to enter the valve of second reaction zone first bed propylene feed, 11 for controlling to enter the valve of second reaction zone the 2nd bed propylene feed, 12 is the first reaction zone discharging, 13 is second reaction zone discharging, 14 is isopropyl benzene product stream, 15 is that second reaction zone is gone in the first reaction zone discharging, 16 go to the first reaction zone for second reaction zone discharging, 17 is that the first reaction zone discharging is to recycle pump, 18 for second reaction zone discharging is to recycle pump, 19 is recycle pump combined feed total feed, 20 is the total discharging of recycle pump, 21 is the first reaction zone global cycle charging, 22 is second reaction zone global cycle charging, 23 ~ 32 is all valve.
In Fig. 2,33 is reactor, and 34 is benzene charging, and 35 is propylene feed, and 36 is product stream.
In Fig. 1, when the first reaction zone is main reaction region, when second reaction zone is secondary response district, first burst of benzene logistics 4 enters from the first top, reaction zone, first strand of propylene stream 5 enters two beds by valve 6 and 7 respectively, contact with catalyzer and react, obtain comprising the logistics 12 of benzene, isopropyl benzene, polyisopropylbenzene and trace amount. The logistics 12 flowed out from the first reaction zone is divided into two strands: one logistics 17 sends the first reaction zone back to through recycle pump, and another burst of logistics 15 directly enters second reaction zone and continue reaction, obtains the product stream 14 containing isopropyl benzene bottom second reaction zone. Under the operational condition that above-mentioned first reactor is in position, main reaction region, valve 6,7,28,29,30,31 and 32 is in open state, and valve 10,11,23,24,25,26 and 27 is in cut-out state or only allows less logistics to pass through, make the 2nd strand of benzene feed stream 8 of second reaction zone, the 2nd burst of propylene feed logistics 9, to all only less logistics in the pipeline of the logistics 16 of the first reaction zone and product circulation logistics 18 and 22 or do not have logistics to pass through.
When second reaction zone is main reaction region, when first reaction zone is secondary response district, 2nd burst of benzene logistics 8 enters from top, second reaction zone, 2nd strand of propylene stream 9 enters two beds by valve 10 and 11 respectively, contact with catalyzer and react, obtain comprising the product stream 13 of benzene, isopropyl benzene, polyisopropylbenzene. The logistics 13 flowed out from second reaction zone is divided into two strands: one logistics 18 sends second reaction zone back to through recycle pump, and another burst of logistics 16 directly enters the first reaction zone and continue reaction, obtains the product stream 14 containing isopropyl benzene bottom the first reaction zone. Be in the operational condition of position, main reaction region in above-mentioned second reaction zone under, valve 10,11,23,24,25,26 and 27 is in open state, and valve 6,7,28,29,30,31 and 32 is in cut-out state or only allows less logistics to pass through, make first strand of benzene feed stream, 4, first burst of propylene feed logistics 5, all only less or do not have material to pass through in the logistics 15 and product circulation logistics 17 and 21 pipeline of second reaction zone of the first reaction zone.
In Fig. 2, an only reactor, reactor comprises four sections of beds, and propylene is divided into four parts to enter four beds respectively, and benzene enters from reactor head, and reactor bottom flows out logistics and is partly recycled to reactor head.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By the technical process of Fig. 1, comprising two reactors, each reactor comprises two beds, and wherein each beds of each reactor is mounted with 10 grams of preformed catalysts containing MCM-22 zeolite. First reactor is main reactor, and the 2nd reactor is secondary response device. Wherein, valve (6), (7), (28), (29), (30), (31) and (32) are in the state opened, and valve (10), (11), (23), (25) and (27) are in cut-out state, valve (24) and (26) only have a small amount of recycle to flow through. At this moment the reaction conditions of the first reactor is: every section of bed temperature of reaction 105 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 10 Grams Per Hours, and benzene flow is 75 Grams Per Hours, and propylene weight air speed is 1.0 hours-1, circular flow is 475 Grams Per Hours, and recycle ratio is 5.0.
