CN102059081A - Tubular reactor for performing liquid phase oxidation on cyclohexane by utilizing pure oxygen (enriched oxygen) - Google Patents
Tubular reactor for performing liquid phase oxidation on cyclohexane by utilizing pure oxygen (enriched oxygen) Download PDFInfo
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Abstract
The invention belongs to the field of energy resource and chemical industry, and relates to a tubular reactor for performing liquid phase oxidation on hydrocarbons by utilizing pure oxygen (enriched oxygen). The tubular reactor comprises a gas distribution unit, a tubular reactor and a highly integrated reaction heat removal and utilization mode. A gas forms a large number of bubbles with the diameters below 2 mm by the shearing action of liquid in a cross-flow aeration unit; the bubbles are uniformly mixed with a reaction liquid phase; the obtained gas-liquid mixture passes through a tubular reaction area with a high slenderness ratio in a laminar flow mode; and oxygen in a gas phase is completely transformed in the process. The reactor and a heat exchanger are highly integrated; and high degree of energy integration is realized by combining reaction heat removal with liquid-phase raw material preheating. The reactor designed in the invention has the advantages that: the structure is compact, the space utilization ratio is high, the highly integrated design greatly improves the comprehensive utilization level of heat energy, the internal security is high, the temperature is controlled accurately, products have high selectivity and high yield, and the tubular reactor can be used for pure oxygen and enriched oxygen oxidation, has a simple structure, is easy to maintain and enlarge and the like.
Description
Technical field
The present invention relates to the energy and chemical field, relate to the production preparation of oxygen-containing organic compound, belong to cleaning green chemical industry process, is a kind of hydro carbons liquid-phase oxidation reactor.Be particularly related to a kind of tubular reactor that is applicable to the gas liquid reaction of strong heat release, be specially adapted to the hydro carbons liquid phase oxidation reaction that carries out as oxidant with pure oxygen (oxygen enrichment).Gas is configured to a large amount of micro-bubbles and evenly mixes with the liquid phase cyclohexane through the cross-flow aerator, mix back gas-liquid material with the mode of laminar flow and stream by reaction zone, wherein the oxygen in the gas phase is realized conversion fully in this process.
Background technology
Oxidation reaction is one of most important reaction in the chemicals process, is a crucial conversion reaction of step of producing oxygen-bearing organic matter with hydrocarbon compound.P xylene oxidation system in toluene oxidation system benzoic acid in producing as caprolactam, cyclohexane oxidation system cyclohexanone, nylon 6 productions is to processes such as dibenzoic acids, and oxidation of isobutane is courses of industrialization such as the TBHP and the tert-butyl alcohol, all is typical strong heat release gas liquid reaction in the petrochemical industry.A lot of oxidation reactions adopt liquid phase oxidation techniques, compare with gaseous oxidation technology have the reaction condition gentleness, the selectivity advantages of higher.Tank reactor or bubble tower that existing industrialization hydro carbons liquid-phase oxidation reactor adopts band to stir usually.Stirred tank has moving component, and it seals difficulty, the operation and maintenance cost height of equipment.Backmixing of liquid phase is serious in stirred tank and the bubbling column reactor simultaneously, brings adverse effect for raising liquid phase oxidation product selectivity.
The hydro carbons liquid phase oxidation reaction is highly favourable on thermodynamics, generally is the free chain reaction of strong heat release, and thermal explosion or branched chain explosion take place easily.In bubble tower or the stirring bubbling reactor, air passes through reactor by the form of bubbling, has bigger gas-phase space on the top of reactor, and danger easily sets off an explosion.Pre-existing reactors gas-liquid back-mixing is serious, and the gas-liquid back-mixing not only influences the selectivity of reaction, also causes bubble time of staying distribution broadening, and the control of tail gas oxygen concentration is difficulty more.In order to guarantee safety, the oxygen concentration that the mode of oxygen content is controlled in the tail gas in employing restriction oxygen-supplying amount or the reaction gas is no more than explosion limit in the production.This makes course of reaction be in the state of oxygen supply deficiency all the time, and causes reactor volume huge, and utilization of space is low, and production efficiency is low.In the industry oxidation reaction process, the conversion per pass of hydrocarbon is low, and a large amount of reactant liquor circulations cause separation process long flow path, energy consumption height.
