CN104971674B - Liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst - Google Patents

Liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst Download PDF

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Publication number
CN104971674B
CN104971674B CN201410137686.9A CN201410137686A CN104971674B CN 104971674 B CN104971674 B CN 104971674B CN 201410137686 A CN201410137686 A CN 201410137686A CN 104971674 B CN104971674 B CN 104971674B
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catalyst
liquid
cyclone separator
catalytic reaction
circulating tank
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CN104971674A (en
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王振波
刘植昌
徐春明
张睿
金有海
陈阿强
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China University of Petroleum Beijing
China University of Petroleum CUP
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China University of Petroleum Beijing
China University of Petroleum CUP
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Abstract

Based on the liquid liquid heterogeneous catalytic reaction separation integrated apparatus of liquid-phase catalyst, belong to catalytic reaction separation equipment field and in particular to a kind of liquid liquid heterogeneous catalytic reaction separation integrated apparatus.Including riser reactor(3), high-efficiency cyclone separator(5)With catalyst circulating tank(7), riser reactor(3)Top exit passes through connecting tube(16)It is sequentially communicated high-efficiency cyclone separator(5)With catalyst circulating tank(7);Catalyst circulating tank(7)The catalyst circulation pipe of bottom side(10)Connection riser reactor(3)Bottom, middle part side is provided with fresh catalyst supply port(8), bottom is provided with reclaimable catalyst outlet(9).Present invention achieves the integrated circular response separation process such as the mixing of liquid liquid, reaction, product ON-LINE SEPARATION and catalyst circulation in liquid liquid heterogeneous catalytic reaction, reach the purpose of the online sharp separation of quick mixing, fast reaction and product and catalyst.

Description

Liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst
Technical field
Based on the liquid liquid heterogeneous catalytic reaction separation integrated apparatus of liquid-phase catalyst, belong to catalytic reaction separation equipment Field is and in particular to a kind of liquid liquid heterogeneous catalytic reaction separation integrated apparatus.
Background technology
Catalytic reaction is common course of reaction in the fields such as petrochemical industry, and some of which catalytic reaction uses liquid Catalyst.As common sulfuric acid process alkylation process, hydrogen fluoride alkylation process, the catalytic esterification work based on liquid-phase catalyst Skill, the homogeneous alkylation techniques of Kerr, McGee company(HAT), ethylene moiety oxidation method of preparing aldehyde, methanol acetic acid process with And the many catalytic reaction processes based on ionic-liquid catalyst of increasingly rise in the last few years, these courses of reaction need solve The problems such as liquid liquid is sufficiently mixed, the efficient circulation of fast reaction, product and catalyst sharp separation and catalyst utilizes.
These are primarily present the problem of the following aspects based on the industrial processes of liquid catalyst at present:
1st, realize using by traditional kettle style stirring mixing more than the mixing of liquid phase feed and liquid-phase catalyst, there is production Efficiency is low, mixing is uneven, reaction is insufficient and the low problem of catalyst utilization;
2nd, product separate with catalyst more than using traditional gravitational settling mode, there is time of staying length, separate The problems such as effect is poor, catalyst inventory is big, also leads to the overreaction problem of product simultaneously because the time of staying is long;
Additionally, current these course of reaction generally existing technological process length, catalyst separation/circulation process length etc. are asked Topic, leads to the problems such as equipment investment is big, system controls difficulty, high energy consumption, catalyst attrition big.Therefore, how Simplified flowsheet road Line, reduce equipment investment, reduce device in catalyst inventory, reduce production run energy consumption cost, become such technology further The important directions of development.
Content of the invention
The technical problem to be solved is:Overcome the deficiencies in the prior art, a kind of Simplified flowsheet route, fall are provided Low equipment investment, the liquid liquid heterogeneous catalytic reaction isolation integral based on liquid-phase catalyst of reduction production run energy consumption cost Device.