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 125 DEG C, reaction pressure 2.5MPa, every section of beds propylene flow is 0 Grams Per Hour, and benzene flow is 0 Grams Per Hour, and circular flow is 95 grams hours, and recycle ratio is 1.0, and liquid phase air speed is 9.5 hours-1��
Run 30 days continuously, reaction result: the first reaction outlet propylene conversion the 99.95%, two reacts outlet propylene conversion the 99.99%, two and reacts positive propyl benzene content 60mg/kg isopropyl benzene in outlet reaction product.
According to above-mentioned processing condition, continuing to run 150 days, the first reactor outlet propylene conversion the 99.91%, two reacts outlet propylene conversion 99.99%. Carrying out the blocked operation of two reactors, and make the 2nd reactor be in the state of online main reactor, make the first reactor be in the catalyst regeneration state of off-line, namely at this moment only a reactor is in online response location. Valve (6), (7), (25), (27), (28), (29), (30) and (31) are in the state closed completely, do not have logistics to pass through completely; And valve (10), (11), (23), (24), (26) and (32) are in the state opened.
At this moment the reaction conditions being in the 2nd online reactor is: every section of bed temperature of reaction 135 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 10 Grams Per Hours, and benzene flow is 75 Grams Per Hours, and propylene weight air speed is 1.0 hours-1, circular flow is 475 Grams Per Hours, and recycle ratio is 5.0. Reaction result is: reaction outlet propylene conversion 99.99%, positive propyl benzene content 76mg/kg isopropyl benzene in reaction product.
After first reactor catalyst regeneration ending, being incorporated to online reactive system, maintaining the 2nd reactor is the state of main reactor, makes the first reactor after regeneration be in the state of secondary response device. Valve (10), (11), (23), (24), (25), (26) and (27) are in the state opened; And valve (6), (7), (28), (31) and (32) are in cut-out state, valve (30) and (29) only less recycle flow through. At this moment the concrete reaction conditions of each reactor is: the reaction conditions as the 2nd reactor of main reactor is: every section of bed temperature of reaction 135 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 10 Grams Per Hours, benzene flow is 75 Grams Per Hours, and propylene weight air speed is 1.0 hours-1, circular flow is 475 Grams Per Hours, and recycle ratio is 5.0. The reaction conditions of secondary response device first reactor is: every section of bed temperature of reaction 125 DEG C, reaction pressure 2.5MPa, and every section of beds propylene flow is 0 Grams Per Hour, benzene flow is 0 Grams Per Hour, circular flow is 95 grams hours, and recycle ratio is 1.0, and liquid phase air speed is 9.5 hours-1��
Run 30 days continuously, reaction result: the first reaction outlet propylene conversion the 99.96%, two reacts outlet propylene conversion the 99.99%, two and reacts positive propyl benzene content 66mg/kg isopropyl benzene in outlet reaction product.
[embodiment 2]
By the technical process of Fig. 1, comprising two reactors, each reactor comprises two beds, and wherein each beds of each reactor is mounted with 10 grams of catalyzer, and catalyzer is prepared according to method disclosed in document CN200410066636.2. 2nd reactor is main reactor, and the first reactor is secondary response device.
The reaction conditions of the first reactor is: every section of bed temperature of reaction 110 DEG C, reaction pressure 2.5MPa, and every section of beds propylene flow is 2 Grams Per Hours, benzene flow is 0 Grams Per Hour, circular flow is 120 Grams Per Hours, and recycle ratio is 0.9, and liquid phase air speed is 13 hours-1��
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 125 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 15 Grams Per Hours, and benzene flow is 105 Grams Per Hours, and propylene weight air speed is 1.5 hours-1, circular flow is 800 Grams Per Hours, and recycle ratio is 5.9.
Run 30 days continuously, reaction result: propylene conversion 99.99%, positive propyl benzene content 95mg/kg isopropyl benzene in product.
[embodiment 3]
By the technical process of Fig. 1, comprising two reactors, just each reactor comprises three beds, and wherein each beds of each reactor is mounted with 10 grams of catalyzer, and catalyzer is prepared according to method disclosed in document CN200410066636.2. First reactor is main reactor, and the 2nd reactor is secondary response device.