Structural shape by adjusting reactor or gas distributor and improve the gas-liquid mixed situation, the oxygen delivery capacity that improves reactor is expected to improve reactor generative capacity and selectivity of product.Patent CN 1090165C is being divided into a plurality of reative cells with vertical reactor with metallic porous sheet, adopts the mode of gas-liquid counter current to operate, and makes gas dispersion even, thus the selectivity of raising conversion of cyclohexane and cyclohexanol, cyclohexanone.Patent CN 1142129C improves the oxygen delivery capacity of reactor by setting up air feed and aeration unit for existing stirring bubbling reactor, the production capacity of device can be brought up to 133 tons/day from 100 tons/day.Patent CN 100522897C is then by to being provided with certain packing section in the bubble tower, and adopt the mode of stage aeration to transform, make the reaction liquid phase pass through reactor, effectively improve the back-mixing problem of reactant, improve the selectivity of cyclohexane in the mode of laminar flow.Patent CN 1243704C adjusts the paddle in the stirred reactor, baffle plate and ventilating mode, has improved material dispersed situation in the oxidation reactor, has improved gas processing capability.Patent CN 101143811A is divided into two relatively independent reaction zones up and down with bubble tower, and the bubble tower bottom has also increased mechanical agitation and improved mixing efficiency, improves the efficient and the selectivity of reaction.
Up-to-date studies show that, the cyclohexane liquid-phase oxidation process is subjected to the influence of oxygen concentration and mass transfer bigger, and cyclohexane catalytic oxidation dynamics is first-order kinetics to oxygen.Therefore adopt pure oxygen (oxygen enrichment) to carry out the hydro carbons liquid phase oxidation and can improve oxygen concentration, thereby improve reaction rate and selectivity.Adopt pure oxygen (oxygen enrichment) to carry out the hydro carbons liquid phase oxidation simultaneously, can reduce the tail gas amount, reduce the vent gas treatment cost.But in existing stirring bubbling reactor and bubbling column reactor, use pure oxygen (oxygen enrichment) oxidant,, can bring the uppity shortcoming of oxygen concentration in the tail gas, have potential safety hazard for reaction as the cyclohexane liquid-phase oxidation.
For pure oxygen (oxygen enrichment) oxidation, Taiwan's scholars Chen Zheng appoints the characteristics that propose to utilize water and cyclohexane formation azeotropic mixture, dilutes as the oxygen concentration of inert media to gas-phase space with steam, guarantees the safety of reactor.Patent US 5880683 discloses a kind of mechanically stirred reactor and has been used for pure oxygen (oxygen enrichment) liquid phase oxidation, adopts powerful stirring of turbine stirrer that bubble breaking is disperseed, and sets up the mixing that guide shell is strengthened gas-liquid two-phase, improves the reaction depth of oxygen as far as possible.Adopt the perforate dividing plate that the gas-phase space and the liquid phase body portion at top are separated in reactor top simultaneously, and feeding nitrogen dilute to guarantee the safety of reactor to the top gas-phase space.But the result is a mechanical agitation can strengthen backmixing of liquid phase, and the existence of moving component makes the difficult in maintenance of reactor.Simultaneously, add nitrogen dilution tail gas and make the extra increasing of vent gas treatment load.
