CN104557437A - Method for producing cumene - Google Patents
Method for producing cumene Download PDFInfo
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- CN104557437A CN104557437A CN201310512503.2A CN201310512503A CN104557437A CN 104557437 A CN104557437 A CN 104557437A CN 201310512503 A CN201310512503 A CN 201310512503A CN 104557437 A CN104557437 A CN 104557437A
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Abstract
The invention relates to a method for producing cumene. The method is mainly used for solving the problems of low propylene conversion rate, high propylbenzene content in a cumene product and low device production efficiency in the prior art. The following technical scheme is adopted in the invention to well solve the problem: at least two reaction areas are arranged, and the two reaction areas are alternatively operated, and the processes are combined, and the method can be used in the industrial production of producing cumene through benzene and propylene.
Description
Technical field
The present invention relates to a kind of method of 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, because solid phosphoric acid can not 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 yield of its isopropyl benzene is only about 95%.Last century the eighties, Monsanto company exploitation with AlCl
3for the isopropyl benzene production technique of alkylation catalyst, and realize industrial application.Due to AlCl
3equally can not catalysis transalkylation reaction, therefore, with AlCl
3it is still lower in the yield of isopropyl benzene that method produces isopropyl benzene, also there is serious pollution problem and corrosion of equipment problem simultaneously.
In the nineties in last century, it is catalyzer that (US4992606, US5362697, US5453554, US5522984, US5672799, US6162416, US6051521) companies such as Dow, CD Tech, Mobil-Badger, Enichem and UOP disclose with 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 transalkylation reaction is carried out in polysubstituted isopropyl benzene enters single bed transalkylation reaction zone after mixing with benzene again.
In existing disclosed isopropyl benzene technology, the alkylation of benzene and propylene is all adopt single, multistage laminar fixed-bed reactor, propylene sectional feeding pattern and reaction solution outside circulation, its object is to: 1, reduce the propylene content in reactor, to reduce catalyst deactivation rate; 2, by reducing the temperature of beds, the generation of impurity n-proplbenzene is reduced, to improve the quality of products.In fact, avoiding the inactivation of catalyzer, reducing impurity n-proplbenzene content is 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 be 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 of propylene is reduced; 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, and in isopropyl benzene product, n-proplbenzene content is high, and cause because of more catalyst changeout the problem that device production efficiency is low, provides a kind of method of production isopropyl benzene newly.It is high that the method has propylene conversion, and in product isopropyl benzene, n-proplbenzene 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 of 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, with catalyst exposure, 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; Enter logistics and the catalyst exposure of second reaction zone, generate the product stream containing isopropyl benzene; Wherein, valve (10), (11), (23), (24), (25), (26) and (27) are in dissengaged positions 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), second burst of benzene logistics and second strand of propylene stream is made to enter second reaction zone, with catalyst exposure, generate second strand of cumene stream; Second 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; Enter logistics and the catalyst exposure of the first reaction zone, generate the product stream containing isopropyl benzene; Wherein, valve (6), (7), (28), (29), (30), (31) and (32) are in dissengaged positions 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 by the reaction zone of at least two single hop reactors in series, or the reaction zone of at least one single hop reactor and at least one reactors in series of at least two sections.
In technique scheme, preferably, 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, preferably, in step b), the operational condition of described second reaction zone is: the mol ratio of second burst of benzene logistics and second strand of propylene stream is 0 ~ 10, second 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 second burst of benzene logistics and second strand of propylene stream is 0 ~ 5, second 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 second strand of propylene stream weight space velocity is 0 ~ 1.0 hour
-1.
In technique scheme, preferably, in step b), the recycle ratio of the first reaction zone is greater than the recycle ratio of second reaction zone.
In technique scheme, preferably, 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, preferably, in step c), the operational condition of second reaction zone is: the mol ratio of second burst of benzene logistics and second strand of propylene stream is 1 ~ 10, second 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 second burst of benzene logistics and second strand of propylene stream is 1.5 ~ 4, second 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 second strand of propylene stream weight space velocity is 0.4 ~ 3.0 hour
-1.
In technique scheme, preferably, in step c), the recycle ratio of second reaction zone is greater than the recycle ratio of the first reaction zone.
In technique scheme, preferably, described catalyzer is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.
In technique scheme, preferably, propylene segmentation enters reaction zone.
In technique scheme, preferably, benzene enters from the top of reaction zone.
In technique scheme, preferably, 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 the weight ratio of logistics and the reaction zone effluent stream looping back reaction zone.