The reaction conditions of the first reactor is: every section of bed temperature of reaction 95 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 15 Grams Per Hours, and benzene flow is 210 Grams Per Hours, and propylene weight air speed is 1.5 hours-1, circular flow is 1500 Grams Per Hours, and recycle ratio is 5.9.
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 110 DEG C, reaction pressure 2.5MPa, first paragraph beds propylene flow is 5 Grams Per Hours, in addition two-stage catalytic agent bed obstructed enter propylene, benzene flow is 20 Grams Per Hours, circular flow is 320 Grams Per Hours, and recycle ratio is 1.1, and liquid phase air speed is 20 hours-1��
Run 7 days continuously, reaction result: propylene conversion 99.99%, positive propyl benzene content 50mg/kg isopropyl benzene in product.
[embodiment 4]
By the technical process of Fig. 1, comprising two reactors, just each reactor comprises a beds, and wherein each beds of each reactor is mounted with 20 grams of catalyzer, and catalyzer is prepared according to method disclosed in document CN200410066636.2. First reactor is main reactor, and the 2nd reactor is secondary response device.
The reaction conditions of the first reactor is: catalyst bed reaction temperature 135 DEG C, reaction pressure 3.0MPa, and the propylene flow entering beds is 60 Grams Per Hours, and benzene flow is 167 Grams Per Hours, and propylene weight air speed is 1.5 hours-1, circular flow is 2360 Grams Per Hours, and recycle ratio is 10.
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 110 DEG C, reaction pressure 3.0MPa, beds propylene flow is 0 Grams Per Hour, and benzene flow is 0 Grams Per Hour, and circular flow is 0 gram hour, and recycle ratio is 0, and liquid phase air speed is 5.6 hours-1��
Run 15 days continuously, reaction result: propylene conversion 99.99%, positive propyl benzene content 105mg/kg isopropyl benzene in product.
[embodiment 5]
By the technical process of Fig. 1, comprising two reactors, just each reactor comprises two beds, and wherein each beds of each reactor is mounted with 30 grams of catalyzer, and catalyzer is prepared according to method disclosed in document CN200410066636.2. First reactor is main reactor, and the 2nd reactor is secondary response device.
The reaction conditions of the first reactor is: catalyst bed reaction temperature 125 DEG C, reaction pressure 2.7MPa, and the propylene flow entering beds is 30 Grams Per Hours, and benzene flow is 178 Grams Per Hours, and propylene weight air speed is 1.0 hours-1, circular flow is 1200 Grams Per Hours, and recycle ratio is 5.0.
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 110 DEG C, reaction pressure 2.7MPa, beds propylene flow is 0 Grams Per Hour, and benzene flow is 0 Grams Per Hour, and circular flow is 0 gram hour, and recycle ratio is 0, and liquid phase air speed is 7.9 hours-1��
Run 10 days continuously, reaction result: propylene conversion 99.99%, positive propyl benzene content 88mg/kg isopropyl benzene in product.
[embodiment 6]
By the technical process of Fig. 1, comprising two reactors, each reactor comprises two beds, and wherein each beds of each reactor is mounted with 10 grams of preformed catalysts containing MCM-56 zeolite. 2nd reactor is main reactor, and the first reactor is secondary response device.
The reaction conditions of the first reactor is: every section of bed temperature of reaction 110 DEG C, reaction pressure 2.5MPa, and first paragraph beds propylene flow is 2 Grams Per Hours, the propylene flow of the 2nd section of beds is 0 Grams Per Hour, circular flow is 0 gram hour, and recycle ratio is 0, and liquid phase air speed is 25 hours-1��
The reaction conditions of the 2nd reactor is: every section of bed temperature of reaction 100 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 30 Grams Per Hours, and benzene flow is 450 Grams Per Hours, and propylene weight air speed is 3.0 hours-1, circular flow is 2550 Grams Per Hours, and recycle ratio is 5.0.
Run 7 days continuously, reaction result: propylene conversion 99.98%, positive propyl benzene content 55mg/kg isopropyl benzene in product.
[comparative example 1]
Adopt the technical process of an only reactor, as shown in Figure 2, reactor comprises four sections of beds, and propylene is divided into four parts to enter four beds respectively, benzene enters from reactor head, and each beds is mounted with 10 grams of preformed catalysts containing MCM-22 zeolite.