Summary of the invention
The present invention is directed to the deficiency of existing liquid-phase oxidation reactor, a kind of novel reactor that can be used for the hydro carbons liquid phase oxidation is provided, particularly is directed to a kind of tubular reactor of hydro carbons liquid phase oxidation reactions such as thiacyclohexane liquid phase pure oxygen (oxygen enrichment) oxidation reaction, toluene liquid phase pure oxygen (oxygen enrichment) oxidation reaction.Improve the efficient and the security of oxidation reactor, must break through existing reaction technology, improve reaction rate, dwindle the reactor free space.Strengthen mass transfer with the minor diameter bubble, utilize channel diameter limited reactions degree, and augmentation of heat transfer and the time to remove reaction heat be to guarantee the basic measures of reacting safe.Patent of the present invention is designed a kind of tubular reactor that can be used for the hydro carbons liquid phase oxidation based on this principle, has safe, good reaction selectivity, reaction conversion ratio height, is convenient to advantages such as amplification.
Porous aeration generally speaking because bubble becomes air pocket at the coalescence of eating dishes without rice or wine, leave the aperture after, air pocket is broken into minute bubbles.Owing to the restriction of maximum stable bubble size, generally can only obtain the bubble of maximum stable bubble size size.The maximum stable bubble size is about 4 ~ 6mm generally speaking, and general porous aeration is difficult to obtain having the littler bubble of high mass transfer surfaces.According to our research, the cross-flow micro-pore aeration can obtain gas distributor less than the incipient bubble cross-flow micro-pore aeration mode of maximum stable bubble size and can produce the Sauter average diameter and be not more than 2.0 mm(or 1.5 mm) small oxygen bubble.Therefore, the cross-flow aeration can obtain higher gas-liquid mass transfer efficient.
There are some researches show that the possibility that the bubble that liquid phase is disperseed is hung fire occurs in the air pocket greater than 4 ~ 6mm, the bubble below the 1.5 ~ 2.0mm that produces for the cross-flow micro-pore aeration is safe in reaction tube.Because the heat transfer efficiency height of sleeve pipe tubular reactor also can avoid reacting the situation that thermal explosion occurs effectively.Adopt single tube reactor, oxygen is consumed in course of reaction in a large number, can reduce the gas compartment of oxygen (or oxygen enrichment) tail gas after gas-liquid separation, has also reduced the explosion danger of gas-phase space.
The technical scheme that realizes above-mentioned purpose is as follows:
With liquid hydrocarbons such as cyclohexane, toluene, paraxylene, iso-butane, isopropylbenzenes is raw material, and pure oxygen or oxygen-enriched air are oxidant.Liquid charging stock mixes with the catalyst (as cobalt naphthenate, cobalt acetate etc.) of specified rate earlier, then gas-liquid two-phase fluid through pre-heating temperature elevation to 120 ~ 220 ℃ of reaction temperatures, mix at micropore cross-flow aeration unit, obtain that bubble diameter is little, quantity is big, and the gas-liquid mixed logistics that is evenly distributed, the gas-liquid mixed logistics is fully reacted in tubular reactor, and oxygen expenditure wherein is complete.
Described reaction unit of the present invention comprises two types of single channel and multichannels, and single-stage and multistage two kinds of patterns.
The single channel reaction unit is made of gas liquid cross-flow mode aeration element and tubular reactor.Gas liquid cross-flow aeration component structure as shown in Figure 1, liquid with the process of certain flow rate by interior pipe in, oxygen (or oxygen enrichment) is distributed in the liquid phase by a porous metal film pipe (or ceramic post sintering film pipe), under liquid cross-flow shear action, be separated into the bubble of Sauter average diameter, flow to into reaction tube with liquid less than 2.0mm.The reaction tube design is sleeve structure as shown in Figure 2, and the outer logical cooling fluid of pipe is in time removed reaction heat, guarantees that reaction temperature is constant.Gas-liquid two-phase dispersion and stream pass through in the reaction tube, and reaction mass flows through reactor with plug flow mode.
The pipe reaction district is the stainless steel tube formation of 2 ~ 50 mm by diameter, and the flow pattern of gas-liquid mixture is near laminar flow in the reaction zone.Can obtain the little and gas-liquid mixed logistics that is evenly distributed of bubble diameter by cross-flow aeration type gas distributor, gas-liquid two-phase mixes fully, can effectively promote the carrying out that reacts.