The catalyzer used in the inventive method is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.Wherein, the zeolite having a MWW laminate structure described in 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 n-proplbenzene content in product, usually adopt 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 stream enters almost does not have second reaction zone (secondary response district) of recycle stream to continue reaction, this extends the residence time in fact, make to continue reaction at the unreacted a small amount of propylene of the first 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, achieve the steady production of device.The present invention, by adopting the combination of at least two reactors, achieves by adjustment temperature by a relatively large margin, reduces impurity n-proplbenzene content, improves propylene conversion, achieve blocked operation and the process combination of reactor, improve device operational stability.Alkylating temperature of reaction is usually at about 150 DEG C in the prior art, 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 can have a strong impact on the transformation efficiency of propylene and the content of impurity n-proplbenzene.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, and 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, the switchover operation of a reactor, even on-line regeneration can be realized: even only have a reactor to put into operation, and the reactor that another catalyst activity reduces carries out the on-line regeneration of catalyzer.Adopt the inventive method, do not need whole device to stop more catalyst changeout, n-proplbenzene 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 process flow diagram of the present invention, and to contain 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 the valve entering the first reaction zone first bed propylene feed, 7 for controlling the valve entering the first reaction zone second bed propylene feed, 8 is second strand of benzene raw materials, 9 is second burst of propylene feedstocks, 10 for controlling the valve entering second reaction zone first bed propylene feed, 11 for controlling the valve entering second reaction zone second 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 respectively by valve 6 and 7, react with catalyst exposure, obtain the logistics 12 comprising 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 above-mentioned first reactor is in the operational condition of 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 dissengaged positions or only allow less logistics to pass through, makes 8, the second burst of propylene feed logistics 9 of second of second reaction zone strand of benzene feed stream, all only have less logistics or do not have logistics to pass through in the logistics 16 of the first reaction zone and the pipeline of product circulation logistics 18 and 22.
When second reaction zone is main reaction region, when first reaction zone is secondary response district, second burst of benzene logistics 8 enters from top, second reaction zone, second strand of propylene stream 9 enters two beds respectively by valve 10 and 11, react with catalyst exposure, obtain the product stream 13 comprising 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 dissengaged positions or only allow less logistics to pass through, makes 4, the first burst of propylene feed logistics 5 of first of the first reaction zone strand of benzene feed stream, all only have less in the logistics 15 and product circulation logistics 17 and 21 pipeline of second reaction zone or do not have material to pass through.
In Fig. 2, only have a 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 effluent stream 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, comprise 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 second 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 dissengaged positions, valve (24) and (26) only have a small amount of recycle stream to pass 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 second 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.
Continuous operation 30 days, reaction result: the first reaction outlet propylene conversion 99.95%, second reacts outlet propylene conversion 99.99%, second and reacts n-proplbenzene content 60mg/kg isopropyl benzene in outlet reaction product.
According to above-mentioned processing condition, continue operation 150 days, the first reactor outlet propylene conversion 99.91%, second reacts outlet propylene conversion 99.99%.Carry out the blocked operation of two reactors, and make the second 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 have a reactor to be in online response location.Valve (6), (7), (25), (27), (28), (29), (30) and (31) are in the state of closing 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 second 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%, n-proplbenzene content 76mg/kg isopropyl benzene in reaction product.
After first reactor catalyst regeneration ending, be incorporated to online reactive system, maintain the state that the second reactor is main reactor, make 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 dissengaged positions, valve (30) and (29) only have less recycle stream to pass through.At this moment the concrete reaction conditions of each reactor is: the reaction conditions as the second 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.
Continuous operation 30 days, reaction result: the first reaction outlet propylene conversion 99.96%, second reacts outlet propylene conversion 99.99%, second and reacts n-proplbenzene content 66mg/kg isopropyl benzene in outlet reaction product.
[embodiment 2]
By the technical process of Fig. 1, comprise two reactors, each reactor comprises two beds, and wherein each beds of each reactor is mounted with 10 grams of catalyzer, and catalyzer is according to method preparation disclosed in document CN200410066636.2.Second 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 second 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.
Continuous operation 30 days, reaction result: propylene conversion 99.99%, n-proplbenzene content 95mg/kg isopropyl benzene in product.
[embodiment 3]
By the technical process of Fig. 1, comprise 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 according to method preparation disclosed in document CN200410066636.2.First reactor is main reactor, and the second 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 second 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, two-stage catalytic agent bed does not pass into propylene in addition, 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.
Continuous operation 7 days, reaction result: propylene conversion 99.99%, n-proplbenzene content 50mg/kg isopropyl benzene in product.
[embodiment 4]
By the technical process of Fig. 1, comprise 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 according to method preparation disclosed in document CN200410066636.2.First reactor is main reactor, and the second 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 second 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.
Continuous operation 15 days, reaction result: propylene conversion 99.99%, n-proplbenzene content 105mg/kg isopropyl benzene in product.