The technical solution adopted for the present invention to solve the technical problems is:Should liquid liquid based on liquid-phase catalyst be heterogeneous urges Change integrated reaction and separation device it is characterised in that:Including the circulation of riser reactor, high-efficiency cyclone separator and catalyst Tank, riser reactor bottom is provided with material feeding tube, and riser reactor top exit is sequentially communicated efficiently by connecting tube Cyclone separator and catalyst circulating tank;Under the catalyst circulation pipe connection riser reactor of catalyst circulating tank bottom side Portion, middle part side is provided with fresh catalyst supply port, and bottom is provided with reclaimable catalyst outlet.By riser reactor, efficient rotary Stream separator, catalyst circulating tank, catalyst circulation pipe, catalyst circulation control device form a circular response system;Vertical The draw ratio of tubular reactor determines according to response speed and disposal ability;Riser reactor exports direct connection efficient rotary flow point From device, realize online sharp separation, the efficient circulation of catalyst of product and catalyst, effectively prevent reaction simultaneously and produce The overreaction problem of thing.
Described riser reactor is the multi-stage reacting device of raw material successively up reaction, including body, feedstock Pipe and static mixer, its bottom is provided with three groups or more than three groups material feeding tubes, and body side is laid with from the bottom up Multigroup material feeding tube, is correspondingly provided with multigroup static mixer in tubular body, and multigroup static mixer is partitioned in body Multiple raw material reaction spaces, multigroup material feeding tube one end is respectively communicated with multiple raw material reaction spaces.Riser reactor bottom Be provided with one or more groups of material feeding tubes, raw material and catalyst after riser reactor bottom mixes up mixing further and Reaction;In riser reactor, one or more snippets static mixer and flow distributor are set, to guarantee the efficient of liquid-liquid diphase Mixing and flowing are uniformly distributed, and the draw ratio of reactor determines according to response speed and disposal ability.
Described body internal upper part is additionally provided with flow of fluid distributor.
Described catalyst circulation pipe is provided with the speed governing pipeline circulating pump controlling catalyst circulating load.Facilitate implementation anti- Should, detached flexible control.
Described catalyst circulation pipe is provided with the catalyst circulation adjustable valve controlling catalyst circulating load.
Described high-efficiency cyclone separator is arranged between connecting tube and catalyst circulating tank, high-efficiency cyclone separator top Side connects connecting tube, and bottom connects catalyst by cyclone separator underflow regulating valve and circulates tank top, and efficient rotary flow point It is provided with overflow head piece from device top.Riser reactor exports direct connection high-efficiency cyclone separator, realizes product and catalyst Online sharp separation, the efficient circulation of catalyst, effectively prevent the overreaction problem of product simultaneously.
Secondary response segregation apparatuss are set up, secondary response is divided between described high-efficiency cyclone separator and catalyst circulating tank Include second level cyclone separator, catalyst surge tank and adjusting control valve, the overflow at high-efficiency cyclone separator top from device Head piece connects second level cyclone separator top entry by pipeline, and second level cyclone separator bottom connects catalyst buffering Tank, catalyst surge tank passes through to buffer connecting tube and adjusting control valve connects catalyst circulating tank.
Described high-efficiency cyclone separator is arranged in the connecting tube between riser reactor and catalyst circulating tank, high Tank top is circulated by pipeline connection catalyst in effect cyclone separator top, is provided with cyclone separator underflow and adjusts at outlet at bottom Valve.
Compared with prior art, the present invention is had an advantageous effect in that:
1st, reaction, isolation integral:By riser reactor, cyclone separator, catalyst circulating tank, catalyst circulation Pipe, catalyst circulating load control realize liquid liquid heterogeneous catalysis with the circular response device of governor impeller or flow control valve composition In course of reaction, the mixing of liquid liquid, reaction, product ON-LINE SEPARATION and catalyst circulate this integrated circular response separation process, real Showed liquid charging stock and liquid catalyst quick mix, quickly the dividing online of fast reaction and product and catalyst From Reaction Separation controls flexibly;Decrease system catalyst reserve simultaneously, reduce production cost and equipment investment.
2nd, in being realized based on blender in riser reactor, reactor feed system, device, raw material and catalyst is efficient Mixing, fast reaction;The riser reactor of the multistage hybrid reaction of logical upstriker, and the high-efficiency cyclone using cooperatively separates Device, it is achieved that product and online, the quick, high efficiency separation of catalyst and the efficient circulation of catalyst, significantly shorten Reaction time, reduce catalyst inventory in system.