The outside of conversion zone pipe is a shell side of walking cooling medium, and cooling medium can be special cooling agent such as cooling water, also can be the raw material hydrocarbon for the treatment of preheating.Originally the reactor and the heat exchanger of independent operating are integrated into the incorporate reactor of reacting replacing heat thus, can effectively remove reaction heat, and comprehensive utilization that again can realization response heat reduces plant energy consumption.Its good heat transfer property has guaranteed the accurate control of reaction, has dwindled the fluctuation range of reaction temperature, and the phenomenon that the temperature that tank reactor is occurred surpasses the control temperature is solved at all.The degree that the feasible on the one hand side reaction that is caused by the temperature rising of the accurate control of reaction temperature takes place reduces, thereby improves the yield of purpose product.
The multi-channel reaction device then is made of multichannel aeration unit and multi-channel reaction unit.The multi-channel reaction device is arranged by the parallel connection of a plurality of cross-flow micro-pore aeration single tube reactor and is formed, and each pipe reaction element design is the shell-and-tube heat exchanger structure, and reaction tube is outward the shell side cooling medium.Multichannel aeration unit structure is a microporous membrane pipe array as shown in Figure 3, and the multi-channel reaction unit is an array as shown in Figure 4, and the arrangement form of the passage of aeration unit is corresponding one by one with the arrangement form of reaction member passage.Its package assembly as shown in Figure 5.Because gas distributor and reaction zone are tubular structure, form is simple, therefore can amplify by the realization response device by the quantity that increases parallel tubular structure.What the modes that number increases amplification can avoid that traditional reactor runs in size is amplified flows, and the problem that the mass transfer situation changes makes this reactor have and amplifies simple characteristics.When reaction time is longer, can as required single channel and multi-channel reaction device be carried out plural serial stage according to the form shown in the accompanying drawing 6, cooling medium can adopt the form with reactant liquor Cheng Bingliu or adverse current.
The useful result of the present invention has:
1. compact equipment, space reactor utilization rate height.
Reactor and heat exchanger height are integrated, but that preheating of realization response material and reactor move the heat of heat is integrated, reduce energy consumption.Simultaneously high heat exchange efficiency makes and need not to establish in addition the outer circulation heat exchanger.
The control of reaction temperature is accurately high, and the selectivity of goal response is good, the yield height of purpose product.
Reactor intrinsic safety height can utilize oxygen enrichment or pure oxygen to carry out the hydro carbons liquid phase oxidation reaction.
Simple in structure, maintenance cost is low, and realizes the industry amplification easily.
Description of drawings
Fig. 1 single channel gas liquid cross-flow micro-pore aeration cellular construction schematic diagram; 1 is gas feed among the figure, and 2 is liquid-inlet, and 3 are the gas-liquid mixture outlet, and 4 is porous membrane tube.
Fig. 2 single channel tubular reactor structural representation; 1 is gas feed among the figure, and 2 is liquid-inlet, and 3 is liquid outlet, and 4 is coolant inlet, and 5 is coolant outlet.
Fig. 3 multi-channel reaction device aeration unit structural representation; 1 is gas feed among the figure.
Fig. 4 multi-channel reaction device reaction segment structure schematic diagram; 1 is coolant inlet among the figure, and 2 is coolant outlet.
Fig. 5 multi-channel reaction device assembling schematic diagram; 1 is gas feed among the figure, and 2 is liquid-inlet, and 3 is liquid outlet, and 4 is coolant inlet, and 5 is coolant outlet, and 6 are the rectification baffle plate.
Fig. 6 list/multi-channel reaction device plural serial stage schematic diagram; (a) coolant line parallel-connection structure; (b) coolant line cascaded structure; 1, gas supply main; 2, gas is supplied with branch road; 3, cooling agent supply main; 4, cooling agent is supplied with branch road; 5, coolant outlet pipeline; 6, cooling agent compiles house steward, and 7, the reactant liquor import; 8, reactant liquor outlet.