[embodiment 5]
By the technical process of Fig. 1, comprise 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 according to method preparation disclosed in document CN200410066636.2.First reactor is main reactor, and the second 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 second 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.
Continuous operation 10 days, reaction result: propylene conversion 99.99%, n-proplbenzene content 88mg/kg isopropyl benzene in product.
[embodiment 6]
By the technical process of Fig. 1, comprise 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.Second 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 second segment 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 second 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.
Continuous operation 7 days, reaction result: propylene conversion 99.98%, n-proplbenzene content 55mg/kg isopropyl benzene in product.
[comparative example 1]
Adopt the technical process only having a 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.
Continuous operation 90 days, reaction result: propylene conversion 99.91%, n-proplbenzene content 220mg/kg isopropyl benzene in product.
The above results illustrates, in the prior art, when under higher reaction temperatures condition, propylene can keep higher transformation efficiency, but makes impurity n-proplbenzene content also higher.
[comparative example 2]
Adopt the technical process only having a 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.
Continuous operation 120 days, reaction result: propylene conversion 99.30%, n-proplbenzene content 97 mg/kg isopropyl benzene in product.
The above results illustrate, in the prior art, when adopt comparatively low reaction temperatures time, although impurity n-proplbenzene content can be made to reduce, while the transformation efficiency of propylene also can be made to reduce.
Claims (10)
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, with catalyst exposure, 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; Enter logistics and the catalyst exposure of second reaction zone, generate the product stream containing isopropyl benzene; Wherein, valve (10), (11), (23), (24), (25), (26) and (27) are in dissengaged positions 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), second burst of benzene logistics and second strand of propylene stream is made to enter second reaction zone, with catalyst exposure, generate second strand of cumene stream; Second 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; Enter logistics and the catalyst exposure of the first reaction zone, generate the product stream containing isopropyl benzene; Wherein, valve (6), (7), (28), (29), (30), (31) and (32) are in dissengaged positions or only allow less logistics to pass through;
D) second reaction zone catalyst activity reduces or after inactivation, repeating step b) and c).
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 by the reaction zone of at least two single hop reactors in series, or the reaction zone of at least one single hop reactor and at least one reactors in series of at least two sections.
3. produce the method for isopropyl benzene according to claim 1, it is characterized in 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;
The operational condition of described second reaction zone is: the mol ratio of second burst of benzene logistics and second strand of propylene stream is 0 ~ 10, second 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.
4. produce the method for isopropyl benzene according to claim 3, it is characterized in that in step b), 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 second burst of benzene logistics and second strand of propylene stream is 0 ~ 5, second 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.
5. produce the method for isopropyl benzene according to claim 1, it is characterized in that in step c), 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 second burst of benzene logistics and second strand of propylene stream is 1 ~ 10, second 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.
6. produce the method for isopropyl benzene according to claim 5, it is characterized in that in step c), 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 second burst of benzene logistics and second strand of propylene stream is 1.5 ~ 4, second 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.
7. produce the method for isopropyl benzene according to claim 1, it is characterized in that described catalyzer is selected from Beta zeolite, mordenite or has the zeolite of MWW laminate structure.
8. produce the method for isopropyl benzene according to claim 1, it is characterized in that propylene segmentation enters reaction zone.
9. produce the method for isopropyl benzene according to claim 1, it is characterized in that benzene enters from the top of reaction zone.
10. produce the method for isopropyl benzene according to claim 1, it is characterized 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 |
| BR102014026858-8A BR102014026858B1 (en) | 2013-10-28 | 2014-10-27 | method for producing isopropylbenzene from benzene and propylene |
| ES14190441.7T ES2581914T3 (en) | 2013-10-28 | 2014-10-27 | Method for producing isopropylbenzene from benzene and propylene |
| TW103137062A TWI674252B (en) | 2013-10-28 | 2014-10-27 | Method for producing cumene 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 |
| JP2014219538A JP6599609B2 (en) | 2013-10-28 | 2014-10-28 | Process for producing isopropylbenzene from benzene and propylene |
| US14/525,857 US9828307B2 (en) | 2013-10-28 | 2014-10-28 | Method for producing isopropyl benzene from benzene and propylene |
| KR1020140147268A KR102229126B1 (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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530246A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of benzene and production of propylene n-proplbenzene |
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| 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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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530246A (en) * | 2017-03-03 | 2018-09-14 | 中国石油化工股份有限公司 | The method of benzene and production of propylene n-proplbenzene |
| CN108530246B (en) * | 2017-03-03 | 2021-03-30 | 中国石油化工股份有限公司 | Method for producing n-propylbenzene from benzene and propylene |
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