3rd, set technique device technique flow process is short, compact equipment, treating capacity are big, investment and maintenance cost is low, operation Convenient, strong adaptability.
Brief description
Fig. 1 is the annexation schematic diagram of the embodiment of the present invention 1.
Fig. 2 is the annexation schematic diagram of the embodiment of the present invention 2.
Fig. 3 is the annexation schematic diagram of the embodiment of the present invention 3.
Fig. 4 is the annexation schematic diagram of the embodiment of the present invention 4.
Fig. 5 is the high-efficiency cyclone separator structure cross-sectional schematic of the present invention.
Wherein, 1, material feeding tube 2, static mixer 3, riser reactor 4, liquid flow distribution device 5, High-efficiency cyclone separator 501, overflow head piece 6, cyclone separator underflow regulating valve 7, catalyst circulating tank 8, fresh Catalyst make-up mouth 9, reclaimable catalyst outlet 10, catalyst circulation pipe 11, speed governing pipeline circulating pump 12, catalyst Circulation adjustable valve 13, second level cyclone separator 14, catalyst surge tank 1401, buffering connecting tube 15, regulation Control valve 16, connecting tube 17, light phase overflow outlet 18, guide vane 19, light phase feed tube 20, outer cylinder body 21st, inner barrel 22, conical pipe 23, heavy phase underflow outlet pipe 24, material currency structure.
Specific embodiment
Fig. 1,5 it is highly preferred embodiment of the present invention, 1 ~ 5 the present invention will be further described below in conjunction with the accompanying drawings.
Embodiment 1
Referring to the drawings 1:Based on the liquid liquid heterogeneous catalytic reaction separation integrated apparatus of liquid-phase catalyst, including vertical pipe type Reactor 3, high-efficiency cyclone separator 5 and catalyst circulating tank 7, riser reactor 3 bottom is provided with material feeding tube 1, standpipe Formula reactor 3 top exit is sequentially communicated high-efficiency cyclone separator 5 and catalyst circulating tank 7 by connecting tube 16;Catalyst follows Catalyst circulation pipe 10 connection riser reactor 3 bottom of ring tank 7 bottom side, catalyst circulating tank 7 is followed by catalyst Endless tube 10 is connected with reactor bottom, realizes the Rapid Circulation of catalyst, and catalyst circulation pipe 10 is provided with control catalyst and follows The speed governing pipeline circulating pump 11 of circular rector, catalyst circulating tank 7 middle part side is provided with fresh catalyst supply port 8, and bottom is provided with treats Raw catalyst outlet 9.
Riser reactor 3 is the multi-stage reacting device of raw material successively up reaction, including body, material feeding tube 1 and Static mixer 2, its bottom is provided with three groups or more than three groups material feeding tubes 1, and multigroup material feeding tube 1 of its bottom is in Radial be distributed on its bottom, body side is laid with multigroup material feeding tube 1 from the bottom up, accordingly sets in tubular body There is multigroup static mixer 2, multigroup static mixer 2 will be partitioned into multiple raw material reaction spaces, multigroup feedstock in body Pipe 1 one end is respectively communicated with multiple raw material reaction spaces, and every material feeding tube 1 corresponds to a raw material reaction space, feedstock Pipe 1 and static mixer 2 interval setting, in body, topmost is additionally provided with flow of fluid distributor 4.
High-efficiency cyclone separator 5 is arranged between connecting tube 16 and catalyst circulating tank 7, high-efficiency cyclone separator 5 top Side connects connecting tube 16, and bottom connects catalyst circulating tank 7 top by cyclone separator underflow regulating valve 6, and efficient rotary Stream separator 5 top is provided with overflow head piece 501.This structure is used for the course of reaction that catalyst proportion is more than product, efficiently The overflow head piece 501 of cyclone separator 5 is reacting product outlet, high-efficiency cyclone separator 5 outlet at bottom and catalyst circulating tank 7 It is connected.