The specific embodiment
Embodiment 1:
Gas liquid cross-flow aeration unit basic structure in the present embodiment as shown in Figure 1.Basic structure after the reactor assembling as shown in Figure 2.Wherein aeration unit is a sleeve structure, and interior pipe is the microporous barrier pipe, and film length of tube and diameter can be according to actual needs by calculating.Usually the film length of tube is 0.003 ~ 0.03 m, and film pipe diameter is 0.002 ~ 0.10 m, and the average pore size of micropore is 0.01 ~ 1000 μ m on the film pipe.The length of conversion zone and diameter are absorbed the required time fully according to the required time of staying of the reaction of actual needs and oxygen and are designed.Wherein the scope of length is 0.5 ~ 500 m; The diameter of reaction tube is 0.002 ~ 0.10 m, and its big I is consistent with the diameter of aeration unit film pipe, also can be greater than the diameter of film pipe.It is made material and can be nonmetallic materials such as stainless steel and other metal materials and pottery.
Wherein oxygen (or oxygen enrichment) enters the annular space of aeration unit sleeve pipe by the gas feed among Fig. 1, and through micropore penetrated the microporous barrier pipe within it side mix with the liquid reaction raw material.The flow direction of liquid hydrocarbon is vertical mutually with gas flow direction, and consequent shear action makes the diameter of bubble be evenly distributed, and average diameter is not more than 2.0 mm.The minute bubbles that aeration unit produces are taken away by the reactant liquor that flows rapidly after formation, leave the aeration zone, are evenly dispersed in the liquid phase, thereby have suppressed coalescence effect between bubble effectively.
Gas-liquid mixture enters reaction zone after leaving aeration unit.Reaction zone is similarly sleeve structure, and the gas-liquid reactant mixture is walked in its middle sleeve inboard, and reactant mixture fully reacts complete until oxygen expenditure at this; The annular space of sleeve pipe is walked cooling medium (cold conditions raw material hydrocarbon or cooling water etc.), and cooling medium can be so that also the mode of stream or adverse current and the gas-liquid mixture in the pipe carry out heat exchange.Because the caliber of sleeve structure is little, heat exchange area is big, and therefore the heat exchange efficiency height can effectively avoid occurring in the reactor focus.Gas-liquid mixture flowing near laminar flow in pipe under high length-diameter ratio significantly reduced the back-mixing of intermediate oxidation product as alcohol, ketone simultaneously, avoids it that deep oxidation takes place, and can improve to a certain extent the purpose product selectivity.Oxygen in the gas phase is absorbed fully in reaction or is almost completely absorbed, thereby does not have a large amount of oxygen tail gas that contain.This has not only guaranteed the security of reactor, can also save the expense of vent gas treatment, has reduced the loss of reaction raw materials with tail gas.