Reaction conditions is: every section of bed temperature of reaction 145 DEG C, reaction pressure 2.7MPa, the propylene flow entering every section of beds is 20 Grams Per Hours, and benzene flow is 370 Grams Per Hours, and circular flow is 700 Grams Per Hours.
Run 90 days continuously, reaction result: propylene conversion 99.91%, positive propyl benzene content 220mg/kg isopropyl benzene in product.
The above results illustrates, in the prior art, when when higher reaction temperatures, propylene can keep higher transformation efficiency, but makes impurity positive propyl benzene content also higher.
[comparative example 2]
Adopt the technical process of an only reactor, as shown in Figure 2, reactor comprises four sections of beds, and propylene is divided into four parts to enter four beds respectively, benzene enters from reactor head, and each beds is mounted with 10 grams of preformed catalysts containing MCM-22 zeolite.
Reaction conditions is: every section of bed temperature of reaction 115 DEG C, reaction pressure 2.5MPa, the propylene flow entering every section of beds is 10 Grams Per Hours, and benzene flow is 75 Grams Per Hours, and circular flow is 570 Grams Per Hours.
Run 120 days continuously, reaction result: propylene conversion 99.30%, positive propyl benzene content 97mg/kg isopropyl benzene in product.
The above results illustrates, in the prior art, when adopt relatively low reaction temperatures time, although the positive propyl benzene content of impurity can be made to reduce, but the transformation efficiency of propylene also can be made to reduce simultaneously.
Claims (8)
1. produce a method for isopropyl benzene, comprise the following steps:
A) device at least comprising the first reaction zone and second reaction zone is provided;
B) valve (6), (7), (28), (29), (30), (31) and (32) are opened, first burst of benzene logistics and first strand of propylene stream is made to enter the first reaction zone, contact with catalyzer, generate first strand of cumene stream; First strand of cumene stream is divided into two portions, and a part loops back the first reaction zone, and another part enters second reaction zone; The logistics entering second reaction zone contacts with catalyzer, generates the product stream containing isopropyl benzene; Wherein, valve (10), (11), (23), (24), (25), (26) and (27) are in cut-out state or only allow less logistics to pass through;
C) the first reaction zone catalyst activity reduces or after inactivation, open valve (10), (11), (23), (24), (25), (26) and (27), the 2nd burst of benzene logistics and the 2nd strand of propylene stream is made to enter second reaction zone, contact with catalyzer, generate the 2nd strand of cumene stream; 2nd strand of cumene stream is divided into two portions, and a part loops back second reaction zone, and another part enters the first reaction zone; The logistics entering the first reaction zone contacts with catalyzer, generates the product stream containing isopropyl benzene; Wherein, valve (6), (7), (28), (29), (30), (31) and (32) are in cut-out state or only allow less logistics to pass through;
D) second reaction zone catalyst activity reduces or after inactivation, repeating step b) and c);
Step b) in, the operational condition of described first reaction zone is: the mol ratio of first burst of benzene logistics and first strand of propylene stream is 1��10, first strand of propylene stream weight space velocity is 0.2��10 hour-1, recycle ratio is 2��50, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0Mpa; The operational condition of described second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 0��10, two strand of propylene stream weight space velocity is 0��2.0 hour-1, recycle ratio is 0��10, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa; The recycle ratio of the first reaction zone is greater than the recycle ratio of second reaction zone;
Step c) in, the operational condition of described first reaction zone is: the mol ratio of first burst of benzene logistics and first strand of propylene stream is 0��10, first strand of propylene stream weight space velocity is 0��2.0 hour-1, recycle ratio is 0��10, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa; The operational condition of second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 1��10, two strand of propylene stream weight space velocity is 0.2��10 hour-1, recycle ratio is 2��50, and temperature of reaction is 90��180 DEG C, and reaction pressure is 1.0��4.0MPa; The recycle ratio of second reaction zone is greater than the recycle ratio of the first reaction zone.
2. produce the method for isopropyl benzene according to claim 1, it is characterized in that described first reaction zone and second reaction zone are all the reactors of at least one section, or the reaction zone become by least two single section of reactors in series, or at least one single section of reactor and at least one reactors in series of at least two sections and the reaction zone that becomes.