Followed by riser reactor 3, high-efficiency cyclone separator 5, catalyst circulating tank 7, catalyst circulation pipe 10, catalyst Circulation control forms a circular response system with speed governing pipeline circulating pump 11;Riser reactor 3 bottom is provided with one or more groups of Material feeding tube 1, raw material is up after riser reactor 3 bottom mixes with catalyst to be mixed and reaction further.
Referring to the drawings 5:High-efficiency cyclone separator 5 includes outer cylinder body 20 and inner barrel 21, and outer cylinder body 20 is sleeved on inner barrel 21 outer upper, form toroidal cavity between outer cylinder body 20 and inner barrel 21, toroidal cavity is the relief area of light phase liquid raw material, And outer cylinder body 20 side is provided with light phase feed tube 19, inner barrel 21 barrel is communicated with inner barrel 21 inner chamber and toroidal cavity Material currency structure 24;Inner barrel 21 internal upper part is cased with light phase overflow outlet 17, light phase overflow outlet 17 and inner barrel 21 Between form annular mixing cavity, and light phase overflow outlet 17 top stretches out outside inner barrel 21;Annular mixing cavity top Annular entry at be provided with strong rotational structure, heavy phase liquid raw material passes through strong rotational structure and enters annular mixing cavity and formed strong Rotational flow field, light phase liquid raw material enters annular mixing cavity through light phase feed tube 19 and material currency structure, with heavy phase liquid Mixed and rotated descending, side border ring separates;Light phase product or light phase raw material more than needed are through on light phase overflow outlet 17 Portion discharges, and heavy phase product or heavy phase raw material more than needed are discharged by heavy phase underflow outlet pipe 23 outlet at bottom.
The fixedly sleeved heavy phase underflow outlet pipe 23 of conical pipe 22 is passed through in inner barrel 21 bottom, conical pipe 22 be upper shed big, The little conical tube of under shed, heavy phase underflow outlet pipe 23 is straight tube body isometrical up and down, and heavy phase underflow outlet pipe 23 top covers It is contained in conical pipe 22 outside medium position, and be fixedly connected.
Strong rotational structure is guide vane 18, and guide vane 18 is provided with multigroup, and the square annular of level is distributed on annular mixing Cavity top, annular mixing cavity top is heavy phase feed(raw material)inlet.
Work process:As shown in figure 1, multigroup material feeding tube 1 from riser reactor 3 bottom for the raw material enters(Specifically Quantity is arranged as required to), catalyst enters standpipe by catalyst circulating tank 7 by the catalyst circulation pipe 10 of its underpart side Formula reactor 3 bottom, the speed governing pipeline circulating pump 11 that catalyst circulating load is passed through on catalyst circulation pipe 10 controls;Raw material with urge Agent tentatively mixes in riser reactor 3 bottom, for guaranteeing being sufficiently mixed further of liquid-liquid diphase, in riser reactor Setting multistage static mixer 2 in 3, topmost setting flow of fluid distributor 4 in the body of riser reactor 3 simultaneously; After completion of the reaction, product is introduced directly into high-efficiency cyclone with catalyst mixed liquid by the outlet of riser reactor 3 and separates Device 5 top, carries out quick, the high efficiency separation of product and catalyst, the cyclonic separation of high-efficiency cyclone separator 5 bottom setting Device underflow regulating valve 6 is in order to control the split ratio of high-efficiency cyclone separator 5 and the separation efficiency adjusting high-efficiency cyclone separator 5; This kind of structure is used for the reaction that catalyst proportion is more than product, and high-efficiency cyclone separator 5 bottom directly connects catalyst and follows Ring tank 7 top, catalyst circulating tank 7 middle part side setting fresh catalyst supply port 8 and reclaimable catalyst outlet 9, are producing During can realize the continuous supplementation of fresh catalyst and the continuous extraction of reclaimable catalyst.