Embodiment 2:
Adopt the Pyatyi series system to make up multistage subsection-inlet reactor on the basis of embodiment 1.Gas distributor wherein at different levels is the porous metal film pipe of long 10 mm, internal diameter 4 mm, external diameter 8 mm; Conversion zones at different levels are the stainless pipe of internal diameter 50 mm, and wherein the length in preceding fourth-order reaction district is 2 m, and the length of level V reaction zone is 4 m.With the cobalt naphthenate is catalyst, Co
2+Mass fraction be 1 * 10
-6, 165 ℃ of reaction temperatures under the pressure 1.1MPa, are that oxidant carries out cyclohexane liquid-phase oxidation production KA oil with the pure oxygen.Liquid hot cyclohexane flow is 0.105 m
-3H
-1, the oxygen flow of gas distributors at different levels is 0.0276 m
-3H
-1, the time of staying 10.7 min, bubble Sauter average diameter 1.68 * 10
-3M, cyclohexane conversion is 3.5%, KA oil selectivity 85%.The space-time yield of cyclohexane oxidation is: 1.00 molm
-3H
-1
Embodiment 3:
With embodiment 1 is fundamental construction multi-channel reaction device.Gas liquid cross-flow aeration unit structure in the present embodiment as shown in Figure 3, the structure of conversion zone is as shown in Figure 4.Its set of reactors assembling structure as shown in Figure 5.Wherein the structure of aeration unit (Fig. 3) is a microporous barrier pipe array, and the length of microporous barrier pipe and diameter are with the requirement of embodiment 1, and the quantity of microporous barrier pipe then increases and decreases according to the requirement of production capacity.Aeration unit place oxygen at first enters the cavity in the microporous barrier pipe outside by gas feed, see through each microporous barrier pipe again and enter reaction liquid phase and evenly mixing with it.Reactant liquor enters reactor by the liquid phase import, flows into each microporous barrier pipe respectively after baffle plate is suitably adjusted velocity flow profile, and is the bubble that diameter is not more than 2mm by shear action with the gas dispersion of saturating filmed passing tube.Liquid stream also evenly disperses the minute bubbles band that forms in the reaction liquid phase from the aeration zone rapidly simultaneously.Reaction segment structure as shown in Figure 4, wherein the layout of each microporous barrier pipe of the layout of each pipe and aeration unit is corresponding one by one.
Conversion zone can adopt flange to be connected with the connected mode of aeration section or weld.The length of same conversion zone and the requirement of diameter such as enforcement mode 1, and the required time of staying of reaction according to actual needs and oxygen are absorbed the required time fully and design.The quantity of reaction tube is consistent with the quantity of microporous barrier pipe in the aeration unit.Here the mobile of each pipe is consistent with reactiveness, do not exist in traditional amplification process and have problems such as flow regime changes, need only aeration unit and reaction member number be increased the amplification that suitable layout can finishing device of passing through of going forward side by side according to the requirement of production capacity.Gas-liquid mixture fully reacts back gas phase oxygen and is absorbed fully or almost completely absorb, and reacted liquid phase outflow reactor after the port of export of reaction tube is joined enters next workshop section and handles.
Embodiment 4:
Based on embodiment 1, make up the plural serial stage single pass reactor as shown in Figure 6, each reaction member cooling medium can be serial or parallel connection, with the reactant liquor flow direction is and stream or adverse current.
Embodiment 5:
Based on embodiment 3, make up plural serial stage multi-channel reaction device as shown in Figure 6, each reaction member cooling medium can be serial or parallel connection, with the reactant liquor flow direction is and stream or adverse current.
Claims (10)
1. tubular reactor that is used for hydrocarbon oxidation, this reactor is applicable to the hydro carbons liquid phase oxidation reaction that heat exchange load is very big, it is characterized in that this reactor mainly is made up of gas liquid cross-flow micro-pore aeration unit, tubular type gas-liquid two-phase reaction member and the housing of walking cooling medium.
2. according to claim 1, there is one section pipe to constitute in the passage that is characterized as liquid flow of aeration unit by microporous barrier pipe or side-wall hole, its material can be metal or pottery, the film length of tube is 0.003-0.03 m, film bore/external diameter is 0.002-0.10 m, and the average pore size scope of film pipe micropore is 0.01-1000 μ m.
3. according to claim 1, reaction member be characterized as sleeve structure, interior length of tube is 0.5-500 m, inner/outer diameter is 0.002-0.10 m, its big I is consistent with the inside/outside footpath of aeration unit, also can be than the inside/outside footpath of aeration unit greatly.
4. according to claim 1, the single channel structure that tubular reactor can adopt gas liquid cross-flow micro-pore aeration unit to connect with tubular type gas-liquid two-phase reaction member, reactor can vertically be placed or horizontal positioned, aeration unit can be connected the reaction member top when vertically placing, this moment, gas-liquid mixture also flowed to down, aeration unit can be connected the bottom of reacton, and this moment, gas-liquid mixture also flowed to.