3. produce the method for isopropyl benzene according to claim 1, it is characterised in that step b) in, the mol ratio of first burst of benzene logistics and first strand of propylene stream is 1.5��4, first strand of propylene stream weight space velocity is 0.3��5 hour-1, recycle ratio is 3��25, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa;
The operational condition of described second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 0��5, two strand of propylene stream weight space velocity is 0��1.5 hour-1, recycle ratio is 0��5, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa.
4. produce the method for isopropyl benzene according to claim 1, it is characterized in that step c) in, the operational condition of described first reaction zone is: the mol ratio of first burst of benzene logistics and first strand of propylene stream is 0��5, first strand of propylene stream weight space velocity is 0��1.5 hour-1, recycle ratio is 0��5, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa;
The operational condition of second reaction zone is: the mol ratio of the 2nd burst of benzene logistics and the 2nd strand of propylene stream is the 1.5��4, two strand of propylene stream weight space velocity is 0.3��5 hour-1, recycle ratio is 3��25, and temperature of reaction is 95��170 DEG C, and reaction pressure is 2.0��3.0MPa.
5. produce the method for isopropyl benzene according to claim 1, it is characterised in that described catalyzer is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.
6. produce the method for isopropyl benzene according to claim 1, it is characterised in that propylene segmentation enters reaction zone.
7. produce the method for isopropyl benzene according to claim 1, it is characterised in that benzene enters from the top of reaction zone.
8. produce the method for isopropyl benzene according to claim 1, it is characterised in that the logistics looping back reaction zone enters from the top of reaction zone.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512503.2A CN104557437B (en) | 2013-10-28 | 2013-10-28 | Produce the method for isopropyl benzene |
| ES14190441.7T ES2581914T3 (en) | 2013-10-28 | 2014-10-27 | Method for producing isopropylbenzene from benzene and propylene |
| EP14190441.7A EP2865660B1 (en) | 2013-10-28 | 2014-10-27 | Method for producing isopropyl benzene from benzene and propylene |
| SG10201406982WA SG10201406982WA (en) | 2013-10-28 | 2014-10-27 | Method for Producing Isopropyl Benzene from Benzene and Propylene |
| TW103137062A TWI674252B (en) | 2013-10-28 | 2014-10-27 | Method for producing cumene from benzene and propylene |
| BR102014026858-8A BR102014026858B1 (en) | 2013-10-28 | 2014-10-27 | method for producing isopropylbenzene from benzene and propylene |
| JP2014219538A JP6599609B2 (en) | 2013-10-28 | 2014-10-28 | Process for producing isopropylbenzene from benzene and propylene |
| KR1020140147268A KR102229126B1 (en) | 2013-10-28 | 2014-10-28 | Method for producing isopropyl benzene from benzene and propylene |
| US14/525,857 US9828307B2 (en) | 2013-10-28 | 2014-10-28 | Method for producing isopropyl benzene from benzene and propylene |
| JP2019126986A JP6748266B2 (en) | 2013-10-28 | 2019-07-08 | Method for producing isopropylbenzene from benzene and propylene |
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| CN201310512503.2A CN104557437B (en) | 2013-10-28 | 2013-10-28 | Produce the method for isopropyl benzene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1592592A (en) * | 1978-01-23 | 1981-07-08 | Uop Inc | Cumene production |
| CN1228073A (en) * | 1996-08-20 | 1999-09-08 | 陶氏化学公司 | Process for production of alkylated benzenes |
| US6835862B1 (en) * | 1997-06-16 | 2004-12-28 | Uop Llc | Alkylation process operating at high recycle ratios |
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2013
- 2013-10-28 CN CN201310512503.2A patent/CN104557437B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1592592A (en) * | 1978-01-23 | 1981-07-08 | Uop Inc | Cumene production |
| CN1228073A (en) * | 1996-08-20 | 1999-09-08 | 陶氏化学公司 | Process for production of alkylated benzenes |
| US6835862B1 (en) * | 1997-06-16 | 2004-12-28 | Uop Llc | Alkylation process operating at high recycle ratios |
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