The work process of high-efficiency cyclone separator 5 is as follows:As shown in figure 5, heavy phase liquid raw material is from inner barrel 21 top The annular entry of annular mixing cavity top enters, and heavy phase liquid raw material enters annular mixing cavity through guide vane 18, by This annular mixing cavity enters the inner chamber of inner barrel 21, and heavy phase liquid raw material is in the presence of guide vane 18 in inner barrel 21 Inner chamber makees strong rotational flow;Again due to forming a toroidal cavity between inner barrel 21 and outer cylinder body 20, this toroidal cavity is light Phase liquid charging stock relief area, light phase liquid raw material enters toroidal cavity through the light phase feed tube 19 on outer tube wall, is then passed through interior The material currency structure that on cylinder 21 barrel, relevant position opens up, such as opening or circulation are thin to stitch wind structure, light phase liquid raw material Through material currency structure inner barrel 21 inner chamber on inner barrel 21;Under the strong cyclonic action of heavy phase liquid of inner barrel 21 inner chamber, Uniformly cloth film, in the internal face of inner barrel 21, realizes the high degree of dispersion of light phase liquid first, thus realizing filling of weight light phase liquid Tap is touched, and biphase liquid quickly mixes under strong cyclonic action and reacts;While reaction is carried out, carry out in inner barrel 21 inner chamber Initial gross separation, subsequently enters the conical pipe 22 of inner barrel 21 bottom connection, and then centrifugal force increases, and centrifugation is strengthened, in short-term Interior complete to separate, finally light phase product or light phase raw material more than needed are discharged through light phase overflow outlet 17, heavy phase product or richness Remaining heavy phase raw material is discharged by the heavy phase underflow outlet pipe 23 that conical pipe 22 bottom connects.
Embodiment 2
Referring to the drawings 2:Catalyst circulation pipe 10 is provided with the catalyst circulation adjustable valve 12 controlling catalyst circulating load, The circulating load of catalyst is to circulate adjustable valve 12 come control realization by catalyst, and other are arranged and work process and enforcement Example 1 is identical.
Embodiment 3
Referring to the drawings 3:Secondary response segregation apparatuss are set up between high-efficiency cyclone separator 5 and catalyst circulating tank 7, two grades Reaction separating device includes second level cyclone separator 13, catalyst surge tank 14 and adjusting control valve 15, and high-efficiency cyclone separates The overflow head piece 501 at device 5 top connects second level cyclone separator 13 top entry, second level cyclone separator 13 by pipeline Bottom connects catalyst surge tank 14, and catalyst surge tank 14 passes through to buffer connecting tube 1401 and adjusting control valve 15 connects catalysis Agent circulating tank 7.
On the basis of example 1, it is additionally arranged second level cyclonic separation at the overflow head piece 501 of high-efficiency cyclone separator 5 Device 13, to guarantee the high efficiency separation of catalyst in product;Second level cyclone separator 13 underflow opening setting catalyst buffering Tank 14, catalyst surge tank 14 passes through an inclined tube and catalyst circulating tank 7 UNICOM, and second level cyclone separator 13 underflow is passed through to urge The adjusting control valve of the outlet of agent surge tank 14 controls.Other structures and operation principle are same as Example 1.
Embodiment 4
Referring to the drawings 4:High-efficiency cyclone separator 5 is arranged on the connection between riser reactor 3 and catalyst circulating tank 7 On pipe 16, pipeline connection catalyst circulating tank 7 top is passed through at high-efficiency cyclone separator 5 top, is provided with eddy flow and divides at outlet at bottom From device underflow regulating valve 6.This structure is used for the reaction that catalyst proportion is less than product proportion, high-efficiency cyclone separator 5 Overflow head piece 501 is connected with catalyst circulating tank 7, and high-efficiency cyclone separator 5 outlet at bottom is reacting product outlet.
Other structures and operation principle are same as Example 1.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention is made with other forms, appoints What those skilled in the art possibly also with the disclosure above technology contents changed or be modified as equivalent variations etc. Effect embodiment.But every without departing from technical solution of the present invention content, according to the present invention technical spirit to above example institute Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.