5. according to claim 1, tubular reactor can adopt the multi-channel structure that is made of jointly aeration unit array and reaction member array, the geometry spread pattern of microporous barrier pipe and reaction member pipe can be equilateral triangle, form such as square or staggered square pitch, all film pipes are included in the same housing, the air inlet that one or more symmetrical distributions are arranged on the housing, all pipes of reaction member then are wrapped in another housing, the shell internal clearance is the cooling medium flowing space, has the cooling medium of one or more symmetrical distributions to import and export on the housing.
6. according to claim 1, the liquid phase feeding mouth of multi-channel structure tubular reactor sets up the baffle plate or the porous plate of appropriate size the velocity flow profile of liquid charging is adjusted, make flow rate of liquid on whole space, be evenly distributed, the flow rate of liquid basically identical in each film pipe.
7. according to claim 1, in the reactor reaction unit pipe is the flow channel of gas-liquid two-phase reactant mixture, space between pipe and the shell is the flow of coolant space, cooling agent can be liquid hydrocarbon to be heated, also can be special-purpose cooling mediums such as cooling water, and the flow direction of cooling agent and reaction logistics can be for also flowing or adverse current.
8. according to claim 1, the film intraluminal fluid speed of aeration unit is 0.25 m.s
-1-25 m.s
-1, the gas speed at place, micropore aperture is 0.1 m.s
-1-50 m.s
-1, the gained bubble diameter is not more than 2.0 mm.
9. according to claim 1, single channel and multichannel tubular type reactor all can directly utilize pure oxygen or oxygen concentration to carry out the hydro carbons liquid phase oxidation reaction greater than 30% oxygen-containing gas, are 100 ℃-250 ℃ according to the differential responses temperature of hydrocarbon raw material.
10. according to claim 1, the structure of tubular reactor can be by a plurality of single channel aeration units and single channel reaction member, and a plurality of multichannel aeration units and multi-channel reaction unit, the reaction of high order system that the mode that replaces according to aeration unit, reaction member is connected and formed.
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| WO2013143248A1 (en) * | 2012-03-30 | 2013-10-03 | 凯莱英医药集团（天津）股份有限公司 | Continuous ozonation reaction device and operating method therefor |
| CN109589880A (en) * | 2019-01-22 | 2019-04-09 | 常州瑞华化工工程技术股份有限公司 | A kind of horizontal efficient plug flow bubbling reactor |
| CN110698319A (en) * | 2019-09-30 | 2020-01-17 | 河北美邦工程科技股份有限公司 | Gas-liquid phase chloroethylene production process and device |
| CN111111600A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Reactor with a reactor shell |
| CN112973614A (en) * | 2021-02-10 | 2021-06-18 | 中国科学院过程工程研究所 | Gas-liquid reaction device, and use method and application thereof |
| CN113522192A (en) * | 2020-04-20 | 2021-10-22 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013143248A1 (en) * | 2012-03-30 | 2013-10-03 | 凯莱英医药集团（天津）股份有限公司 | Continuous ozonation reaction device and operating method therefor |
| CN111111600A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Reactor with a reactor shell |
| CN109589880A (en) * | 2019-01-22 | 2019-04-09 | 常州瑞华化工工程技术股份有限公司 | A kind of horizontal efficient plug flow bubbling reactor |
| CN109589880B (en) * | 2019-01-22 | 2023-09-19 | 常州瑞华化工工程技术股份有限公司 | Horizontal high-efficiency plug flow bubbling reactor |
| CN110698319A (en) * | 2019-09-30 | 2020-01-17 | 河北美邦工程科技股份有限公司 | Gas-liquid phase chloroethylene production process and device |
| CN110698319B (en) * | 2019-09-30 | 2022-03-29 | 河北美邦工程科技股份有限公司 | Gas-liquid phase chloroethylene production process and device |
| CN113522192A (en) * | 2020-04-20 | 2021-10-22 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
| CN112973614A (en) * | 2021-02-10 | 2021-06-18 | 中国科学院过程工程研究所 | Gas-liquid reaction device, and use method and application thereof |
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Application publication date: 20110518 |