Claims (8)

1. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst it is characterised in that:Including vertical pipe type Reactor(3), high-efficiency cyclone separator(5)With catalyst circulating tank(7), riser reactor(3)Bottom is provided with feedstock Pipe(1), riser reactor(3)Top exit passes through connecting tube(16)It is sequentially communicated high-efficiency cyclone separator(5)And catalyst Circulating tank(7);Catalyst circulating tank(7)The catalyst circulation pipe of bottom side(10)Connection riser reactor(3)Bottom, urges Agent circulating tank(7)Middle part side is provided with fresh catalyst supply port(8), catalyst circulating tank(7)Bottom is provided with catalysis to be generated Agent exports(9);
High-efficiency cyclone separator(5)Including outer cylinder body(20)And inner barrel(21), outer cylinder body(20)It is sleeved on inner barrel(21)Outward Upper lateral part, outer cylinder body(20)With inner barrel(21)Between formed toroidal cavity, toroidal cavity be light phase liquid raw material relief area, And outer cylinder body(20)Side is provided with light phase feed tube(19), inner barrel(21)Inner barrel is communicated with barrel(21)Inner chamber and ring The material currency structure of shape cavity(24);Inner barrel(21)Internal upper part is cased with light phase overflow outlet(17), light phase overflow outlet Pipe(17)With inner barrel(21)Between form annular mixing cavity, and light phase overflow outlet(17)Inner barrel is stretched out on top(21) Outside;It is provided with strong rotational structure, heavy phase liquid raw material is entered by strong rotational structure at the annular entry on annular mixing cavity top Enter annular mixing cavity and form strong rotational flow field.
2. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1, its It is characterised by:Described riser reactor(3)For the multi-stage reacting device of raw material successively up reaction, including body, raw material Feed pipe(1)And static mixer(2), its bottom is provided with three groups or more than three groups material feeding tubes(1), body side under Up it is laid with multigroup material feeding tube(1), it is correspondingly provided with multigroup static mixer in tubular body(2), multigroup static mixed Clutch(2)Multiple raw material reaction spaces, multigroup material feeding tube will be partitioned in body(1)It is anti-that one end is respectively communicated with multiple raw materials Answer space.
3. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 2, its It is characterised by:Described body internal upper part is additionally provided with flow of fluid distributor(4).
4. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1, its It is characterised by:Described catalyst circulation pipe(10)It is provided with the speed governing pipeline circulating pump controlling catalyst circulating load(11).
5. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1, its It is characterised by:Described catalyst circulation pipe(10)It is provided with the catalyst circulation adjustable valve controlling catalyst circulating load (12).
6. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1, its It is characterised by:Described high-efficiency cyclone separator(5)It is arranged on connecting tube(16)With catalyst circulating tank(7)Between, efficient rotary Stream separator(5)Top side connects connecting tube(16), cyclone separator underflow regulating valve is passed through in bottom(6)Connection catalyst follows Ring tank(7)Top, and high-efficiency cyclone separator(5)Top is provided with overflow head piece(501).
7. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1 or 6, It is characterized in that:Described high-efficiency cyclone separator(5)With catalyst circulating tank(7)Between set up secondary response segregation apparatuss, Secondary response segregation apparatuss include second level cyclone separator(13), catalyst surge tank(14)And adjusting control valve(15), high Effect cyclone separator(5)The overflow head piece at top(501)Second level cyclone separator is connected by pipeline(13)Top entry, the Two-stage cyclone separator(13)Bottom connects catalyst surge tank(14), catalyst surge tank(14)By buffering connecting tube (1401)And adjusting control valve(15)Connect catalyst circulating tank(7).
8. the liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst according to claim 1, its It is characterised by:Described high-efficiency cyclone separator(5)It is arranged on riser reactor(3)With catalyst circulating tank(7)Between Connecting tube(16)On, high-efficiency cyclone separator(5)Pipeline connection catalyst circulating tank is passed through at top(7)Top, at outlet at bottom It is provided with cyclone separator underflow regulating valve(6).
CN201410137686.9A 2014-04-08 2014-04-08 Liquid liquid heterogeneous catalytic reaction separation integrated apparatus based on liquid-phase catalyst Active CN104971674B (en)

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CN103551085A (en) * 2013-11-08 2014-02-05 神马实业股份有限公司 Catalyst separation device for cyclohexanone ammoximation reaction

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CN102108306A (en) * 2009-12-28 2011-06-29 中国石油大学(北京) Alkylation reaction method using ionic liquid as catalyst
CN103551085A (en) * 2013-11-08 2014-02-05 神马实业股份有限公司 Catalyst separation device for cyclohexanone ammoximation reaction

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